CN1753930A - Polybutylene terephthalate, method for producing same, composition and film thereof - Google Patents

Abstract

The present invention relates to polybutylene terephthalate (PBT) containing titanium and having a content of 33ppm or less or 33ppm or less in terms of titanium atom, and a composition thereof. In the PBT and the composition thereof of a preferred embodiment of the present invention, the temperature-lowering crystallization temperature is 170 to 190 ℃, the terminal vinyl group concentration is 0.1 to 10. mu. eq/g, the solution haze is 10% or less, and the increase in the terminal carboxyl group concentration upon heat treatment under a predetermined condition is 0.1 to 30. mu. eq/g, and 50 foreign matters of 5 μm or more are 50 foreign matters per 10g of polymer or 50 foreign matters per 10g of polymer. Such PBT and a composition thereof are excellent in color tone, hydrolysis resistance, thermal stability, transparency and moldability, and can be suitably used for films, monofilaments, fibers, electric and electronic parts, automobile parts and the like, with reduced foreign matter.

Description

Polybutylene terephthalate, method for producing same, composition and film thereof

technical field

The present invention relates to polybutylene terephthalate and its production method as well as its composition and film. More specifically, the present invention relates to a polymer that is excellent in color tone, hydrolysis resistance, heat stability, transparency, and formability, and can reduce foreign matter, and is applicable to polymers such as films, monofilaments, fibers, electrical and electronic parts, and automotive parts. Butylene terephthalate, method for its manufacture, and compositions and films thereof.

Background technique

Polybutylene terephthalate, which is a representative engineering plastic among thermoplastic polyester resins, is difficult to process due to its ease of molding, mechanical properties, heat resistance, chemical resistance, fragrance retention, and other physical and chemical properties. It has excellent properties and is widely used in injection molded products such as automotive parts, electrical and electronic parts, and precision machine parts. In recent years, it has been widely used in fields such as films, sheets, monofilaments, and fibers by making effective use of its excellent properties.

We know that, generally speaking, the higher the concentration of terminal carboxyl groups in polyester, the worse the hydrolysis resistance (for example, on December 22, 1989, Nikkan Kogyo Shimbun issued "Saturated Polyester Resin Handbook" pp. 192-193), In polybutylene terephthalate, the concentration of terminal carboxyl groups is high, and the hydrolysis reaction rate under moist heat also increases, and there are serious problems such as reduction of molecular weight due to hydrolysis, and further reduction of mechanical properties.

In addition, since the usual melt molding is carried out at or above the melting point of polybutylene terephthalate, the concentration of terminal carboxyl groups increases again during molding, and when it becomes a molded product, the hydrolysis resistance is further deteriorated. The problem.

In order to solve the above-mentioned problems, once the polybutylene terephthalate obtained by melt polymerization is solidified, it is solid-phase polymerized at a temperature below its melting point or the melting point, so that the method of reducing the carboxyl group concentration at the terminal is widely carried out ( For example, JP-A-9-316183). However, as mentioned above, in the original polybutylene terephthalate, although the concentration of the terminal carboxyl group is reduced by solid-state polymerization, the concentration of the terminal carboxyl group is again increased during molding, and the product after molding When , there is a problem that the effect of solid phase polymerization becomes small.

On the other hand, especially in applications such as films, sheets, monofilaments, fibers, etc., since the commercial value is largely influenced by foreign matter, fogging, coloring, etc., reduction or improvement of these problems is strongly demanded. Foreign matter or haze in polybutylene terephthalate is considered to be deactivated matter or agglomeration of metal compounds added as a catalyst, in addition to resin deterioration products generally called scorch or die coke Matter is also its cause.

Therefore, it is proposed to divide the continuous esterification reaction of terephthalic acid and 1,4-butanediol into two stages, in the esterification reaction of the first stage, only the organic tin compound is added, and in the esterification reaction of the second stage A method of reducing foreign matter or haze from the catalyst by adding an organic titanium compound during the reaction (for example, JP-A-10-330468).

However, due to the high concentration of metals in the finally obtained polybutylene terephthalate, the effect of reducing foreign matter or haze is limited, and these metal compounds cause problems such as deterioration of the color tone of the polymer or deterioration of heat resistance (see Patent Document 4). In addition, the above-mentioned increase in the terminal carboxyl group concentration at the time of melting is accelerated by the metal compound as a catalyst, and as a result, there is also a disadvantage of deteriorating the hydrolysis resistance.

A brief description of the drawings

FIG. 1 is an explanatory diagram of 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 the transesterification reaction step used in the present invention.

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

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

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

Fig. 6 is an explanatory diagram of an example of a 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.

Contents of the invention

The present invention has been made in view of the above-mentioned circumstances, and its object is to provide a product that is excellent in color tone, hydrolysis resistance, thermal stability, transparency, and formability, and has reduced foreign matter, and can be applied to films, monofilaments, fibers, and electrical and electronic components. Polybutylene terephthalate, automotive parts, etc., a method for producing the polybutylene terephthalate, and a polybutylene terephthalate composition and film containing the polybutylene terephthalate and having various functions.

The inventors of the present invention conducted intensive studies to solve the above-mentioned problems, and as a result found that if esterification or transesterification is carried out under specific conditions, the utilization efficiency of the catalyst can be improved, and the usage amount of the catalyst can be significantly reduced. As a result, The novel polybutylene terephthalate having significantly reduced catalyst content can easily solve the above-mentioned problems. It has also been found that by carrying out esterification or transesterification under specific conditions, the conversion rate can be increased, foreign substances can be reduced, and side reactions can be suppressed.

The present invention is accomplished based on the above-mentioned idea, and its first gist is a polybutylene terephthalate, which is characterized in that the polybutylene terephthalate contains titanium, and its titanium atom counts The content is 33ppm or less.

The second gist of the present invention is a method for producing polybutylene terephthalate, which is characterized in that in the esterification reaction tank, in the presence of a titanium catalyst, there is a continuous supply of terephthalic acid and 1,4 In the method for producing polybutylene terephthalate in which butanediol undergoes an esterification reaction, at least a part of 1,4-butanediol is independently supplied to the esterification reaction without terephthalic acid 10% by weight or more than 10% by weight of the 1,4-butanediol that is independently supplied to the esterification reaction tank is provided to the liquid phase part of the reaction liquid, and 10% by weight or 10% by weight of the titanium catalyst % or more is supplied to the liquid phase part of the reaction liquid independently without terephthalic acid.

The third gist of the present invention is a method for producing polybutylene terephthalate, which is characterized in that, in the transesterification reaction tank, in the presence of a titanium catalyst, there is continuous supply of dialkyl terephthalate In the method for producing polybutylene terephthalate in the process of transesterification with 1,4-butanediol, at least a part of 1,4-butanediol is not mixed with dialkyl terephthalate And independently supplied to the transesterification reaction tank, and 10% by weight or more of the 1,4-butanediol independently supplied to the transesterification reaction tank is provided to the liquid phase part of the reaction liquid, and the titanium 10% by weight or more of the catalyst is supplied independently to the liquid phase portion of the reaction liquid without terephthalic acid.

The fourth gist of the present invention is a method for producing polybutylene terephthalate, which is characterized in that in the esterification reaction tank, in the presence of a titanium catalyst, there is a continuous supply of terephthalic acid and relative to the terephthalate In the method for producing polybutylene terephthalate in which excess 1,4-butanediol of phthalic acid undergoes an esterification reaction, the terephthalic acid and 1 supplied to the esterification reaction tank are controlled per unit time, The molar ratio of 4-butanediol (the number of moles of 1,4-butanediol/the number of moles of terephthalic acid) was kept constant.

The fifth gist of the present invention is a method for producing polybutylene terephthalate, which is characterized in that, in the transesterification reaction tank, in the presence of a titanium catalyst, there is continuous supply of dialkyl terephthalate In the production method of polybutylene terephthalate in the process of performing transesterification reaction with 1,4-butanediol in excess relative to dialkyl terephthalate, the supply to the transesterification reaction tank is controlled per unit time The molar ratio of dialkyl terephthalate to 1,4-butanediol (the number of moles of 1,4-butanediol/the number of moles of terephthalic acid) was kept constant.

The sixth point of the present invention is a heat-resistant polybutylene terephthalate composition, which is characterized in that it contains polybutylene terephthalate selected from the first point, and phenols One or more antioxidants selected from antioxidant (B1), sulfur-based antioxidant (B2), and phosphorus-based antioxidant (B3).

The seventh point of the present invention is a polybutylene terephthalate composition with good mold release properties, characterized in that, relative to 100 parts by weight of the polybutylene terephthalate mentioned in the first point, containing Release agent (C) 0.01 to 2 selected from fatty acid esters (C1) containing fatty acid residues with 12 to 36 carbon atoms and alcohol residues with 1 to 36 carbon atoms, and paraffin wax and polyethylene wax (C2) parts by weight.

The eighth point of the present invention is a hydrolysis-resistant polybutylene terephthalate composition, which is characterized in that, relative to 100 parts by weight of the polybutylene terephthalate mentioned in the first point, a reinforcing filler ( D) 0-200 weight part and epoxy compound (E) 0.01-20 weight part.

The ninth point of the present invention is an impact-resistant polybutylene terephthalate composition, which is characterized in that, relative to 100 parts by weight of the polybutylene terephthalate mentioned in the first point, an impact-resistant 0.5-40 parts by weight of the improving material (F) and 0-200 parts by weight of the reinforcing filler (D).

The tenth point of the present invention is a flame-retardant polybutylene terephthalate composition, which is characterized in that, relative to 100 parts by weight of the polybutylene terephthalate mentioned in the first point, bromo 3-50 parts by weight of aromatic compound flame retardant (G), 1-30 parts by weight of antimony compound (H), 0-15 parts by weight of anti-dripping agent (I) and 0-200 parts by weight of reinforcing filler (D) .

The eleventh point of the present invention is a non-halogen flame-retardant polybutylene terephthalate composition, which is characterized in that, relative to the polybutylene terephthalate mentioned in the first point, 50 to 95 parts by weight 100 parts by weight in total of 5 to 50 parts by weight of polyphenylene ether resin (J), containing 0.05 to 10 parts by weight of solubilizer (K), and at least one compound (L) 2 to 45 selected from phosphoric acid ester or phosphazene Parts by weight, 0-200 parts by weight of reinforcing filler (D), 0-15 parts by weight of anti-dripping agent (I), 0-45 parts by weight of melamine cyanurate (M) and 0-50 parts by weight of metal borate (N) parts by weight.

The 12th point of the present invention is a kind of polybutylene terephthalate composition, it is characterized in that, with respect to 100 parts by weight of the polybutylene terephthalate mentioned in the 1st point, containing polycarbonate resin ( O) 5-100 parts by weight, organophosphorus compound (P) 0.01-1 parts by weight, reinforcing filler (D) 0-200 parts by weight, and impact modifier (F) 0-50 parts by weight.

The thirteenth point of the present invention is a polybutylene terephthalate composition, which is characterized in that, relative to 100 parts by weight of the polybutylene terephthalate mentioned in the first point, polybutylene terephthalate 5-100 parts by weight of aromatic polyester-based resin (Q) other than butylene diester, and 0-200 parts by weight of reinforcing filler (D).

The 14th point of the present invention is a kind of polybutylene terephthalate composition, it is characterized in that, with respect to 100 parts by weight of the polybutylene terephthalate mentioned in the 1st point, containing styrene resin ( R) 5-100 parts by weight, maleic anhydride-modified polystyrene resin (S) or polycarbonate resin (O) 0-40 parts by weight, reinforcing filler (D) 0-200 parts by weight.

A fifteenth gist of the present invention resides in a film characterized in that the film contains polybutylene terephthalate containing titanium and its content is 33 ppm or 33 ppm in terms of titanium atoms the following.

A sixteenth gist of the present invention resides in a film comprising 1 to 99% by weight of polybutylene terephthalate and 1 to 99% by weight of polyethylene terephthalate (however, both 100% by weight in total), the polybutylene terephthalate contains titanium and its content is 33 ppm or less in terms of titanium atoms.

A seventeenth aspect of the present invention resides in a film comprising 1 to 99% by weight of polybutylene terephthalate and 1 to 99% by weight of aromatic polyester copolymerized with polytetramethylene glycol. % (however, the total of the two is 100% by weight), the polybutylene terephthalate contains titanium and its content is 33 ppm or less in terms of titanium atoms.

Best way to implement the invention

<Polybutylene terephthalate>

Hereinafter, the present invention will be described in detail. The polybutylene terephthalate of the present invention (hereinafter, abbreviated as PBT) refers to a structure in which terephthalic acid units and 1,4-butanediol units are ester-bonded, dicarboxylic acid A polymer in which 50 mol% or more of the units are composed of terephthalic acid units and 50 mol% or more of the diol component is composed of 1,4-butanediol units. The proportion of terephthalic acid units in all dicarboxylic acid units is preferably 70 mol% or more, more preferably 80 mol% or more, particularly preferably 95 mol% or more, and all diols The proportion of 1,4-butanediol units in the units is preferably 70 mol% or more, more preferably 80 mol% or more, particularly preferably 95 mol% or more. When the terephthalic acid unit or the 1,4-butanediol unit is less than 50 mol%, the crystallization rate of PBT will fall, and formability will deteriorate.

In the present invention, the dicarboxylic acid components other than terephthalic acid are not particularly limited, and examples thereof include phthalic acid, isophthalic acid, 4,4'-biphenyldicarboxylic acid, 4, 4'-diphenyl ether dicarboxylic acid, 4,4'-benzophenone dicarboxylic acid, 4,4'-diphenoxyethane dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, Aromatic dicarboxylic acids such as 2,6-naphthalene dicarboxylic acid, alicyclic compounds such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid Aliphatic dicarboxylic acids such as dicarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid, and the like. These dicarboxylic acid components can be introduced into the polymer skeleton as dicarboxylic acids or dicarboxylic acid derivatives such as dicarboxylic acid esters and dicarboxylic acid halides as raw materials.

In the present invention, the diol components other than 1,4-butanediol are not particularly limited, and examples thereof include ethylene glycol, diethylene glycol, polyethylene glycol, 1,2-propylene glycol, 1 , 3-propanediol, polypropylene glycol, polytetramethylene glycol, dibutylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, etc. Aliphatic diol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-dimethylolcyclohexane, 1,4-dimethylolcyclohexane and other alicyclic Aromatic diols such as diol, xylylene glycol, 4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfone, and the like.

In the present invention, hydroxycarboxylic acids such as lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and p-β-hydroxyethoxybenzoic acid, alkoxy Carboxylic acid, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, tert-butylbenzoic acid, benzoylbenzoic acid and other monofunctional ingredients, glycerin, trimellitic acid, trimellitic acid, tribenzene Trifunctional or higher polyfunctional components such as tetraacid, trihydroxybenzoic acid, trimethylolethane, trimethylolpropane, glycerin, and pentaerythritol are used as copolymerization components.

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

Common titanium compounds can be used as the titanium catalyst, and specific examples thereof include inorganic titanium compounds such as titanium oxide and titanium tetrachloride, tetramethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, etc. Titanium alcoholate, titanium phenoxide such as tetraphenyl titanate, etc. Among them, tetraalkyl titanate is preferable, and among them, tetrabutyl titanate is preferable.

Besides titanium, tin can also be used as a catalyst. Tin is usually used as a tin compound, and specific examples thereof include dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, cyclohexylditin oxide, didecyltin oxide, and didecyltin oxide. Dialkyltin, triethyltin hydroxide, triphenyltin hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, tributyltin chloride, dibutyltin sulfide , Butyl hydroxytin oxide, methyl stannoic acid, ethyl stannic acid, butyl stannic acid, etc.

In addition to titanium, magnesium compounds such as magnesium acetate, magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium alkoxide, and magnesium hydrogen phosphate, calcium acetate, calcium hydroxide, calcium carbonate, calcium oxide, calcium alkoxide, and hydrogen phosphate can also be used. Calcium compounds such as calcium, antimony compounds such as antimony trioxide, germanium compounds such as germanium dioxide and germanium tetroxide, manganese compounds, zinc compounds, zirconium compounds, cobalt compounds, orthophosphoric acid, phosphorous acid, hypophosphoric acid, polyphosphoric acid, Phosphorus compounds such as esters or metal salts, reaction aids such as sodium hydroxide and sodium benzoate.

The above-mentioned catalyst or reaction auxiliary agent may be added in batches when the esterification reaction (or transesterification reaction) is a plurality of reaction tanks, or may be added in a continuous polycondensation reaction stage.

The PBT of the present invention is characterized by containing titanium at a content of 33 ppm or less in terms of titanium atoms. The above-mentioned value is the weight ratio with respect to the atom of PBT. In the present invention, the lower limit of the aforementioned titanium content is usually 1 ppm, preferably 3 ppm, more preferably 5 ppm, particularly preferably 8 ppm, and very preferably 15 ppm. The upper limit of the titanium content is preferably 30 ppm, more preferably 27 ppm. When the titanium content is more than 33 ppm, the color tone, hydrolysis resistance, transparency, formability, etc. deteriorate, and foreign matter tends to increase, and when it is less than 1 ppm, the polymerizability may deteriorate.

In the present invention, a tin catalyst may be used together with a titanium catalyst. In general, since tin catalysts have lower catalytic performance than titanium catalysts, they need to be added in a larger amount than titanium catalysts. However, if the tin catalyst is used in an excessive amount, the color tone will be deteriorated, and tin is also toxic. Therefore, the usage amount of tin catalyst is usually 100ppm or less, preferably 50ppm or less, more preferably 20ppm or less, and the best solution is not to use tin catalyst. The content of titanium atoms and the like can be measured by methods such as atomic emission, atomic absorption, and induced coupled plasma (ICP) after recovering the metals in the polymer by wet incineration or other methods.

The intrinsic viscosity of the PBT of the present invention is usually 0.60 to 2.00 dL/g, preferably 0.65 to 1.50 dL/g, more preferably 0.75 to 1.30 dL/g. When the intrinsic viscosity is less than 0.60 dL/g, the mechanical strength of the molded product is insufficient, and when it exceeds 2.00 dL/g, the melt viscosity tends to increase, fluidity deteriorates, and formability tends to deteriorate. The above intrinsic viscosity is a value measured at 30° C. using a mixed solvent of phenol/tetrachloroethane (weight ratio 1/1).

In the present invention, two or more PBTs having different intrinsic viscosities may be used in combination. At this time, it is preferable that any of the intrinsic viscosities of the plurality of PBTs used is within the above range of 0.60 to 2.00 dL/g, and the intrinsic viscosity of the composition is also preferably within the above range. For example, PBT (A1) having an intrinsic viscosity of 0.60 to 0.90 dL/g and PBT (A2) having an intrinsic viscosity of 0.91 to 1.50 dL/g can be mixed and used at a weight ratio of 5:95 to 95:5.

The terminal carboxyl group concentration of the PBT of the present invention is usually 0.1-35 μeq/g, preferably 1-25 μeq/g, more preferably 1-20 μeq/g, particularly preferably 1-15 μeq/g. When the terminal carboxyl group concentration is too high, the hydrolysis resistance of PBT deteriorates.

The terminal carboxyl group concentration preferably has a small molecular weight and is as low as possible within a low molecular weight range that is easily affected by a decrease in molecular weight due to hydrolysis. That is, it is recommended to satisfy the following formula (I-1), preferably formula (I-2), more preferably formula (I-3), and particularly preferably formula (I-4).

20×IV+6≥[COOH]≥20×IV-12 (I-1)

20×IV+4≥[COOH]≥20×IV-12 (I-2)

20×IV+2≥[COOH]≥20×IV-12 (I-3)

20×IV≥[COOH]≥20×IV-12 (I-4)

(Wherein, [COOH] is the terminal carboxyl group concentration (unit is μ eq/g), [COOH] > 0, IV represents intrinsic viscosity).

In addition, if the terminal carboxyl group concentration of PBT decreases, but increases due to heat during kneading or molding, it will not only deteriorate the hydrolysis resistance of the product, but also cause the generation of gases such as tetrahydrofuran. Therefore, in an inert gas atmosphere such as nitrogen, helium, argon, etc., the increase in the concentration of terminal carboxyl groups in the removal of the hydrolysis reaction when heat treatment is performed at 245° C. for 40 minutes is usually 0.1 to 30 μeq/g, preferably 1 to 10 μeq /g, more preferably 1 to 8 μeq/g. Generally, when the content of the catalytic substance is low, or when the molecular weight is high, the increase in the concentration of the terminal carboxyl group during heating tends to be small.

In the above-mentioned evaluation method, the reason for specifying the temperature or time is that if the temperature is too low or the time is too short, the rate of increase of the terminal carboxyl group concentration will be too small, and if it is too high, the evaluation will be incorrect. In addition, if the evaluation is performed at an extremely high temperature, side reactions other than the generation of terminal carboxyl groups occur simultaneously, and the evaluation becomes inaccurate, which is also one of the reasons. In this heat treatment condition, the reduction in the number average molecular weight caused by reactions other than the hydrolysis reaction caused by the moisture contained in PBT is negligible, and it can be considered that the increase in the concentration of terminal carboxyl groups caused by the hydrolysis reaction is related to the concentration of terminal hydroxyl groups before and after heat treatment. Therefore, the increase in the terminal carboxyl group concentration caused by thermal decomposition reactions other than the hydrolysis reaction that is a problem during kneading or molding can be obtained by the following formula (II).

ΔAV(d)＝ΔAV(t)-ΔAV(h)＝ΔAV(t)-ΔOH (II)

Here, ΔAV(d) represents the amount of change in the concentration of terminal carboxyl groups due to the thermal decomposition reaction, ΔAV(t) represents the total change in the concentration of terminal carboxyl groups before and after heat treatment, and ΔAV(h) represents the amount of change in the concentration of terminal carboxyl groups caused by the hydrolysis reaction The amount of change, ΔOH represents the amount of change in the concentration of terminal hydroxyl groups before and after heat treatment.

From the viewpoint of the reliability of thermal decomposition reaction evaluation, those with less hydrolysis reaction are preferred, and the water content of PBT used for heat treatment is generally recommended to be 300 ppm or less. The concentration of terminal hydroxyl groups before and after heat treatment can be quantified by ¹ H-NMR.

The terminal carboxyl group concentration of PBT can be calculated|required by dissolving PBT in an organic solvent etc., and then titrating using alkali solutions, such as a sodium hydroxide solution.

In addition, the terminal vinyl group concentration of the PBT of the present invention is usually 15 μeq/g or less, preferably 0.1 to 10 μeq/g, more preferably 1 to 8 μeq/g, particularly preferably 1 to 5 μeq/g. When the terminal vinyl group concentration is too high, it will cause deterioration of color tone or deterioration of solid-phase polymerizability. When producing PBT with a large molecular weight or PBT with a low catalyst concentration without reducing productivity, it is generally required to increase the polymerization temperature or prolong the reaction time, so the concentration of terminal vinyl groups tends to increase. The terminal vinyl group concentration can be quantified by dissolving PBT in a mixed solvent of deuterated chloroform/hexafluoroisopropanol=7/3 (volume ratio), and measuring ¹ H-NMR.

At the terminal of PBT, in addition to hydroxyl group, carboxyl group and vinyl group, methoxycarbonyl group derived from the raw material may remain, and especially when dimethyl terephthalate is used as the raw material, a large amount may remain. However, the methoxycarbonyl terminal generates methanol, formaldehyde, and formic acid by heat generated by solid-state polymerization, kneading, molding, etc., and especially when used in food applications, the toxicity of these substances becomes a problem. Additionally, formic acid can damage metal forming machines or vacuum-related machines. Therefore, the terminal methoxycarbonyl concentration in the present invention is usually 0.5 μeq/g or less, preferably 0.3 μeq/g or less, more preferably 0.2 μeq/g or less, especially It is preferably 0.1 μeq/g or less.

The concentration of each of the above terminal groups other than the terminal carboxyl group can be quantified by dissolving PBT in deuterated chloroform/hexafluoroisopropanol=7/3 (volume ratio) and measuring ¹ H-NMR. At this time, in order to prevent signal overlap with the solvent, a very small amount of basic components such as deuterated pyridine may be added.

The cooling crystallization temperature of the PBT of the present invention is usually 170-200°C, preferably 172-195°C, more preferably 175-190°C. The temperature-lowering crystallization temperature in the present invention is the temperature of the exothermic peak due to crystallization exhibited when the resin is cooled from a molten state at a cooling rate of 20°C/min using a differential scanning calorimeter. The cooling crystallization temperature corresponds to the crystallization speed, because the higher the cooling crystallization temperature is, the faster the crystallization speed is, and the cooling time can be shortened and the productivity can be improved during injection molding. When the cooling crystallization temperature is low, it takes time for crystallization during injection molding, and the cooling time after injection molding has to be prolonged, which tends to prolong the molding cycle and reduce productivity.

The solution mist value of PBT of the present invention is not particularly limited, is the solution mist value when the PBT of 2.7g is dissolved in 20mL phenol/tetrachloroethane mixed solvent (weight ratio 3/2) and measures, is usually 10 % or less, preferably 5% or less, more preferably 3% or less, particularly preferably 1% or less. When the haze value of the solution is high, the transparency tends to deteriorate and foreign matter also increases. Therefore, the commercial value of films, monofilaments, fibers, etc., especially in applications requiring transparency, significantly decreases. The fog value of the solution tends to increase when the catalyst content is high or the catalyst deactivation is large.

In addition, the foreign matter with a length of 5 μm or more contained in the PBT of the present invention is usually 60 pieces/10 g of polymer or less than 60 pieces/10 g of polymer. In particular, foreign matter in the raw material PBT resin such as film and monofilament is preferably 50 or less, more preferably 40 or less, and particularly preferably 30 when it is used for applications that greatly affect product quality. or less than 30.

The amount of foreign matter mentioned above can be obtained by dissolving 10 g of PBT in a mixed solvent of hexafluoroisopropanol/chloroform=2/3 (volume ratio) at a concentration of 20% by weight, and using a membrane made of polytetrafluoroethylene with a pore diameter of 5 μm After the filter is filtered, it is fully washed with the mixed solvent, and the amount of foreign matter remaining on the filter is observed and counted with an optical microscope.

Next, the manufacturing method of the PBT of this invention is demonstrated. The production method of PBT is divided into a so-called direct polymerization method using a dicarboxylic acid as a main raw material and a transesterification method using a dicarboxylic acid dialkyl ester as a main raw material in terms of raw materials. The difference between the two is that the former generates water in the initial esterification reaction, and the latter generates alcohol in the initial transesterification reaction.

In addition, the production method of PBT can be divided into a batch method and a continuous method in terms of raw material supply or polymer output form. It is also possible to carry out initial esterification or transesterification by continuous operation, followed by polycondensation by batch operation, or conversely, perform initial esterification or transesterification by batch operation, and then carry out polycondensation by continuous operation.

In the present invention, the direct polymerization method is preferred from the viewpoints of obtaining stability of raw materials, ease of handling of distillates, cost per unit consumption of raw materials, improvement effect of the present invention, and the like. In addition, in the present invention, from the viewpoints of productivity, stability of product quality, improvement effect of the present invention, etc., a method of continuously supplying raw materials and continuously performing esterification or transesterification is adopted. Furthermore, in the present invention, a so-called continuous method in which the polycondensation reaction carried out next to the esterification reaction or the transesterification reaction is also carried out continuously is preferable.

In the present invention, preferably in the esterification reaction tank (or transesterification reaction tank), in the presence of a titanium catalyst, at least a part of 1,4-butanediol is not mixed with terephthalic acid (or terephthalic acid) Dialkyl diformate) are fed together and independently into the esterification reaction tank (or transesterification reaction tank), while terephthalic acid (or dialkyl terephthalate) and 1,4-butanedi Alcohol is continuously subjected to the process of esterification (or transesterification).

That is, in the present invention, 1,4 - Unlike butanediol, 1,4-butanediol supplied independently without terephthalic acid or dialkyl terephthalate is supplied to the esterification reaction tank or the transesterification reaction tank. Hereinafter, this 1,4-butanediol may be referred to as "1,4-butanediol supplied separately".

The above-mentioned "1,4-butanediol supplied separately" can be used as fresh 1,4-butanediol not related to the process. In addition, "separately supplied 1,4-butanediol" can collect 1,4-butanediol distilled from the esterification reaction tank or the transesterification reaction tank with a condenser or the like, and store it as it is or temporarily in a tank. etc., and then return to the reaction tank, or separate and refine impurities, and supply them as 1,4-butanediol with improved purity. Hereinafter, "1,4-butanediol supplied separately" composed of 1,4-butanediol collected by a condenser or the like may be referred to as "recycled 1,4-butanediol". From the viewpoint of effective utilization of resources and simplification of equipment, it is preferable to use "recycled 1,4-butanediol" as "1,4-butanediol supplied separately".

In addition, 1,4-butanediol distilled from an esterification reaction tank or a transesterification reaction tank usually contains components, such as water, alcohol, tetrahydrofuran, dihydrofuran, etc. other than a 1,4-butanediol component. Therefore, the 1,4-butanediol of the above-mentioned distillate is preferably collected by a condenser or the like, or while being collected, components such as water, alcohol, and tetrahydrofuran are separated and purified, and returned to the reaction tank.

Furthermore, in the present invention, it is preferable to directly return 10% by weight or more of the "1,4-butanediol supplied separately" to the liquid phase portion of the reaction liquid. Here, the so-called liquid phase part of the reaction liquid means the liquid phase side of the gas-liquid interface in the esterification reaction tank or the transesterification reaction tank, and the part directly returning to the liquid phase of the reaction liquid means the use of piping etc., " The 1,4-butanediol supplied separately is directly supplied to the liquid phase without passing through the gas phase. The ratio of directly returning to the liquid phase portion of the reaction liquid is preferably 30% by weight or more, more preferably 50% by weight or more than 50% by weight, particularly preferably 80% by weight or more than 80% by weight, most preferably 90% by weight or 90% by weight % by weight or more. When the amount of "1,4-butanediol supplied separately" returned directly to the liquid phase of the reaction liquid is small, foreign substances tend to increase.

In addition, the temperature of "1,4-butanediol supplied separately" at the time of returning to the reactor is usually 50 to 220°C, preferably 100 to 200°C, more preferably 150 to 190°C. When the temperature of "1,4-butanediol supplied separately" is too high, the amount of tetrahydrofuran by-products tends to increase, and when it is too low, the heat load tends to increase, resulting in energy loss.

In addition, in the present invention, in order to reduce the haze or foreign matter from the catalyst without reducing the activity of the catalyst, it is preferable to use 10% by weight or more of the titanium catalyst used in the esterification reaction (or transesterification reaction) It is directly supplied to the reaction liquid liquid phase part independently, not together with terephthalic acid (or dialkyl terephthalate). Here, the so-called liquid phase part of the reaction liquid means the liquid phase side of the gas-liquid interface in the esterification reaction tank or the transesterification reaction tank, and the part directly supplied to the liquid phase of the reaction liquid means the use of pipes, etc., titanium The catalyst is directly supplied to the liquid phase without passing through the gas phase of the reactor. The proportion of the titanium catalyst directly added to the liquid phase of the reaction solution is preferably 30% by weight or more, more preferably 50% by weight or more, particularly preferably 80% by weight or more, most preferably 90% by weight % or more than 90% by weight.

Although the above-mentioned titanium catalyst can also be dissolved in a solvent or the like or not dissolved in a solvent, it can be directly supplied to the reaction liquid liquid phase part of the esterification reaction tank or the transesterification reaction tank, but in order to stabilize the supply amount and reduce the It is preferable to dilute with a solvent such as 1,4-butanediol for adverse effects such as denaturation caused by heat such as heat transfer medium jacket of the reactor. The concentration at this time is usually 0.01 to 20% by weight, preferably 0.05 to 10% by weight, more preferably 0.08 to 8% by weight, as the concentration of the titanium catalyst relative to the entire solution. In addition, from the viewpoint of reducing foreign matter, the water concentration in the solution is usually 0.05 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 or aggregation. In addition, the catalyst solution is preferably mixed with "separately supplied 1,4-butanediol" in piping or the like, and supplied to an esterification reaction tank or a transesterification reaction tank from the viewpoint of deterioration prevention, precipitation prevention, and foreign matter suppression.

An example of the continuous method using the direct polymerization method is as follows. That is, the above-mentioned dicarboxylic acid component having terephthalic acid as the main component and the above-mentioned diol component having 1,4-butanediol as the main component are mixed in a raw material mixing tank to prepare a slurry, which is then esterified in single or multiple In the reaction tank, in the presence of a titanium catalyst, the temperature is usually 180-260°C, preferably 200-245°C, more preferably 210-235°C, and usually 10-133kPa, preferably 13-101kPa, more preferably 60-90kPa Under the pressure of 0.5 to 10 hours, the esterification reaction is usually carried out continuously for 0.5 to 10 hours, preferably 1 to 6 hours, and the oligomer as the product of the esterification reaction obtained is transferred to the polycondensation reaction tank, and in the single or multiple polycondensation reactions In the tank, in the presence of a polycondensation reaction catalyst, preferably continuously, usually at a temperature of 210 to 280°C, preferably 220 to 265°C, usually at 27kPa or below, preferably at or below 20kPa, more preferably at or below 13kPa Under reduced pressure, the polycondensation reaction is usually carried out for 2 to 12 hours, preferably 3 to 10 hours, under stirring. The polymer obtained by the polycondensation reaction is usually extracted from the bottom of the polycondensation reaction tank, transferred to the mold, drawn out into strands, cooled with water or cut off with a knife, and made into granules, flakes, etc. granular body.

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

BM/TM＝1.1～4.5(mol/mol) (III)

(In the formula, BM represents the number of moles of 1,4-butanediol supplied from the outside to the esterification reaction tank per unit time, and TM represents the mole number of terephthalate supplied to the esterification reaction tank from the outside per unit time. moles of formic acid).

When the above-mentioned BM/TM value is less than 1.1, the conversion rate decreases or the catalyst is deactivated. When it is greater than 4.5, not only the thermal efficiency decreases, but also the by-products such as tetrahydrofuran tend to increase. The value of BM/TM is preferably 1.5 to 4.0, more preferably 2.0 to 3.8, particularly preferably 2.7 to 3.5.

An example of the continuous method using the transesterification method is as follows. That is, in single or multiple transesterification reaction tanks, in the presence of a titanium catalyst, it is usually at a temperature of 110 to 260°C, preferably 140 to 245°C, more preferably at a temperature of 180 to 220°C, and usually at 10 to 133kPa, preferably 13～120kPa, more preferably under the pressure of 60～101kPa, carry out continuously usually 0.5～5 hour, preferably 1～3 hour continuous transesterification reaction, will transfer the oligomer as the product of transesterification reaction to polycondensation reaction In the tank, in single or multiple polycondensation reaction tanks, in the presence of a polycondensation reaction catalyst, preferably continuously, usually at a temperature of 210 to 280°C, preferably 220 to 265°C, usually at or below 27kPa, preferably at or below 20kPa The polycondensation reaction is usually carried out for 2 to 12 hours, preferably 3 to 10 hours, under a reduced pressure of 20 kPa or less, more preferably 13 kPa or less, with stirring.

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

BM/DM＝1.1～2.5(mol/mol) (IV)

(In the formula, BM represents the number of moles of 1,4-butanediol supplied from the outside to the transesterification tank per unit time, and DM represents the mole of terephthalic diol per unit time supplied from the outside to the transesterification tank. moles of dialkyl formate).

When the above-mentioned BM/DM value is less than 1.1, the conversion rate or catalyst activity decreases, and when it is greater than 2.5, not only the thermal efficiency decreases, but also the by-products such as tetrahydrofuran tend to increase. The value of BM/DM is preferably 1.1 to 1.8, more preferably 1.2 to 1.5.

The above-mentioned "1,4-butanediol supplied from the outside to the esterification (transesterification) reaction tank" means that it is mixed with terephthalic acid or dialkyl terephthalate as a raw material slurry or solution. In addition to 1,4-butanediol supplied together, 1,4-butanediol supplied separately from these, 1,4-butanediol used as a catalyst solvent, etc., are obtained from the outside of the reaction tank The sum of 1,4-butanediol entering the reaction tank.

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

In the method for producing PBT of the present invention, in order to maintain and stabilize the esterification rate or transesterification rate, further reduce foreign matter, and stabilize the amount of foreign matter, it is preferable to use terephthalic acid or dialkyl terephthalate When carrying out esterification reaction or transesterification reaction continuously with 1,4-butanediol which is excessive with respect to them, control per unit time is supplied from the outside to the reaction tank (esterification reaction tank or transesterification reaction tank) The molar ratio of phthalic acid or dialkyl terephthalate to 1,4-butanediol is constant.

In the present invention, as a method of controlling the molar ratio of terephthalic acid or dialkyl terephthalate and 1,4-butanediol supplied from the outside to the reaction tank per unit time to be constant, for example, Out, when terephthalic acid is used as a raw material, the raw material slurry containing terephthalic acid and 1,4-butanediol is fixed at a certain molar ratio and supplied in a certain amount, and at the same time, the catalyst is made of 1,4-butanediol When the diol solution is constituted, its concentration and supply amount are also set constant, and at the same time, it is a method of supplying a constant amount of "1,4-butanediol supplied separately" 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 reaction tank fluctuates greatly. , 4-butanediol", the 1,4-butanediol obtained by aggregating it fluctuates with a delay of some time relative to the variation of the above-mentioned gas generation amount. In the preferred scheme of the present invention, also control at this moment supply the recycle 1 of esterification reaction tank, the supply rate of 4-butanediol is constant, thereby control the p-benzene that is supplied to the esterification reaction tank The molar ratio (BM/TM) of dicarboxylic acid and 1,4-butanediol did not change. At this time, if the liquid amount of condensed 1,4-butanediol is kept constant and the supply amount of recycled 1,4-butanediol is changed like the reflux control generally performed, the Changes in the conversion rate (esterification rate), depending on the situation, the phase difference between the change in the generation of 1,4-butanediol gas and the change in the liquid amount of condensed 1,4-butanediol results in an increase in the change, resulting in The quality is unstable.

In addition, when the molar ratio of terephthalic acid or dialkyl terephthalate as a raw material to 1,4-butanediol excluding "1,4-butanediol supplied separately" is constant, For example, even when the molar ratio of the raw material slurry of terephthalic acid and 1,4-butanediol is constant, when the supply amount is changed, that is, when the production amount is changed, etc., corresponding to the change, the supply In order to achieve a certain molar ratio (BM/TM or BM/DM) of terephthalic acid or dialkyl terephthalate and 1,4-butanediol in the esterification reaction tank or transesterification reaction tank, change The amount of "1,4-butanediol to be supplied separately". If the supply amount of the terephthalic acid component is increased without increasing the amount of "1,4-butanediol supplied separately", BM/TM or BM/DM will decrease, resulting in a decrease in the conversion rate. On the other hand, if the supply of terephthalic acid is reduced, if the amount of "1,4-butanediol supplied separately" is not reduced, BM/TM or BM/DM will increase. Although the conversion rate will increase, the This will lead to increased side reactions such as the production of tetrahydrofuran, or lead to energy loss.

When changing the supply rate of the terephthalic acid component, in order to keep BM/TM or BM/DM constant, it is preferable to control the supply rate of "1,4-butanediol supplied separately" and, as mentioned above, control the " Separately supplied 1,4-butanediol" so that it will not be fluctuated by short-term 1,4-butanediol gas generation.

As the esterification reaction tank or the transesterification reaction tank, known devices can be used, and any type such as a vertical stirring complete mixing tank, a vertical heat convection mixing tank, a tower type continuous reaction tank, etc. can be used. In addition, it can be used as A single tank can also be used as multiple tanks of the same type or different types of tanks connected in series. Among them, the reaction tank with stirring device is preferred. As the stirring device, in addition to the common type composed of power part, bearing, shaft and stirring blade, turbine guide vane type high-speed rotary type mixer and disc pulverizer can also be used. High-speed rotating types such as mixers, impeller mill type mixers, etc.

The form of stirring is not particularly limited. In addition to the usual stirring method in which the reaction liquid in the reaction tank is directly stirred from the upper part, the lower part, and the horizontal direction of the reaction tank, a part of the reaction liquid can also be taken out to the reaction tank by piping. A method in which the reaction solution is circulated by stirring with a linear stirrer (Rain Mikisa) or the like on the outside of the vessel.

The type of stirring blade can be selected from known ones, specifically, screw propeller blades, screw blades, turbine blades, wind turbine blades, disk turbine blades, three-blade backward curved blades, フルゾ一ン blade, extremely mixing blades, etc. (Maxbrand) wing and so on.

In the manufacture of PBT, a plurality of reaction tanks are usually used, preferably 2 to 5 reaction tanks are used, and the molecular weight is increased sequentially. Usually, polycondensation reaction is performed following initial esterification reaction or transesterification reaction.

In the polycondensation reaction step of PBT, a single reaction tank or a plurality of reaction tanks may be used, but it is preferable to use a plurality of reaction tanks. The form of the reaction tank may be any type such as a vertical stirring complete mixing tank, a vertical heat convection mixing tank, and a tower-type continuous reaction tank, and these may be combined. Among them, the reaction tank with stirring device is preferred. As the stirring device, in addition to the common type made of power part, bearing, shaft and stirring blade, turbine guide blade type high-speed rotary mixer and disc pulverizer can also be used. Type mixers, impeller mill type mixers and other high-speed rotating types.

The form of stirring is not particularly limited. In addition to the usual stirring method in which the reaction liquid in the reaction tank is directly stirred from the upper part, the lower part, and the horizontal direction of the reaction tank, a part of the reaction liquid can also be taken out to the reaction tank by piping. A method in which the reaction liquid is circulated by stirring with a linear stirrer or the like on the outside of the reactor. Among them, it is recommended to use at least one of the polycondensation reaction tanks, and use a horizontal reactor having an axis of rotation in the horizontal direction, which is excellent in 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, it is preferable that the stirring directions of the shafts are in different directions. Among them, it is more preferable to elongate the polymer at the upper part and wrap the polymer at the lower part. direction of rotation.

In addition, in order to suppress coloring or deterioration, and to suppress the increase of terminals such as vinyl groups, in at least one reaction tank, usually 1.3 kPa or less, preferably 0.5 kPa or less, more preferably 0.3 kPa or 0.3 kPa The following high vacuum is preferably carried out at a temperature of usually 225-255°C, preferably 230-250°C, more preferably 233-245°C.

In addition, in the polycondensation reaction process of PBT, it is possible to temporarily use melt polycondensation to produce PBT with a relatively small molecular weight, such as an intrinsic viscosity of about 0.1 to 1.0 dL/g, and then perform solid phase polycondensation at a temperature below the melting point of PBT. phase aggregation).

By performing solid phase polymerization, since the terminal carboxyl group of the obtained PBT can be reduced, the effect of this invention, such as improvement of hydrolysis resistance, becomes more remarkable.

In the PBT of the present invention, since the foreign matter derived from the catalyst is greatly reduced, even if the foreign matter does not need to be removed, a polymer with better quality can be obtained by providing a filter in the polymer precursor or the flow path of the polymer. In the present invention, for the above-mentioned reasons, when using a filter having the same mesh as a filter used in a conventional PBT manufacturing facility, its service life until replacement can be extended. The life is the same, and a filter with a smaller mesh size can be installed.

When the installation position of the filter is upstream in the manufacturing process, the removal of foreign matter generated on the downstream side will not be performed, and the pressure loss of the filter will increase at the downstream side where the viscosity is high. In order to maintain the flow rate, the filter must be The mesh of the filter is enlarged, or the filtering area of the filter or the equipment such as piping becomes too large. In addition, when the fluid passes through, it is subjected to high shear, and the deterioration of PBT due to shear heat is inevitable. Therefore, the installation position of the filter is usually selected where the intrinsic viscosity of PBT or its precursor is 0.1-1.2 dL/g, preferably 0.2-1.0 dL/g, more preferably 0.5-0.9 dL/g.

As the filter material constituting the filter, any one of metal roll, laminated metal mesh, metal non-woven fabric, porous metal plate, etc. can be used. From the viewpoint of filtration accuracy, laminated metal mesh or metal non-woven fabric is preferred, especially, preferably Its mesh is fixed by sintering. The shape of the filter may be any of basket type, disc type, movable disc type, tube type, flat cylindrical type, pleated cylindrical type and the like. In addition, in order not to affect the operation of the machine, it is preferable to install multiple filters for replacement, or to install an automatic filter exchange.

The absolute filtration accuracy of the filter is not particularly limited, and is usually 0.5-200 μm, preferably 1-100 μm, more preferably 5-50 μm, particularly preferably 10-30 μm. When the absolute filtration accuracy is too large, the foreign matter reduction effect in the product disappears, and if it is too small, the productivity decreases or the frequency of filter exchange increases.

Hereinafter, preferred embodiment of the manufacturing method of PBT is demonstrated based on drawing. Fig. 1 is an explanatory diagram of an example of the esterification reaction step or transesterification reaction step used in the present invention, and Figs. 2 to 5 are explanatory diagrams of another example of the esterification reaction step or transesterification reaction step used in the present invention , FIG. 6 is an explanatory diagram of an example of the polycondensation step used in the present invention, and FIGS. 7 to 9 are explanatory diagrams of another example of the polycondensation step used in the present invention.

In Fig. 1, terephthalic acid as a raw material is usually mixed with 1,4-butanediol in a raw material mixing tank (not shown), and supplied to the reaction tank (A) in the form of a slurry from a raw material supply line (1). )middle. In the case of a dialkyl terephthalate, 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 supplied from a catalyst supply line (3) after preparing a 1,4-butanediol solution in a catalyst adjustment tank (not shown). In Fig. 1, it is shown that the catalyst supply line (3) is connected to the recycling line (2) for recycling 1,4-butanediol, the two are mixed, and then supplied to the reaction tank (A). way of the liquid phase.

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

The high-boiling components separated in the rectification column (C) are extracted from the extraction line (6), and through the pump (D), a part is circulated to the reaction tank (A) by the recirculation line (2), and a part is circulated to the reaction tank (A) by the recirculation line (7). Return to rectification column (C). In addition, the remaining part is extracted to the outside through the gas extraction line (8). On the other hand, the low-boiling components separated in the rectification column (C) are extracted from the extraction line (9), condensed by the condenser (G), and temporarily stored in the tank (F) through the condensate line (10). A part of the low boiling point components collected in the tank (F) is returned to the rectification column (C) through the extraction line (11), the pump (E) and the circulation line (12), and the remaining part is extracted through the extraction line (13) to the outside. The condenser (G) is connected to an exhaust (not shown) via a discharge line (14). The oligomer produced in the reaction tank (A) is extracted through 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. In addition, the raw material supply line (1) may be connected to the liquid phase part of the reaction tank (A).

The process shown in Figure 2, compared with the process shown in Figure 1, differs in that a reboiler (H) is equipped on the rectification column (C), and in addition, a Supply line (15) for supplying liquid. The installation of the reboiler (H) facilitates operation control of the distillation column (C).

The process shown in FIG. 3 is different from the process shown in FIG. 1 in that the bypass line (16) branched from the circulation line (7) is connected to the gas phase part of the reaction tank (A). Therefore, in the case of the step shown in FIG. 3 , part of the recycled 1,4-butanediol is returned to the reaction liquid via the gas phase portion of the reaction tank (A).

The process shown in Figure 4, compared with the process shown in Figure 1, is different in that the following control device (L) is provided, and the control device (L) is between the recirculation line (2) and the extraction line ( 8) above, a flow control valve (J) and a flow control valve (K) are arranged respectively; in addition, the liquid level of the rectification column (C) is detected, and the opening degree of the flow control valve (K) is adjusted based on the detected signal, The liquid level of the rectification column (C) is adjusted to be constant. The liquid level at the bottom of the distillation column (C) may vary due to temperature fluctuations in the reaction tank (A), fluctuations in the amount of distilled gas or the composition of the distilled gas, fluctuations in the amount of raw material supplied, and temperature fluctuations in the rectification tower (C). Although it is small, it also fluctuates thereupon, but according to the process shown in Figure 4, the liquid level at the bottom of the rectification tower (C) changes to adjust the extraction amount from the extraction line (8), and maintain the output from the recirculation line ( 2) The amount of recirculation is kept constant.

The process shown in Figure 5, compared with the process shown in Figure 2, is different in that the following control device (L) is provided, and the control device (L) is between the recirculation line (2) and the extraction line ( 8), a flow control valve (J) and a flow control valve (K) are set respectively, and a high boiling point component tank (N) and a reboiler (H) are respectively set on the extraction line (6) and the extraction line (7). ), the supply line (15) is installed at a position downstream of the reboiler (H) of the circulation line (7), and the liquid level of the high boiling point component tank (N) is detected, and the flow control is adjusted based on the detection signal The degree of opening of the valve (K) is adjusted to keep the liquid level of the high boiling point component tank (N) constant. The process shown in FIG. 5 exhibits the same improvement effect as the process shown in FIG. 4 . The process shown in FIG. 5 is clarified, and the signal based on the liquid level fluctuation of the high boiling point component tank (N) can be utilized as an input signal to a control apparatus (L).

In Fig. 6, the oligomer supplied from the extraction line (4) shown in Figs. The gear pump (c) for extraction and the extraction line (L1) are supplied to the 2nd polycondensation reaction tank (d). In the 2nd polycondensation reaction tank (d), polycondensation is further progressed normally at the pressure lower than 1st polycondensation reaction tank (a), and a polymer is obtained. The obtained polymer is drawn out from the die head (g) in the form of molten filaments through the gear pump (e) for extraction and the extraction line (L3), cooled with water, etc., and then cut with a rotary blade (h), get pellets. Symbol (L2) is the discharge line of the first polycondensation reaction tank (a), and symbol (L4) is the discharge line of the second polycondensation reaction tank (d). The process shown in FIG. 7 differs from the process shown in FIG. 6 in that a filter (f) is provided in the flow path of the extraction line (L3).

The step shown in FIG. 8 differs from the step shown in FIG. 6 in that a third polycondensation reaction tank (k) is provided behind the second polycondensation reaction tank (d). The third polycondensation reaction tank (k) is composed of a plurality of stirring blade members, and is a horizontal reaction tank having biaxial self-cleaning type stirring blades. The polymer introduced from the second polycondensation reaction tank (d) to the third polycondensation reaction tank (k) through the extraction line (L3) is further condensed here, and then passes through the extraction gear pump (m) and the extraction line (L5), The melted strands are extracted from the die (g), cooled with water, and then cut with a rotary blade (h) to obtain pellets. Symbol (L6) is the discharge line of the 3rd polycondensation reaction tank (k).

The process shown in Figure 9, compared with the process shown in Figure 8, differs in that in the middle of the extraction line (L3) between the second polycondensation reaction tank (d) and the third polycondensation reaction tank (k) , equipped with a filter (f).

<General composition containing the above-mentioned polybutylene terephthalate>

In the PBT of the present invention, 2,6-di-tert-butyl-4-octylphenol, pentaerythritol tetrakis [3-(3', 5'-tert-butyl-4'-hydroxyphenyl) propyl ester] can be added Phenolic compounds such as dilauryl-3,3'-thiodipropionate, thioether compounds such as pentaerythritol tetrakis(3-laurylthiodipropionate), triphenyl phosphite, trinonyl phosphite Antioxidants such as phenyl esters, phosphorus compounds such as tris(2,4-di-tert-butylphenyl)phosphite, long-chain fatty acids represented by paraffin wax, microcrystalline wax, polyethylene wax, montanic acid or montanic acid ester And its ester, silicone oil and other release agents.

In the PBT of the present invention, a reinforcing filler may be blended. The reinforcing filler is not particularly limited, and examples thereof include glass fiber, carbon fiber, silica-alumina fiber, zirconia fiber, boron fiber, boron nitride fiber, silicon nitride potassium titanate fiber, metal Inorganic fibers such as fibers, organic fibers such as aramid fibers and fluororesin fibers, etc. These reinforcing fillers may be used in combination of two or more. Among the above-mentioned reinforcing fillers, glass fiber is particularly suitably used.

When the reinforcing filler is inorganic fiber or organic fiber, the average fiber diameter is not particularly limited, but is usually 1-100 μm, preferably 2-50 μm, more preferably 3-30 μm, particularly preferably 5-20 μm. In addition, the average fiber length is not particularly limited, but is usually 0.1 to 20 mm, preferably 1 to 10 mm.

In order to improve the interface adhesion with PBT, it is preferable to use a reinforcing filler that is surface-treated with an astringent or a surface treatment agent. Examples of the astringent or surface treatment agent include functional compounds such as epoxy compounds, acrylic compounds, isocyanate compounds, silane compounds, and titanate compounds. The reinforcing filler may be surface-treated in advance with an astringent or a surface treatment agent, or may be surface-treated by adding an astringent or a surface treatment agent when preparing the PBT composition. The added amount of the reinforcing filler 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.

In the PBT of the present invention, other fillers may be blended together with the reinforcing filler. Other fillers to be mixed include, for example, plate-like inorganic fillers, ceramic beads, asbestos, wollastonite, talc, clay, mica, zeolite, kaolin, potassium titanate, barium sulfate , titanium oxide, silicon oxide, aluminum oxide, magnesium hydroxide, etc. Anisotropy and warpage of molded products can be reduced by blending a plate-like inorganic filler. As a plate-shaped inorganic filler, glass flakes, mica, metal foil, etc. are mentioned, for example. Among these, glass flakes are suitably used.

In order to impart flame retardancy, a flame retardant may be blended in the PBT of the present invention. The flame retardant is not particularly limited, and examples thereof include organic halogen compounds, antimony compounds, phosphorus compounds, other organic flame retardants, and inorganic flame retardants. Examples of organic halogen compounds include brominated polycarbonate, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, brominated bisphenol A, poly (pentabromobenzyl acrylate), etc. Examples of antimony compounds include antimony trioxide, antimony pentoxide, and sodium antimonate. Examples of phosphorus compounds include phosphoric acid esters, polyphosphoric acid, ammonium polyphosphate, red phosphorus, and the like. Examples of other organic flame retardants include nitrogen compounds such as melamine and cyanuric acid. Examples of other inorganic flame retardants include aluminum hydroxide, magnesium hydroxide, silicon compounds, boron compounds, and the like.

If necessary, conventional additives and the like may be blended into the PBT of the present invention. Such additives are not particularly limited. For example, in addition to stabilizers such as antioxidants and heat-resistant stabilizers, lubricants, fillers, mold release agents, catalyst deactivators, crystal nucleating agents, crystallization accelerator, etc. These additives may be added during or after polymerization. Examples of the aforementioned crystal nucleating agent include talc, clay, boron nitride, and the like, and examples of the aforementioned filler include phyllosilicates, zeolites, and silica. In addition, in order to impart desired performance, stabilizers such as ultraviolet absorbers and weather stabilizers, colorants such as dyes and pigments, antistatic agents, foaming agents, plasticizers, impact resistance modifiers, etc. can be added to PBT.

If necessary, polyethylene, polypropylene, polystyrene, polyacrylonitrile, polymethacrylate, ABS resin, polycarbonate, polyamide, polyphenylene sulfide, polyparaphenylene, etc. can also be mixed in the PBT of the present invention. Thermoplastic resins such as ethylene glycol diformate, liquid crystal polyester, polyacetal, and polyphenylene ether, and thermosetting resins such as phenolic resins, melamine resins, polysiloxane resins, and epoxy resins. These thermoplastic resins and thermosetting resins may be used in combination of two or more.

The compounding method of the above-mentioned various additives or resins is not particularly limited, but it is preferable to use a single-screw or twin-screw extruder equipped with a device capable of devolatilizing from a discharge port as a kneader. The various ingredients, including additional ingredients, can be fed to the mixer together, or they can be fed sequentially. In addition, including additional components, two or more components selected from various components may be mixed in advance.

<Specific composition containing the above-mentioned polybutylene terephthalate>

The PBT of the present invention, as mentioned above, can be used as a general resin composition by the usual method in the field of resins. In addition, the PBT of the present invention can also be combined with specific additives as a specific polymer with various functions. Butylene terephthalate composition use. Hereinafter, these resin compositions are demonstrated.

(Heat-resistant PBT composition)

The heat-resistant PBT composition of the present invention is characterized in that, contains above-mentioned PBT (A), and is selected from phenolic antioxidant (B1), sulfur antioxidant (B2) and phosphorus antioxidant (B3) ) of one or more antioxidants.

The phenolic antioxidant (B1) used in the present invention refers to an antioxidant having a phenolic hydroxyl group, wherein the so-called hindered phenolic antioxidant refers to an aromatic ring adjacent to a phenolic hydroxyl group. It means an antioxidant in which one or two carbon atoms on the carbon atoms are substituted with a substituent having 4 or more carbon atoms. The substituent having 4 or more carbon atoms may be bonded to the carbon atom of the aromatic ring via a carbon-carbon bond, or may be bonded via an atom other than a carbon atom. Specific examples of the phenolic antioxidant (B1) used in the present invention include p-cyclohexylphenol, 3-tert-butyl-4-methoxyphenol, 4,4'-isopropylidene diphenol, 1,1-bis(4-hydroxyphenyl)cyclohexane and other unhindered phenolic antioxidants, 2-tert-butyl-4-methoxyphenol, 2,6-di-tert-butyl-p-cresol, 2 , 4,6-tri-tert-butylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, styrenated phenol, 2,5-di-tert-butylhydroquinone, octadecyl-3-(3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1, 6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) base) propionate], 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethyl phenol), 2,2'-methylenebis[4-methyl-6-(1,3,5-trimethylhexyl)phenol], 4,4'-methylenebis(2,6-di tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), 2,6-bis(2-hydroxy-3-tert-butyl-5-methylbenzyl ) 4-methylphenol, 1,1,3-tris[2-methyl-4-hydroxyl-5-tert-butylphenyl]butane, 1,3,5-trimethyl-2,4,6 - Tris[3,5-di-tert-butyl-4-hydroxybenzyl]benzene, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, tris[3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2 '-Thiobis(4-methyl-6-tert-butylphenol), 4,4'-thiobis(2-methyl-6-tert-butylphenol), Thiobis(β-naphthol) and other hindered phenolic antioxidants. In particular, hindered phenolic antioxidants can be suitably used as radical scavengers because they tend to become stable radicals themselves. The molecular weight of the hindered phenolic antioxidant is usually 200 or more, preferably 500 or more, and its upper limit is usually 3000.

The sulfur-based antioxidant (B2) used in the present invention refers to an antioxidant that does not have a phenolic hydroxyl group but has a sulfur atom. Specific examples of sulfur-based antioxidants (B2) include didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, and dioctadecylthiodipropionate. ester, pentaerythritol tetrakis(3-dodecylthiopropionate), thiobis(N-phenyl-β-naphthylamine), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramonosulfide Methylthiuram, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropylxanthate, trilauryl trithiophosphite, etc. In particular, thioether-based antioxidants having a thioether structure can be preferably used because they are reduced by receiving oxygen from oxidized substances. The molecular weight of the sulfur antioxidant is usually 200 or more, preferably 500 or more, and its upper limit is usually 3000.

The phosphorus-based antioxidant (B3) of the present invention refers to an antioxidant that does not have a phenolic hydroxyl group or a sulfur atom, but has a phosphorus atom. Phosphorus antioxidant (B3), preferably an antioxidant with a P(OR) ₃ structure. Here, R is an alkyl group, an alkylene group, an aryl group, an arylene group, etc., three R's may be the same or different, and two R's may form a ring structure. As such phosphorus antioxidants, for example, triphenyl phosphite, diphenyldecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, , bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, etc.

In the heat-resistant PBT composition of the present invention, the content of the phenolic antioxidant (B1) is usually 0.001 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 parts by weight, the antioxidant effect may not be fully exhibited, and if it exceeds 2 parts by weight, the thermal stability against oxidation may be poor, or the resin may be decomposed during melt kneading.

In the heat-resistant PBT composition of the present invention, the sulfur-based antioxidant (B2) and/or the phosphorus-based antioxidant (B3) have the functions of improving the heat aging resistance of the resin composition, improving the color tone, tensile strength, elongation The effect of retention rate such as elongation rate.

In the heat-resistant PBT composition of the present invention, the contents of the sulfur-based antioxidant (B2) and the phosphorus-based antioxidant (B3) are usually 0.001 to 1.9 parts by weight, preferably 0.003 parts by weight, relative to 100 parts by weight of PBT. ~1 part by weight. When the content of each antioxidant is less than 0.001 parts by weight, the above-mentioned effect may not be sufficiently exhibited, and when it exceeds 1.9 parts by weight, the oxidation thermal stability may deteriorate, or the resin may be decomposed during melt kneading.

In the heat-resistant PBT composition of the present invention, when containing phenolic antioxidant (B1) and sulfur antioxidant (B2) and/or phosphorus antioxidant (B3), relative to phenolic antioxidant 1 part by weight of agent, the ratio of sulfur antioxidant and/or phosphorus antioxidant is usually 0.2-5 parts by weight. When the proportion of the sulfur-based antioxidant and/or the phosphorus-based antioxidant is less than 0.2 parts by weight or exceeds 5 parts by weight, either, 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, a sulfur antioxidant, and/or a phosphorus antioxidant are contained, the total amount of the antioxidant content per 100 parts by weight of PBT is The amount is usually 2 parts by weight or less. When the total amount of the antioxidant content exceeds 2 parts by weight, the oxidation thermal stability may deteriorate, or the resin may be decomposed during melt-kneading.

(PBT composition with good mold release properties)

The excellent releasable PBT composition of the present invention is characterized in that, relative to 100 parts by weight of the above-mentioned PBT (A), it contains fatty acid residues having 12 to 36 carbon atoms and fatty acid residues having 1 to 36 carbon atoms. 0.01 to 2 parts by weight of the release agent (C) in the ester (C1) of alcohol residues and paraffin wax and polyethylene wax (C2).

As the fatty acid forming the fatty acid ester (C1) used in the present invention, fatty acid esters containing fatty acid residues with 12 to 36 carbon atoms and alcohol residues with 1 to 36 carbon atoms are necessary, preferably containing carbon Fatty acid esters of fatty acid residues with 16 to 32 atoms and alcohol residues with 1 to 36 carbon atoms, more preferably fatty acid residues with 16 to 32 carbon atoms and alcohol residues with 1 to 20 carbon atoms based fatty acid esters.

Specific examples of fatty acids forming fatty acid esters (C1) include lauric acid, myristic acid, palmitic acid, octadecanoic acid, eicosanoic acid, behenic acid, and tetradecanoic acid. , Hexacosanoic acid, Octacosanoic acid, Triacosanoic acid, Tricosanoic acid, etc. When the number of carbon atoms of the fatty acid residue is less than 12, the mold releasability is low, and it is easy to volatilize, which may cause contamination of the mold. When the number of carbon atoms of the fatty acid residue exceeds 36, the effect of improving mold release properties may not be sufficiently exhibited.

As specific examples of the alcohol forming the fatty acid ester (C1), monohydric alcohols, dihydric alcohols, and trivalent or higher polyhydric alcohols can be used. Specific examples of such alcohols include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, cyclohexanol, heptanol, octanol, lauryl alcohol, stearyl alcohol, Monohydric alcohols such as alkanol, glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol and other dihydric alcohols, glycerin , Trihydric alcohols such as trimethylolpropane, tetrahydric alcohols such as pentaerythritol, 1,2,3,4-butanetetraol, etc. When the number of carbon atoms of the alcohol residue exceeds 36, the effect of improving mold release properties may not be sufficiently exhibited.

As a method for producing fatty acid ester (C1), for example, a method of esterifying fatty acid and alcohol as raw materials in the presence of an acid catalyst such as sulfuric acid, hydrochloric acid, or p-toluenesulfonic acid, and a method of reacting fatty acid acid chloride and alcohol can be used. When the method and the alcohol forming the fatty acid ester are high-boiling point alcohols, a method of performing transesterification reaction between lower alkyl esters of fatty acids and high-boiling point alcohols.

Specific examples of fatty acid esters (C1) include methyl laurate, methyl myristate, methyl hexadecanoate, methyl octadecanoate, methyl oleate, behenic acid Methyl ester, methyl octadecanoate, isopropyl myristate, isopropyl palmitate, butyl laurate, butyl octadecanoate, octyl palmitate, octyl octadecanoate , dodecyl dodecanoate, octadecyl octadecanoate, ethylene glycol dilaurate, ethylene glycol dihexadecanoate, ethylene glycol dioctadecanoate, ethyl Diol dioctadecanoate, propylene glycol monolaurate, propylene glycol monooctadecanoate, 1,3-propanediol dilaurate, 1,3-propanediol dioctadecanoate, 1,3- Propylene glycol dioctadecanoate, 1,4-butanediol dilaurate, 1,4-butanediol dioctadecanoate, 1,4-butanediol dioctadecanoate, Glyceryl Monohexadecanoate, Glyceryl Monooctadecanoate, Glyceryl Monooctadecanoate, Glyceryl Dihexadecanoate, Glyceryl Dioctadecanoate, Glyceryl Dioleate, Glyceryl Triglyceride Stearate, Glycerin Trioleate, Pentaerythritol Monohexadecanoate, Pentaerythritol Monooctadecanoate, Pentaerythritol Dihexadecanoate, Pentaerythritol Dioctadecanoate, Pentaerythritol Trihexadecanoate ) ester, pentaerythritol tri(octadecanoate) ester, pentaerythritol tetra(octadecanoate) ester, etc.

The molecular weight of paraffin wax and polyethylene wax (C2) is usually 300-5000, preferably 500-3000. If the molecular weight is less than 300, it will easily volatilize from the vacuum exhaust port during mixing, making it difficult to exert its effect, or the wax will easily be released during molding, which will cause contamination of the metal mold. On the other hand, when the molecular weight exceeds 5000, it does not release, and the effect as a release agent decreases.

In the good releasable PBT composition of this invention, content of fatty acid ester (C1) is 0.01-2 weight part normally with respect to 100 weight part of PBT, Preferably it is 0.1-1 weight part. When the content of the fatty acid ester (C1) is less than 0.01 parts by weight, there is a danger that the effect of improving the mold release property (the effect of shortening the molding cycle) may not be fully exhibited, and when it exceeds 2 parts by weight, the effect corresponding to the increase of the fatty acid ester cannot be obtained. There is a risk that strength and heat resistance may be lowered instead of the mold release property improvement effect.

In the good releasable PBT composition of the present invention, the content of paraffin wax or polyethylene wax (C2) 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 paraffin wax or polyethylene wax (C2) is less than 0.01 parts by weight, there is a danger that the effect of improving mold release properties (effect of shortening the molding cycle) may not be fully exhibited, and if it exceeds 2 parts by weight, it may not be possible to obtain the same effect as paraffin wax or polyethylene wax. The effect of increasing the release property is commensurate with the increase, but there is a danger of reducing the strength or heat resistance.

(hydrolysis resistant PBT composition)

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

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 them. In particular, difunctional, trifunctional, and polyfunctional epoxy compounds, that is, compounds having two or more epoxy groups in one molecule are preferred. In addition, the epoxy compound (E) may be any one of glycidyl compounds obtained by reacting alcohols, phenolic compounds, or carboxylic acids with epichlorohydrin, alicyclic epoxy compounds, and the like.

Specific examples of the epoxy compound (E) include methylglycidyl ether, butylglycidyl ether, 2-ethylhexylglycidyl ether, decylglycidyl ether, stearyl Glycidyl ether, phenylglycidyl ether, butylphenylglycidyl ether, allyl glycidyl ether and other glycidyl ethers; neopentyl glycol diglycidyl ether, Ethylene Glycol Diglycidyl Ether, Glycerol Diglycidyl Ether, Propylene Glycol Diglycidyl Ether, Bisphenol A Diglycidyl Ether and other Diglycidyl Ethers; Glycidyl Benzoate Ester, glycidyl sorbate and other fatty acid glycidyl esters; Diglycidyl adipate, Diglycidyl terephthalate, Diglycidyl phthalate and other bicyclic Oxypropyl esters; alicyclic diepoxy compounds such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, and the like. Among them, glycidyl ether compounds obtained by reacting bisphenol A and epichlorohydrin are preferred, and bisphenol A diglycidyl ether is particularly preferred.

Examples 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, silicon nitride titanate Inorganic fibers such as potassium fibers and metal fibers, organic fibers such as aramid fibers and fluororesin fibers, etc. These reinforcing fillers may be used alone or in combination of two or more. Among these, inorganic fillers are suitably used, and glass fibers are particularly suitably used.

When the reinforcing filler (D) is an inorganic fiber or an organic fiber, its average fiber diameter is usually 1 to 100 μm, preferably 2 to 50 μm, more preferably 3 to 30 μm, particularly preferably 5 to 20 μm. In addition, the average fiber length is usually 0.1 to 20 mm, preferably 1 to 10 mm.

In order to improve the interfacial adhesion with PBT, it is preferable to use the reinforcement filler (D) surface-treated with an astringent or a surface treatment agent. Examples of the astringent or surface treatment agent include functional compounds such as epoxy compounds, acrylic compounds, isocyanate compounds, silane compounds, and titanate compounds. The reinforcing filler (D) may be previously surface-treated with an astringent or a surface treatment agent, or may be surface-treated by adding an astringent or a surface treatment agent when preparing the PBT composition.

Examples of glass fibers 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, the glass fiber of E glass which has few alkali components and has good electrical characteristics is preferable.

The average fiber diameter of the glass fibers is usually 1 to 100 μm, preferably 2 to 50 μm, more preferably 3 to 30 μm, particularly preferably 5 to 20 μm. Glass fibers with an average fiber diameter of less than 1 μm may be difficult to manufacture and may increase the cost. Glass fibers with an average fiber diameter exceeding 100 μm may lower the tensile strength of the glass fibers. The average fiber length of glass fiber is 0.1-20 mm normally, Preferably it is 1-10 mm. When the average fiber length is less than 0.1 mm, there is a risk that the reinforcing effect of the glass fibers cannot be fully exhibited, and when the average fiber length exceeds 20 mm, there is a risk that melt kneading with PBT or molding of a PBT composition becomes difficult.

The glass fibers are preferably glass fibers treated with a surface treatment agent. By treating the surface of the glass fiber with a surface treatment agent, a firm bond or bond is produced at the interface between the PBT and the glass fiber, and the stress is transmitted from the PBT to the glass fiber, thereby reflecting the reinforcing effect produced by the glass fiber.

Examples of the surface treatment agent used include chlorosilane compounds such as vinyltrichlorosilane and methylvinyldichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl Triacetoxysilane, γ-methacryloxypropyltrimethoxysilane and other alkoxysilane compounds, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-epoxy Epoxysilane-based compounds such as propoxypropyltrimethoxysilane, acrylic-based compounds, isocyanate-based compounds, titanate-based compounds, epoxy-based compounds, and the like.

In addition, the glass fibers are preferably glass fibers treated with an astringent. By treating the glass fiber with an astringent, the workability of the glass fiber can be improved, and damage to the glass fiber can be prevented. Examples of the astringent used include resin emulsions such as vinyl acetate resins, ethylene-vinyl acetate copolymers, acrylic resins, epoxy resins, polyurethane resins, and polyester resins.

In the hydrolysis-resistant PBT composition of this invention, content of an epoxy compound (E) is 0.01-20 weight part normally with respect to 100 weight part of PBT, Preferably it is 0.03-10 weight part. When the content of the epoxy compound (E) is less than 0.01 parts by weight, there is almost no effect of improving the hydrolysis resistance, and when it exceeds 20 parts by weight, other mechanical properties decrease, or thermal stability of fusion deteriorates.

Moreover, in the hydrolysis-resistant PBT composition of this invention, content of a reinforcing filler (D) is 0-200 weight part normally with respect to 100 weight part of PBT, Preferably it is 0-150 weight part. When the content of the reinforcing filler (D) exceeds 200 parts by weight, melt kneading or molding of the resin composition may become difficult.

(Impact-resistant PBT composition)

The impact-resistant PBT composition of the present invention is characterized in that it contains 0.5 to 40 parts by weight of an impact-resistant improving material (F) and 0 to 200 parts by weight of a reinforcing filler (D) relative to 100 parts by weight of the above-mentioned PBT (A). share.

The so-called impact modifier (F) used in the present invention is a substance that improves impact values such as Ezod impact value, pendulum impact test value, and surface impact value. For example, acrylic rubber, butadiene rubber, polysiloxane rubber, etc. In particular, acrylic rubber is preferred. Acrylic rubber is a rubber-like elastic body obtained by polymerization of acrylate or copolymerization using it as the main body. As a representative material, an acrylate such as butyl acrylate and a small amount of butanediol diacrylate A rubbery polymer obtained by graft-polymerizing a graft polymerizable monomer such as methyl methacrylate on a polymer obtained by polymerizing such a crosslinkable monomer.

Examples of the above-mentioned acrylate include methyl acrylate, ethyl acrylate, propyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, and the like in addition to butyl acrylate. In addition, examples of crosslinkable monomers include polyalcohols such as butanediol dimethacrylate and trimethylolpropane trimethacrylate, and acrylic acid or methacrylic acid in addition to butanediol diacrylate. Vinyl compounds such as divinylbenzene, vinyl acrylate, vinyl methacrylate, allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate Allyl compounds such as esters, diallyl itaconate, monoallyl maleate, monoallyl fumarate, and triallyl cyanurate.

In addition, as the graft polymerizable monomer mentioned above, in addition to methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, esters, methacrylates such as lauryl methacrylate, styrene, acrylonitrile, etc. These graft-polymerizable monomers can be used for copolymerization when a part of the above-mentioned acrylate ester and cross-linkable monomer are polymerized to produce a polymer.

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, more preferably 2 to 30 parts by weight, based on 100 parts by weight of PBT share. When the content of the impact modifier (F) is less than 0.5 parts by weight, no improvement in impact resistance or thermal shock resistance can be confirmed, and when it exceeds 40 parts by weight, mechanical properties such as tensile strength and bending strength decrease significantly.

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

(flame retardant PBT composition)

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

The brominated aromatic compound flame retardant (G) used in the present invention is an aromatic compound known as a brominated flame retardant used in resins, for example, tetrabromobisphenol A ring Oxygen oligomer, poly(pentabromobenzyl acrylate), polybromophenylene ether, brominated polystyrene, brominated epoxy, brominated imide, brominated polycarbonate, etc.

The antimony compound (H) used in the present invention includes, for example, antimony oxide or antimonate, and specific examples include antimony trioxide (Sb ₂ O ₃ ), antimony tetraoxide (Sb ₂ O ₄ ) , antimony pentoxide (Sb ₂ O ₅ ) and other oxides or antimonates such as sodium antimonate.

The so-called anti-dripping agent (I) used in the present invention refers to a compound having the property of preventing resin from dripping during combustion. Specific examples thereof include silicone oil, silicon dioxide, asbestos, fluororesin, talc, In addition, there are layered silicates such as mica. In particular, preferred anti-dripping agents are fluorine-containing polymers or phyllosilicates from the viewpoint of the flame retardancy of the composition.

Specific examples of the fluororesin used as the anti-dripping agent (I) include polytetrafluoroethylene, tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene /Ethylene copolymer, vinylidene fluoride, polychlorotrifluoroethylene and other fluorinated polyolefins, etc. Among these, polytetrafluoroethylene, tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/ethylene copolymer are preferred, polytetrafluoroethylene, tetrafluoroethylene Ethylene/hexafluoropropylene copolymer.

As polytetrafluoroethylene, polytetrafluoroethylene having fibril-forming ability is preferable. That is, the polytetrafluoroethylene is easily dispersed in the resin, and polymers are bonded to each other to form a fibrous material, and it functions as an anti-dripping agent. Polytetrafluoroethylene having fibril-forming ability is classified into three types according to ASTM standards. Co., Ltd.) and "Teflon (R) 6J" from Mitsui Dupont Fluoro Chemical Co., Ltd.

The melt viscosity at 350°C of the fluororesin used as the anti-dripping agent (I) is usually 1.0×10 ² to 1.0×10 ¹⁵ (Pa·s), preferably 1.0×10 ³ to 1.0×10 ¹⁴ (Pa·s) , more preferably 1.0×10 ¹⁰ to 1.0×10 ¹² (Pa·s). When the melt viscosity is less than 1.0×10 ² (Pa·s), drip prevention during combustion is insufficient. When it is larger than 1.0×10 ¹⁵ (Pa·s), the fluidity of the composition is remarkably reduced.

It is preferable to use a phyllosilicate as the anti-dripping agent (I) from the viewpoint of fluidity when the resin composition of the present invention melts. Examples of layered silicates include layered silicates, modified layered silicates (phyllosilicates in which tetravalent organic onium cations are inserted between layers), and those with reactive functional groups. Layered silicate or modified layered silicate, but from the viewpoint of the dispersibility of the layered silicate to the resin composition of the present invention and the ability to prevent dripping, modified layered silicate, additionally reacted Layered silicate or modified layered silicate with reactive functional groups, especially, layered silicate or modified layered silicate with epoxy, amino, oxazoline, carboxyl, acid anhydride and other reactive functional groups Modified phyllosilicates are more suitable for use. As a method of imparting a functional group, a method of treating with a functionalizing agent (silane coupling agent) is preferable because of its simplicity.

As the functionalizing agent, for example, chlorosilanes having epoxy groups, chlorosilanes having carboxyl groups, chlorosilanes having mercapto groups, alkoxysilanes having amino groups, alkoxysilanes etc. In particular, 3-glycidoxypropyldimethylchlorosilane, β-(3,4-epoxycyclohexyl)ethyldimethylchlorosilane, 3-glycidoxypropyl Chlorosilanes with epoxy groups such as trichlorosilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-( 2-aminoethyl)-3-aminopropylmethyldimethoxysilane and other alkoxysilanes with amino groups, 3-glycidoxypropylmethyldiethoxysilane, 3-epoxy Alkoxysilanes having epoxy groups such as propoxypropyltrimethoxysilane and γ-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. The contacting of the layered silicate with these functionalizing agents is preferably carried out by mixing without solvent or in a polar solvent.

Specific examples of the layered silicate used in the present invention include montmorillonites such as montmorillonite, hectorite, fluorohectorite, saponite, beidellite, subtincite, etc. Clay minerals, Li-type fluorotaenite mica, Na-type fluorotaenoid mica, Na-type tetrasilicon fluorine mica, Li-type tetrasilicon fluorine mica and other swelling synthetic mica, vermiculite, fluorovermiculite, halloysite, etc., natural products , Synthetic products can be. In particular, smectite-based clay minerals such as montmorillonite and hectorite, swelling synthetic micas such as Li-type fluorotaenolite, Na-type fluorotaenolite, and Na-type tetrasilicofluoromica are preferred.

As the tetravalent organic onium cation intercalated between the layers of the modified layered silicate used in the present invention, for example, trimethyloctylammonium, trimethyldecylammonium, trimethyldodecylammonium, trimethyldodecylammonium, Trimethylammonium, trimethyltetradecylammonium, trimethylcetylammonium, trimethyloctadecylammonium, etc. Trimethylalkylammonium, dimethyldioctylammonium, dimethyldidecylammonium Dimethyl di(dodecyl) ammonium, Dimethyl di(tetradecyl) ammonium, Dimethyl di(hexadecyl) ammonium, Dimethyl di(octadecyl) ammonium Such as dimethyl dialkyl ammonium and so on.

As the anti-dripping agent (I), silicone oil is preferred. As silicone oil, it is a compound of dimethyl polysiloxane skeleton represented by the following general formula (1), and a part or all of the terminal or side chain may be modified by amino group, epoxy group, carboxyl group, methanol Modification, methacryl modification, mercapto modification, phenol modification, polyether modification, methyl styrene modification, alkyl modification, advanced fatty acid ester modification, advanced alkoxy modification, Fluorine modification and functionalization.

The viscosity of the silicone oil used as the anti-dripping agent (I) is usually 1,000 to 30,000 (cs.), preferably 2,000 to 25,000 (cs.), more preferably 3,000 to 20,000 (cs.) at 25°C. When the viscosity is less than 1000 (cs.), the anti-dripping effect during combustion becomes insufficient, and the flame retardancy is greatly reduced. When the viscosity is greater than 30000 (cs.), the fluidity of the composition is significantly reduced due to the thickening effect.

In the flame retardant PBT composition of the present invention, the content of the brominated aromatic compound flame retardant (G) is usually 3 to 50 parts by weight, preferably 5 to 40 parts by weight, more preferably 5 to 40 parts by weight, relative to 100 parts by weight of PBT. Preferably, it is 6-30 weight part. 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 decreases and the thermal stability at the time of melting 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, based on 100 parts by weight of PBT. When the content of the antimony compound (H) is less than 1 part by weight, a sufficient flame-retardant effect cannot be obtained, and when it exceeds 30 parts by weight, the mechanical strength decreases and the thermal stability at the time of melting tends to decrease.

In the flame-retardant PBT composition of this invention, content of an anti-dripping agent (I) is 0-15 weight part normally with respect to 100 weight part of PBT. When the content of the anti-dripping agent (I) exceeds 15 parts by weight, fluidity or mechanical properties may decrease.

In the flame-retardant PBT composition of the present invention, the type and content of the reinforcing filler (D) are the same as those described for the aforementioned hydrolysis-resistant PBT composition.

(Non-halogen flame retardant PBT composition)

The flame-retardant PBT composition of the present invention is characterized in that it contains a cosolvent ( K) 0.05-10 parts by weight, 2-45 parts by weight of at least one compound (L) selected from phosphoric acid ester or phosphazene, 0-200 parts by weight of reinforcing filler (D), anti-dripping agent (I) 0 -15 parts by weight, 0-45 parts by weight of melamine cyanurate (M), and 0-50 parts by weight of metal borate (N).

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

(wherein, R ¹⁰ represents a hydrogen atom, a first-level or second-level alkyl, aryl, aminoalkyl or alkoxy group, and R ¹¹ represents a first-level or second-level alkyl, aryl or alkylamino , r represents an integer of 10 or more).

As the primary alkyl group represented by ^R , for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopentyl, 2-methylbutyl, 2 , 3-dimethylbutyl, 2-, 3- or 4-methylpentyl or heptyl. Suitable examples of the secondary alkyl group include isopropyl, sec-butyl or 1-ethylpropyl. A suitable homopolymer of PPE includes, for example, a 2,6-dimethyl-1,4-phenylene ether unit. A suitable copolymer is a random copolymer composed of a combination of the above units and 2,3,6-trimethyl-1,4-phenylene ether units.

The PPE (J) used in the present invention has an intrinsic viscosity measured in chloroform at 30°C, usually from 0.20 to 0.80 dL/g, preferably from 0.25 to 0.70 dL/g, more preferably from 0.30 to 0.60 dL/g. When the intrinsic viscosity is less than 0.20 dL/g, the impact resistance of the composition is insufficient, and when it exceeds 0.80 dL/g, the gel component tends to be too large and the appearance of molded articles tends to deteriorate.

The so-called co-solvent (K) used in the present invention is a compound that improves the dispersibility of PPE in PBT, and polycarbonate resin can be used, which has one or more compounds selected from carboxyl groups, carboxylate groups, and carboxylic acid groups. Amide group, imide group, acid anhydride group, epoxy group, oxazoline group, amino group, compound of functional group in hydroxyl group, phosphite compound, etc.

Specific examples of compounds having functional groups include epoxy-added PPE resins, hydroxyalkylated PPE resins, oxazoline-terminated PPE resins, polyesters modified with polystyrene at the carboxyl end, hydroxyl Polyesters whose ends are modified with polyethylene, etc.

As the cosolvent (K), from the viewpoint of hydrolysis resistance, crystallinity, mechanical properties, and flame retardancy of the composition of the present invention, phosphite or polycarbonate resins are preferred, and among phosphites, phosphorous acid is preferred. As triesters, in particular, phosphite triesters represented by the following general formula (3) or (4) are preferable.

(In the formula, R ¹² to R ¹⁴ are each independently, may contain an oxygen atom, a nitrogen atom, or a sulfur atom, and represent an alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms).

Specific examples of the general formula (3) include trioctyl phosphite, tridecyl phosphite, trilauryl phosphite, trioctadecyl phosphite, triisooctyl phosphite, Tris(nonylphenyl) phosphate, tris(2,4-dinonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite, tri(phosphite Octylphenyl) ester, diphenylisooctyl phosphite, diphenylisodecyl phosphite, octyldiphenyl phosphite, dilaurylphenyl phosphite, diisodecylphenyl phosphite, Bis(nonylphenyl)phenyl phosphate, diisooctylphenyl phosphite, etc.

(In the formula, u is 1 or 2, R ¹⁵ can be the same or different, can contain oxygen atom, nitrogen atom, sulfur atom, represent an alkyl group with 1 to 20 carbon atoms or a substituted or non-substituted group with 6 to 30 carbon atoms Substituted aryl. When u is 1, R ¹⁶ represents an alkylene group with 1 to 20 carbon atoms or a substituted or unsubstituted arylene group with 6 to 30 carbon atoms. When u is 2, it represents 4 carbon atoms. ~18 alkyl tetrayl groups).

Examples of R ¹⁵ include methyl, ethyl, propyl, octyl, isooctyl, isodecyl, decyl, octadecyl, lauryl, phenyl, 2-, 3- or 4 -Methylphenyl, 2,4- or 2,6-dimethylphenyl, 2,3,6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2-,4 - or 2-, 6-diethylphenyl, 2,3,6-triethylphenyl, 2-, 3- or 4-tert-butylphenyl, 2,4- or 2,6-di-tert Butylphenyl, 2,6-di-tert-butyl-4-methylphenyl, 2,6-di-tert-butyl-4-ethylphenyl, octylphenyl, isooctylphenyl, 2- , 3- or 4-nonylphenyl, 2,4-dinonylphenyl, biphenyl, naphthyl, etc. In particular, substituted or unsubstituted aryl groups are preferred. As R ¹⁶ , when u=1 in the general formula (4), examples include 1,2-phenylene, ethylene, propylene, trimethylene, tetramethylene, hexamethylene, etc. Polymethylene.

As a specific example 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-propane Diol) 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-methylphenyl) (1,3-propanediol) phosphite, (phenyl) (1,2-ethanediol ) phosphite, (4-methylphenyl) (1,2-ethanediol) phosphite, (2,6-dimethylphenyl) (1,2-ethanediol) phosphorous acid Esters, (4-tert-butylphenyl)(1,2-ethanediol) phosphite, (2,6-di-tert-butylphenyl)(1,2-ethanediol) phosphite , (2,6-di-tert-butyl-4-methylphenyl) (1,2-ethanediol) phosphite, (2,6-di-tert-butyl-4-methylphenyl) ( 1,4-butanediol) phosphite, etc.

In addition, when u=2, R ¹⁶ includes a tetrayl group of a pentaerythritol structure represented by the following general formula (5), and the like.

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

As specific examples, diisodecyl pentaerythritol diphosphite, dilauryl pentaerythritol diphosphite, dioctadecyl pentaerythritol diphosphite, diphenyl pentaerythritol diphosphite, bis(2- Methylphenyl) pentaerythritol diphosphite, bis(3-methylphenyl) pentaerythritol diphosphite, bis(4-methylphenyl) pentaerythritol diphosphite, bis(2,4-dimethyl Phenyl) pentaerythritol diphosphite, bis(2,6-dimethylphenyl) pentaerythritol diphosphite, bis(2,3,6-trimethylphenyl) pentaerythritol diphosphite, bis(2 -tert-butylphenyl) pentaerythritol diphosphite, bis(3-tert-butylphenyl) pentaerythritol diphosphite, bis(4-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4 -Di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl ) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, bis(biphenyl) Pentaerythritol diphosphite, dinaphthyl pentaerythritol diphosphite, etc.

In the above-mentioned phosphite triester, in formula (4), preferred u is the compound represented by 1 or 2, in addition, when u=2 of more preferred formula (4), R ¹⁶ is represented by general formula (5) Compounds such as pentaerythritol-structured tetrayl groups. Among them, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methyl phenyl) pentaerythritol diphosphite, etc., particularly preferably bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) Pentaerythritol diphosphite. In addition, the composition of the present invention may contain compounds produced by decomposition (hydrolysis, thermal decomposition, etc.) of these phosphite triesters.

As the polycarbonate resin used as a cosolvent (K) in the present invention, there may be mentioned polycarbonate resins produced by reacting aromatic dihydroxy compounds or a small amount of polyhydroxy compounds with phosgene or carbonic acid diesters, which may also be branched. thermoplastic aromatic polycarbonate polymers or copolymers.

Examples of aromatic dihydroxy compounds include 2,2-bis(4-hydroxyphenyl)propane (=bisphenol A), tetramethylbisphenol A, bis(4-hydroxyphenyl)-p-diisopropyl Benzene, hydroquinone, cresol, 4,4-dihydroxybiphenyl, etc., preferably bisphenol A.

In order to obtain branched polycarbonate resins, pyroglucinol, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,4,6-dimethyl -2,4,6-tris(4-hydroxyphenyl)heptane, 2,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-3,1,3,5 -Polyol compounds represented by tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, etc., or 3,3-bis(4-hydroxyaryl)oxyindole Indole (=isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin, etc. are used as part of the above-mentioned aromatic dihydroxy compounds, and the amount used is usually 0.01 to 10 mol%, preferably 0.1 to 2 mol%.

As the aromatic polycarbonate resin, preferably, a polycarbonate resin derived from 2,2-bis(4-hydroxyphenyl)propane, or a polycarbonate resin derived from 2,2-bis(4-hydroxyphenyl)propane and Other polycarbonate copolymers derived from aromatic dihydroxy compounds.

The molecular weight of the polycarbonate resin used as a cosolvent (K) is usually 16,000 to 30,000, preferably 18,000 to 23,000 as a viscosity average molecular weight converted from a solution viscosity measured at a temperature of 25° C. using dichloromethane as a solvent. As the polycarbonate resin, two or more polycarbonate resins may be mixed and used.

As the phosphoric acid ester compound (L) used in the present invention, a wide range of phosphoric acid esters can be included. Specific examples thereof include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, trimethylol Base phosphate, hydroxycresyl diphenyl phosphate, octyl diphenyl phosphate, etc. In particular, compounds represented by the following general formula (6) are preferred.

(In the formula, R ¹ to R ⁸ each independently represent a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, m is an integer of 0 or 1 to 4, R ⁹ is p-phenylene, m-phenylene, 4 , 4'-biphenylene group or a divalent group selected from the following).

In the above general formula (6), R ¹ to R ⁸ are preferably alkyl groups having 6 or less carbon atoms, more preferably 2 or less carbon atoms, from the viewpoint of improving the hydrolysis resistance of the composition of the present invention. Alkyl, particularly preferably methyl. m is preferably 1-3, more preferably 1. R ⁹ is preferably p-phenylene or m-phenylene, more preferably m-phenylene.

In addition, as the component (L), a phosphazene compound having a group represented by the following general formula (7) is suitably used.

(In the formula, X represents -O-, -S-, -NH- or a direct bond, R ¹⁷ and R ¹⁸ represent an aryl group, an alkyl group, or a cycloalkyl group with 1 to 20 carbon atoms, and R ¹⁷ -X- and R ¹⁸ -X- may be the same or different, and n represents an integer of 1 to 12).

In the general formula (7), specific examples of ^R17 and ^R18 include alkyl groups which may be substituted by methyl, ethyl, butyl, hexyl, benzyl, etc., cycloalkyl groups such as cyclohexyl, benzene, etc. Aryl, naphthyl and other aryl groups. n is preferably 3-10, more preferably 3 or 4. The phosphazene compound of the general formula (7) may be a linear polymer or a cyclic polymer, but is preferably a cyclic polymer. X is preferably -O- or -NH-, particularly preferably -O-.

Specific examples of the phosphazene compound represented by the general formula (7) include hexaphenoxycyclotriphosphazene, hexa(hydroxyphenoxy)cyclotriphosphazene, octaphenoxycyclotetraphosphazene, octaphenoxycyclotetraphosphazene, and octaphenoxycyclotriphosphazene. (Hydroxyphenoxy) cyclotetraphosphazene, etc.

The so-called melamine cyanurate (M) used in the present invention is an approximately equimolar reactant of cyanuric acid and melamine. For example, it can be mixed with an aqueous solution of cyanuric acid and an aqueous solution of melamine. The reaction was stirred, and the resulting precipitate was filtered. The particle size of melamine cyanurate is usually 0.01 to 1000 μm, preferably 0.01 to 500 μm. Some of the amino groups or hydroxyl groups of melamine cyanurate may also be substituted by other substituents.

The boric acid metal salt (N) used in the present invention is preferably stable under commonly used processing conditions and has no volatile components. Examples of boric acid metal salts (N) include alkali metal salts of boric acid (for example, sodium tetraborate, potassium metaborate, etc.), alkaline earth metal salts (for example, calcium borate, magnesium orthoborate, barium orthoborate, zinc borate, etc.) wait. Of these, zinc borate is preferred. Zinc borate is generally represented by 2ZnO·3B ₂ O ₃ ·xH ₂ O (x=3.3-3.7). Zinc borate hydrate is preferably represented by the formula 2ZnO.3B ₂ O ₃ .3.5H ₂ O and is stable at 260° C. or higher.

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

In the non-halogen flame-retardant PBT composition of the present invention, the content of co-solvent (K) is 0.05-10 parts by weight, preferably 0.1-8 parts by weight, more preferably 0.3- 5 parts by weight. When the content of the co-solvent (K) is less than 0.05 parts by weight, the physical properties of the composition, especially the mechanical strength and flame retardancy will decrease, and if it exceeds 10 parts by weight, the flame retardancy and the surface appearance of the product will decrease. In the non-halogen flame-retardant PBT composition of the present invention, the content of phosphoric acid ester or phosphonium (L) is 2 to 45 parts by weight, preferably 3 to 40 parts by weight, more preferably 5 to 30 parts by weight. When the content of phosphoric acid ester or phosphonium (L) exceeds 2 parts by weight, the flame retardancy of the composition is insufficient, and when it exceeds 45 parts by weight, the mechanical properties, hydrolysis resistance, and moldability are remarkably 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 as those described for the aforementioned 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 for the above-mentioned flame-retardant PBT composition.

In the non-halogen flame-retardant PBT composition of the present invention, when layered silicate is used as the anti-dripping agent (I), its content is usually 0 to 15 parts by weight based on 100 parts by weight of the total of PBT and PPE, Preferably it is 0.3-12 weight part, More preferably, it is 0.5-10 weight part. When the layered silicate content exceeds 15 parts by weight, fluidity and mechanical properties will be extremely reduced. In addition, layered silicates may be used alone or in combination of two or more.

In the non-halogen flame-retardant PBT composition of the present invention, when silicone oil is used as the anti-dripping agent (I), its content is 0 to 15 parts by weight, preferably 0.005 to 8 parts by weight, based on 100 parts by weight of the total of PBT and PPE. parts, more preferably 0 to 5.0 parts by weight. When the content of the silicone oil exceeds 15 parts by weight, fluidity and mechanical properties are remarkably reduced.

In the non-halogen 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, more preferably 100 parts by weight of the total of PBT and PPE. Preferably it is 5-30 weight part. When the content of melamine cyanurate (M) exceeds 45 parts by weight, toughness or ductility decreases, or bleeding or plate-out of one component occurs.

In the non-halogen flame-retardant PBT composition of the present invention, the ratio of at least one compound (L) selected from phosphoric acid ester or phosphazene to melamine cyanurate (M) is usually 1:9 to 9:1 , preferably 2:8 to 8:2, more preferably 2.5:7.5 to 7.5:2.5.

In the non-halogen flame-retardant PBT composition of the present invention, the content of borate metal salt (N) is 0 to 50 parts by weight, preferably 2 to 45 parts by weight, more preferably 3 parts by weight relative to the total of 100 parts by weight of PBT and PPE. ~40 parts by weight. When the content of boric acid metal salt (N) exceeds 50 parts by weight, mechanical properties tend to decrease.

(Other functional PBT compositions-1)

Another functional PBT composition-1 of the present invention is characterized in that it contains 5 to 100 parts by weight of polycarbonate resin (O) and 0.01 parts by weight of organophosphorus compound (P) relative to 100 parts by weight of the above-mentioned PBT (A). ~ 1 part by weight, 0-200 parts by weight of the reinforcing filler (D), and 0-50 parts by weight of the impact modifier (F). This functional PBT composition-1, especially when used as a molded article, has reduced shrinkage and inflexion, and is excellent in dimensional stability.

Examples of the polycarbonate resin (O) used in the present invention include polycarbonate polymers that can also be branched, produced by reacting an aromatic dihydroxy compound or a diester of a small amount of a polyhydroxy compound with phosgene or carbonic acid or copolymers.

Examples of aromatic dihydroxy compounds include 2,2-bis(4-hydroxyphenyl)propane (=bisphenol A), tetramethylbisphenol A, bis(4-hydroxyphenyl)-p-diisopropyl Benzene, hydroquinone, cresol, 4,4-monohydroxybiphenyl, etc., preferably bisphenol A.

In order to obtain branched aromatic polycarbonate resins, pyroglucinol, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,4,6-di Methyl-2,4,6-tris(4-hydroxyphenyl)heptane, 2,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-3,1,3 , 5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, etc., or 3,3-bis(4-hydroxyaryl)oxy Kelindole (=isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin, etc. are used as part of the above-mentioned aromatic dihydroxy compounds, and the amount used is usually 0.01 ~10 mol%, preferably 0.1 to 2 mol%.

As aromatic polycarbonate resin, preferably can enumerate the polycarbonate resin that will 2,2-bis(4-hydroxyphenyl)propane react with phosgene or carbonate diester, or use 2,2-bis( Polycarbonate copolymers made from 4-hydroxyphenyl)propane and other aromatic dihydroxy compounds. In addition, two or more 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 25,000 as a viscosity average molecular weight converted from a solution viscosity measured at a temperature of 25° C. using dichloromethane as a solvent.

Examples of the organophosphorus compound (P) used in the present invention include an organophosphate compound, an organophosphite compound, an organophosphonite compound, and the like. Among these, organic phosphate ester compounds are preferable, and in particular, long-chain alkyl acid phosphate ester compounds represented by the following general formula (8) are preferable.

(RO) _n P(O)(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), specific examples of the alkyl group having 8 to 30 carbon atoms represented by R include n-octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, Decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, triaconyl, etc. In addition, a monoalkyl acid phosphate in which n is 1, a dialkyl acid phosphate in which n is 2, or a mixture thereof can also be used.

In other functional PBT composition-1 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, relative to 100 parts by weight of PBT. 80 parts by weight. When the content of the polycarbonate resin (O) is less than 5 parts by weight, the effect of reducing the shrinkage rate or deflection of the molded article is insufficient, and when it exceeds 100 parts by weight, the crystallization rate is slow, the melt viscosity increases, and the formability is extremely low. deterioration.

In other functional PBT composition-1 of the present invention, the content of the organophosphorus 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 10 parts by weight, relative to 100 parts by weight of PBT. 0.4 parts by weight. When the content of the organophosphorus compound (P) is less than 0.01 part by weight, the effect of improving the thermal stability and retention stability of the composition decreases, and when it exceeds 1 part by weight, the hydrolysis resistance decreases. Organophosphorus compounds (P) may be used alone or in combination of two or more.

In other functional PBT composition-1 of this invention, the kind and content of a reinforcing filler (D) are the same kind and content as what was demonstrated in the said hydrolysis-resistant PBT composition.

In other functional PBT composition-1 of the present invention, as the type of impact resistance modifier (F), the same type of substance as described in the above-mentioned impact resistance PBT composition can be used, with respect to 100 parts by weight The content of PBT is 0 to 50 parts by weight, preferably 1 to 45 parts by weight, more preferably 2 to 40 parts by weight. When the content of the impact modifier (F) exceeds 50 parts by weight, mechanical properties such as tensile strength and flexural strength decrease significantly.

(Other functional PBT compositions-2)

Another functional PBT composition-2 of the present invention is characterized in that it contains 5 to 100 parts by weight of an aromatic polyester resin (Q) other than PBT and a reinforcing filler Material (D) 0-200 weight part. This functional PBT composition-2 is excellent in surface appearance (transparency) especially when used as a molded article.

Examples of the aromatic polyester-based resin (Q) other than PBT used in the present invention include polyalkylene terephthalate, polyalkylene naphthalate, and the like. Specific examples of these include poly(1,4-cyclohexanedimethylene terephthalate) (PCT), polyethylene terephthalate (PET), polytrimethylene terephthalate ( PPT), polyethylene naphthalate (PEN), polytrimethylene naphthalate (PPN), polybutylene naphthalate (PBN), etc. Among these, polyethylene terephthalate and polytrimethylene terephthalate are preferable, and polyethylene terephthalate is more preferable.

The polyethylene terephthalate referred to here is obtained by polycondensing terephthalic acid or its ester-forming derivatives with an alkylene glycol having 2 carbon atoms or its ester-forming derivatives. The polymer may be a copolymer containing 70% by weight or more of polyethylene terephthalate. As monomers to be copolymerized, dibasic acid components other than terephthalic acid and its lower alcohol esters include isophthalic acid, naphthalene dicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, butyric acid, Aliphatic and aromatic polybasic acids such as diacids, or their ester-forming derivatives, etc., and diol components other than ethylene glycol are usually alkylene glycols, for example, diethylene glycol, propylene glycol, In addition to 1,3-propanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, etc., lower alkylene glycols such as 1,3-octanediol, bisphenol A Alcohols such as ethylene oxide 2-mole adducts of bisphenol A, propylene oxide 3-mole adducts of bisphenol A, polyols such as glycerol and pentaerythritol, and ester-forming derivatives thereof.

In the present invention, the polytrimethylene terephthalate resin refers to a polymer or copolymer obtained by condensation reaction of terephthalic acid or its ester-forming derivative and 1,3-propanediol as main components. . In this polymer, either a part of terephthalic acid may be substituted with other dicarboxylic acids or its ester-forming derivatives, or a part of 1,3-propanediol may be substituted with other Substances replaced by diols and/or triols. As the ester-forming derivatives, esters are preferred, and dimethyl terephthalate is particularly preferred.

In 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 7 to 90 parts by weight, more preferably 7 to 90 parts by weight, relative to 100 parts by weight of PBT. Preferably, it is 10 to 70 parts by weight. When the content of the aromatic polyester (Q) other than PBT is less than 5 parts by weight, almost no improvement in the surface appearance of the molded product is found, and when it exceeds 100 parts by weight, the increase in the molding cycle, the deterioration of the mold release property, etc., occur. Furthermore, problems in molding and degradation of mechanical properties of molded products occur.

In other functional PBT composition-2 of this invention, the kind and content of a reinforcing filler (D) are the same kind and content as what was demonstrated in the said hydrolysis-resistant PBT composition. In addition, as a means of further improving the surface appearance (transparency), it is effective to add a catalyst that promotes transesterification. The catalyst for promoting transesterification can be selected from oxides, hydroxides, and organic metal salts of metals belonging to Group 1A, Group 2A, Group 2B, Group 4A, Group 4B, Group 5B, Group 7A, and Group 8, but among them, as Metals are preferably sodium, calcium, lithium zinc, cobalt, manganese, etc., especially organic metal salts such as sodium stearate, calcium stearate, and magnesium stearate. The added amount is usually 0.001 to 1% by weight.

(Other functional PBT compositions-3)

Another functional PBT composition-3 of the present invention is characterized by containing 5 to 100 parts by weight of styrene-based resin (R), maleic anhydride-modified polystyrene 0-40 parts by weight of vinyl resin (S) or polycarbonate resin (O), 0-200 parts by weight of reinforcing filler (D). This functional PBT composition-3, especially when used as a molded article, has reduced shrinkage and inflexion, and is excellent in dimensional stability.

The styrenic resin (R) used in the present invention may be a rubber-modified styrenic resin, for example, (1) a homopolymer or a copolymer of an aromatic vinyl monomer, (2) an aromatic vinyl monomer selected from A copolymer of at least one of a base monomer, a comonomer (for example, a nitrile vinyl monomer) and a rubber component, and the like. Styrenic resins may be used alone or in combination of two or more.

Examples of the above-mentioned aromatic vinyl monomer include styrene, vinyltoluene, α-methylstyrene, and the like, and styrene is particularly preferable. Examples of the above-mentioned nitrilated vinyl monomers include unsaturated nitriles such as acrylonitrile and methacrylonitrile. These nitrile vinyl monomers can be used alone or in combination of two or more. Acrylonitrile is a preferred nitrile vinyl monomer. Examples of rubber-modified styrene-based resins include ABS resins, HIPS resins, and the like.

The number average molecular weight of the above-mentioned styrene-based resin (matrix resin in rubber-modified styrene-based resin) is usually 0.5×10 ⁴ to 200×10 ⁴ , preferably 1×10 ⁴ to 100×10 ⁴ . When the number average molecular weight is less than 0.5×10 ⁴ , the strength decreases, and when it is larger than 200×10 ⁴ , the fluidity decreases.

The maleic anhydride-modified polystyrene resin (S) used in the present invention refers to polystyrene containing maleic anhydride. Examples of the method of adding maleic anhydride to polystyrene include a method of simply mechanically mixing the two, a method of copolymerizing maleic anhydride with a styrene-based monomer, and the like. Examples of the latter copolymerization method include emulsion polymerization, solution polymerization, suspension polymerization and the like. 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 this invention, content of a styrene resin (R) is 5-100 weight part with respect to 100 weight part of PBT, Preferably it is 7-90 weight part, More preferably, it is 10-80 weight part. When the content of the styrene-based resin (R) is less than 5 parts by weight, the effect of reducing the shrinkage rate of the molded article or the inflexibility is insufficient, and when it exceeds 100 parts by weight, the mechanical properties are significantly lowered.

In the PBT composition-3 of the present invention, the maleic anhydride-modified polystyrene resin (S) or polycarbonate resin (O) is a styrene-based resin that does not contain nitrile vinyl monomers such as HIPS and PBT The co-solvent works. The content of these resins is 0-40 weight part with respect to 100 weight part of PBT, Preferably it is 5-30 weight part, More preferably, it is 10-20 weight part. When the content of these resins exceeds 40 parts by weight, the mechanical properties decrease.

In the PBT composition-3 of the present invention, the type and content of the reinforcing filler (D) are the same as those described for the aforementioned hydrolysis-resistant PBT resin. In addition, for the above-mentioned polycarbonate resin (O), the same type as that described for the above-mentioned hydrolysis-resistant PBT resin can also be used.

In the present invention, as a method of adding various additives to PBT, a method of adding additives by melt kneading is preferable. As the melt-kneading method, a kneading method generally used for thermoplastic resins can be used. For example, after uniformly mixing various components and additional components added as needed by a Henschel mixer, propeller mixer, V-type mixer, etc., using a single-screw mixing extruder, multi-screw mixing extruder, etc. Extruder, roll, Banbury mixer, Brabender machine (ブラベンダ one) for mixing.

The ingredients, including additional ingredients, can be fed together to the mixer. In addition, they may be supplied sequentially, and two or more components selected from each component including the additional component may be mixed in advance. Reinforcing fillers such as glass fibers can be added after the resin is melted during extrusion to avoid breakage and exhibit high performance. In addition, when adding the liquid epoxy compound, it may be added by pressing the epoxy compound into a PBT melt-kneading machine during extrusion.

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 compression molding, can be used.

The PBT of the present invention is suitable as injection molded parts such as electrical, electronic parts, and automotive parts due to its excellent color tone, hydrolysis resistance, thermal stability, transparency, and formability. It has excellent thermal stability, and has a remarkable improvement effect 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 containing PBT which contains titanium and whose content is 33 ppm or less in terms of titanium atoms. As such PBT, the above-mentioned PBT can be used. The intrinsic viscosity of PBT for films is usually 0.80 to 2.50 dL/g, preferably 0.90 to 1.80 dL/g, more preferably 1.00 to 1.30 dL/g. Other physical property values of PBT are the same as above.

The film forming method of PBT of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, T-die casting method, air-cooled expansion molding method, water-cooled expansion molding injection molding method, and polishing roll method can be used. wait.

In addition, the PBT film of the present invention can become a composite film with other resin films. As the resin of the composite resin film, polyolefin resins (low-density polyethylene: LDPE) and linear low-density polyethylene: LLDPE), high-density polyethylene: HDPE), homopolypropylene), block copolymerized polypropylene in which olefins with 2 to 8 carbon atoms are copolymerized as comonomers, random copolymerized polypropylene, ethylene-vinyl acetate copolymer , Partial saponification of ethylene-vinyl acetate copolymer (EVOH), ethylene-ethyl acrylate copolymer, ionomers, styrene-ethylene copolymer, ethylene-butylene copolymer, styrene-ethylene-butylene copolymer things etc.

In the case of a combination of polyolefin-based resins that are not sufficiently bonded to PBT and easily peeled off between layers, acid-modified or epoxy-modified resins (so-called adhesive resins) can be mixed between layers, and three types of resins can be used. layer film.

In addition, in order to increase strength, three types of three-layer films (PBT/adhesive/polyamide) using polyamide instead of polyolefin resin, or between PBT and polyamide, polyamide and polyolefin, respectively, can be mentioned. 5 types of 5-layer film (PBT/adhesive/polyamide/adhesive/polyolefin) with adhesive resin, 5 types of 5-layer film with EVOH instead of polyamide (PBT/adhesive/EVOH/adhesive/polyolefin) alkenes) etc. In addition, considering both strength and oxygen barrier properties, it can also be a 6-layer film (PBT/EVOH/polyamide/polyolefin) in which both polyamide and EVOH are blended between PBT and polyolefin. 6-layer film (PBT/adhesive/EVOH/polyamide/adhesive/polyolefin) with adhesive resin blended between them.

As a means of producing a composite film, the co-extrusion method is generally used, but it is also possible to use the dry lamination method of laminating the PBT film on a polyolefin film or polyester film using an adhesive after forming the PBT film once. , or other known methods such as an extrusion lamination method in which molten resin is extruded on a PBT film.

In the extrusion lamination method, coupling agents or reactive adhesives such as epoxies, urethanes, titanates, and siloxanes can be coated on the surface of the pre-manufactured film, or an electric current can be applied. Known surface treatments such as corona discharge.

The thickness of the PBT film of the present invention (in the case of a composite film, the thickness of the PBT film layer) is generally 5 to 200 μm. In particular, in the case of a single-layer film, it is usually 10 to 150 μm, preferably 20 to 100 μm, and in the case of a composite film (PBT film layer), it is usually 5 to 100 μm, preferably 10 to 80 μm. The overall thickness of the composite film Usually 20 to 300 μm, preferably 50 to 200 μm.

Generally, the haze value of PBT film is affected by film thickness and forming conditions. The thicker the film, or the higher the cooling temperature after extrusion, the higher the haze value. Therefore, in the present invention, when a PBT film of 50 μm is formed by the T-die casting method or the water-cooled expansion method, it is preferable that the haze value of the film is less than 2%. The cooling temperature at the time of 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 lower, and the cooling water temperature in the case of the water-cooled expansion method is 70°C or lower . When the haze value of the film formed under these forming conditions exceeds 2%, the film becomes white and loses transparency in appearance, thereby deteriorating the commercial value. In addition, when adding additives to the PBT of the present invention, the addition amount is preferably adjusted so that the crystallization temperature of the PBT resin composition does not exceed 200° C., and the haze value when formed into a film with a thickness of 50 μm does not exceed 2%. Add amount.

The PBT of the present invention, as mentioned above, can be copolymerized or mixed (alloyed) with other resins. Especially in films, the PBT of the present invention is easy to control the crystallinity or transparency. In addition, in order to improve each For mechanical properties, it is preferable to mix with other resins. Examples of suitable mixed resins especially in the case of films include polyester, polycarbonate, polyamide, polyphenylene oxide, polystyrene, polymethacrylic acid or polymethacrylate, polyacrylic acid or polyacrylic acid esters, polyolefins, etc. In addition, as the mixed resin, PBT other than the PBT of the present invention may be used. In addition, PBT of the present invention having different compositions or molecular weights may be mixed. Among these, polyester is preferable from the viewpoint of compatibility or transparency, and aromatic polyester is particularly preferable. Among the aromatic polyesters, the aromatic polyesters exemplified in the above-mentioned "other functional PBT composition-2" are preferable.

Generally, in order to maximize the performance of a film that uses a mixture of PBT and other polyesters as a raw material, it is important to control the transesterification reaction between them. If there are too many catalysts remaining in PBT, the transesterification reaction will Too fast and it becomes difficult to control. However, in the PBT of the present invention, since the amount of the catalyst is significantly reduced, the control of the transesterification reaction becomes easy, and a wide range of compounding or molding conditions can be adopted. In particular, the improvement effect is also large in a mixed system of polyethylene terephthalate, polyethylene naphthalate, etc., which have a higher melting point than PBT and require a high molding temperature.

In addition, even in a mixed system with a polyester (preferably an aromatic polyester) copolymerized with poly-1,4-butanediol whose decomposition reaction is accelerated due to the remaining catalyst, the use of the remaining catalyst significantly reduces the PBT can reduce decomposition even more.

The mixing ratio (weight ratio) of PBT of the present invention to other resins is not particularly limited, but is usually 99:1 to 1:99, preferably 95:5 to 5:95, more preferably 90:10 to 10:90.

The PBT film of the present invention has the characteristics of being able to clearly see the contents due to the above-mentioned characteristics. Films and other patterned surface coating materials, laminated steel sheets for construction and food cans, etc.

Example

Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited at all by the following Example unless the summary is exceeded. In addition, the measurement methods of the physical properties and evaluation items used in each of the following examples are as follows.

(1) Esterification rate:

Calculated from the acid value and the saponification value by the following calculation formula (V). The acid value was determined by dissolving the oligomer in dimethylformamide and titrating it with a 0.1N KOH/methanol solution. The saponification value is obtained by hydrolyzing oligomers with 0.5N KOH/ethanol solution and titrating with 0.5N hydrochloric acid.

Esterification rate = [(saponification value-acid value)/(saponification value)]×100 (V)

(2) Terminal carboxyl concentration:

In 25 mL of benzyl alcohol, dissolve 0.5 g of PBT or oligomer, and titrate with a 0.01 mol/L benzyl alcohol solution of sodium hydroxide.

(3) Intrinsic viscosity (IV):

Use Ubbelohde viscometer to obtain according to the following method. That is, using a mixed solvent of phenol/tetrachloroethane (weight ratio 1/1), at 30°C, measure the number of seconds for the polymer solution with a concentration of 1.0g/dL and only the solvent to fall, according to the following formula (VI) Find out.

[VI]＝((1+4K _H η _sp ) ^0.5 -1)/(2KHC) (VI)

(In the _formula , η = η/η ₀ -1, η is the falling seconds of the polymer solution, η ₀ is the falling seconds of the solvent, C is the polymer solution concentration (g/dL), K _H is Parkin Adams constant, K _H adopts 0.33).

(4) Titanium concentration in PBT:

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

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

About 100 mg of PBT was dissolved in 1 mL of a mixed solvent of deuterated chloroform/hexafluoroisopropanol = 7/3 (volume ratio), and 36 μL of deuterated pyridine was added, followed by ¹ H-NMR measurement at 50°C. As an NMR apparatus, "α-400" or "JNM270" manufactured by JEOL Ltd. was used.

(6) The number of foreign matter of 5 μm or more in PBT:

In a mixed solvent of hexafluoroisopropanol/chloroform=2/3 (volume ratio), 10 g of PBT was dissolved at a concentration of 20% by weight, filtered through a polytetrafluoroethylene membrane filter with a pore diameter of 5 μm, and then filtered with the above-mentioned Wash the mixed solvent thoroughly, observe and count the number of foreign matter remaining on the filter with an optical microscope.

(7) cooling crystallization temperature (Tc):

Using a differential scanning calorimeter (Perkin Elma Co., model DSC7), after heating up from room temperature to 300°C at a heating rate of 20°C/min, the temperature was lowered to 80°C at a cooling rate of 20°C/min. The temperature is used as the cooling crystallization temperature. The higher the Tc, the faster the crystallization rate and the shorter the molding cycle.

(8) Solution fog value:

Dissolve 2.70 g of PBT in 20 mL of a mixed solution of phenol/tetrachloroethane = 3/2 (weight ratio) at 110°C for 30 minutes, then cool in a constant temperature water bath at 30°C for 15 minutes, and use Nippon Denshoku A turbidimeter (NDH-300A) manufactured by Co., Ltd. was used for measurement with a measuring cell length of 10 mm. Lower values indicate better transparency.

(9) Grain tone:

Using a color difference meter (Z-300A type) manufactured by Nippon Denshoku Co., Ltd., the yellowness index b value was calculated and evaluated. Lower values indicate less yellow and better hues.

(10) Increase in terminal carboxyl group concentration caused by thermal decomposition (Δ[COOH])

After vacuum-drying PBT to a moisture content of 300ppm or below, in a glass tube, under a dry nitrogen atmosphere, heat treatment with an oil bath at 245°C for 45 minutes, and measure the concentration of terminal carboxyl groups and terminal hydroxyl groups before and after heat treatment, using the following Formula (VII) is calculated.

Δ[COOH] = change in terminal carboxyl group concentration before and after heat treatment - change in terminal hydroxyl group concentration before and after heat treatment (VII)

(11) Melt molecular flow rate:

According to ISO1133, it is measured at 250° C. under a load of 2.16 kg.

(12) Tensile strength and tensile elongation at break:

Using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.: Model S-75MIII), mold an ISO test piece of the resin composition at a cylinder temperature of 250° C. and a mold temperature of 80° C., and measure the tensile strength ( TS) and tensile elongation at break. For any of these, the average value of five times was used.

(13) Bending properties:

According to ISO178, the flexural strength and the flexural modulus of elasticity were measured for the same ISO test piece as above.

(14) Pendulum impact strength (Charpy impact strength):

The pendulum impact strength was measured in accordance with ISO179 after notching was applied to the same ISO test piece as above.

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

Put the same ISO test piece as above into a pressure vessel filled with pure water, and keep it out of direct contact with water. After sealing it, treat it under pressure at 121°C for 100 hours, and perform the same tensile test as above. (The average value of the tensile strength after the treatment is defined as TS'). And, the strength retention rate was calculated according to the following formula (VIII). However, the wet heat treatment is 100 hours in the case of the resin composition containing the reinforcing filler, and 60 hours in the case of the resin composition not containing the reinforcing filler. A high strength retention rate indicates good hydrolysis resistance.

Strength retention (%)=(TS’/TS)×100 (VIII)

(16) Terminal hub features:

Metal wire terminals for automobiles having a pivot portion were injection molded at a cylinder temperature of 270°C and a mold temperature of 80°C, and the flexability of the pivot portion was evaluated. When the pivot portion was bent 90 degrees at -10°C, the number of cracks generated in the pivot portion was measured. The measurement was performed on 40 terminals.

(17) Release property:

The 16-pole terminal was continuously molded by an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.: model SG-75MIII), and the minimum cooling time for continuous molding 20 times without the molded product remaining in the fixed metal mold was obtained. The filling time is 1 second, the pressure holding time is 8 seconds, and the cooling time is taken after the pressure holding. The barrel temperature was set to 250°C, and the initial mold temperature was set to 45°C. The above-mentioned minimum cooling time refers to the cooling time that causes mold release defects remaining in the fixed metal mold when the cooling time is shortened to a shorter time. In other words, it is the shortest cooling time that enables stable continuous production. cooldown time.

(18) Generate gas:

5 g of resin composition pellets were put into a 26-mL glass vial and heated at 150° C. for 2 hours, and then a sample was taken from the gas phase portion with a microsyringe. Analysis by gas chromatography. The peak area of the chromatogram was obtained and represented by the ratio (ppm) of the weight of tetrahydrofuran corresponding to the area to the resin composition. The majority (approximately 90%) of the gas produced was tetrahydrofuran.

(19) Reflex amount:

A disc having a diameter of 100 mm and a thickness of 1.6 mm was molded at a cylinder temperature of 250° C. using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.: Model SG-75MIII). Gate (ゲ一ト) is a 1-point gate on the circumference. One end of the circular plate is fixed on the flat plate, and the distance from the opposite side to the flat plate is measured as the deflection amount.

(20) Fog value of the film:

The haze value at a thickness of 50 μm was measured using an automatic 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 60°C slurry in which 1,4-butanediol was mixed at a ratio of 1.80 mol with respect to 1.00 mol of terephthalic acid was continuously supplied at 41 kg/h to In the esterification reaction tank (A) which had the helical type agitator and filled the PBT oligomer of esterification rate 99% beforehand. At the same time, the bottom component of the rectification column (C) at 185° C. is supplied at 17.2 kg/h from the recirculation line (2), and tetrabutylene at 65° C. as a catalyst is supplied at 97 g/h from the catalyst supply line (3). 6.0% by weight of 1,4-butanediol solution (30 ppm relative to the theoretical polymer yield) of the base titanate. The moisture in this solution was 0.20% by weight.

The internal temperature of the reaction tank (A) is 230°C and the pressure is 78kPa. The generated water, tetrahydrofuran and remaining 1,4-butanediol are distilled from the distillation line (5) and separated in the rectification tower (C). High boiling point components and low boiling point components. The high boiling point component at the bottom of the column after the system is stabilized is 98% by weight or more than 98% by weight of 1,4-butanediol. In order to keep the liquid level of the rectifying column (C) constant, a part of it is drawn through the extraction line (8). Draw out to the outside. On the other hand, the low-boiling point components are extracted from the top of the tower in the form of gas, condensed by the condenser (G), and extracted to the outside through the extraction line (13) to keep the liquid level of the tank (F) constant.

A certain amount of oligomers generated in the reaction tank (A) was extracted from the extraction line (4) using a pump (B), and the liquid level was controlled so that the average residence time of the liquid in the reaction tank (A) was 3.3hr. The oligomer extracted from the extraction line (4) is continuously supplied to the first polycondensation reaction tank (a). After the system stabilized, the esterification rate of the oligomer collected at the outlet of the reaction tank (A) was 97.5%.

The internal temperature of the 1st polycondensation reaction tank (a) was 240 degreeC, the pressure was 2.1 kPa, and liquid level control was performed so that residence time might be 120 minutes. Water, tetrahydrofuran, and 1,4-butanediol are extracted from a discharge line (L2) connected to a decompressor (not shown), and the initial polycondensation reaction is carried out, and the extracted reaction solution is continuously supplied to the second polycondensation process. In the reaction tank (d).

The inner temperature of the second polycondensation reaction tank (d) is 245° C., the pressure is 130 Pa, and the liquid level is controlled so that the residence time is 90 minutes. From the discharge line (L4) connected to the depressurizer (not shown), While extracting water, tetrahydrofuran, and 1,4-butanediol, the polycondensation reaction further proceeded. The obtained polymer is continuously drawn out from the die head (g) in a thread-like form through the drawing line (L3) by the gear pump (e) for drawing out, and cut by the rotary blade (h).

The obtained polymer had an intrinsic viscosity of 0.85 dL/g and a terminal carboxyl group concentration of 12.2 μeq/g. Other analytical values are summarized in Table 1. It is possible to obtain PBT with less foreign matter, excellent color tone, good transparency, and excellent thermal stability.

Example 2

In Example 1, it carried out similarly to Example 1 except having adopted the polycondensation process shown in FIG. 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 μm was used. Compared with Example 1, the PBT which reduced foreign matter was obtained. The analytical values are summarized in Table 1.

Example 3 and Example 4

In Example 1, except that the supply of tetrabutyl titanate was adjusted so that the titanium content in the polymer was as shown in Table 1, and the pressure of the second polycondensation reaction tank (d) was 100 Pa, the same method as in the implementation Example 1 was performed in the same manner. It is possible to obtain PBT with less foreign matter, excellent color tone, good transparency, and excellent thermal stability. The analytical values are summarized in Table 1.

Example 5

In Example 1, except that the supply of tetrabutyl titanate was adjusted so that the titanium content in the polymer was as shown in Table 1, and the temperature of the second polycondensation reaction tank (d) was 250°C, the same as Example 1 was carried out in the same manner. It is possible to obtain PBT with less foreign matter, excellent color tone, good transparency, and excellent thermal stability. The analytical values are summarized in Table 1.

Example 6

In Example 1, it carried out similarly to Example 1 except having adopted the polycondensation process shown in FIG. At this time, the same conditions as in Example 1 were used until the second polycondensation reaction tank (d), and the internal temperature of the third polycondensation reaction tank (k) was 240° C., the pressure was 130 Pa, and the residence time was 60 minutes. It was possible to obtain PBT having less foreign matter, excellent color tone, good transparency, excellent thermal stability, and higher molecular weight than Example 1. The analytical values are summarized in Table 1.

Example 7

In Example 6, it carried out similarly to Example 6 except having adopted the polycondensation process shown in FIG. 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 μm was used. Compared with Example 6, the PBT which reduced foreign matter was obtained. The analytical values are summarized in Table 2.

Example 8

In Example 1, it carried out similarly to Example 1 except having changed the ratio of the column bottom component supplied to the distillation column (C) of reaction tank (A) from the recirculation line (2) to 8.0 kg/h. It is possible to obtain PBT with less foreign matter, excellent color tone, good transparency, and excellent thermal stability. The analytical values are summarized in Table 2.

Example 9

In Example 7, the internal temperature of the third polycondensation reaction tank (k) was 245° C., the pressure was 130 Pa, and the residence time was 70 minutes until the second polycondensation reaction tank (d) was performed under the same conditions as in Example 1. PBT with a higher viscosity than Example 7 could be obtained.

Comparative example 1

In Example 1, except that the catalyst supply line (3) of the esterification process shown in FIG. , and, except that the supply rate of the 1,4-butanediol solution of tetrabutyl titanate is 194 g/h, and the supply rate of the bottom component of the rectification column (C) is 17.1 kg, it is the same as in Example 1 conduct. As shown in the table, the haze value and color tone deteriorated, and there were also many foreign substances. The analytical values are summarized in Table 2.

Comparative example 2

272.9mol of terephthalic acid, 491.3mol of 1,4-butanediol, 0.126mol (as the amount of titanium, 100ppm per theoretical yield polymer ) Tetrabutyl titanate for sufficient nitrogen exchange. Then, the system was heated up, and after 60 minutes, the temperature reached 220°C and the pressure reached 80kPa, while the generated water, tetrahydrofuran, and remaining 1,4-butanediol were distilled out of the system, and the esterification reaction was carried out for 2 hours ( The reaction start time is set as the time when the predetermined temperature and predetermined pressure are reached). At this time, a part of the sample was collected and the esterification rate was measured to be 99%.

The oligomer obtained above was transferred to a 200-L stainless steel reactor with an elbow tube and a double-helical stirring blade, and the temperature reached 245°C and the pressure was 100 Pa in 60 minutes, and the polycondensation reaction was carried out for 1.5 hours while maintaining this state. . After the reaction, the polymer is drawn out in the form of strands and cut into granules. The intrinsic viscosity of the obtained polymer was 0.85, the terminal carboxyl group concentration was as high as 44.5 μeq/g, the thermal stability was not good, and the Tc was also low. The analytical values are summarized in Table 2.

Comparative example 3

272.9 mol of dimethyl terephthalate (DMT), 327.5 mol of 1,4-butanediol, 0.126 mol (as the amount of titanium, per Theoretical yield polymer 100ppm) tetrabutyl titanate, carry out sufficient nitrogen exchange. Next, the system was heated up, and after 60 minutes, the temperature was 210°C. Under nitrogen atmosphere, under atmospheric pressure, while distilling the generated methanol, 1,4-butanediol, and tetrahydrofuran out of the system, esterification was carried out for 2 hours. Exchange reaction (the reaction start time is set to the time when the specified temperature and pressure are reached).

The oligomer obtained above was transferred to a 200-L stainless steel reactor having a discharge pipe and a double-helical stirring blade, and then reached a temperature of 245° C. and a pressure of 100 Pa over 60 minutes, and polycondensation reaction was performed for 1.5 hours while maintaining this state. After the reaction, the polymer is drawn out in the form of strands and cut into granules. The intrinsic viscosity of the obtained polymer was 0.85, the terminal carboxyl group concentration was as high as 37.4 μeq/g, the thermal stability was not good, and the Tc was also low. The analytical values are summarized in Table 2.

Comparative example 4

In Example 1, except that the catalyst supply line (3) of the esterification step shown in Figure 1 is connected to the raw material supply line (1), and the circulation line (2) is located in the gas phase of the reaction tank (A) , and, the supply rate of 1,4-butanediol solution of tetrabutyl titanate is 194g/h, the supply rate of the column bottom component of rectification column (C) is 17.1kg, adopts the polymerization shown in Figure 8 The process was carried out in the same manner as in Example 1, except that the polycondensation process shown in FIG. 6 was replaced. At this time, the same conditions as in Example 1 were used until the second polymerization reaction tank (d), and the inner temperature of the third polymerization reaction tank (k) was 240° C., the pressure was 130 Pa, and the residence time was 60 minutes. The resulting PBT had many foreign substances and had a high haze value or b value. The analytical values are summarized in Table 2.

Comparative Example 5

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

Next, the oligomer is transferred to the polycondensation reaction tank, and in the same manner as Comparative Example 2, the temperature reaches 245° C. and the pressure is 100 Pa in 60 minutes, and the polycondensation reaction is carried out in this state for 5 hours. As it rises, the polymer is pumped out. The intrinsic viscosity of the obtained polymer was 1.03, and both the terminal carboxyl group concentration and the terminal vinyl group concentration were high.

Table 1 project unit Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 BM/TM Mol/mol 3.35 3.35 3.35 3.35 3.35 3.35 3.35 Ti content ppm 30 30 25 10 10 30 30 IV dL/g 0.85 0.85 0.85 0.76 0.85 1.20 1.20 terminal carboxyl concentration µeq/g 12.2 12.2 11.3 8.0 11.5 22.2 22.2 Tc ℃ 177.5 177.5 176.4 176.0 176.5 175.8 175.8 Terminal Vinyl Concentration µeq/g 6.5 6.5 6.3 5.5 9.2 9.5 9.5 Terminal methoxycarbonyl concentration µeq/g 0.1 or less 0.1 or less 0.1 or less 0.1 or less 0.1 or less 0.1 or less 0.1 or less 5μm or more than 5μm number of foreign objects pcs/10g polymer 11 5 9 7 8 12 6 Solution fog value % 0.3 0.3 0.2 0.1 0.1 0.3 0.3 Δ[COOH] μeq/g (40 minutes) 4.3 4.3 3.6 1.7 1.7 1.8 1.8 particle b value -1.6 -1.6 -1.8 -2.0 -0.5 -1.2 -1.2

Table 2 project unit Example 8 Example 9 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 BM/TM Mol/mol 2.52 3.35 3.35 1.80 1.20 3.35 1.80 Ti content ppm 30 30 60 100 100 60 35 IV dL/g 0.85 1.26 0.85 0.85 0.85 1.20 1.03 terminal carboxyl concentration µeq/g 13.0 28.4 13.5 44.5 37.4 25.6 36.0 Tc ℃ 179.1 175.0 178.5 175.6 168.7 175.9 172.4 Terminal Vinyl Concentration µeq/g 7.8 10.7 6.9 7.0 6.7 10.5 12.5 Terminal methoxycarbonyl concentration µeq/g 0.1 or less 0.1 or less 0.1 or less 0.1 or less 2.3 0.1 or less 0.1 or less 5μm or more than 5μm number of foreign objects pcs/10g polymer 20 5 67 20 15 70 29 Solution fog value % 1.0 0.2 22.5 0.4 0.1 21.7 0.4 Δ[COOH] μeq/g (40 minutes) 2.9 1.5 4.5 9.0 10.1 2.0 2.9 particle b value -1.0 -0.8 0.2 0.0 -1.5 0.8 1.5

Examples 10-12 and Comparative Examples 6-8 (mixed PBT)

Use 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 PBT of Comparative Example 4, mix with the compounding composition shown in Table 3, and pass through a belt with a screw diameter of 30 mm. A twin-screw extruder with a vent port [Nippon Steel Works: TEX30C] melted and kneaded the mixture at a temperature of 260° C. and a screw rotation speed of 200 rpm to extrude into strands and pelletize. And the evaluation shown in Table 3 and Table 4 was performed, and the result is shown in the same table.

table 3 Example 10 11 12 Composition (parts by weight) Example 1 - PBT 40 29 71 Example 6-PBT 60 71 29 The melt flow rate g/10min 28 twenty four 45 mechanical properties Tensile Strength MPa 53 52 54 Tensile elongation at break % 100 120 90 Bending strength MPa 80 79 82 Flexural modulus of elasticity MPa 2280 2200 2350 Charpy impact strength KJ/m 4.0 4.4 3.3 Hydrolysis resistance Tensile strength: MPa Before heat treatment 53 52 54 After heat treatment 39 41 36 Strength retention rate (%) 74 79 66 Terminal Pivot Breaks/40 Pieces 0 1 0

Table 4 comparative example 6 7 8 Composition (parts by weight) Comparative Example 1-PBT 40 29 71 Comparative Example 4-PBT 60 71 29 The melt flow rate g/10min 28 twenty four 45 mechanical properties Tensile Strength MPa 53 52 54 Tensile elongation at break % 80 100 60 Bending strength MPa 80 78 83 Flexural modulus of elasticity MPa 2280 2200 2350 Charpy impact strength KJ/m 4.0 4.4 3.3 Hydrolysis resistance Tensile strength: MPa Before heat treatment 53 52 54 After heat treatment 37 38 33 Strength retention rate (%) 69 74 62 Terminal Pivot Breaks/40 Pieces 2 2 3

As shown in Tables 3 and 4, by mixing PBTs having 33 ppm or less of titanium atoms and different intrinsic viscosities, PBT with adjusted fluidity, hydrolysis resistance, elongation at break, and excellent pin joint properties of the terminal can be obtained. This is because, since the amount of the titanium catalyst is reduced, the hydrolysis resistance is improved, and the agglomerated foreign matters of the titanium catalyst are reduced.

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

With respect to 99.7 parts by weight of the pellets of each PBT obtained in Example 1, Example 6, Comparative Example 1, and Comparative Example 2, the following ingredients (1) to (3) were mixed in the compounding composition of Table 5, and compared with Example 9 Granulate in the same way.

(1) Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (manufactured by Chibagaigi, trade name: Irganox 1010)

(2) Pentaerythritol tetrakis(3-laurylthiodipropionate) (manufactured by Shipro Chemical Co., Ltd., trade name: SEENOX412S)

(3) Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite (manufactured by Asahi Denka Co., Ltd., trade name: Adecastab PEP36) was formed into an ISO test piece from the above-mentioned pellets, The color tone b value, tensile strength, and tensile elongation at break were measured. Moreover, in order to evaluate heat aging resistance, the color tone b value, tensile strength, and tensile elongation at break were measured about the ISO test piece processed in the hot-air drying oven of 150 degreeC for 250 hours or 500 hours. Moreover, hydrolysis resistance was also evaluated using the ISO test piece. These results are shown in Table 5 and Table 6.

table 5 Example 13 14 15 Composition (parts by weight) Example 1 - PBT 99.7 99.7 99.7 Irganox1010 0.1 0.1 0.3 SEENOX412S 0.2 - - PEP36 - 0.2 - Heat aging resistance Hue b value unprocessed -0.3 -0.5 -0.2 250 hours later 5.4 4.9 9.9 after 500 hours 8.0 7.3 13.4 Tensile strength: MPa unprocessed 52 53 51 250 hours later 61 60 59 after 500 hours 58 56 58 Tensile elongation: % unprocessed 65 59 62 250 hours later 17.4 16.5 15.5 after 500 hours 13.5 14 12.6 Hydrolysis resistance Tensile strength: MPa Before heat treatment 52 53 51 After heat treatment twenty three 17 twenty four Strength retention rate (%) 44 32 47

Table 6 Example comparative example 16 9 10 Composition (parts by weight) Example 6-PBT 99.7 - - Comparative Example 1-PBT - 99.7 - Comparative example 2-PBT - - 99.7 Irganox1010 - 0.1 0.1 SEENOX412S 0.3 0.2 0.2 PEP36 - - - Heat aging resistance Hue b value unprocessed 0.2 1.0 1.3 250 hours later 7.1 7.8 8.2 after 500 hours 9.8 10.2 11.5 Tensile strength: MPa unprocessed 50 51 50 250 hours later 60 58 57 after 500 hours 61 56 55 Tensile elongation: % unprocessed 160 29 57 250 hours later 19.2 14.7 13.9 after 500 hours 15.7 9.3 8.1 Hydrolysis resistance Tensile strength: MPa Before heat treatment 50 51 50 After heat treatment 33 19 16 Strength retention rate (%) 66 37 32

As shown in Table 5 and Table 6, by adding an antioxidant to PBT having 33 ppm or less of titanium atoms, it is possible to obtain heat resistance, no change in color tone, no decrease in tensile elongation, and excellent hydrolysis resistance. PBT composition. This is because, since the amount of the titanium catalyst is small, thermal decomposition, oxidation, and hydrolysis are suppressed.

Examples 17-18 and Comparative Examples 11-13 (PBT composition with good mold release properties)

In 100 parts by weight of the various PBT obtained in Example 1, Comparative Example 1, and Comparative Example 2, the following (1) and (2) components were mixed according to the composition of Table 7, and passed through a twin-screw extruder at 260 ° C. Kneading, extruding into strands and granulating.

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

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

The molecular weight of the above-mentioned montanic acid ester is measured by the melt viscosity method as follows. Fill the constant temperature oil tank with polyethylene glycol, adjust the Atlas (Atlantic) type viscometer to 135 ° C, keep the viscometer vertically, dilute the necessary amount of wax with decahydronaphthalene, and measure the concentration of the sample solution with an automatic viscometer. Flow down seconds, converted to molecular weight.

ISO test pieces were molded from the above-mentioned pellets, and mold releasability was also evaluated. In addition, hydrolysis resistance was evaluated. These results are shown in Table 7.

Table 7 Example comparative example 17 18 11 12 13 Composition (parts by weight) Example 1 - PBT 100 100 - - - Comparative Example 1-PBT - - 100 100 - Comparative example 2-PBT - - - - 100 montanate 0.3 - 0.3 - 0.3 polyethylene wax - 0.3 - - - Hydrolysis resistance Tensile strength: MPa Before heat treatment 52 52 51 51 50 After heat treatment twenty three twenty two 19 19 16 Strength retention rate (%) 44 43 37 37 32 Release property: minimum cooling time (seconds) 12 15 12 17 14

As shown in Table 7, by adding montanic acid ester as a mold release agent to PBT having 33 ppm or less of titanium atoms, a PBT composition excellent in hydrolysis resistance and mold release properties (shortened molding cycle) can be obtained.

Examples 19-20 and Comparative Examples 14-15 (hydrolysis-resistant PBT composition)

With respect to 100 parts by weight of PBT particles of Example 1, Comparative Example 1, and Comparative Example 2. The following components (1) and (2) were blended according to the composition in Table 8, and granulated in the same manner as in Example 9.

(1) Glass fiber (manufactured by NEC Glass Co., Ltd., brand name T-187, diameter 13 μm, fiber length 3 mm)

(2) Diglycidyl ether of bisphenol A (manufactured by Asahi Denka Co., Ltd., trade name: ADEKA SAISA-EP-17)

An ISO test piece was formed from the above-mentioned pellets, and the hydrolysis resistance was evaluated. In addition, releasability was also evaluated. These results are shown in Table 8.

Table 8 Example comparative example 19 20 14 15 Composition (parts by weight) Example 1 - PBT 100 100 - - Comparative Example 1-PBT - - 100 - Comparative example 2-PBT - - - 100 glass fiber 43 18 43 43 epoxy compound 0.43 0.35 0.43 0.43 Hydrolysis resistance Tensile strength: MPa Before heat treatment 149 97 147 148 After heat treatment 112 72 101 82 Strength retention rate (%) 75 74 69 55

As shown in Table 8, by adding a reinforced filler (glass fiber) and an epoxy compound to PBT having 33 ppm or less of titanium atoms, a reinforced PBT composition excellent in hydrolysis resistance can be obtained.

Implementations 21-22 and Comparative Examples 16-17 (impact-resistant PBT compositions)

With respect to 100 parts by weight of PBT particles of Example 1, Comparative Example 1, and Comparative Example 2. According to the composition of Table 9, the following components (1) and (2) were blended, and the same method as in Example 10 was granulated.

(1) Acrylic rubber (chemical name: alkyl acrylate/alkyl methacrylate copolymer, manufactured by Kureha Chemical Industry Co., Ltd., trade name: クレハパラライド EXL2315) (2) glass fiber (same as Example 19 used the same fiberglass)

ISO test pieces were produced from the above-mentioned pellets with an injection molding machine, and the tensile strength, flexural strength, flexural modulus, and Charpy impact value were measured. In addition, hydrolysis resistance was evaluated. These results are shown in Table 9.

Table 9 Example comparative example twenty one twenty two 16 17 Composition (parts by weight) Example 1 - PBT 100 100 - - Comparative Example 1-PBT - - 100 - Comparative example 2-PBT - - - 100 acrylic rubber 8 17 17 17 glass fiber 46 50 50 50 mechanical properties Tensile Strength MPa 109 100 99 101 Bending strength MPa 188 169 167 170 Flexural modulus of elasticity MPa 8600 8300 8300 8300 Charpy impact strength KJ/m 10.4 11.6 11.5 11.7 Hydrolysis resistance Tensile strength: MPa Before heat treatment 109 100 99 101 After heat treatment 45 43 38 29 Strength retention rate (%) 41 43 38 29

As shown in Table 9, by adding an impact modifier (acrylic rubber) and a reinforcing filler (glass fiber) to PBT containing 33 ppm or less of titanium atoms, a PBT combination with excellent hydrolysis resistance and impact properties can be obtained. things.

Embodiment 23-24 and comparative examples 18-19 (flame-retardant PBT composition)

With respect to 100 parts by weight of PBT particles of Example 1, Comparative Example 1, and Comparative Example 2. The following components (1) to (4) were blended according to the composition in Table 10, and granulated in the same manner as in Example 10.

(1) Brominated aromatic compound: poly(pentabromobenzyl acrylate) (Promochem Fayisto Co., trade name: PBBPA-FR1025)

(2) Antimony trioxide (manufactured by Mori Rokusha)

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

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

A UL-94 (1/32 inch) test piece was formed from the above pellets, and a flammability test was performed according to UL-94. The UL-94 test piece was molded with an injection molding machine (manufactured by Nippon Steel Works: Model J28SA) at a cylinder temperature of 270°C and a mold temperature of 80°C. In addition, an ISO tensile test piece was formed from the above-mentioned pellets, and the hydrolysis resistance was evaluated. In addition, gas evolution from the particles was measured. These results are shown in Table 10.

Table 10 Example comparative example twenty three twenty four 18 19 Composition (parts by weight) Example 1 - PBT 100 100 - - Comparative Example 1-PBT - - 100 - Comparative example 2-PBT - - - 100 PBBPA 15.4 12.6 12.6 12.6 Antimony trioxide 7.7 4.4 4.4 4.4 PTFE 1.0 3.0 3.0 3.0 glass fiber 53.2 51.4 51.4 51.4 flame retardant UL-94 V-0 V-0 V-0 V-0 Hydrolysis resistance Tensile strength: MPa Before heat treatment 132.0 135.0 134.0 136.0 After heat treatment 79.0 83.0 78.0 65.0 Strength retention rate (%) 60 61 58 48 Gas produced (ppm) 9 8 12 17

As shown in Table 10, by adding brominated aromatic compound flame retardant (PBBPA), antimony compound (antimony trioxide), anti-dripping agent (PTFE), reinforcing filler ( glass fiber), a PBT composition with excellent hydrolysis resistance and flame retardancy and less gas generation can be obtained.

Examples 25-27 and Comparative Examples 20-21 (non-halogen flame-retardant PBT composition)

With respect to 100 parts by weight of PBT particles of Example 1, Comparative Example 1, and Comparative Example 2. The following components (1) to (7) were blended according to the composition in Table 11, and granulated in the same manner as in Example 10.

(1) Polyphenylene ether (PPE) (manufactured by Mitsubishi Engineering Plastic Co., Ltd., trade name: Upiece (registered trademark), intrinsic viscosity 0.36 dL/g)

(2) Polycarbonate (PC) (manufactured by Mitsubishi Engineering Plastic Co., Ltd., grade 7022PJ, viscosity average molecular weight: about 21000)

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

(4) Melamine cyanurate (manufactured by Mitsubishi Chemical Corporation)

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

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

(7) Zinc borate (manufactured by Boracus Japan Co., Ltd., trade name: Firebrake ZB)

A UL-94 (1/32 inch) test piece was formed from the above pellets, and a flammability test was performed according to UL-94. The UL-94 test piece was molded with an injection molding machine (manufactured by Nippon Steel Works: Model J28SA) at a cylinder temperature of 270°C and a mold temperature of 80°C. In addition, an ISO tensile test piece was formed from the above-mentioned pellets, and the hydrolysis resistance was evaluated. These results are shown in Table 11.

Table 11 Example comparative example 25 26 27 twenty one twenty one Composition (parts by weight) Example 1 - PBT 70 70 70 - - Comparative Example 1-PBT - - - 70 - Comparative example 2-PBT - - - - 70 PPE 30 30 30 30 30 PC 2 2 2 2 2 Phosphate 15 20 15 15 15 Melamine cyanurate 15 20 15 15 15 glass fiber 59 62 - 59 59 PTFE 1 0.5 1 11 1 Zinc borate 4 1 4 4 4 flame retardant UL-94 V-0 V-0 V-0 V-0 V-0 Hydrolysis resistance Tensile strength: MPa Before heat treatment 103 101 46 103 100 After heat treatment 57 53 30 49 42 Strength retention rate (%) 55 52 65 48 42

As shown in Table 11, by adding co-solvent (polycarbonate), phosphoric acid ester, melamine cyanurate, reinforcing filler (glass fiber), anti-drip Agent (PTFE), borate metal salt, PBT composition with excellent hydrolysis resistance and flame retardancy can be obtained.

Examples 28-30 and comparative examples 22-25 (other functional PBT compositions-1)

With respect to 100 parts by weight of PBT particles of Example 1, Comparative Example 1, and Comparative Example 2. According to the composition of Table 12 and Table 13, the following components (1)-(4) were mixed, and it granulated by the method similar to Example 10.

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

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

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

(4) Acrylic rubber (chemical name: alkyl acrylate/alkyl methacrylate copolymer, manufactured by Kureha Chemical Industry Co., Ltd., trade name: CLEARHAPARALOID EXL2315) The cooling crystallization temperature of the above pellets was measured. In addition, ISO test pieces were produced from the above pellets, and the tensile strength, flexural strength, flexural modulus, and Charpy impact value were measured. In addition, hydrolysis resistance was evaluated. These results are shown in Table 12 and Table 13.

Table 12 Example 28 29 30 Composition (parts by weight) Example 1 - PBT 100 100 100 polycarbonate 43 67 50 Phosphorus compounds 0.2 0.2 0.2 glass fiber 61 71 - acrylic rubber - - 17 cooling crystallization temperature ℃ 182 178 185 Reflex mm 7.7 4.1 13.1 mechanical properties Tensile Strength MPa 126 119 49 Bending strength MPa 192 190 77 Flexural modulus of elasticity MPa 8620 8420 2210 Charpy impact value KJ/m 8.9 9.4 13.1 Hydrolysis resistance Tensile strength: MPa Before heat treatment 126 119 49 After heat treatment 45 34 31 Strength retention rate (%) 36 29 63

Table 13 comparative example twenty two twenty three twenty four 25 Composition (parts by weight) Comparative Example 1-PBT 100 100 - 100 Comparative example 2-PBT - - 100 - polycarbonate 43 50 43 - Phosphorus compounds 0.2 0.2 0.2 - glass fiber 61 - 61 43 acrylic rubber - 17 - - cooling crystallization temperature ℃ 177 181 175 187 Reflex mm 8.1 14.2 8.8 23.4 mechanical properties Tensile Strength MPa 124 48 122 130 Bending strength MPa 190 76 188 203 Flexural modulus of elasticity MPa 8510 2200 8490 8690 Charpy impact value KJ/m 8.5 12.2 8.2 7.3 Hydrolysis resistance Tensile strength: MPa Before heat treatment 124 48 122 130 After heat treatment 42 29 37 43 Strength retention rate (%) 34 60 30 33

As shown in Table 12 and Table 13, by adding polycarbonate, organic phosphorus compound, and reinforcing filler (glass fiber) to PBT with 33 ppm or less of titanium atoms, excellent hydrolysis resistance and high crystallization temperature can be obtained. , can shorten the molding cycle and increase productivity) PBT composition.

Examples 31-34 and comparative examples 26-28 (other functional PBT compositions-2)

With respect to 100 parts by weight of PBT particles of Example 1, Comparative Example 1, and Comparative Example 2. According to the composition of Table 14 and Table 15, the following components (1)-(3) were mixed, and it granulated by the method similar to Example 10.

(1) Polyethylene terephthalate (manufactured by Mitsubishi Chemical Co., Ltd., trade name: GS385, intrinsic viscosity 0.65 dL/g)

(2) Polytrimethylene terephthalate [manufactured by Shiel Chemical Corporation, trade name: Cortera CP509200, intrinsic viscosity 0.92dL/g: in a mixed solvent of dichloromethane-trifluoroacetic acid (weight ratio: 1:1), at 30 measured at °C]

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

The cooling crystallization temperature of the above particles was measured by DSC. In addition, ISO test pieces were produced from the above pellets, and the tensile strength, flexural strength, flexural modulus, and Charpy impact value were measured. In addition, hydrolysis resistance was evaluated. These results are shown in Table 14 and Table 15.

Table 14 Example 31 32 33 34 Composition (parts by weight) Example 1 - PBT 100 100 100 100 polyethylene terephthalate 43 67 25 - Polytrimethylene terephthalate - - - 67 glass fiber 51 71 54 71 cooling crystallization temperature ℃ 185 182 187 179 Reflex mm 13.5 11.1 16.2 12.3 mechanical properties Tensile Strength MPa 129 120 133 118 Bending strength MPa 210 207 213 206 Flexural modulus of elasticity MPa 9100 9000 8900 8900 Charpy impact value KJ/m 5.9 4.7 7.2 4.9 Hydrolysis resistance Tensile strength: MPa Before heat treatment 129 120 133 118 After heat treatment 49 43 53 42 Strength retention rate (%) 38 36 40 36

Table 15 comparative example 26 27 28 Composition (parts by weight) Comparative Example 1-PBT 100 - 100 Comparative example 2-PBT - 100 - polyethylene terephthalate 67 67 - Polytrimethylene terephthalate - - - glass fiber 71 71 43 cooling crystallization temperature ℃ 178 176 187 Reflex mm 11.6 10.9 23.4 mechanical properties Tensile Strength MPa 127 125 130 Bending strength MPa 208 206 203 Flexural modulus of elasticity MPa 9000 8900 8690 Charpy impact value KJ/m 4.6 4.4 7.3 Hydrolysis resistance Tensile strength: MPa Before heat treatment 127 125 130 After heat treatment 41 31 43 Strength retention rate (%) 32 25 33

As shown in Table 14 and Table 15, by adding polyethylene terephthalate or polytrimethylene terephthalate and reinforcing filler (glass fiber) to PBT with 33 ppm or less of titanium atoms, water-resistant It is a PBT composition with excellent desolvability and high crystallization temperature (thus, the molding cycle can be shortened and the productivity can be improved).

Examples 35-39 and comparative examples 29-32 (other functional PBT compositions-3)

With respect to 100 parts by weight of PBT particles of Example 1, Comparative Example 1, and Comparative Example 2. According to the composition of Table 16 and Table 17, the following components (1)-(4) were mixed, and it granulated by the method similar to Example 10.

(1) HIPS: rubber (polybutadiene) content rate 8.8% by weight, average rubber particle size 1.8 μm, number average molecular weight 92000, weight average molecular weight 230000, melt flow rate (temperature 200 ° C, load 5 kgf) 1.8 g/10 Minute rubber-modified polystyrene resin (manufactured by A&M Co., trade name: Dialex HT478)

(2) AS: acrylonitrile styrene resin with a number average molecular weight of 96,000 and a weight average molecular weight of 240,000 (manufactured by Technopoly Corporation, trade name: SANREX S90)

(3) Dielark (DIELARK): Maleic anhydride-modified polystyrene with a maleic anhydride content of 9% by weight, a weight-average molecular weight of 240,000, and a melt flow rate (temperature of 230° C., load of 2.16 kgf) of 2.0 g/10 minutes (Manufactured by Noba Chemical Japan Co., Ltd., product name: Dairaichiku D232)

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

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

ISO test pieces were produced from the above-mentioned pellets, and the tensile strength, flexural strength, flexural modulus, and Charpy impact value were measured. In addition, hydrolysis resistance was evaluated. These results are shown in Table 16 and Table 17.

Table 16 Example 35 36 37 38 39 Composition (parts by weight) Example 1 - PBT 100 100 100 100 100 HIPS 29 29 - 29 - AS - - 43 - 43 Dairaichiku 14 - - 14 - PC - 14 - - - glass fiber 60 60 60 - - Reflex mm 8.3 9.2 10.5 13.2 14.3 mechanical properties Tensile Strength MPa 118 120 137 38 53 Bending strength MPa 187 189 200 72 93 Flexural modulus of elasticity MPa 8290 8690 9160 2230 2620 Charpy impact strength KJ/m 11.0 12.7 7.8 2.7 1.3 Hydrolysis resistance Tensile strength: MPa Before heat treatment 118 120 137 38 53 After heat treatment 59 61 66 twenty four 33 Strength retention rate (%) 50 51 48 64 62

Table 17 comparative example 29 30 31 32 Composition (parts by weight) Comparative Example 1-PBT 100 100 - 100 Comparative example 2-PBT - - 100 - HIPS 29 29 29 - AS - - - - Dairaichiku 14 - 14 - PC - 14 - - glass fiber 60 60 60 43 Reflex mm 8.6 9.4 10.2 23.4 mechanical properties Tensile Strength MPa 117 119 119 130 Bending strength MPa 185 188 188 203 Flexural modulus of elasticity MPa 8270 8670 8670 8690 Charpy impact strength KJ/m 10.8 11.9 11.9 7.3 Hydrolysis resistance Tensile strength: MPa Before heat treatment 117 119 119 130 After heat treatment 54 56 38 43 Strength retention rate (%) 46 47 32 33

Examples 40-47 and Comparative Examples 33-34

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-mentioned PBT was put into a vacuum dryer, and after the temperature of the particles reached 120° C., they were dried while vacuuming for 4 hours or more. Then, the dried PBT pellets were charged into a hopper of an extruder having a diameter of 40φ, L/D=25, and a compression ratio of 3.5 inserted into a full flight screw. A T-die with a width of 600 mm and a lip opening of 0.4 mm was installed at the front end of the extruder, and was extruded into a curtain shape at a resin temperature of about 260° C. at a discharge rate of 5 kg/hr. The extruded resin was continuously extruded on a polished metal roll having a surface temperature of 60° C. and rotating at a peripheral speed of about 3 m/min, and rapidly cooled to obtain a single-layer film. The analytical values are summarized in Table 18.

Table 18 Raw material PBT Fog value (%) of single layer film (50μm) Membrane Appearance Example 40 Example 1 - PBT 1.2 no problem Example 41 Example 2 - PBT 1.2 no problem Example 42 Example 3 - PBT 1.1 no problem Example 43 Example 5-PBT 1.1 no problem Example 44 Example 6-PBT 0.5 no problem Example 45 Example 7-PBT 0.5 no problem Example 46 Example 8-PBT 1.6 no problem Example 47 Example 9-PBT 0.5 no problem Comparative Example 33 Comparative Example 1-PBT 2.5 Many foreign bodies Comparative Example 34 Comparative Example 4-PBT 2.5 Many foreign bodies

Example 48

Using the polymer obtained in Example 9, a composite film was produced by the coextrusion method in the following manner. As the apparatus, three types of 3-layer water-cooled multilayer expansion film forming apparatuses were used. In this device, the extruder for the outer layer is inserted into a full-flight screw with a diameter of 40φ, L/D=24 and a compression ratio of 3.5, and the extruders for the middle layer and the inner layer are inserted into a diameter of 40φ, L/D=24 And a fully threaded screw with a compression ratio of 2.5.

First, put PBT into a vacuum dryer, and after the particle temperature reaches 120° C., dry it while vacuuming for 4 hours or more. Next, PBT was filled in the extruder for the outer layer, and LLDPE (MI=2.0, density=0.925g/cc) was filled in the extruders for the middle layer and the inner layer, under the condition of expansion ratio (BUR) 1.3 , coextruded PBT and olefin resin, and cooled with water at a water temperature of 30° C. to obtain a two-layer film with a diameter of 170 mm, a PBT layer of 50 μm and an olefin layer of 30 μm. The PBT layer and olefin layer of this film could be easily peeled off, where only the PBT layer was evaluated. When the haze value of the PBT layer was measured, it was 0%, and foreign matter was hardly observed, and a good appearance was obtained.

Example 50

Using the 50 μm PBT film produced in Example 49 for the measurement of the haze value, a composite film was produced by the dry lamination method in the following manner. That is, first, using a tie coater, apply 6/1 of a two-component dry lamination adhesive (manufactured by Toyo Motor Corporation: main agent (TM-51) and curing agent 5 (CAT-RT8) weight ratio mixture) was coated on the above-mentioned PBT film so that the dry weight was 5 g/m ² , and then dried. Next, on the above-mentioned coated surface, under the conditions of temperature 100°C and pressure 5g/m ² , a linear low-density polyethylene with a thickness of 50 μm ("Nobatec UF230" manufactured by Japan Polychem Co., Ltd., MI: 21.1, density 0.921g/cc). The haze value was 1.5%, and a good film with high transparency and almost no foreign matter was obtained.

Industrial Applicability

According to the present invention described above, it is excellent in color tone, hydrolysis resistance, thermal stability, transparency, and moldability, and has reduced foreign matter, which can be applied to films, monofilaments, fibers, electrical and electronic parts, automotive parts, etc. PBT of stable quality, the industrial value of the present invention is remarkable.

Claims (45)

1. a polybutylene terephthalate is characterized in that, this polybutylene terephthalate contains titanium, and in titanium atom, and its content is 33ppm or below the 33ppm.

2. according to the polybutylene terephthalate of claim 1 record, wherein, the decrease temperature crystalline temperature of measuring with differential scanning calorimeter under 20 ℃/min of cooling rate is 170～200 ℃.

3. according to the polybutylene terephthalate of claim 1 or 2 records, wherein, terminal ethylenyl groups concentration is 0.1～10 μ eq/g.

4. according to the polybutylene terephthalate of each record in the claim 1～3, wherein, dissolving 2.7g polybutylene terephthalate in 20mL phenol/tetrachloroethane mixed solvent (weight ratio 3/2), the mist value of the solution of mensuration is below 10% or 10%.

5. according to the polybutylene terephthalate of each record in the claim 1～4, wherein, under reactive gas atmosphere not, the end carboxy concentration of removing hydrolysis reaction when carrying out 40 minutes thermal treatment for 245 ℃ rise to 0.1～30 μ eq/g.

6. according to the polybutylene terephthalate of each record in the claim 1～5, wherein, the above foreign matter of 5 μ m or 5 μ m is 50 a/10g polymkeric substance or below the 50/10g polymkeric substance.

7. according to the polybutylene terephthalate of each record in the claim 1～6, wherein, the following 1ppm that is limited to of the amount of titanium.

8. according to the polybutylene terephthalate of each record in the claim 1～7, wherein, the following 3ppm that is limited to of the amount of titanium.

9. according to the polybutylene terephthalate of each record in the claim 1～8, wherein, it is the polybutylene terephthalate of 0.91～1.50dL/g that this polybutylene terephthalate contains polybutylene terephthalate and the limiting viscosity that limiting viscosity is 0.60～0.90dL/g, and its weight ratio is 5～95: 95～5 ratio.

10. the manufacture method of a polybutylene terephthalate, it is characterized in that, have in the esterification groove, in the presence of titanium catalyst, supply with terephthalic acid and 1 continuously, the 4-butyleneglycol carries out in the manufacture method of polybutylene terephthalate of process of esterification, with 1, at least a portion of 4-butyleneglycol does not supply to the esterification groove independently with terephthalic acid, 1 of esterification groove will do not supplied to independently with terephthalic acid, 10 weight % in the 4-butyleneglycol or offer the liquid phase part of reaction solution more than the 10 weight % are with 10 weight % of titanium catalyst or do not supply to the liquid phase part of reaction solution more than the 10 weight % independently with terephthalic acid.

11. manufacture method according to claim 10 record, wherein, by the condenser of on the esterification groove, equipping, to from the esterification groove, distill out 1, the cohesion of 4-butyleneglycol, and will condense 1, at least a portion of 4-butyleneglycol is not re-supplied in the esterification groove independently with terephthalic acid.

12. according to the manufacture method of claim 10 or 11 polybutylene terephthalates of putting down in writing, wherein, time per unit offers the terephthalic acid and 1 of esterification groove, the mol ratio of 4-butyleneglycol (1,4-butyleneglycol/terephthalic acid) is 1.6～4.5.

13. the manufacture method of a polybutylene terephthalate, it is characterized in that, have in the transesterification reaction groove, in the presence of titanium catalyst, supply with dimethyl terephthalate ester and 1 continuously, the 4-butyleneglycol carries out in the manufacture method of polybutylene terephthalate of process of transesterification reaction, with 1, at least a portion of 4-butyleneglycol does not supply to the transesterification reaction groove independently with dimethyl terephthalate ester, 1 of transesterification reaction groove will do not supplied to independently with dimethyl terephthalate ester, 10 weight % in the 4-butyleneglycol or offer the liquid phase part of reaction solution more than the 10 weight % are with 10 weight % of titanium catalyst or do not supply to the liquid phase part of reaction solution more than the 10 weight % independently with terephthalic acid.

14. manufacture method according to claim 13 record, wherein, by the condenser of in the transesterification reaction groove, equipping, to from the transesterification reaction groove, distill out 1, the cohesion of 4-butyleneglycol, and will condense 1, at least a portion of 4-butyleneglycol is not re-supplied in the esterification groove independently with dimethyl terephthalate ester.

15. manufacture method according to claim 13 or 14 polybutylene terephthalates of putting down in writing, wherein, time per unit offers the dimethyl terephthalate ester and 1 of transesterification reaction groove, and the mol ratio of 4-butyleneglycol (1,4-butyleneglycol/dimethyl terephthalate ester) is 1.1～1.8.

16. manufacture method according to each record in the claim 10～15, wherein, as 1 of 0.01～30 weight %, the 4-butanediol solution is not with terephthalic acid or dimethyl terephthalate ester and supply to reaction solution liquid phase portion independently with titanium catalyst.

17. according to the manufacture method of claim 16 record, wherein, 1 of titanium catalyst, the 4-butanediol solution contains the moisture of 0.05～1.0 weight %.

18. according to the manufacture method of each record in the claim 10～17, wherein, titanium catalyst is an organic titanic compound.

19. according to the manufacture method of each record in the claim 10～18, wherein, the temperature of reaction of esterification or transesterification reaction be under this reaction pressure 1, the boiling point of 4-butyleneglycol or more than the boiling point.

20. manufacture method according to each record in the claim 10～19, wherein, not with terephthalic acid or dimethyl terephthalate ester and supply to 1 in esterification groove or the esterification groove independently, the temperature of 4-butyleneglycol is 100～200 ℃ a scope.

21. according to the manufacture method of claim 16 record, wherein, in the solvent of titanium catalyst, use 1, the 4-butyleneglycol condenses by condenser.

22. according to the manufacture method of each record in the claim 10～21, wherein, then esterification or transesterification reaction have the operation of carrying out polycondensation.

23. the manufacture method of a polybutylene terephthalate, it is characterized in that, have in the esterification groove, in the presence of titanium catalyst, supply with terephthalic acid continuously and with respect to 1 of terephthaldehyde's excessive acid, the 4-butyleneglycol carries out in the manufacture method of polybutylene terephthalate of process of esterification, the control time per unit supplies to the terephthalic acid and 1 of esterification groove, it is certain that the mol ratio of 4-butyleneglycol (1, the mole number of the mole number/terephthalic acid of 4-butyleneglycol) keeps.

24. the manufacture method of a polybutylene terephthalate, it is characterized in that, have in the transesterification reaction groove, in the presence of titanium catalyst, supply with continuously dimethyl terephthalate ester and with respect to dimethyl terephthalate ester excessive 1, the 4-butyleneglycol carries out in the manufacture method of polybutylene terephthalate of process of transesterification reaction, the control time per unit supplies to the dimethyl terephthalate ester and 1 of transesterification reaction groove, it is certain that the mol ratio of 4-butyleneglycol (1, the mole number of the mole number/terephthalic acid of 4-butyleneglycol) keeps.

25. according to the manufacture method of claim 23 or 24 records, wherein, titanium catalyst is an organic titanic compound.

26. according to the manufacture method of each record in the claim 23～25, wherein, then esterification or transesterification reaction have the operation of carrying out polycondensation.

27. heat resistant poly butylene terephthalate composition, it is characterized in that said composition contains the polybutylene terephthalate and the oxidation inhibitor more than a kind or a kind that is selected from phenolic antioxidant (B1), sulfur type antioxidant (B2) and the Phosphorus oxidation inhibitor (B3) of each record in the claim 1～9.

28. the polybutylene terephthalate composition of a good release property, it is characterized in that, with respect to polybutylene terephthalate 100 weight parts of each record in the claim 1～9, contain the fatty acid ester (C1) of the pure residue that is selected from the fatty acid residue that contains carbonatoms 12～36 and carbonatoms 1～36 and releasing agent (C) 0.01～2 weight part of paraffin and polyethylene wax (C2).

29. hydrolytic resistance polybutylene terephthalate composition, it is characterized in that, with respect to polybutylene terephthalate 100 weight parts of each record in the claim 1～9, contain and strengthen weighting agent (D) 0～200 weight part and epoxy compounds (E) 0.01～20 weight part.

30. shock-resistance polybutylene terephthalate composition, it is characterized in that, with respect to polybutylene terephthalate 100 weight parts of each record in the claim 1～9, contain shock-resistant improvement material (F) 0.5～40 weight part and strengthen weighting agent (D) 0～200 weight part.

31. flame retardance poly butylene terephthalate composition, it is characterized in that, with respect to polybutylene terephthalate 100 weight parts of each record in the claim 1～9, contain bromo aromatics based flame retardant (G) 3～50 weight parts, antimony compounds (H) 1～30 weight part, dripping inhibitor (I) 0～15 weight part and strengthen packing material (D) 0～200 weight part.

32. non-halogen fire retardant polybutylene terephthalate composition, it is characterized in that, with respect to polybutylene terephthalate 50～95 weight parts of each record in the claim 1～9 and total 100 weight parts of polyphenylene oxide resin (J) 5～50 weight parts, contain solubilizing agent (K) 0.05～10 weight part, be selected from least a kind compound (L) 2～45 weight parts of phosphoric acid ester or phosphonitrile, strengthen packing material (D) 0～200 weight part, dripping inhibitor (I) 0～15 weight part, melamine cyanurate (M) 0～45 weight part and borate metal salt (N) 0～50 weight part.

33. polybutylene terephthalate composition, it is characterized in that, with respect to polybutylene terephthalate 100 weight parts of each record in the claim 1～9, contain polycarbonate resin (O) 5～100 weight parts, organo phosphorous compounds (P) 0.01～1 weight part, strengthen packing material (D) 0～200 weight part and shock-resistant modifying agent (F) 0～50 weight part.

34. polybutylene terephthalate composition, it is characterized in that, with respect to polybutylene terephthalate 100 weight parts of each record in the claim 1～9, contain polybutylene terephthalate aromatic polyester-based resin (Q) 5～100 weight parts and reinforcement packing material (D) 0～200 weight part in addition.

35. polybutylene terephthalate composition, it is characterized in that, with respect to polybutylene terephthalate 100 weight parts of each record in the claim 1～9, contain styrene resin (R) 5～100 weight parts, maleic anhydride modified polystyrene resin (S) or polycarbonate resin (O) 0～40 weight part, strengthen packing material (D) 0～200 weight part.

36. a film is characterized in that this film contains polybutylene terephthalate, wherein, described polybutylene terephthalate contains titanium and is 33ppm or below the 33ppm in its content of titanium atom.

37. according to the film of claim 36 record, wherein, the decrease temperature crystalline temperature of measuring with differential scanning calorimeter under 20 ℃/min of cooling rate of polybutylene terephthalate is 170～200 ℃.

38. according to the film of claim 36 or 37 records, wherein, the limiting viscosity of polybutylene terephthalate is 0.60～2.50dL/g.

39. according to the film of each record in the claim 36～38, wherein, the end carboxy concentration of polybutylene terephthalate is 1～45 μ eq/g.

40. according to the film of each record in the claim 36～39, wherein, the above foreign matter of 5 μ m of polybutylene terephthalate or 5 μ m is 50 a/10g polymkeric substance or below the 50/10g polymkeric substance.

41. according to the film of each record in the claim 36～40, wherein, the thickness of described film is 5～200 μ m.

42. compoundization film, it is characterized in that this composite membrane is to contain the compoundization film that the different resin layer more than 2 kinds or 2 kinds constitutes, wherein, at least 1 layer is the polybutylene terephthalate film of each record in the claim 36～41, and other at least 1 layer is the polyolefins film.

43. according to the compoundization film of claim 42 record, wherein, outermost layer is made of polybutylene terephthalate film and/or polyolefin resin.

44. film, it is characterized in that, this film contains polybutylene terephthalate 1～99 weight % and polyethylene terephthalate 1～99 weight % (both add up to 100 weight %), wherein, described polybutylene terephthalate contains titanium and is 33ppm or below the 33ppm in its content of titanium atom.

45. film, it is characterized in that, this film has contained polybutylene terephthalate 1～99 weight % and copolymerization aromatic polyester 1～99 weight % (both add up to 100 weight %) of polytetramethylene glycol, wherein, described polybutylene terephthalate contains titanium and is 33ppm or below the 33ppm in its content of titanium atom.

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