JP2004143439A - Catalyst for producing polyester and method for producing the polyester by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a catalyst for producing a polyester having a good color tone (b-value), scarcely containing foreign matter, excellent in heat stability when molten, and suitably used in various purposes, such as a use in a fiber and another use as a film in the materials including a magnetic material, a packaging material, and an optical material, and to provide a method for producing the polyester by using the same. <P>SOLUTION: This catalyst for producing the polyester contains a reaction product of at least one kind of titanium compound with a coordination compound, wherein the titanium compound is selected from a compound expressed by the formula (1): Ti(OR)<SB>4</SB>[Rs are each a 2-10C organic residue (Rs may be identical to or different from each other)] and a compound expressed by the formula (2): Ti(OH)<SB>m</SB>(OR)<SB>4-m</SB>((m) is 1-4), and the coordination compound contains at least one kind of atom selected from the group consisting of nitrogen, sulfur, and oxygen atoms as a donor atom and is coordinated in a state of a bidentate or higher polydentate ligand. <P>COPYRIGHT: (C)2004,JPO

Description

INDUSTRIAL APPLICABILITY The present invention has a good color tone (b value), has a small amount of foreign matter, and has excellent fusion heat stability, and can be suitably used for various uses such as a fiber use and a film use such as a magnetic material, a packaging material, and an optical material. The present invention relates to a catalyst for producing an excellent polyester, and a method for producing a polyester using the same.

Polyesters, especially polyethylene terephthalate, have excellent mechanical, thermal and electrical properties, are widely used for industrial purposes, and their demand is increasing. However, with the expansion of applications and demands, the demands on the properties and productivity required for polyester in each field are becoming more and more severe. For this reason, polyesters are produced in a wide variety, but there are many problems to be solved.

For example, when an antimony compound is used as a polycondensation catalyst in a polyester of polyethylene terephthalate, when the polyester is continuously formed over a long period of time, foreign matter adheres and accumulates in the vicinity of the die, and when the film is formed, die streaks are generated. However, there is a problem that it is deposited on the surface of the film and causes surface defects.

It has also been proposed to use a titanium compound such as titanium tetrabutoxide as a polycondensation catalyst other than the antimony compound. However, when such a titanium compound is used, problems such as the above-mentioned streaks and surface defects of the film are caused. However, there is a problem that the obtained polyester itself is colored yellow, the stability of the melt heat becomes unstable, the film is broken, and the productivity is deteriorated. In order to solve the above-mentioned coloring problem, it is common practice to add a cobalt compound to the polyester to suppress yellowing, but the melt heat stability becomes unstable, and this also causes a decrease in productivity. As a method for improving the color tone and heat resistance of a titanium-based catalyst, for example, Patent Literature 1 discloses a method using a composite oxide composed of titanium and silicon as a catalyst, and Patent Literature 2 discloses a method in which a titanium halide compound is hydrolyzed. A titanium compound catalyst that has been decomposed has been proposed.For example, when the obtained polyester is used for film applications, foreign matter due to the catalyst frequently causes thread breakage or increases the filtration pressure during polymer filtration. Of the film, which may not be sufficiently resolved, the dispersibility of the color tone adjuster itself may be poor, and foreign matter may be produced, or the productivity may be impaired by scattering, or a slight difference in color tone may cause a problem. There have been problems such as insufficient improvement in color tone for applications.
WO 95/18839 pamphlet JP-A-2001-89557

An object of the present invention is to solve the above-mentioned problems of the prior art, and to substantially contain an antimony compound, to provide a color tone, an excellent heat resistance, and a catalyst for producing a highly productive polyester, and a polyester using the same. It is to provide a manufacturing method of.

In order to achieve the above object, the present invention provides a compound comprising at least one compound selected from compounds represented by the following general formula (1) or (2), and a nitrogen atom, a sulfur atom and an oxygen atom as donor atoms. The catalyst for polyester production contains a reaction product with a coordination compound capable of coordinating at least bidentate containing at least one atom selected from the group consisting of:

Ti (OR) ₄ (1)
Ti (OH) _m (OR) _4-m (2)
(R: an organic group having 2 to 10 carbon atoms (which may be the same or different)
m: an integer from 1 to 4)
It is also preferable that the coordination compound of the catalyst is at least one compound selected from the group consisting of metal-free phthalocyanine, indanthrone, anthraquinone and methine, and furthermore, the above-mentioned general formula (1) or (2) It is also preferable that the compound represented by is a tetraalkoxytitanium compound or a titanium chelate compound. In the above general formulas (1) and (2), R is also preferably an alkyl group having 2 to 10 carbon atoms (which may be the same or different).

Further, a method for producing a polyester using the above catalyst is also preferable.

As will be described below, by using the above-described catalyst with less foreign matter generation, the foreign matter is less, and problems such as die streaks and film surface defects are solved, which is suitable for magnetic material film applications and the like. Catalyst for producing an excellent polyester which has a good color tone (b value) and which can be suitably used for applications such as packaging materials and optical materials in which the obtained polyester itself was difficult to color yellow. , And a method for producing polyester using the same.

The catalyst for polyester production of the present invention comprises at least one compound (α) selected from the compounds represented by the following general formulas (1) and (2), and a nitrogen atom, a sulfur atom and an oxygen atom as donor atoms. And a reaction product with a coordination compound (β) capable of coordinating at least bidentate containing at least one atom selected from the group.

Ti (OR) ₄ (1)
Ti (OH) _m (OR) _4-m (2)
(However, in the formulas (1) and (2), R represents an organic group having 2 to 10 carbon atoms, m represents an integer of 1 to 4, and the R groups may be the same as each other. Or may be different.)
It is also preferable that the coordination compound β is at least one compound selected from the group consisting of metal-free phthalocyanine, indanthrone, anthraquinone and methine, and is further represented by the general formula (1) or (2). It is also preferred that the compound is a tetraalkoxytitanium compound or a titanium chelate compound. Further, in the above formulas (1) and (2), it is also preferable that R is an alkyl group having 2 to 10 carbon atoms (which may be the same or different).

Examples of the compound used as the compound α include titanium chelates such as titanium acetylacetonate, titanium tetraacetylacetonate, titanium octylene glycolate, titanium lactate, titanium ethyl acetoacetate, titanium citrate, titanium ammonium peroxocitrate, and the like. Examples thereof include alkyl titanates such as tetraisopropyl titanate, tetrabutyl titanate, tetra (2-ethylhexyl) titanate, and tetramethyl titanate. Among them, it is preferable to use titanium chelates and tetrabutyl titanates. Use of titanium acetylacetonate, titanium citrate, titanium ammonium peroxocitrate, etc. having good reactivity with the used coordination compound β Is more preferred.

Examples of the compound used as the coordination compound β include indanthrone having a structural formula such as A, anthraquinone having a structural formula such as B, C, D, E, and F, and a structural formula such as G It is selected from methine, metal-free phthalocyanine having a structural formula such as H, and the like.

　化合物αと配位化合物βの触媒調製は、たとえば、エチレングリコールに配位化合物βを溶解し、化合物αを加え、反応系を０〜２００℃の温度に１０分以上、好ましくは４０〜１５０℃の温度に３０分〜２時間、加熱することによって行うことができる。また、常温〜１５０℃の温度で混合してもよい。ここでエチレングリコールの代わりにプロピレングリコール、テトラメチレングリコール、酢酸などを用いても良く、ポリエステルの原料に親和性の高い化合物が特に好ましい。化合物αと配位化合物βとの反応生成物は、エバポレーターや遠心分離機やろ過法などを用いて分離した後、再結晶し精製し、その精製物を触媒として用いるとよい。また、混合して添加しても効果がある。ここで、この反応生成物は化合物αに配位化合物βを配位させており、そのまま配位化合物βをポリエステルに添加させた場合と明らかに異なる。このような反応生成物にすることにより配位化合物βをポリエステルに添加したときに問題となる分散性の悪さや反応系外に飛散して生産性を悪化させることを防ぐ。この反応生成物は予め所定時間混合することにより調製することが可能である。また、この反応生成物中の化合物αと配位化合物βのモル比については０．００１≦（配位化合物β／化合物α）≦１が好ましい。モル比が０．００１未満であると配位化合物βによる配位効果がうまく得られない場合があり、また、色調改善効果が乏しくなる。また、１を超えるとポリマーの青味が強くなりすぎて問題となりやすい。さらにチタン金属量としての添加量は重量基準で１〜３０ｐｐｍが好ましい。１ｐｐｍ未満であると十分な触媒活性が得られず、３０ｐｐｍを超えると良好なポリマーの色調および耐熱性を維持できなくなる傾向にある。

The catalyst preparation of the compound α and the coordination compound β is performed, for example, by dissolving the coordination compound β in ethylene glycol, adding the compound α, and bringing the reaction system to a temperature of 0 to 200 ° C. for 10 minutes or more, preferably 40 to 150 ° C. For 30 minutes to 2 hours. Moreover, you may mix at the temperature of normal temperature-150 degreeC. Here, propylene glycol, tetramethylene glycol, acetic acid or the like may be used instead of ethylene glycol, and a compound having a high affinity for the raw material of the polyester is particularly preferable. The reaction product of the compound α and the coordination compound β may be separated using an evaporator, a centrifuge, a filtration method, or the like, and then recrystallized and purified, and the purified product may be used as a catalyst. It is also effective to mix and add. Here, this reaction product coordinates the coordination compound β to the compound α, which is clearly different from the case where the coordination compound β is directly added to the polyester. By using such a reaction product, it is possible to prevent poor dispersibility, which is a problem when the coordinating compound β is added to the polyester, and prevent the productivity from being deteriorated due to scattering outside the reaction system. This reaction product can be prepared by mixing in advance for a predetermined time. The molar ratio of compound α to coordination compound β in the reaction product is preferably 0.001 ≦ (coordination compound β / compound α) ≦ 1. If the molar ratio is less than 0.001, the coordination effect of the coordination compound β may not be obtained well, and the color tone improving effect may be poor. On the other hand, if it exceeds 1, the bluish tint of the polymer becomes too strong, which tends to cause a problem. Further, the amount of titanium metal added is preferably 1 to 30 ppm on a weight basis. If it is less than 1 ppm, sufficient catalytic activity cannot be obtained, and if it exceeds 30 ppm, it tends to be impossible to maintain good color tone and heat resistance of the polymer.

リ ン Also, a phosphorus compound can be used in combination as a color tone improver for polyester produced using the present catalyst. Examples of such phosphorus compounds include phosphoric acid such as phosphoric acid, monomethyl phosphoric acid, monoethyl phosphoric acid, and trimethyl phosphoric acid, phosphorous acid such as dimethyl phosphite, trimethyl phosphite, and ethyl diethylphosphonoacetate; Examples include acids, phosphonic acids such as dimethylphenylphosphonate, dimethylbenzylphosphonate, dimethylmethylphosphonate and dipropynylmethylphosphonate, and phosphinic acids such as diphenylphosphinic acid. The addition amount of such a compound is preferably 1 to 50 ppm on a weight basis. More preferably, it is 5 to 20 ppm. If the amount is less than 5 ppm, it is difficult to suppress a change in color due to titanium because the amount of the ligand is too small. If the amount is 20 ppm or more, the polymerization activity is excessively suppressed and productivity is deteriorated.

ポ リ エ ス テ ル The polyester composition of the present invention preferably contains an alkaline earth metal compound in an amount of 0 to 80 ppm in terms of the total weight of the alkaline earth metal atom weight with respect to the polyester. In particular, when the content is in the range of 1 to 60 ppm, it is preferable because productivity is good and heat resistance can be maintained.

When the polyester composition of the present invention is used as a film, the polyester composition preferably has a melting specific resistance of 1 × 10 ⁶ Ω · cm to 1 × 10 ⁹ Ω · cm. Particularly preferably, it is 1 × 10 ⁷ Ω · cm to 5 × 10 ⁸ Ω · cm. By satisfying this range, the castability of the electrostatic application is improved, the adhesion between the film and the casting drum is improved during the melt-extrusion casting, the air is hard to enter, and the film forming speed can be increased.

Examples of the dicarboxylic acid component of the aromatic dicarboxylic acid or an ester-forming derivative thereof as one of the raw materials used in the present invention include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5- Use of naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, or an ester-forming derivative thereof, or the like Can be. The diol component includes ethylene glycol, 1,2-propanediol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, , 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyalkylene glycol, 2,2-bis (4′-β-hydroxyethoxyphenyl) propane, etc. And aliphatic, alicyclic and aromatic diols. These components may be used alone or in combination of two or more.

Other examples of the alicyclic dicarboxylic acid component that can be copolymerized include 1,4-cyclohexanedicarboxylic acid. In addition, aliphatic dicarboxylic acids such as sebacic acid and dimer acid, and other dicarboxylic acids can be used as the copolymerization component.

各種 Various catalysts can be used for the esterification and transesterification reactions. For example, acetates such as calcium acetate, magnesium acetate, and lithium acetate can be used.

In the present invention, a stabilizer may be added in the polycondensation step in order to prevent side reactions such as thermal decomposition of the polyester. Examples of the stabilizer include diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, tetrakismethylene-3- (dodecylthio) propionate} methane, and tetrakismethylene- (3,5-t-butyl-4-hydroxyhydrocinnamate)｝ methane, tridecyl phosphate, tris (2,4-dibutylphenyl) phosphite, tetrakis ｛methylene-3- (3 ′, 5′-di -T-butyl-4'-hydroxyphenyl) propionate @ methane, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, and the like. These can be used in combination. The amount of the stabilizer added is preferably 0.03 to 2% by weight, more preferably 0.05 to 1.9% by weight, based on the obtained polyester resin composition. If the amount of the stabilizer is less than 0.03% by weight, the effect of improving the oxidation stability is small, and if it exceeds 2% by weight, the polycondensation reaction may be inhibited.

場合 However, when the stabilizer is mixed with the catalyst in advance and added, it is effective even at 0.003 to 1% by weight. Particularly, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di -Phosphite is preferable, and adding 0.003 to 0.1% by weight results in a polyester composition excellent in heat resistance, foreign matter, and color tone.

In the present invention, when a small amount of a basic compound is added in the esterification step, a polyester resin composition having a small amount of by-products can be obtained. As such a basic compound, triethylamine, tributylamine, tertiary amines such as benzylmethylamine, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, quaternary amines such as trimethylbenzylammonium hydroxide, potassium hydroxide, Examples include sodium hydroxide, potassium acetate, and sodium acetate.

製造 The production method of the present invention will be described using polyethylene terephthalate as an example. Polyethylene terephthalate used for fibers, films and the like is usually produced by any of the following processes. That is, (1) a process in which terephthalic acid and ethylene glycol are used as raw materials to obtain a low-molecular-weight polyethylene terephthalate or an oligomer by a direct esterification reaction and further obtain a high-molecular-weight polymer by a subsequent polycondensation reaction; In this process, ethylene glycol is used as a raw material to obtain a low-molecular-weight product by a transesterification reaction, and then to obtain a high-molecular-weight polymer by a polycondensation reaction. Here, the esterification proceeds without a catalyst, but the transesterification reaction usually proceeds using a compound such as manganese, calcium, magnesium, zinc, lithium, or titanium as a catalyst. After completion of the reaction, a phosphorus compound may be added for the purpose of inactivating the catalyst used in the reaction.

The production method of the present invention comprises adding a polycondensation catalyst to the low polymer obtained in any stage of the series of reactions (1) or (2), preferably in the first half of the series of reactions (1) or (2). And a polycondensation by adding titanium oxide, a basic compound, and an antioxidant as particles as needed to obtain a high molecular weight polyethylene terephthalate.

The above reaction is carried out in a batch system, a semi-batch system or a continuous system, but the production method of the present invention can be applied to any of these systems.

ポ リ エ ス テ ル The polyester composition of the present invention can be formed into a film by, for example, a melt extrusion film forming method. That is, after drying the polyester composition, it is supplied to a single-screw or twin-screw extruder equipped with a T-type die, extruded at a polyester melting temperature onto a casting drum, and subjected to electrostatic application casting to obtain an unstretched film. In addition, in order to obtain an oriented polyester film, it can be successively biaxially stretched or simultaneously biaxially stretched and heat-treated to obtain an oriented polyester film.

At this time, a film may be formed using the polyester of the present invention alone, or a method in which the polyester composition of the present invention is mixed at 1% by weight or more with another polyester composition to obtain a film having a changed metal concentration. It is preferable from the viewpoint of improving the productivity and heat resistance of other varieties.

こ と Further, by forming a layered structure of the layer composed of the polyester composition of the present invention and a layer composed of another polyester composition, a laminated film having the characteristics of each layer can also be obtained. The laminated film of the present invention, for example, after drying the polyester composition of the present invention and another polyester composition, according to a conventional method, two or more confluent blocks having a rectangular laminated portion, each layer is intended for It can be manufactured by melt-extruding from a die to form an unstretched sheet, followed by biaxial stretching and heat treatment so that the sheets are laminated with the thickness ratio and configuration described above.

In the case of a biaxially stretched film, the stretching ratio is not particularly limited, but usually, a range of 2 to 5 times each in the vertical and horizontal directions is appropriate. Alternatively, after stretching in the longitudinal and transverse directions, the film may be stretched again in any of the longitudinal and transverse directions, or, of course, may be simultaneously biaxially stretched. When an easy-adhesion layer, a particle layer, or the like is formed, a coating component may be applied in-line before stretching or between longitudinal stretching and transverse stretching, or may be offline-coated after stretching.

INDUSTRIAL APPLICABILITY The present invention has a good color tone (b value), has a small amount of foreign matter, and has excellent fusion heat stability, and can be suitably used for various uses such as a fiber use and a film use such as a magnetic material, a packaging material, and an optical material. A catalyst for producing an excellent polyester and a method for producing a polyester using the same.

Hereinafter, the present invention will be described in more detail with reference to examples. In addition, each characteristic in an Example was measured by the following method.

(1) Intrinsic viscosity of polymer ([η] (dL / g))
It measured at 25 degreeC using o-chlorophenol as a solvent.

(2) Polymer Color Tone Hunter values (L, a, b values) were measured using a color difference meter (SM Color Computer Model SM-3) manufactured by Suga Test Instruments Co., Ltd.

(3) Content of each element such as titanium, cobalt, and phosphorus in polyester Using a fluorescent X-ray apparatus (Model No. 3270) manufactured by Rigaku Corporation, 8 g of the polymer is melted and molded into a plate shape, and the intensity of the fluorescent X-ray is measured. did. This value was converted to a metal content using a calibration curve prepared in advance with a sample having a known content.

(4) Content of alkali metals such as lithium in polyester (atomic absorption method)
Polarized Zeeman atomic absorption spectrometer manufactured by Hitachi, Ltd. Model No. 180-80 (frame: acetylene-air) Alkali metal was measured by an atomic absorption method. Using a hollow cathode lamp as a light source, 8 g of the polymer was atomized by flame-type atomization, detected by a photometry unit, and converted into a metal content using a calibration curve prepared in advance.

(5) Carboxyl end group content of polyester (COOH)
Maurice et al., Anal. Chim. Acta, 22, p363 (1960).

(6) Thermal stability of polymer (% BB)
8 g of the polymer was placed in a test tube and subjected to a heat treatment at 300 ° C. for 10 minutes (t ₀ ) and 6 hours (t) under a pressure of 0.1 MPa in a nitrogen atmosphere. It was calculated by the equation.

% BB _t = (1 / [η] _t ^{(1 / 0.75)} −1 / [η] _t0 ^{(1 / 0.75)} )
Here, [η] _t is the value at the time of heat treatment for 6 hours, and [η] _t0 is the value at the time of heat treatment for 10 minutes.

(7) Number of foreign substances Foreign substances in the polyester can be observed in about 500 fields by washing the polyester chip with hydrochloric acid and then with purified water, collecting 10 mg, and dissolving it on a preparation heated to 260 ° C. The number of foreign substances having a maximum diameter of 1 μm or more was counted, and the average was taken.

(8) Number of coarse protrusions H1 and H2 on film
After ^two measurement surfaces (100 cm ² ) are superimposed on each other and brought into close contact with each other by electrostatic force (applied voltage: 5.4 kV), the height of the coarse projections from the Newton ring generated by interference of light of the coarse projections between the two films Was determined, and the number of coarse projections having a single ring or more was designated as H1, and the number of coarse projections having a double ring or more was designated as H2. The light source used was a halogen lamp with a 564 nm band-pass filter.

However, when it is difficult to measure with the above measurement area, the measurement area may be appropriately changed and converted to 100 cm ² . (For example, assuming that the measurement area is 1 cm ² , measurement is performed for 50 visual fields and converted to 100 cm ^2. )
When it is difficult to perform measurement by the above method, a three-dimensional roughness meter (SE-3AK manufactured by Kosaka Laboratories: scanning is performed in the film width direction under the following conditions, and measurement is performed 50 times. Using a stylus load of 0.07 g, a measurement area width of 0.5 mm × length of 15 mm (pitch of 0.1 mm), and a cutoff value of 0.08 mm), the number of protrusions having a height of 0.28 μm or more and a height of 0.08 μm were used. H1 and H2 may be obtained by measuring the number of protrusions of 56 μm or more and converting the number to 100 cm ² . Further, if necessary, a known method for measuring the number of protrusions on the film surface such as an atomic force microscope (AFM) or a four-detection SEM may be used in combination.

(9) Melt specific resistance Two copper plates are used as electrodes, and a Teflon (registered trademark) spacer is interposed therebetween to form electrodes having a copper plate of 22 cm ² and a copper plate interval of 9 mm. The electrode was immersed in a polymer melted at 290 ° C., and the resistance was calculated from the amount of current when a voltage of 5,000 V was applied between the electrodes.

(10) Casting performance by electrostatic application A DC voltage of 6 kv was applied between the electrode placed on the melt-extruded film and the rotary cooling body, and the casting speed was gradually increased. m / min) and according to the following criteria. A score of B or higher was regarded as a pass.

60 m / min S
50-60 m / min A
40-50 m / min B
30-40 m / min C
Less than 30 m / min D
(Example 1)
(Preparation of catalyst)
In 94.95 parts by weight of ethylene glycol, 0.05 part by weight of a compound represented by the structural formula D as a coordination compound β was dissolved by heating at 150 ° C. for 30 minutes. To this ethylene glycol solution, 5 parts by weight of titanium acetylacetonate (isopropyl alcohol solution: titanium concentration of 10% by weight) was added as compound α and dissolved at 150 ° C. for 1 hour to obtain a catalyst slurry (titanium content of 5,000 ppm). there were).

(Manufacture of polyester)
The esterification reaction product with 86 parts by weight of terephthalic acid and 39 parts by weight of ethylene glycol was used as a reserve, and 86 parts by weight of terephthalic acid and 39 parts by weight of ethylene glycol were added thereto. The esterification reaction was continued at 250 ° C. A reaction product corresponding to 86 parts by weight of terephthalic acid was transferred from the esterification reaction product having a conversion of 97% or more to a polycondensation reactor, and then 0.1 parts by weight of the above catalyst and 0.004 parts by weight of dimethylmethylphosphonate were added. Was added and the mixture was transferred to a polycondensation reaction layer. Then, the reaction system was gradually depressurized while heating and raising the temperature, and polymerized under a reduced pressure of 133 Pa at 285 ° C. for 3 hours under a constant stirring speed by a conventional method to obtain a polyester composition having an intrinsic viscosity [η] = 0.630. I "was obtained. Table 1 shows the results.

(Examples 2 to 4)
In Examples 2 to 4, polyester was produced using the above catalyst in the same manner as in Example 1. However, the catalyst preparation and addition amount were changed as shown in Table 1. Table 1 shows the results. Polyester compositions “II, III, IV” having an intrinsic viscosity [η] of 0.630 to 0.640 were obtained. Table 1 shows the results.

(Example 5)
(Preparation of catalyst)
In 25.975 parts by weight of ethylene glycol, 0.025 parts by weight of a compound represented by the structural formula D as a coordination compound β was dissolved by heating at 150 ° C. for 30 minutes. To this ethylene glycol solution, 5 parts by weight of tetrabutyl titanate (isopropyl alcohol solution: titanium concentration: 10% by weight) was added as compound α and dissolved at 150 ° C. for 1 hour to obtain a catalyst slurry (titanium content was 5,000 ppm). T).

(Manufacture of polyester)
The esterification reaction product with 86 parts by weight of terephthalic acid and 39 parts by weight of ethylene glycol was used as a reserve, and 86 parts by weight of terephthalic acid and 39 parts by weight of ethylene glycol were added thereto. The esterification reaction was continued at 250 ° C. The reaction product corresponding to 86 parts by weight of terephthalic acid was transferred to the polycondensation reactor from the esterification reaction product whose ratio reached 97% or more, and then 0.1 parts by weight of the above catalyst and 0.005 parts by weight of dipropynylmethylphosphonate. And the mixture was transferred to a polycondensation reaction layer. Then, the reaction system was gradually depressurized while heating and raising the temperature, and polymerized under a reduced pressure of 133 Pa at 285 ° C. for 3 hours under a constant stirring speed by a conventional method to obtain a polyester composition having an intrinsic viscosity [η] = 0.630. V "was obtained. Table 1 shows the results.

(Example 6)
(Preparation of catalyst)
0.3 parts by weight of a compound represented by the structural formula D as a coordination compound β was mixed at 25 ° C. with 94.7 parts by weight of ethylene glycol. To this ethylene glycol solution, 5 parts by weight of titanium citrate chelate (isopropyl alcohol solution: titanium concentration 10% by weight) was added as compound α and mixed at room temperature to obtain a catalyst slurry (titanium content was 5,000 ppm). .

(Manufacture of polyester)
The esterification reaction product with 86 parts by weight of terephthalic acid and 39 parts by weight of ethylene glycol was used as a reserve, and 86 parts by weight of terephthalic acid and 39 parts by weight of ethylene glycol were added thereto. The esterification reaction was continued at 250 ° C. A reaction product corresponding to 86 parts by weight of terephthalic acid was transferred from the esterification reaction product having a conversion of 97% or more to a polycondensation reactor, and then 0.16 parts by weight of the above catalyst and 0.004 parts of ethyl diethylphosphonoacetate were added. 0.03 parts by weight of magnesium acetate tetrahydrate was added to the polycondensation reaction layer. Then, the reaction system was gradually depressurized while increasing the temperature by heating, and polymerized under a reduced pressure of 133 Pa at 285 ° C. for 3 hours under a constant stirring speed by a conventional method to obtain a polyester composition having an intrinsic viscosity [η] = 0.63. VI "was obtained. Table 1 shows the results.

(Example 7)
A polyester was produced in the same manner as in Example 6. However, an aqueous solution of titanium ammonium peroxocitrate: a titanium concentration of 10% by weight was used as the titanium compound. Table 1 shows the results. A polyester composition “VII” having an intrinsic viscosity [η] of 0.64 was obtained. Table 1 shows the results.

(Example 8)
The polyester composition "V" obtained in Example 5 was sufficiently dried, supplied to an extruder, melt-extruded on a casting drum, and fused and quenched and solidified on a cast drum while applying static electricity. After forming a single-layer unstretched film, the film was stretched 3.5 times vertically at 90 ° C. and 3.5 times horizontally at 105 ° C. to obtain a polyester film having a thickness of 10 μm. The film forming property was good. The film thus obtained had few coarse projections and had a good color tone. Table 2 shows the results.

(Example 9)
The polyester composition "III" obtained in Example 3 was sufficiently dried and supplied to a main layer (layer A) extruder. Further, after drying the polyester composition “IV” obtained in Example 4, the polyester composition “IV” was supplied to a sub-layer (layer B) extruder, melt-extruded from a two-layer die onto a casting drum, and placed on a cast drum. It was fused and quenched and solidified while applying an electric voltage to obtain an A / B type (thickness ratio: 6/1) two-layer unstretched film. Next, this unstretched film was stretched 3.5 times vertically at 90 ° C. and 3.5 times horizontally at 105 ° C. to obtain a laminated polyester film having a thickness of 8 μm (laminated thickness of layer B: 1.33 μm). The film forming property was good. The film thus obtained had few coarse projections and had a good color tone. Table 2 shows the results.
(Example 10)
The polyester composition "III" obtained in Example 3 was sufficiently dried and supplied to a main layer (layer A) extruder. Further, after drying the polyester composition "V" obtained in Example 4, it was supplied to a sub-layer (layer B) extruder, and was melt-extruded from a two-layer die onto a casting drum, and was statically placed on a cast drum. It was fused and quenched and solidified while applying an electric voltage to obtain an A / B type (thickness ratio: 6/1) two-layer unstretched film. Next, this unstretched film was stretched 3.5 times vertically at 90 ° C. and 3.5 times horizontally at 105 ° C. to obtain a laminated polyester film having a thickness of 8 μm (laminated thickness of layer B: 1.33 μm). The film forming property was good. The film thus obtained had few coarse projections and had a good color tone. Table 2 shows the results.

(Example 11)
The polyester composition "VI" obtained in Example 5 was sufficiently dried, supplied to an extruder, melt-extruded on a casting drum, and fused and quenched on a cast drum while applying static electricity. After forming a single-layer unstretched film, the film was stretched 3.5 times vertically at 90 ° C. and 3.5 times horizontally at 105 ° C. to obtain a polyester film having a thickness of 10 μm. The film forming properties were very good. The film thus obtained had few coarse projections and had a good color tone. Table 2 shows the results.

(Comparative Example 1)
The esterification reaction product with 86 parts by weight of terephthalic acid and 39 parts by weight of ethylene glycol was used as a reserve, and 86 parts by weight of terephthalic acid and 39 parts by weight of ethylene glycol were added thereto. The esterification reaction was continued at 250 ° C. From the esterification reaction product whose conversion reached 97% or more, a reaction product corresponding to 86 parts by weight of terephthalic acid was transferred to a polycondensation reactor, and then 0.0035 parts by weight of tetrabutyl titanate and 0.005 parts by weight of dipropynylmethylphosphonate were added. By weight, the mixture was transferred to the polycondensation reaction layer. Then, the reaction system was gradually depressurized while heating and raising the temperature, and polymerized under a reduced pressure of 133 Pa at 285 ° C. for 3 hours under a constant stirring speed by a conventional method to obtain a polyester composition having an intrinsic viscosity [η] = 0.630. VIII ". Table 1 shows the results.

(Comparative Example 2)
A polyethylene terephthalate “IX” chip having an intrinsic viscosity [η] of 0.63 was obtained in the same manner as in Comparative Example 1 except that dipropynylmethylphosphonate was not added. Table 1 shows the results.

(Comparative Example 3)
A polyethylene terephthalate chip “X” having an intrinsic viscosity [η] of 0.63 was obtained in the same manner as in Example 1 except that 0.012 part by weight of diantimony trioxide was added instead of the above catalyst. Table 1 shows the results.

(Comparative Example 4)
The polyester composition "IX" obtained in Comparative Example 2 was sufficiently dried, supplied to an extruder, melt-extruded on a casting drum, and fused and quenched and solidified on a cast drum while applying static electricity. After forming a single-layer unstretched film, the film was stretched 3.5 times vertically at 90 ° C. and 3.5 times horizontally at 105 ° C. to obtain a polyester film having a thickness of 10 μm. The film forming property was good. Although the film thus obtained had few coarse projections, the color tone was poor, the thermal stability was poor, and the productivity was poor. Table 2 shows the results.

(Comparative Example 5)
The polyester composition "X" obtained in Comparative Example 3 was sufficiently dried and supplied to a main layer (layer A) extruder. Further, after drying the polyester composition “IX” obtained in Comparative Example 2, it was supplied to a sub-layer (B-layer) extruder, melt-extruded from a two-layer die onto a casting drum, and was statically placed on a cast drum. It was fused and quenched and solidified while applying an electric voltage to obtain an A / B type (thickness ratio: 6/1) two-layer unstretched film. Next, this unstretched film was stretched 3.5 times vertically at 90 ° C. and 3.5 times horizontally at 105 ° C. to obtain a laminated polyester film having a thickness of 8 μm (laminated thickness of layer B: 1.33 μm). The film forming property was good. The film thus obtained had many coarse projections, poor color tone, poor thermal stability, and reduced productivity. Table 2 shows the results.

Claims (6)

At least one compound selected from the compounds represented by the following general formulas (1) and (2) and at least one atom selected from the group consisting of nitrogen, sulfur and oxygen as donor atoms A catalyst for producing polyester comprising a reaction product with a coordination compound capable of coordinating at least bidentate.
Ti (OR) ₄ (1)
Ti (OH) _m (OR) _4-m (2)
(R: an organic group having 2 to 10 carbon atoms (which may be the same or different)
m: an integer from 1 to 4) The polyester production catalyst according to claim 1, wherein the coordination compound is at least one compound selected from the group consisting of metal-free phthalocyanine, indanthrone, anthraquinone and methine. The polyester production catalyst according to claim 1 or 2, wherein the compound represented by the general formula (1) or (2) is a tetraalkoxytitanium compound or a titanium chelate compound. At least one compound selected from the compounds represented by the following general formulas (1) and (2) and at least one atom selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom as a donor atom A catalyst for producing polyester comprising a reaction product with a coordination compound capable of coordinating at least bidentate.
Ti (OR) ₄ (1)
Ti (OH) _m (OR) _4-m (2)
(R: an alkyl group having 2 to 10 carbon atoms (which may be the same or different)
m: an integer from 1 to 4) A method for producing polyester using the catalyst for producing polyester according to any one of claims 1 to 4. A polyester film containing the polyester obtained by the production method according to claim 5.