JP4665389B2 - Polyester composition and polyester film - Google Patents

Description

  The present invention relates to a polyester composition and a polyester film that contain substantially no antimony compound, are excellent in color tone and heat resistance, have few foreign matters, and have high productivity.

  In general, polyethylene terephthalate is produced from terephthalic acid or an ester-forming derivative thereof and ethylene glycol. In a commercial process for producing a high molecular weight polymer, an antimony compound is widely used as a polycondensation catalyst. However, polymers containing antimony compounds have some undesirable properties as described below.

  For example, when a polymer obtained using an antimony catalyst is melt-spun into a fiber, it is known that an antimony catalyst residue is deposited around the die hole. As this deposition progresses, it becomes a cause of defects in the filament, so that it needs to be removed in a timely manner. The deposition of the antimony catalyst residue is considered to be due to the fact that the antimony compound in the polymer is denatured in the vicinity of the die and a part thereof is vaporized and dissipated, and then a component mainly composed of antimony remains in the die. In addition, when an antimony compound is used as a polycondensation catalyst in the production of polyester such as polyethylene terephthalate, if polyester is formed continuously over a long period of time, foreign matter adheres to and deposits around the die, and the May occur or may precipitate on the surface of the film and cause surface defects.

  Further, germanium compounds are known as catalysts, but germanium compounds are very expensive and difficult to use for general purposes.

Furthermore, it has 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, there are problems such as the above-mentioned base streaks and film surface defects. However, there are problems that the obtained polyester itself is colored yellow, the heat stability of the melt becomes unstable, the film is torn, and the productivity is deteriorated. In order to solve the above-mentioned coloring problem, a cobalt compound is generally added to polyester to suppress yellowing, but the heat stability of melting is lowered, which also deteriorates productivity. As a method for improving the color tone and heat resistance problems in a titanium-based catalyst, for example, Patent Document 1 proposes a method using a composite oxide composed of titanium and silicon as a catalyst. When the obtained polyester is used for a film, there are problems such as frequent yarn breakage due to catalyst-derived foreign matters, and problems such as an increase in filtration pressure during polymer filtration cannot be solved sufficiently. Patent Document 2 proposes a titanium compound catalyst obtained by hydrolyzing a titanium halogen compound. For example, when a thick film is produced, the polyester itself has a large yellow tint, and the color tone adjusting agent itself produces a film. Has been insufficiently improved, for example, when the difference in color tone becomes a problem, such as in optical applications.
WO95 / 18839 pamphlet JP 2001-89557 A

  The object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a polyester composition and a polyester film which are substantially free of antimony compounds, have excellent color tone and heat resistance, have little foreign matter, and have high productivity. There is.

In order to achieve the above object, the present invention includes a titanium element , an alkali metal element, and a sterically hindered phenol compound , and the titanium element content is 0.5 to 50 ppm as a titanium metal atomic weight, and the alkali metal element. Is characterized by a polyester composition having an alkali metal atomic weight of 1 to 30 ppm as an alkali metal atomic weight and an antimony element content of 30 ppm or less as an antimony metal atomic weight.

Ti (OR) ₄ (1)
Ti (OH) _m (OR) _4-m (2)
(R: an organic group having 2 to 10 carbon atoms (may be the same or different)
m: integer of 1 to 4)

  According to the present invention, it is possible to provide a polyester composition having good color tone, good oxidative degradation resistance, and less foreign matter.

  The polyester composition of the present invention is not particularly limited as long as it is a polymer synthesized from a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof.

  As such a polyester composition, you may contain the copolymerization component with respect to all the acid components. Specifically, aromatic dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid or ester-forming derivatives thereof, aliphatic dicarboxylic acids such as adipic acid and sebacic acid, or ester-forming derivatives thereof And alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid or ester-forming derivatives thereof.

  Further, the polyester composition of the present invention may contain a copolymer component of a diol component. Specific examples include propanediol, butanediol, neopentyl glycol, hexamethylene glycol, polyethylene glycol, polypropylene glycol, cyclohexane dimethanol and the like, and ester-forming derivatives thereof.

The polyester composition of the present invention contains a titanium element, an alkali metal element, and a sterically hindered phenol compound. This titanium element exists as an element derived from, for example, a titanium compound used as a catalyst. Since the titanium complex compound is formed by the presence of the compound having a catalytic ability and containing the titanium element and the sterically hindered compound, the activity of titanium can be moderately suppressed. As a result, hydrolysis of the catalyst itself and thermal decomposition of the polyester composition can be suppressed, and the color tone can be remarkably improved.

In addition, the polyester composition of the present invention,
(1) titanium element;
(2) an alkali metal element;
(3) and steric hindered phenol compound, and a reaction product of a compound containing a titanium element, 0.5～50Ppm content as titanium metal atom weight of the titanium element, the alkali content of the alkali metal element The polyester composition may have a metal atomic weight of 1 to 30 ppm and an antimony element content of 30 ppm or less as the antimony metal atomic weight.

  The titanium compound used as a catalyst in the present invention is preferably a titanium chelate compound or a tetraalkoxy titanium compound. For example, titanium chelates such as titanium acetylacetonate, titanium tetraacetylacetonate, titanium octylene glycolate, titanium lactate, titanium ethylacetoacetate, titanium citrate, titanium peroxocitrate ammonium ammonium, tetraisopropyl titanate, tetrabutyl titanate, tetra Alkyl titanates such as (2-ethylhexyl) titanate and tetramethyl titanate can be mentioned, among which titanium chelate and tetrabutyl titanate are preferably used.

  Moreover, it becomes alkaline by making content of an alkali metal element into 1-30 ppm as an alkali metal atomic weight, and it can suppress a hydrolysis of a titanium compound. The content of the alkali metal element is preferably 1 to 15 ppm. If the content exceeds 30 ppm, foreign matter may be generated. The introduction of the alkali metal element can be realized, for example, by adding a predetermined amount of a compound such as sodium hydroxide, potassium hydroxide, sodium acetate or potassium acetate.

  Furthermore, the polyester resin of the present invention preferably contains a phosphorus compound. Specifically, at least one phosphorus selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphine oxide, phosphonous acid, phosphinic acid, phosphine, phosphate, phosphite, phosphonate and phosphinate. Compounds can be used. As specific compounds, phosphoric acid, trimethyl phosphoric acid, ethyl diethylphosphonoacetate, phenyldipropylphosphonate and the like are preferable. By containing these phosphorus compounds, the heat resistance of the titanium catalyst can be improved and the color tone b value can be improved.

  The titanium compound preferably forms a titanium complex. A titanium complex is a titanium compound containing a chelating agent capable of coordinating with a titanium atom, and is not particularly limited. However, when a titanium chelate compound of a polyvalent carboxylic acid is used, the color tone of the resulting polymer is It is preferable and less foreign matter is generated. In particular, it is preferable that a hydroxy polyvalent carboxylic acid or a nitrogen-containing polyvalent carboxylic acid is contained and these form a titanium chelate. More preferably, it is a titanium chelate compound of hydroxy polyvalent carboxylic acid. As a chelating agent that forms such a titanium complex, polyvalent carboxylic acids such as phthalic acid, trimellitic acid, trimesic acid, hemimellitic acid and pyromellitic acid, hydroxy polyvalent carboxylic acids such as malic acid and citric acid, Ethylenediaminetetraacetic acid, nitrilotripropionic acid, carboxyiminodiacetic acid, carboxymethyliminodipropionic acid, diethylenetriaminopentaacetic acid, triethylenetetraminohexaacetic acid, iminodiacetic acid, iminodipropionic acid, hydroxyethyliminodiacetic acid, hydroxyethylimino Examples thereof include nitrogen-containing polycarboxylic acids such as dipropionic acid and methoxyethyliminodiacetic acid.

It is also preferable to form a sterically hindered phenolic compound and titanium complexes. Titanium complexes of this, since the activity is weakened as compared with the case of not forming the complex, it is possible to suppress the thermal decomposition of the catalyst itself hydrolysis or polyester composition. Moreover, since a color tone improvement effect and a radical suppression effect are exhibited, it acts as a stabilizer for the polyester composition.

  As the sterically hindered phenol compound, any compound having a phenol structure and having at least one bulky group in the phenol ring can be used. Specifically, a compound having the following structure is preferable.

  (Formula 1)

（但し、Ｒ¹、Ｒ²：アルキル基、置換アルキル基、または、置換トリアゾール基（それぞれ同一でも異なっていてもよい）
Ｒ³：アルキル基、置換アルキル基、アルコキシ基、または、置換アミノ基）
このような化合物の例としては２，２’−メチレンビス（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、１，６ヘキサンジオールビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオナート］、ペンタエリスリトールテトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオナート］、ジステアリル３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジルホスホナート、２，６，７−トリオキサ−１−ホスファビシクロ［２．２．２］オクタ−４−イルメチル３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシヒドロシンナマート、３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル−３，５−ジステアリルチオトリアジルアミン、２−（２'−ヒドロキシ−３’−ヒドロキシ−３’，５’−ジ−ｔｅｒｔ−ブチルフェニル）−５−クロロベンゾトリアゾール、２，６−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシメチルフェノール、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、４，４’−メチレンビス（２，６−ジ−ｔｅｒｔ−ブチルフェノール）、３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジルジメチルアミン、Ｎ，Ｎ’−ヘキサメチレンビス−３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシヒドロシンナミドなどがある。中でも、ジエチル［［３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル］メチル］ホスフォネートが特に効果が優れており好ましい。この化合物は、例えばチバ・スペシャリティー・ケミカルズ社から“ＩＲＧＡＮＯＸ１２２２”として市販されている。

(However, R ¹ , R ² : alkyl group, substituted alkyl group, or substituted triazole group (may be the same or different from each other)
R ³ : an alkyl group, a substituted alkyl group, an alkoxy group, or a substituted amino group)
Examples of such compounds are 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 1,6 hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate], pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], distearyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2, 6,7-trioxa-1-phosphabicyclo [2.2.2] oct-4-ylmethyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 3,5-di-tert-butyl- 4-hydroxyphenyl-3,5-distearylthiotriazylamine, 2- (2′-hydroxy-3′-hydroxy) -3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2,6-di-tert-butyl-4-hydroxymethylphenol, 1,3,5-trimethyl-2,4,6 -Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 4,4'-methylenebis (2,6-di-tert-butylphenol), 3,5-di-tert-butyl-4- Examples include hydroxybenzyldimethylamine, N, N′-hexamethylenebis-3,5-di-tert-butyl-4-hydroxyhydrocinnamide. Among them, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate is particularly preferable because of its excellent effect. This compound is commercially available, for example, as “IRGANOX1222” from Ciba Specialty Chemicals.

  These can be used individually or as a mixture, the amount used being 0.0001 to 1% by weight, preferably 0.001 to 0.00%, based on the weight of the molding material. 1% by weight.

  When the titanium compound as a polymerization catalyst in the present invention is contained in an amount of 0.5 to 50 ppm as an elemental titanium weight with respect to the obtained polymer weight, the polymerization activity is high, and the resulting polymer has good color tone and heat resistance, which is preferable. When the amount exceeds 50 ppm, the heat resistance is deteriorated, and further causes foreign matters due to the catalyst. As content, More preferably, it is 1-30 ppm, More preferably, it is 1-20 ppm. In order to contain a predetermined amount of these titanium compounds in the polymer, a predetermined amount may be added when the compounds are added (the added amount is maintained in the polymer as it is).

  The titanium compound as the polymerization catalyst of the present invention may be added as it is to the reaction system of polyethylene terephthalate, but the compound is mixed with a solvent containing a diol component that forms a polyester such as ethylene glycol in advance to obtain a solution or slurry. If necessary, it is preferable to remove the low-boiling components such as alcohol used at the time of synthesizing the compound and then add it to the reaction system because the generation of foreign matters in the polymer is further suppressed. As the esterification reaction catalyst and the transesterification reaction catalyst, there are a method of adding a catalyst immediately after the addition of the raw material and a method of adding the catalyst together with the raw material. Moreover, when adding as a polycondensation reaction catalyst, it should just be substantially before the polycondensation reaction start, and a polycondensation reaction catalyst may be added together with an esterification reaction catalyst or a transesterification reaction catalyst.

  In the polyethylene terephthalate of the present invention, the contents of the antimony compound and the germanium compound are each preferably 30 ppm or less in terms of the weight of metal atoms. By setting it within this range, it is possible to obtain a polymer that is less likely to cause contamination of the die during molding and is relatively inexpensive. More preferably, the content of each compound is 10 ppm or less, and it is particularly preferable that the content is not substantially contained.

When the polyester composition is used as a film, for example, the alkali metal element content is Ma (mol / t ), the alkaline earth metal element content is Md (mol / t ), and the phosphorus element content is Mp. It is preferable that Ma, Md, and Mp satisfy the following formula:

Ma + 2 × Md ≧ 3 × Mp
The above formula is synonymous with MP ≧ 0, preferably MP−0.5, where Ma + 2 × Md is M and 3 × Mp is P. When M−P <0, the antistatic application castability becomes poor, air tends to enter between the film and the casting drum at the time of melt extrusion casting, and the film forming speed tends to be reduced. Productivity will be degraded. The alkali metal element-containing compound and the alkaline earth metal element-containing compound used for satisfying the above formula are not particularly limited, but specific examples include lithium acetate, sodium acetate, potassium acetate, magnesium acetate, potassium hydroxide. Sodium hydroxide, magnesium hydroxide and the like can be used.

  In the present invention, a phosphorus compound may be used for the purpose of improving the color tone of the polymer during the polymerization reaction or improving the heat resistance of the resulting polymer, but the titanium compound as a polymerization catalyst is easily deactivated. In addition, it is preferable to add to the obtained polymer so that the phosphorus atom weight is 20 ppm or less, more preferably from the viewpoint of polymerization activity. However, it is preferable to add it from the viewpoint of color tone, and it is preferable to add a small amount when considered as a whole. In addition, when a titanium compound is added as a polymerization catalyst after the phosphorus compound is added, the delay of the polymerization time is preferably reduced. Here, as the phosphorus compound, phosphoric acid, phosphorous acid, phosphonic acid, phenylphosphonic acid, phosphinic acid, or a methyl ester or ethyl ester thereof can be used, but is not particularly limited thereto.

  In addition, fluorescent whitening agents such as those listed in “Plastics Additives Handbook”, Ed. R. Gacher and H. Muller, Hanser verlag, 3rd Ed., 1990 P775-789 ”are added. It is also possible to improve the color tone.

  In addition, a color adjuster comprising at least one organic blue pigment and inorganic blue pigment such as azo, triphenylmethane, quinoline, methine, dioxazine, quinacridone, anthraquinone, and phthalocyanine is added. Can do.

  Next, the manufacturing method of the polyester composition of this invention is demonstrated.

  Polyethylene terephthalate can be manufactured, for example, by any of the following processes. (1) A process in which terephthalic acid and ethylene glycol are used as raw materials, a low polymer is obtained by direct esterification reaction, and a high molecular weight polymer is obtained by subsequent polycondensation reaction, and (2) dimethyl terephthalate and ethylene glycol are used as raw materials. In this process, a low polymer is obtained by a transesterification reaction, and a high molecular weight polymer is obtained by a subsequent polycondensation reaction. Although the esterification reaction proceeds even without a catalyst, the titanium compound of the present invention may be added as a catalyst. Further, in the transesterification reaction, for example, it proceeds using a compound having catalytic ability including an element such as manganese, calcium, magnesium, lithium or the titanium catalyst of the present invention, and after the transesterification reaction is substantially completed. In order to inactivate the catalyst used in the reaction, a phosphorus compound is added.

  In the present invention, titanium as a polycondensation catalyst is added 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). A method of obtaining a high molecular weight polyethylene terephthalate by adding a compound and conducting a polycondensation reaction can be employed.

  Moreover, although said reaction is implemented by forms, such as a batch type, a semibatch type, or a continuous type, the manufacturing method of this invention can be applied to any of those forms.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the physical-property value in an Example was measured by the method described below.

(1) Content of titanium element, antimony element, and germanium element in polyethylene terephthalate Obtained with a fluorescent X-ray elemental analyzer (manufactured by Horiba, Ltd., MESA-500W type) or an ICP emission analyzer (manufactured by Seiko Instruments Inc., SPS1700). It was. In addition, in order to remove the influence of inorganic particles such as titanium oxide particles in the target polyethylene terephthalate as necessary, the following pretreatment was performed and then fluorescent X-ray or ICP emission analysis was performed. That is, polyethylene terephthalate is dissolved in orthochlorophenol, the viscosity of the polymer solution is adjusted with chloroform as necessary, and then the particles are precipitated with a centrifuge. Thereafter, only the supernatant liquid is collected by a gradient method, and the polymer is reprecipitated by adding acetone, filtered and washed to obtain a polymer from which particles are removed. The polymer obtained by removing the particles obtained by the above pretreatment was analyzed for the amount of titanium element, antimony element and germanium element.

(2) Intrinsic viscosity of polymer (η)
Measurement was performed at 25 ° C. using orthochlorophenol as a solvent. Hereinafter referred to as η.

(3) Melting point About 10 mg of a sample to be measured is precisely weighed and sealed using an aluminum open pan and pan cover, and 20 ° C. under a nitrogen stream using a differential scanning calorimeter (Perkin Elmer, DSC7 type). The temperature was raised at a rate of 16 ° C./min from 285 ° C. to 285 ° C., and the melting point peak temperature observed along the way was taken as the melting point.

(4) Solution haze About 2 g of the sample to be measured was dissolved in 20 mL of orthochlorophenol, and analysis was performed by an integrating sphere photoelectric photometry method using a haze meter (manufactured by Suga Test Instruments Co., Ltd., HGM-2DP type). In addition, in order to remove the influence of inorganic particles such as titanium oxide particles in the target polyethylene terephthalate, the same pretreatment as described in the above (1) was performed to obtain a polymer.

  If the solution haze is less than 1%, the content of foreign matter is small, and it can be said that the polymer has excellent film forming properties.

(5) Color tone of polymer Using a color difference meter (SM color computer format SM-3) manufactured by Suga Test Instruments Co., Ltd., it was measured as a Hunter value (L, a, b value).

(6) Gelation rate of polymer (%)
About 2 g of polymer chips are frozen and ground with a freezer mill, sifted with # 42 (350 μm or less), dried under reduced pressure (100 ° C., 40 minutes, pressure 133 Pa), weighed (1.0 ± 0.01 g), and then heat treated (predetermined) Time, 300 ° C., in air) at a flow rate of 100 ml / min).

  After heat treatment, dissolve at 80 ° C x 0.5 hr (orthochlorophenol), filter through glass filter (3G3), wash with about 50-100 ml of dichloromethane, and dry under reduced pressure (110 ° C x 2.0 hr, pressure 133 Pa) Then, the filtered material on the filter was weighed, and the gelation rate (%) with respect to the weight of the treated polymer was calculated.

(7) Number of foreign objects The chip is ultrasonically cleaned with (concentrated hydrochloric acid: pure water = 1: 1) for 1 minute in a class 100 clean room, then ultrasonically cleaned with pure water for 1 minute, and then the cover on the hot plate A sample was prepared by melting on glass and placing a cover glass so that no air bubbles would enter. Using a digital microscope (VHZ-450) manufactured by Keyence Corporation, four fields were measured by the dark field method (450 times), and the average was obtained. Observed. A defect of 1 μm or more was judged as a foreign substance. Foreign matter in a chip having a visual field area of 0.0034 cm ² and a thickness of about 40 μm to 0.02 mg is measured.

(8) Number of coarse projections H1 and H2 of the film
After ^two measurement surfaces (100 cm ² ) are stacked and brought into close contact with each other by electrostatic force (applied voltage 5.4 kV), the height of the coarse protrusion from the Newton ring caused by the interference of the coarse protrusion light between the two films. The number of coarse protrusions of a single ring or more was H1, and the number of coarse protrusions of a double ring or more was H2. The light source used was a halogen lamp with a 564 nm bandpass filter.

However, when measurement is difficult with the measurement area, the measurement area may be changed as appropriate and converted to 100 cm ² . (For example, a measurement area of 1 cm ² is measured for 50 visual fields and converted to 100 cm ^2. )
In addition, when measurement by the above method is difficult, a three-dimensional roughness meter (SE-3AK manufactured by Kosaka Laboratory: scans in the film width direction under the following conditions and performs measurement 50 times. Radius of tip of stylus is 2 μm. 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 cut-off value of 0.08 mm) H1 and H2 may be obtained by measuring the number of protrusions of 56 μm or more and converting it to 100 cm ² . Furthermore, if necessary, various methods for measuring the number of protrusions on the surface of the film such as an atomic force microscope (AFM) and a 4-detection SEM may be used in combination.

(9) Content of alkali metals such as lithium in polyester (atomic absorption method)
This was measured by atomic absorption spectrometry using a polarized Zeeman atomic absorption spectrophotometer model number 180-80 (frame: acetylene-air) manufactured by Hitachi, Ltd. Using a hollow cathode lamp with 8 g of polymer as a light source, it was atomized by a frame method, detected by a photometric unit, and converted into metal content using a calibration curve prepared in advance.

(10) Melting specific resistance An electrode having a copper plate of 22 cm ² and a copper plate interval of 9 mm is prepared by sandwiching a Teflon (registered trademark) spacer between ^two copper plates as an electrode. This electrode is immersed in a polymer melted at 290 ° C. The resistance value was calculated from the amount of current when a voltage of 5,000 V was applied between them.

(Method for synthesizing titanium malate chelate compound)
Titanium tetraisopropoxide (284.8 g, 1.00 mol) stirred in a 1 L flask equipped with stirrer, condenser and thermometer was added from the dropping funnel to ethylene glycol (217.85 g, 3.51 mol). ) Was added. The addition rate was adjusted so that the heat of reaction warmed the flask contents to about 50 ° C. To the solution was added a 32 wt / wt% aqueous solution of NaOH (380 g, 3.04 mol) slowly via a dropping funnel. The reaction mixture was stirred for 15 minutes and an 85 wt / wt% aqueous solution of ammonium malate (355.0 g, 2.00 mol) was added to the reaction flask to give a clear light yellow product. (Ti content 3.9% by weight) was obtained.

(Method for synthesizing reaction product of titanium malate chelate compound and sterically hindered phosphorus compound)
Titanium tetraisopropoxide (284.8 g, 1.00 mol) stirred in a 1 L flask equipped with stirrer, condenser and thermometer was added from the dropping funnel to ethylene glycol (217.85 g, 3.51 mol). ) Was added. The addition rate was adjusted so that the heat of reaction warmed the flask contents to about 50 ° C. To the solution was added a 32 wt / wt% aqueous solution of NaOH (380 g, 3.04 mol) slowly via a dropping funnel. The reaction mixture was stirred for 15 minutes and 85 wt / wt% aqueous solution of ammonium malate (355.0 g, 2.00 mol), sterically hindered phosphorus compound: “IRGAFOS12” (registered trademark) 100 g was added to the reaction flask. A pale yellow product (Ti content 3.6% by weight) was obtained. {Catalyst i}
(Method for synthesizing reaction product of titanium malate chelate compound and sterically hindered phenol compound)
Titanium tetraisopropoxide (284.8 g, 1.00 mol) stirred in a 1 L flask equipped with stirrer, condenser and thermometer was added from the dropping funnel to ethylene glycol (217.85 g, 3.51 mol). ) Was added. The addition rate was adjusted so that the heat of reaction warmed the flask contents to about 50 ° C. To the solution was added a 32 wt / wt% aqueous solution of NaOH (380 g, 3.04 mol) slowly via a dropping funnel. The reaction mixture was stirred for 15 minutes and 85 wt / wt% aqueous solution of ammonium malate (355.0 g, 2.00 mol), sterically hindered phenolic compound: “IRGANOX1222” (100 g) was added to the reaction flask. A pale yellow product (Ti content 3.6% by weight) was obtained. {Catalyst ii}
(Method for synthesizing reaction product of titanium malate chelate compound and sterically hindered phenol compound)
Titanium tetraisopropoxide (284.8 g, 1.00 mol) stirred in a 1 L flask equipped with stirrer, condenser and thermometer was added from the dropping funnel to ethylene glycol (217.85 g, 3.51 mol). ) Was added. The addition rate was adjusted so that the heat of reaction warmed the flask contents to about 50 ° C. To the solution was added a 32 wt / wt% aqueous solution of NaOH (380 g, 3.04 mol) slowly via a dropping funnel. The reaction mixture was stirred for 15 minutes, and 85 wt / wt% aqueous solution of ammonium malate (355.0 g, 2.00 mol), sterically hindered phenolic compound: “IRGANOX1010” (registered trademark) 100 g was added to the reaction flask. A pale yellow product (Ti content 3.6% by weight) was obtained. {Catalyst iii}
(Method for synthesizing reaction product of titanium lactic acid chelate compound and sterically hindered phenol compound)
Titanium tetraisopropoxide (284.8 g, 1.00 mol) stirred in a 1 L flask equipped with stirrer, condenser and thermometer was added from the dropping funnel to ethylene glycol (217.85 g, 3.51 mol). ) Was added. The addition rate was adjusted so that the heat of reaction warmed the flask contents to about 50 ° C. To the solution was added a 32 wt / wt% aqueous solution of NaOH (380 g, 3.04 mol) slowly via a dropping funnel. The reaction mixture was stirred for 15 minutes and 85 wt / wt% aqueous ammonium lactate solution (251.98 g, 2.00 mol) was added to the reaction flask and 100 g of sterically hindered phenolic compound: “IRGANOX1222” (registered trademark). In addition, a pale yellow product (Ti content 3.9% by weight) {catalyst iv} was obtained.

(Synthesis method of reaction product of titanium citrate chelate compound and sterically hindered phenol compound)
Titanium tetraisopropoxide (284.8 g, 1.00 mol) stirred in a 1 L flask equipped with stirrer, condenser and thermometer was added from the dropping funnel to ethylene glycol (217.85 g, 3.51 mol). ) Was added. The addition rate was adjusted so that the heat of reaction warmed the flask contents to about 50 ° C. To the solution was added a 32 wt / wt% aqueous solution of NaOH (380 g, 3.04 mol) slowly via a dropping funnel. The reaction mixture was stirred for 15 minutes and 85 wt / wt% aqueous solution of ammonium citrate (492.0 g, 2.00 mol), sterically hindered phenolic compound: “IRGANOX1222” (100 g) was added to the reaction flask. A pale yellow product (Ti content 3.5% by weight) was obtained. {Catalyst v}
(Method for synthesizing titanium alkoxide compound)
Ethylene glycol (217.85 g, 3.51 mol) was added from a dropping funnel to titanium tetrabutoxide (340 g, 1.00 mol) stirred in a 1 L flask equipped with a stirrer, condenser and thermometer. . The addition rate was adjusted so that the heat of reaction warmed the flask contents to about 50 ° C. The reaction mixture was stirred for 15 minutes and a 32 wt / wt% aqueous solution of NaOH (125 g, 1.00 mol) was slowly added to the reaction flask via a dropping funnel to give a clear yellow liquid (Ti content 7 0.02% by weight). {Catalyst vi}
(Method for synthesizing reaction product of titanium alkoxide compound and sterically hindered phenol compound)
Ethylene glycol (217.85 g, 3.51 mol) was added from a dropping funnel to titanium tetrabutoxide (340 g, 1.00 mol) being stirred into a 1 L flask equipped with a stirrer, condenser and thermometer. It was. The addition rate was adjusted so that the heat of reaction warmed the flask contents to about 50 ° C. The reaction mixture was stirred for 15 minutes and a 32 wt / wt% aqueous solution of NaOH (125 g, 1.00 mol) was slowly added to the reaction flask via a dropping funnel. Thereto, 100 g of a sterically hindered phenol compound: “IRGANOX1222” (registered trademark) was added to obtain a transparent yellow liquid (Ti content: 6.13% by weight). {Catalyst vii}
(Method for synthesizing reaction product of titanium citrate chelate compound and sterically hindered phosphorus compound)
Citric acid monohydrate (532 g, 2.52 mol), sterically hindered phosphorus compound (bis (2,6-di-)) in warm water (371 g) in a 3 L flask equipped with stirrer, condenser and thermometer. tert-butyl-4-methylphenyl) pentaerythritol-diphosphite) (316 g, 0.5 mol) was dissolved. To this stirred solution was slowly added titanium tetraisopropoxide (288 g, 1.00 mol) from the addition funnel. The mixture was heated to reflux for 1 hour to produce a cloudy solution from which the isopropanol / water mixture was distilled under reduced pressure. The product was cooled to a temperature below 70 ° C., and a 32 wt / wt% aqueous solution of NaOH (380 g, 3.04 mol) was slowly added via a dropping funnel to the stirred solution. The resulting product was filtered and then mixed with ethylene glycol (504 g, 80 mol) and heated under reduced pressure to remove isopropanol / water and a slightly cloudy light yellow product (Ti content 3 0.07% by weight). {Catalyst viii}
Example 1
About 123 kg of bis (hydroxyethyl) terephthalate was previously charged in a slurry of 100 kg of high-purity terephthalic acid (manufactured by Mitsui Chemicals) and 45 kg of ethylene glycol (manufactured by Nippon Shokubai Co., Ltd.) at a temperature of 250 ° C. and a pressure of 1.2 × 10 ⁵ Pa. The esterification reaction tank was sequentially supplied to the held esterification reaction tank over 4 hours, and after the completion of the supply, the esterification reaction was further performed over 1 hour, and 123 kg of this esterification reaction product was transferred to the polycondensation tank.

  Subsequently, the catalyst vi is added to the polycondensation reaction tank to which the esterification reaction product has been transferred so that the titanium atom weight is 5 ppm with respect to the resulting polymer, and then the sterically hindered phenol compound: “IRGANOX1222”. "(Registered trademark) is added to the polymer so as to be 10 ppm, the magnesium acetate solution is added so that the magnesium atomic weight is 50 ppm, and phosphoric acid is added as the phosphorus compound so that the phosphorus atomic weight is 10 ppm. Then, while stirring the low polymer at 30 rpm, the reaction system was gradually heated from 250 ° C. to 285 ° C. and the pressure was reduced to 40 Pa. The time to reach the final temperature and final pressure was both 60 minutes. When the predetermined stirring torque was reached, the reaction system was purged with nitrogen, returned to normal pressure, the polycondensation reaction was stopped, discharged into cold water in the form of a strand, and immediately cut to obtain a polymer pellet polyester composition (A). The time from the start of decompression to the arrival of the predetermined stirring torque was 3 hours.

  The obtained polymer had η of 0.63, the melting point of the polymer was 259 ° C., and the solution haze was 0.8%. Moreover, it confirmed that content of the titanium atom derived from the titanium catalyst measured from the polymer was 5 ppm. The color tone was good, the oxidative degradation resistance was good, and there were few foreign substances. The results are shown in Table 1.

( Example 2)
Polymer pellets (polyester composition (B)) were obtained in the same manner as in Example 1 except that the catalyst vii was used in place of the catalyst vi used in Example 1. The obtained polymer had η of 0.64, the melting point of the polymer was 260 ° C., and the solution haze was 0.5%. The color tone was good, the oxidative degradation resistance was good, and there were few foreign substances. The results are shown in Table 1.

(Reference Example 1 )
About 123 kg of bis (hydroxyethyl) terephthalate was previously charged in a slurry of 100 kg of high-purity terephthalic acid (manufactured by Mitsui Chemicals) and 45 kg of ethylene glycol (manufactured by Nippon Shokubai Co., Ltd.) at a temperature of 250 ° C. and a pressure of 1.2 × 10 ⁵ Pa. It was sequentially supplied to the held esterification reaction tank over 4 hours, and after completion of the supply, the esterification reaction was further performed over 1 hour, and 123 kg of this esterification reaction product was transferred to the polycondensation tank.

  Subsequently, to the polycondensation reaction vessel to which the esterification reaction product has been transferred, the catalyst i solution is added so as to be 5 ppm in terms of titanium atomic weight relative to the polymer from which the catalyst i solution is obtained, and the magnesium acetate solution is added in an amount of 50 ppm by magnesium atomic weight. Then, phosphoric acid is added as a phosphorus compound so as to have a phosphorus atomic weight of 10 ppm, and then the reaction system is gradually heated from 250 ° C. to 285 ° C. while stirring the low polymer at 30 rpm. In addition, the pressure was reduced to 40 Pa. The time to reach the final temperature and final pressure was both 60 minutes. When the predetermined stirring torque was reached, the reaction system was purged with nitrogen, returned to normal pressure, the polycondensation reaction was stopped, discharged into cold water in the form of a strand, and immediately cut to obtain a polymer pellet polyester composition (C). The time from the start of decompression to the arrival of the predetermined stirring torque was 3 hours.

  Η of the obtained polymer was 0.63, the melting point of the polymer was 259 ° C., and the solution haze was 0.6%. Moreover, it confirmed that content of the titanium atom derived from the titanium catalyst measured from the polymer was 5 ppm. The color tone was good, the oxidative degradation resistance was good, and there were few foreign substances. The results are shown in Table 1.

Example 4
Polymer pellets (polyester composition (D)) were obtained in the same manner as in Example 3 except that catalyst ii was used in place of catalyst i used in Example 3. The obtained polymer had η of 0.64, the melting point of the polymer was 260 ° C., and the solution haze was 0.5%. The color tone was good, the oxidative degradation resistance was good, and there were few foreign substances. The results are shown in Table 1.

(Example 5)
Polymer pellets (polyester composition (E)) were obtained in the same manner as in Example 3 except that catalyst iii was used in place of catalyst i used in Example 3. The obtained polymer had η of 0.64, the melting point of the polymer was 260 ° C., and the solution haze was 0.5%. The color tone was good, the oxidative degradation resistance was good, and there were few foreign substances. The results are shown in Table 1.

(Example 6)
Polymer pellets (polyester composition (F)) were obtained in the same manner as in Example 3 except that catalyst iv was used in place of catalyst i used in Example 3. Η of the obtained polymer was 0.63, the melting point of the polymer was 259 ° C., and the solution haze was 0.5%. The color tone was good, the oxidative degradation resistance was good, and there were few foreign substances. The results are shown in Table 1.

(Example 7)
Polymer pellets (polyester composition (G)) were obtained in the same manner as in Example 3 except that catalyst v was used in place of catalyst i used in Example 3. Η of the obtained polymer was 0.63, the melting point of the polymer was 259 ° C., and the solution haze was 0.5%. The color tone was good, the oxidative degradation resistance was good, and there were few foreign substances. The results are shown in Table 1.

(Comparative Example 1)
Polymer pellets (polyester composition (H)) were obtained in the same manner as in Example 3 except that titanium malate chelate was used in place of catalyst i used in Example 3. The obtained polymer had η of 0.64, the melting point of the polymer was 260 ° C., and the solution haze was 0.5%. Although there were few foreign substances, the oxidation-degradation resistance was poor, and the color tone also deteriorated. The results are shown in Table 1.

(Comparative Example 2)
Polymer pellets (polyester composition (I)) were used in the same manner as in Example 3 except that antimony trioxide (manufactured by Sumitomo Metal Mining Co., Ltd.) was used as the antimony atomic weight in an amount of 200 ppm instead of catalyst i used in Example 3. Got. The obtained polymer had η of 0.64, the melting point of the polymer was 262 ° C., and the solution haze was 1.3%. In addition to many foreign substances, the oxidative degradation was also deteriorated. The results are shown in Table 1.

(Comparative Example 3)
Polymer pellets (polyester composition) were used in the same manner as in Example 3 except that tetrabutyl titanate (manufactured by Nippon Soda Co., Ltd., TBT-100) was used instead of catalyst i used in Example 3 and no magnesium acetate was added. Thing (J)) was obtained. The polymer obtained had a η of 0.64, a melting point of the polymer of 260 ° C., and a solution haze of 0.8%. The results are shown in Table 1.

( Example 8 )
The polyester composition (A) obtained in Example 1 was dried at 180 ° C. for 3 hours under reduced pressure at 133 Pa and fed to an extruder A heated to 280 ° C., and then placed on a casting drum having a surface temperature of 25 ° C. After melt-extrusion, it was melted and rapidly cooled and solidified by applying electrostatic force on a cast drum to obtain a single-layer unstretched film, and this unstretched film was longitudinally stretched at 90 ° C. at 3.5 ° C. Further, using a tenter, the film was stretched 3.5 times horizontally at 105 ° C., heat treated for 10 seconds at a temperature of 200 ° C. under a constant length, and then subjected to a relaxation treatment of 2% in the width direction. An axially oriented polyester film was obtained.

( Example 9 )
Using two extruders, the polyester composition (A) obtained in Example 1 was dried under reduced pressure at 180 ° C. for 3 hours at 133 Pa and supplied to the main layer (A layer) extruder. Further, after drying the polyester composition (B) obtained in Example 2 under reduced pressure at 133 Pa for 3 hours at 180 ° C., the polyester composition (B) was supplied to a sub-layer (B layer) extruder and merged in a T-die. It is melt-extruded from a layer die onto a casting drum, fused onto a cast drum having a surface temperature of 25 ° C. while applying antistatic force, and rapidly cooled and solidified. A / B type (thickness ratio 6/1) two-layer unstretched A film was obtained. Next, this unstretched film was stretched 3.5 times vertically at 90 ° C. with a roll-type stretching machine, and further stretched 3.5 times horizontally at 105 ° C. using a tenter, and the temperature was 200 ° C. under constant length. After 10 seconds of heat treatment, a relaxation treatment of 2% in the width direction was performed to obtain a laminated polyester film having a thickness of 8 μm (layer B laminated thickness of 1.33 μm). The film forming property was good. The film thus obtained had few coarse protrusions and good color tone. The results are shown in Table 2.

(Example 10)
Using two extruders, the polyester composition (D) obtained in Example 4 was dried under reduced pressure at 133 Pa at 180 ° C. for 3 hours and supplied to the main layer (A layer) extruder. Further, after drying the polyester composition (G) obtained in Example 7 under reduced pressure at 133 Pa for 3 hours at 180 ° C., the polyester composition (G) was supplied to a sub-layer (B layer) extruder and merged in a T-die. It is melt-extruded from a layer die onto a casting drum, fused onto a cast drum having a surface temperature of 25 ° C. while applying antistatic force, and rapidly cooled and solidified. A / B type (thickness ratio 6/1) two-layer unstretched A film was obtained. Next, this unstretched film was stretched 3.5 times vertically at 90 ° C. with a roll-type stretching machine, and further stretched 3.5 times horizontally at 105 ° C. using a tenter, and the temperature was 200 ° C. under constant length. After 10 seconds of heat treatment, a relaxation treatment of 2% in the width direction was performed to obtain a laminated polyester film having a thickness of 8 μm (layer B laminated thickness of 1.33 μm). The film forming property was good. The film thus obtained had few coarse protrusions and good color tone. The results are shown in Table 2.

(Comparative Example 4)
The polyester composition (H) obtained in Comparative Example 1 was dried at 180 ° C. for 3 hours under reduced pressure at 133 Pa, supplied to an extruder, melt-extruded on a casting drum, and statically placed on a cast drum having a surface temperature of 25 ° C. After applying electric power to melt and quenching and solidifying into a single-layer unstretched film, this unstretched film was longitudinally stretched at 90 ° C. by a roll-type stretcher, and further using a tenter, The film was stretched 3.5 times horizontally at 105 ° C., heat treated for 10 seconds at a temperature of 200 ° C. under a constant length, and then subjected to a relaxation treatment of 2% in the width direction 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 protrusions, the color tone was poor, the thermal stability was poor, and the productivity was deteriorated. The results are shown in Table 2.

(Comparative Example 5)
The polyester composition (H) obtained in Comparative Example 1 was dried under reduced pressure at 133 Pa at 180 ° C. for 3 hours and supplied to the main layer (A layer) extruder. The polyester composition (I) obtained in Comparative Example 2 was dried under reduced pressure at 133 Pa at 180 ° C. for 3 hours, and then supplied to a sublayer (B layer) extruder to be merged in a T die. It is melt-extruded from a layer die onto a casting drum having a surface temperature of 25 ° C., fused onto the cast drum while applying an antistatic force, and rapidly cooled and solidified. A / B type (thickness ratio 6/1) two-layer unstretched A film was obtained. Next, this unstretched film was stretched 3.5 times vertically at 90 ° C. with a roll-type stretching machine, and further stretched 3.5 times horizontally at 105 ° C. using a tenter, and the temperature was 200 ° C. under constant length. After 10 seconds of heat treatment, a relaxation treatment of 2% in the width direction was performed to obtain a laminated polyester film having a thickness of 8 μm (layer B laminated thickness of 1.33 μm). The film forming property was. The film thus obtained had many coarse protrusions, poor color tone, poor thermal stability, and deteriorated productivity. The results are shown in Table 2.

(Comparative Example 6)
The polyester composition (J) obtained in Comparative Example 3 was dried at 180 ° C. for 3 hours under reduced pressure at 133 Pa, supplied to an extruder, melt-extruded on a casting drum having a surface temperature of 25 ° C., and placed on a cast drum. The film was melted and rapidly solidified by applying electric power to obtain a single-layer unstretched film, but the adhesion was weak and the film was uneven. The results are shown in Table 2.

(Reference Example 2 )
Polymer pellets (polyester composition (K)) were obtained in the same manner as in Example 3 except that catalyst viii was used instead of catalyst i used in Example 3. The obtained polymer had η of 0.62, the melting point of the polymer was 259 ° C., and the solution haze was 0.4%.

Claims (5)

And titanium element, and an alkali metal element, and a standing member hindered phenol compounds, 0.5～50Ppm content of the titanium element as a titanium metal atom weight content of the alkali metal element as alkali metal atom weight 1 A polyester composition having -30 ppm and an antimony element content of 30 ppm or less as an antimony metal atomic weight. Phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphine oxide, phosphonous acid,
The polyester composition according to claim 1 , comprising at least one phosphorus compound selected from the group consisting of phosphinic acid, phosphine, phosphate, phosphite, phosphonate and phosphinate. The polyester composition according to claim 1 or 2, comprising a titanium chelate compound obtained by reacting a hydroxy polyvalent carboxylic acid or a nitrogen-containing polyvalent carboxylic acid. When the content of the alkali metal element is Ma (mol / g), the content of the alkaline earth metal element is Md (mol / g), and the content of the phosphorus element is Mp, Ma, Md and Mp are expressed by the following formulas: The polyester composition according to any one of claims 1 to 3, which is satisfied.
Ma + 2 × Md ≧ 3 × Mp The polyester film containing the polyester composition in any one of Claims 1-4.