JP2006265376A - Polyester composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester composition sufficiently keeping its catalytic activity as titanium catalyst even if titanium oxide content is high, showing no rise in filter pressure at its molding, good in reeling property, and excellent in polymer color tone and heat resistance compared with current products, and a fiber made therefrom. <P>SOLUTION: In a polyester containing 1.5-7.0 wt.% titanium oxide particles, this polyester composition contains 1-150 ppm, in terms of titanium atoms, titanium compound other than titanium oxide, 0.1-200 ppm, in terms of phosphorus atoms, phosphorus compound, 1-200 ppm, in terms of atoms, at least a compound selected from the group consisting of a magnesium compound, a manganese compound, and a calcium compound, and 1-1,000 ppm crystallization promoter. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polyester composition excellent in yarn-making property, color tone, and thermal stability. More specifically, it has a sufficient polymerization activity, there is no increase in the filtration pressure during melt spinning due to foreign matters caused by the catalyst used during the polymerization, the spinning performance is particularly good at high speeds, and the polymer is superior to conventional products. The polyester composition is excellent in heat stability and color tone.

  Polyester is used for various purposes because of its useful functionality, and is used for clothing, materials, and medical use, for example. Among them, polyethylene terephthalate is excellent in terms of versatility and practicality and is preferably used.

  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 antimony compound in the polymer being transformed in the vicinity of the die and partially vaporizing and dissipating, and then a component mainly composed of antimony remains in the die.

  In addition, the antimony catalyst residue in the polymer tends to be relatively large particles, and it becomes a foreign substance, causing an increase in the filtration pressure of the filter during molding, causing yarn breakage during spinning or film tearing during film formation, etc. It has undesirable characteristics and contributes to a decrease in operability.

  In view of the above background, there is a demand for polyesters that contain little or no antimony. Thus, germanium compounds are known when the role of the polycondensation catalyst is required for compounds other than antimony compounds. However, germanium compounds are difficult to use for general purposes because they have a small reserve and rare value. Moreover, when a titanium catalyst is used, the above-mentioned problems can be solved, but the obtained polyester has poor heat resistance and the color tone of the polyester is yellowish.

  On the other hand, the proposal which uses the titanium complex which consists of a titanium compound and a phosphorus compound as a polymerization catalyst as a catalyst for polyester polymerization is made (refer patent documents 1-5). According to this method, foreign matters caused by the catalyst can be reduced and the heat resistance of the melt can be improved, but the color tone of the obtained polymer is not sufficient before.

  Further, when a polyester polymerization catalyst containing a titanium compound comes into contact with a phosphorus compound, the catalyst of the titanium compound may be deactivated and sufficient polymerization activity may not be obtained. In order to suppress this phenomenon, there are a method of additionally adding to different reaction tanks and a method of separating the addition interval and addition position of the titanium compound and the phosphorus compound in the same reaction tank. According to this method, when the amount of the phosphorus compound is small, the catalyst deactivation of the titanium compound can be prevented, but when the amount of the phosphorus compound added is large, the deactivation of the catalyst still occurs. Titanium oxide, which is used as a matting agent or anti-glare agent in the fiber field, generally contains a phosphorus compound in order to adjust the particle size of titanium oxide particles. For this reason, when producing a polyester containing a large amount of titanium oxide, sufficient polymerization activity may not be obtained due to the deactivation of the titanium catalyst, preventing the deactivation of the catalytic activity of the titanium compound by the phosphorus compound. A method is needed. Accordingly, there is a need for further improvements in titanium compounds.

  Furthermore, in recent years, high-speed spinning has been progressing so as to be produced at a spinning speed of 6000 m / min or more in the spinning process, but polyester using a titanium catalyst performs spinning at a speed exceeding 6000 m / min. As a result, many yarn breaks occur and the operability is remarkably deteriorated.

Therefore, in the present invention, as a result of intensive studies on improving the quality and production defects of the polyester composition, at least one selected from the group consisting of a specific titanium compound and a phosphorus compound, and magnesium, manganese, and calcium. The present inventors have found that the object of the present invention can be achieved by a polyester composition comprising a polyester polymerization catalyst comprising an element and a crystallization accelerator.
JP 2001-524536 A (1st page) Japanese translation of PCT publication No. 2002-512267 (first page) JP 2002-293909 A (first page) JP2003-40991A (first page) Japanese Patent Laying-Open No. 2003-40994 (first page)

  The object of the present invention is to solve the above-mentioned conventional problems, and even if the titanium oxide is contained in a large amount, the titanium catalyst keeps the catalytic activity sufficiently, there is no increase in the filtration pressure during the molding of the polyester composition, and the yarn-forming property particularly at high speed. It is related with the polyester composition which can obtain polyester which is favorable, and was excellent in the thermal stability and color tone of a polymer compared with the conventional product.

  The subject of the present invention is a polyester containing 1.5 to 7.0% by weight of titanium oxide particles, in which a titanium compound other than the titanium oxide particles is 1 to 150 ppm in terms of titanium atom relative to the polyester, and the phosphorus compound is a phosphorus atom relative to the polyester. 0.1 to 200 ppm in terms of conversion, at least one selected from the group consisting of magnesium compounds, manganese compounds, and calcium compounds in terms of atomic conversion with respect to polyester, 1 to 200 ppm, and crystallization accelerator is included in an amount of 1 to 1000 ppm. This can be achieved with a polyester composition.

  The polyester composition comprising the specific titanium compound and phosphorus compound of the present invention and a compound containing at least one element selected from the group consisting of magnesium, manganese, and calcium and a crystallization accelerator is moldable. In the production of molded articles for fibers, films, bottles, etc., it is possible to solve problems such as color tone deterioration, die contamination, increased filtration pressure, and thread breakage. In particular, when producing fibers by performing high-speed spinning, it is possible to solve the problem of yarn breakage and improve the yarn-making property and operability.

  The polyester of the present invention is a polymer synthesized from a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof. What can be used as molded articles, such as a fiber, a film, and a bottle, is preferable.

  Specific examples of such polyester include polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, polyethylene-1,2- And bis (2-chlorophenoxy) ethane-4,4′-dicarboxylate. The present invention is suitable for polyethylene terephthalate or polyester copolymers mainly containing ethylene terephthalate units, which are most commonly used.

  The polyester of the present invention needs to contain 1.5 to 7.0% by weight of titanium oxide particles. When there are too many titanium oxide particles, the content of phosphorus contained in the titanium oxide increases and the titanium catalyst is deactivated. On the other hand, if the amount is too small, the effects of matteness and anti-glare properties, which are the purpose of adding titanium oxide, cannot be obtained sufficiently. Preferably it is 1.7 to 5.0 weight%, More preferably, it is 2.0 to 3.0 weight%. The average particle size of the titanium oxide particles is 1.0 μm or less, and the integral ratio of the particles of 2.0 μm or more in the frequency distribution is 5% or less in the yarn process when the fibers are used. This is preferable from the viewpoint of reducing wear of guides and the like.

  The titanium compound in the present invention is preferably contained in an amount of 1 to 150 ppm in terms of titanium atoms, excluding titanium oxide particles, with respect to the obtained polymer. When it is 3 to 75 ppm, the thermal stability and color tone of the polymer become better, and it is more preferably 5 to 20 ppm. Moreover, the polyester of this invention needs to contain 0.1-200 ppm of phosphorus compounds in conversion of a phosphorus atom with respect to polyester with a titanium compound. The phosphorus content is preferably 1 to 100 ppm, more preferably 10 to 50 ppm, from the viewpoint of thermal stability and color tone of the polyester during yarn production. Further, it is preferable that the molar ratio of Ti / P = 0.05 to 10 as the phosphorus atom in the phosphorus compound with respect to the titanium atom of the titanium compound is good in terms of thermal stability and color tone of the polyester. More preferably, Ti / P = 0.05-5, and still more preferably Ti / P = 0.1-1.

  At this time, in order to suppress deactivation of the catalyst by the phosphorus compound of the polyester polymerization catalyst of the present invention containing a titanium compound, at least one selected from the group consisting of a magnesium compound, a manganese compound, and a calcium compound is used. It is necessary to contain 1 to 200 ppm as the total in terms of atoms with respect to polyester of manganese and calcium. If the total of atoms in terms of magnesium, manganese, and calcium is less than 1 ppm, deactivation of the titanium catalyst cannot be sufficiently suppressed, and if it exceeds 200 ppm, thermal stability and color tone are deteriorated. More preferably, it is 10-100 ppm, Most preferably, it is 20-50 ppm. At this time, it is preferable that the molar ratio (Mg + Mn + Ca / P) of the total amount of magnesium, manganese, and calcium in terms of atoms and the phosphorus atom of the phosphorus compound is 0.1 to 10. More preferably, it is 0.3-7, More preferably, it is 0.5-5. In particular, when the atomic equivalent amount of magnesium to polyester is 11 to 100 ppm, and when the molar ratio Mg / P of the phosphorus atom of the phosphorus compound to the total of magnesium atom is 0.5 to 2.5, the color tone, heat Both stability is good. At present, the detailed mechanism of the deactivation suppression of this catalyst is unknown, but the added magnesium compound, manganese compound, and calcium compound act as a trapping agent for the phosphorus compound, and the phosphorus compound loses the catalytic activity of the titanium compound. It seems to prevent it from being alive. Specific examples of the magnesium compound used in this case include magnesium oxide, magnesium hydroxide, magnesium alkoxide, magnesium acetate, and magnesium carbonate. Specific examples of the manganese compound include manganese chloride, manganese bromide, manganese nitrate, manganese carbonate, manganese acetylacetonate, and manganese acetate. Specific examples of the calcium compound include calcium oxide, calcium hydroxide, calcium alkoxide, calcium acetate, and calcium carbonate. Among these, a magnesium compound is preferable in terms of color tone and polymerization activity, and magnesium acetate is particularly preferable.

  In order to improve the spinning performance in the high speed spinning which is the object in the present invention, it is necessary to contain 1 to 1000 ppm of a crystallization accelerator. The crystallization accelerator is not particularly limited as long as it is a compound that promotes the crystallinity of the polyester composition. The term “accelerating crystallinity” as used herein means that the temperature rising crystallization temperature is shifted to a lower temperature side or the temperature falling crystallization temperature is shifted to a higher temperature side in differential scanning calorimetry (DSC analysis). Specifically, talc, mica, kaolin, silica, metal oxide, inorganic carboxylate, inorganic sulfonate, fatty acid metal salt, organic sulfonate, carbonate and the like are preferably used. The crystallization accelerators may be used alone or in a mixture of two or more. Among these, a fatty acid metal salt represented by the following general formula is more preferable because it dissolves in polyester and has an effect of remarkably improving crystal acceleration in a small amount. Specific examples include sodium acetate, lithium acetate, and potassium acetate. The titanium oxide particles do not correspond to the crystallization accelerator. It is preferable that the obtained polyester has a temperature rising crystallization temperature of 165 ° C. or lower and a temperature falling crystallization temperature of 165 ° C. or higher in the differential scanning calorimetry (DSC analysis), because the spinning property in high speed spinning is good. In particular, the temperature rising crystallization temperature is preferably in the range of 135 to 155 ° C, and the temperature falling crystallization temperature is in the range of 170 to 190 ° C.

  A polyester composition comprising the titanium compound and phosphorus compound of the present invention and a compound containing at least one element selected from the group consisting of magnesium, manganese and calcium is used as a polymerization catalyst. A titanium compound having a group selected from the group consisting of functional groups represented by the following chemical formulas 1 to 5 and containing at least a carbonyl group, a carboxyl group, or an ester group can be produced at any time when a polyester is produced. It can be obtained by adding.

(In Chemical Formula 1 to Chemical Formula 5, R _{1 to} R ₃ each independently have hydrogen, a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group, a hydroxyl group, a carbonyl group, an acetyl group, a carboxyl group, an ester group, or an amino group. This represents a hydrocarbon group having 1 to 30 carbon atoms, and the titanium compound contains at least a carbonyl group, a carboxyl group or an ester group.)
The chemical formula 1 of the present invention includes a functional group composed of a hydroxy polyvalent carboxylic acid compound such as lactic acid, malic acid, tartaric acid, citric acid and the like.

  Further, as the chemical formula 2, a functional group composed of a β-diketone compound such as acetylacetone and a ketoester compound such as methyl acetoacetate and ethyl acetoacetate can be mentioned.

  In addition, as the chemical formula 3, functional groups composed of phenoxy, cresylate, salicylic acid, and the like can be given.

  Further, as Chemical Formula 4, acylate groups such as lactate and stearate, phthalic acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacin Polycarboxylic acid compounds such as acid, maleic acid, fumaric acid, cyclohexanedicarboxylic acid or their anhydrides, ethylenediaminetetraacetic acid, nitrilotripropionic acid, carboxyiminodiacetic acid, carboxymethyliminodipropionic acid, diethylenetriaminopentaacetic acid And functional groups composed of nitrogen-containing polyvalent carboxylic acids such as triethylenetetraminohexaacetic acid, iminodiacetic acid, iminodipropionic acid, hydroxyethyliminodiacetic acid, hydroxyethyliminodipropionic acid, and methoxyethyliminodiacetic acid.

  Further, as the chemical formula 5, a functional group composed of aniline, phenylamine, diphenylamine, or the like can be given.

  Among these, the chemical formula 1 and / or the chemical formula 4 are preferably included from the viewpoint of the thermal stability and color tone of the polymer.

  Examples of the titanium compound include titanium diisopropoxybisacetylacetonate and titanium triethanolamate isopropoxide containing two or more of the substituents represented by chemical formulas 1 to 5.

  Note that conventionally known alkoxytitanium compounds containing no carbonyl group, carboxyl group, and ester group, such as tetraisopropoxytitanium and tetrabutoxytitanium, are not included in Chemical Formula 1 of the present invention.

The catalyst of the present invention is a polymer synthesized from a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof. All or some of the following reactions (1) to (3) Refers to a compound that substantially contributes to the promotion of the reaction.
(1) Esterification reaction which is reaction of dicarboxylic acid component and diol component (2) Transesterification reaction which is reaction of ester-forming derivative component of dicarboxylic acid and diol component (3) Substantially ester reaction or transesterification Polycondensation reaction in which the reaction is completed and the resulting polyethylene terephthalate low polymer is depolymerized to increase the degree of polymerization. Therefore, titanium oxide particles generally used as inorganic particles in fiber matting agents and the like are It has substantially no catalytic action on the above reaction and is different from the titanium compound that can be used as the catalyst of the present invention.

  In addition, the polyester composition formed by adding a compound containing at least one element selected from the group consisting of the titanium compound and phosphorus compound of the present invention and magnesium, manganese, and calcium is used as a phosphorus compound. The phosphorus compound whose substituent is represented by the following chemical formula 6 can be obtained by adding at any time when the polyester is produced.

(In the above chemical formula 6, R ₁ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a hydrocarbon group having 1 to 50 carbon atoms including an alkoxy group, and has two or more with respect to the benzene ring. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl, an aliphatic branched structure, and an aromatic ring structure such as phenyl or naphthyl, and R ₂ and R ₃ are each independently An alkoxy group that represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, or an alkoxy group and that is —OR ₂ or —OR ₃ with respect to a phosphorus atom may be used. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl, an aliphatic branched structure, and an aromatic ring structure such as phenyl or naphthyl, L + M + N = 3, and L is an integer of 1 to 3. , M and N are integers from 0 to 2 A.)
Examples of the phosphorus compound represented by the above chemical formula 6 include phosphites, alkyl diarylphosphites, aryl diarylphosphites, dialkylarylphosphonites, and arylarylphosphonites. A phosphite is preferable from the viewpoint of stability and color tone improvement. Specifically, as a phosphorus compound having no cyclic structure, triphenyl phosphite, tris (4-monononylphenyl) phosphite, trimethyl phosphite as a compound of L = 3, M = 0, and N = 0 in Chemical Formula 6 (Monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, etc., and monooctyl diphenyl phosphite as a compound of L = 2, M = 1, and N = 0 Monodecyldiphenyl phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl phosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4′- Diphenylene diphenyl phosphite as a compound of L = 1, M = 1 and N = 1, such as biphenylene diphosphite And didecyl monophenyl phosphite, among which tris (2,4-di-tert-butylphenyl) phosphite is preferable. This compound is available as ADK STAB 2112 (Asahi Denka Co., Ltd.) or IRGAFOS 168 (Ciba Specialty Chemicals).

  Moreover, it is preferable that the phosphorus compound represented by Chemical formula 6 is a compound which has a 6-membered ring structure or more containing a phosphorus atom from a viewpoint of thermal stability and a color tone improvement. Specific phosphorus compounds include bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite, bis (2) as compounds of L = 1, M = 1, and N = 1. 2,4-di-tert-butylphenyl) pentaerythritol-di-phosphite, 3,9-bis (2,4-dicumylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [ 5,5] undecane, phenyl-neopentylene glycol phosphite, etc., and 2,2-methylenebis (4,6-di-tert-butyl as a compound of L = 2, M = 1 and N = 0 Phenyl) octyl phosphite and the like. Furthermore, the compound described in the following chemical formula 7 is preferable from the viewpoint of thermal stability and color tone improvement.

R ₁ and R ₂ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxy group, and two or more of them are present with respect to the benzene ring. It may be a different group. The hydrocarbon group in this case may contain an alicyclic structure such as cyclohexyl, an aliphatic branched structure, and an aromatic ring structure such as phenyl or naphthyl. Specific examples of the compound include bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite represented by the following chemical formula 8, bis (2 , 4-Di-tert-butylphenyl) pentaerythritol di-phosphite is preferred. These compounds of Chemical Formulas 8 to 9 are available from Asahi Denka Co., Ltd. (registered trademark No. 2477085) as ADK STAB PEP-36 and ADK STAB PEP-24G, respectively, and Chemical Formula 9 is Ciba Specialty Chemicals as IRGAFOS126. (Registered Trademark No. 1068887). These compounds may be used alone or in combination.

  When the phosphorus compound of the present invention is added, the phosphorus compound is preferably dissolved or dispersed in the above-mentioned diol component such as ethylene glycol.

  In addition, you may add phosphorus compound other than Chemical formula 6 from the viewpoint of thermal stability and a color tone improvement to the phosphorus contained in the polyester of this invention. Examples of such phosphorus compounds include one or two of phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphine oxide, phosphonous acid, phosphinic acid, and phosphine compounds. It is preferable. Specifically, for example, phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate and the like phosphoric acid series, phosphorous acid, trimethyl phosphite, triethyl phosphite, triphenyl phosphite and the like. Phosphate, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, isopropylphosphonic acid, butylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, tolylphosphonic acid, xylylphosphonic acid, biphenylphosphonic acid, naphthylphosphonic acid, anthryl Phosphonic acid, 2-carboxyphenylphosphonic acid, 3-carboxyphenylphosphonic acid, 4-carboxyphenylphosphonic acid, 2,3-dicarboxyphenylphosphonic acid, 2,4-dicarboxyphenylphosphonic acid, 2,5-dicarboxy Phenylphosphonic acid, 2,6-dicarboxyl Nylphosphonic acid, 3,4-dicarboxyphenylphosphonic acid, 3,5-dicarboxyphenylphosphonic acid, 2,3,4-tricarboxyphenylphosphonic acid, 2,3,5-tricarboxyphenylphosphonic acid, 2,3 , 6-tricarboxyphenylphosphonic acid, 2,4,5-tricarboxyphenylphosphonic acid, 2,4,6-tricarboxyphenylphosphonic acid, methylphosphonic acid dimethyl ester, methylphosphonic acid diethyl ester, ethylphosphonic acid dimethyl ester, ethyl Phosphonic acid diethyl ester, phenylphosphonic acid dimethyl ester, phenylphosphonic acid diethyl ester, phenylphosphonic acid diphenyl ester, benzylphosphonic acid dimethyl ester, benzylphosphonic acid diethyl ester, benzylphosphonic acid diester Phenyl ester, lithium (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), sodium (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), magnesium bis (3 Ethyl 5-di-tert-butyl-4-hydroxybenzylphosphonate), calcium bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonate), diethylphosphonoacetic acid, methyl diethylphosphonoacetate, Phosphonic acid compounds such as ethyl diethylphosphonoacetate, hypophosphorous acid, sodium hypophosphite, methylphosphinic acid, ethylphosphinic acid, propylphosphinic acid, isopropylphosphinic acid, butylphosphinic acid, phenylphosphinic acid, tolylphosphinic acid Xylylphosphinic acid, Biphenylylphosphinic acid, diphenylphosphinic acid, dimethylphosphinic acid, diethylphosphinic acid, dipropylphosphinic acid, diisopropylphosphinic acid, dibutylphosphinic acid, ditolylphosphinic acid, dixylphosphinic acid, dibiphenylylphosphinic acid, naphthylphosphinic acid, Anthrylphosphinic acid, 2-carboxyphenylphosphinic acid, 3-carboxyphenylphosphinic acid, 4-carboxyphenylphosphinic acid, 2,3-dicarboxyphenylphosphinic acid, 2,4-dicarboxyphenylphosphinic acid, 2,5- Dicarboxyphenylphosphinic acid, 2,6-dicarboxyphenylphosphinic acid, 3,4-dicarboxyphenylphosphinic acid, 3,5-dicarboxyphenylphosphinic acid, 2,3,4-trica Boxyphenylphosphinic acid, 2,3,5-tricarboxyphenylphosphinic acid, 2,3,6-tricarboxyphenylphosphinic acid, 2,4,5-tricarboxyphenylphosphinic acid, 2,4,6-tricarboxy Phenylphosphinic acid, bis (2-carboxyphenyl) phosphinic acid, bis (3-carboxyphenyl) phosphinic acid, bis (4-carboxyphenyl) phosphinic acid, bis (2,3-dicarboxylphenyl) phosphinic acid, bis ( 2,4-dicarboxyphenyl) phosphinic acid, bis (2,5-dicarboxyphenyl) phosphinic acid, bis (2,6-dicarboxyphenyl) phosphinic acid, bis (3,4-dicarboxyphenyl) phosphinic acid, Bis (3,5-dicarboxyphenyl) phosphinic acid, bis (2,3 4-tricarboxyphenyl) phosphinic acid, bis (2,3,5-tricarboxyphenyl) phosphinic acid, bis (2,3,6-tricarboxyphenyl) phosphinic acid, bis (2,4,5-tricarboxyphenyl) ) Phosphinic acid and bis (2,4,6-tricarboxyphenyl) phosphinic acid, methylphosphinic acid methyl ester, dimethylphosphinic acid methyl ester, methylphosphinic acid ethyl ester, dimethylphosphinic acid ethyl ester, ethylphosphinic acid methyl ester, Diethylphosphinic acid methyl ester, ethylphosphinic acid ethyl ester, diethylphosphinic acid ethyl ester, phenylphosphinic acid methyl ester, phenylphosphinic acid ethyl ester, phenylphosphinic acid phenyl ester, diphenyl Nylphosphinic acid methyl ester, diphenylphosphinic acid ethyl ester, diphenylphosphinic acid phenyl ester, benzylphosphinic acid methyl ester, benzylphosphinic acid ethyl ester, benzylphosphinic acid phenyl ester, bisbenzylphosphinic acid methyl ester, bisbenzylphosphinic acid ethyl ester, Phosphinic acids such as bisbenzylphosphinic acid phenyl ester, trimethylphosphine oxide, triethylphosphine oxide, tripropylphosphine oxide, triisopropylphosphine oxide, tributylphosphine oxide, phosphine oxides such as triphenylphosphine oxide, methylphosphonous acid, ethyl Phosphonous acid, propylphosphonous acid, isopropyl phosphite Phosphonic acid series such as phonic acid, butylphosphonous acid, phenylphosphonous acid, methylphosphinic acid, ethylphosphinic acid, propylphosphinic acid, isopropylphosphinic acid, butylphosphinic acid, phenylphosphinic acid, dimethyl Phosphinic acid, diethylphosphinic acid, dipropylphosphinic acid, diisopropylphosphinic acid, dibutylphosphinic acid, diphenylphosphinic acid and other phosphinic acid systems, methylphosphine, dimethylphosphine, trimethylphosphine, methylphosphine, diethylphosphine, Examples include phosphines such as triethylphosphine, phenylphosphine, diphenylphosphine, and triphenylphosphine, and these phosphorus compounds may be used alone or in combination.

  Specific solvents for the polyester polymerization catalyst of the present invention include water, methanol, ethanol, ethylene glycol, propanediol, butanediol, benzene and xylene, and any one or two of these may be used. preferable. Further, in order to prepare a titanium compound and a phosphorus compound in a solvent having a pH of 4 to 6 from the viewpoint of thermal stability and color tone, acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, MES (pH = 5) .6 to 6.8), Good buffer such as ADA (pH = 5.6 to 7.5) or the above phosphorus compound may be used.

  The method for synthesizing a catalyst for polyester polymerization of the present invention is as follows. (1) A titanium compound is mixed with a solvent, and a part or all of the titanium compound is dissolved in the solvent. To do. (2) When using a ligand of a titanium compound such as the hydroxycarboxylic acid compound or the polyvalent carboxylic acid compound, the titanium compound or the ligand compound is mixed in a solvent and a part or all of the mixture is in the solvent. In this mixed solution, the ligand compound or titanium compound is dissolved and diluted in a stock solution or solvent and added dropwise. In addition, it is preferable from the viewpoint of thermal stability and color tone improvement that a phosphorus compound is further dissolved and diluted in a stock solution or a solvent and added dropwise to the mixed solution. There is no restriction | limiting in particular in said dilution concentration. Said reaction conditions are performed by heating at the temperature of 0-200 degreeC for 1 minute or more, Preferably it is 2-100 minutes at the temperature of 20-100 degreeC. The reaction pressure at this time is not particularly limited, and may be normal pressure. The mixed solvent is charged into a reaction apparatus equipped with a thermometer and a stirring blade, and is stirred and mixed at a temperature of 0 to 200 ° C. for 1 minute or longer, preferably at a temperature of 10 to 100 ° C. for 2 to 60 minutes.

  The polyester polymerization catalyst of the present invention may be added to the polyester reaction system as it is, but the compound is mixed with a solvent containing a diol component that forms a polyester such as ethylene glycol or propylene glycol in advance, If it is made into a slurry and, if necessary, low boiling components such as alcohol used at the time of synthesizing the compound are removed and then added to the reaction system, foreign matter formation in the polymer is further suppressed, which is preferable. 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. In addition, when added as a polycondensation reaction catalyst, it may be substantially before the start of the polycondensation reaction, before the esterification reaction or transesterification reaction, or after the completion of the reaction, before the polycondensation reaction catalyst is started. You may add to. Further, a phosphorus compound may be additionally added from the viewpoint of improving thermal stability and color tone.

  In the polymerization reaction of the polyester of the present invention, the following formula 1 is preferably satisfied.

If T exceeds 300, side reactions such as thermal decomposition proceed and polymer characteristics deteriorate. On the other hand, when T is 60 or less, since the polymerization reaction proceeds rapidly, it is difficult to obtain a polymer having stable physical properties. Preferably, 90 ≦ T ≦ 250, and more preferably 120 ≦ T ≦ 200.

  In the polyester of the present invention, it is necessary that the antimony compound is not contained or the content of the polyester in terms of antimony atoms is 30 ppm or less. 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, it is preferably 10 ppm or less, and particularly not substantially contained. The term “substantially” here means that it is below the lower limit of detection in elemental analysis by a fluorescent X-ray elemental analyzer.

  Moreover, in the polyester of this invention, when a cobalt compound is further contained 1-400 ppm in conversion of the cobalt atom with respect to polyester, a color tone becomes favorable and it is preferable. The cobalt compound used in this case is not particularly limited, and specific examples include cobalt chloride, cobalt nitrate, cobalt carbonate, cobalt acetylacetonate, cobalt naphthenate, and cobalt acetate tetrahydrate.

  Further, it is preferable that the polyester of the present invention further contains a blue-based adjusting agent and / or a red-based adjusting agent as a color adjusting agent, because the color tone is good.

  The color tone adjusting agent of the present invention is a dye used for a resin or the like. Specifically, in the COLOR INDEX GENERIC NAME, blue color tone adjusting agents such as SOLVENT BLUE 104, SOLVENT BLUE 122, SOLVENT BLUE 45, SOLVENT RED 111, SOLVENT RED 179, SOLVENT RED 195, SOLVENT RED 135, PIGMENT RED 263, VAT RED 41, etc. Examples thereof include system color adjusting agents. Among them, SOLVENT BLUE 104, SOLVENT BLUE 45, SOLVENT RED 179, SOLVENT RED 195, SOLVENT RED 135, which do not contain halogen that is likely to cause corrosion of equipment, have relatively good heat resistance at high temperatures and excellent color developability, SOLVENT VIOLET 49 is preferably used.

  Further, one or more of these color tone adjusting agents can be used depending on the purpose. In particular, it is preferable to use one or more blue-type adjusting agents and red-type adjusting agents, since the color tone can be finely controlled. Furthermore, in this case, the color tone of the polyester obtained is particularly preferable when the ratio of the blue-based adjusting agent is 50% by weight or more with respect to the total amount of the color adjusting agent to be contained.

  Finally, the content of the color tone adjusting agent with respect to the polyester is preferably 30 ppm or less in total. If it exceeds 30 ppm, the transparency of the polyester may be lowered or the color may become dull.

  In order to balance the polymer color tone, it is preferable that the contents of cobalt and the color tone adjusting agent satisfy the following formula 2.

  The value of this formula is more preferably 4 or more and 10 or less from the viewpoint of color tone.

  Moreover, you may contain an alkali metal compound, an alkaline-earth metal compound, an aluminum compound, a zinc compound, a tin compound etc. in order to improve the thermal stability and color tone of the polymer obtained.

  In addition to particles such as silicon oxide, silicon nitride, clay, and carbon black, additives such as anti-coloring agents, stabilizers, and antioxidants may be contained.

  The polyester of the present invention has a chip-like color tone with a Hunter value and an L value of 50 or more, an a value of -6 to 2, and a b value of -1 to 7, such as molding of fibers and films. It is preferable from the viewpoint of the color tone of the product. More preferably, the L value is 65 or more, the a value is -5 to 1, and the b value is 0 to 6. Especially about b value, the range of 1-5 is more preferable.

  In the present invention, examples of the fiber-forming polymer include, but are not limited to, polyesters such as polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate. Polyester mainly composed of polyethylene terephthalate, which is the most versatile as a synthetic fiber for clothing, is preferable.

  Examples of the synthetic fiber include a core-sheath type composite fiber, a core-sheath type composite hollow fiber, a sea-island type composite fiber, a bonded type composite fiber, and a blend fiber.

  In addition to pigments such as titanium oxide and carbon black, conventionally known antioxidants, anti-coloring agents, light-proofing agents, antistatic agents, ultraviolet absorbers and the like may be added to the fiber-forming polymer.

  The cross-sectional shape of the synthetic fiber of the present invention may be an irregular cross-section such as a triangle, a flat shape, and a multi-leaf type other than a circle. Further, the filamentous form of the synthetic fiber may be either a filament or a staple, and is appropriately selected depending on the application. The fabric form can be appropriately selected according to the purpose, such as woven fabric, knitted fabric, and non-woven fabric.

  The manufacturing method of the polyester composition of this invention is demonstrated. Although the example of a polyethylene terephthalate is described as a specific example, it is not limited to this.

Polyethylene terephthalate is usually produced by one of the following processes.
That is, (A) 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 (B) 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. Here, the esterification reaction proceeds even without a catalyst, but the aforementioned titanium compound may be added as a catalyst. In the transesterification reaction, the compound such as manganese, calcium, magnesium, cobalt, zinc, lithium, etc. or the above titanium compound is used as a catalyst, and after the transesterification reaction is substantially completed, it is used for the reaction. In order to inactivate the catalyst, the phosphorus compound is added.

  The polyester composition of the present invention is polycondensed to a low polymer obtained in any stage of the series of reactions (A) or (B), preferably in the first half of the series of reactions (A) or (B). After adding at least one compound selected from the above-mentioned titanium compounds, phosphorus compounds, magnesium compounds, manganese compounds, calcium compounds as catalysts, crystallization accelerators, titanium oxide particles, and, if necessary, color tone adjusting agents, cobalt compounds The polycondensation reaction is performed to obtain high molecular weight polyethylene terephthalate.

  Further, the above reaction can be applied to a batch, semi-batch, or continuous system.

  The color tone adjusting agent is preferably added to the polyester at any time after completion of the esterification reaction or transesterification reaction until the polycondensation reaction is completed. In particular, it is preferably added after completion of the esterification reaction or transesterification reaction and before the start of the polycondensation reaction, because the dispersion in the polyester is good.

  It is also possible to add the color tone adjusting agent to the polyester after the polycondensation reaction is substantially completed. In this case, a method of directly melting and kneading the color tone adjusting agent on the chip using a single screw or twin screw extruder, or preparing a polyester containing the color tone adjusting agent at a high concentration separately in advance, You may blend with the chip which does not contain.

  The polyester fiber of the present invention can be produced by a conventionally known method.

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 catalyst-derived titanium element, phosphorus element, antimony element, magnesium element, manganese element, and calcium element in polyester It was determined by a fluorescent X-ray elemental analyzer (manufactured by Horiba, Ltd., MESA-500W type). X-ray fluorescence analysis was performed after the following pretreatment. That is, polyester is dissolved in orthochlorophenol (5 g of polymer per 100 g of solvent), and after adding the same amount of dichloromethane as this polymer solution to adjust the viscosity of the solution, a centrifuge (rotation speed 18000 rpm, 1 hour) To settle the particles. Thereafter, only the supernatant liquid is collected by the gradient method, and the polymer is reprecipitated by adding the same amount of acetone as the supernatant liquid, and then filtered through a 3G3 glass filter (manufactured by IWAKI). After washing with acetone, the acetone was removed by vacuum drying at room temperature for 12 hours. The polymer obtained by the above pretreatment was analyzed for titanium element, phosphorus element, antimony element, magnesium element, manganese element, and calcium element.
(2) Intrinsic viscosity of polymer IV
Measurement was performed at 25 ° C. using orthochlorophenol as a solvent.
(3) Color tone of polymer Using a color difference meter (SM color computer model SM-T45, manufactured by Suga Test Instruments Co., Ltd.), it was measured as a Hunter value (L, a, b value).
(4) Measurement of crystallinity The temperature rise crystallization temperature and the temperature fall crystallization temperature were measured using differential scanning calorimetry (Perkin Elmer, DSC-7). The amount of the sample was 10 mg, and the measurement was performed by the 2nd run method in which the polymer was once melted and then rapidly cooled, and then gradually raised and lowered. The temperature rise was measured in the range of 50 to 300 ° C. at a temperature rise rate of 16 ° C./min, and the temperature drop was measured in the range of 300 ° C. to 75 ° C. at a temperature drop rate of 16 ° C./min.
(5) Observation of deposits in the die The amount of deposits around the die holes 72 hours after spinning of the fibers was observed using a long focus microscope. The state where almost no deposits were observed was judged as ◯, the state where deposits were recognized but operable was judged as Δ, and the state where deposits were found and yarn breakage frequently occurred was judged as ×.
(6) Spinnability during high-speed spinning The obtained polyester is dried to an ultimate moisture content of 50 ppm or less, melted in a melting part at 290 ° C., led to a spin block with a spinning temperature of 300 ° C., and a metal nonwoven fabric having a limit filtration diameter of 10 μm Then, the melt was spun from a die with a die surface temperature of 290 ° C., and the first roller, the second roller and the take-up were each taken up at a speed of 6000 m / min to obtain a drawn yarn of 40 denier 12 filaments. Spinning was performed for 24 hours under these conditions, the number of yarn breaks was measured, and the number of yarn breaks per ton of polymer was measured.

Example 1
About 100 kg of bis (hydroxyethyl) terephthalate is charged in advance with a slurry of 82.5 kg of high-purity terephthalic acid (Mitsui Chemicals) and 35.4 kg of ethylene glycol (Nippon Shokubai Co., Ltd.), temperature 250 ° C., pressure 1.2 × The esterification reaction tank maintained at 10 5 Pa was sequentially supplied over 4 hours, and after the completion of the supply, the esterification reaction was carried out over another 1 hour, and 101.5 kg of this esterification reaction product was transferred to the polycondensation tank. .

  Subsequently, 11.5 g of cobalt acetate (30 ppm in terms of cobalt atom with respect to the polymer) and 23.8 g of magnesium acetate in terms of magnesium atom with respect to the polymer were introduced into the polycondensation reaction tank to which the esterification reaction product had been transferred. 30 ppm), blue color tone adjusting agent SOLVENT BLUE 104 (manufactured by Clariant, Polysynthren Blue RBL) 0.4 g of ethylene glycol solution, 10 ppm equivalent of lactate chelate titanium compound in terms of titanium atom relative to polymer, 100 ppm relative to polymer Mixture of ethylene glycol slurry of bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol di-phosphite (Adeka Stub PEP-36, manufactured by Asahi Denka Co.) equivalent to (10 ppm in terms of phosphorus atom) It was added (100 ppm as sodium acetate to the polymer) of sodium acetate 9.1 g. After stirring for 5 minutes, an ethylene glycol slurry of titanium oxide particles was added to the polymer so as to be 2.5% by weight in terms of titanium oxide particles, and then the reaction system was stirred while stirring the low polymer at 30 rpm. Was gradually raised from 250 ° C. to 290 ° 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 a strand form, and immediately cut to obtain polymer pellets. The time from the start of decompression to the arrival of the predetermined stirring torque was 2 hours and 50 minutes.

  The polymer obtained had an IV of 0.66, a color tone of L = 74, a = -3.3, b = 2.6, a temperature increase crystallization temperature of 152 ° C., and a temperature decrease crystallization temperature of 181 ° C. Further, it was confirmed that the content of antimony atoms measured from the polymer was 0 ppm.

  Further, this polyester was dried to a moisture content of 50 ppm, supplied to a spinning machine, melted at 290 ° C. in the melting section, weighed, discharged from the spinning pack section, and taken up at a speed of 1000 m / min. The obtained undrawn yarn was drawn 2.8 times at 80 ° C. and then heat-set with a roller (125 ° C.) to obtain a drawn yarn of 75 denier 36 filaments. In the melt spinning process, deposits around the mouthpiece holes during spinning and an increase in filtration pressure were hardly observed, and there was almost no yarn breakage during stretching, and the polymer had good moldability.

  The polyester was evaluated for spinning performance during high-speed spinning. As a result, deposits around the mouthpiece hole during spinning and an increase in filtration pressure were hardly observed, and yarn breakage was 0.2 per 1 t of polymer as shown in Table 1. The polymer was excellent in high-speed spinnability with few rotations.

Examples 2-10
Polyester was polymerized and spun in the same manner as in Example 1 except that the addition amounts of the magnesium compound, manganese compound and calcium compound were changed as shown in Table 1. The obtained polymer was excellent in color tone, there was almost no deposit around the die hole during spinning and an increase in filtration pressure, and there were few yarn breaks during high-speed spinning, and the polymer had good moldability. .

Examples 11-14
A polyester was polymerized and spun in the same manner as in Example 1 except that the addition amount and added species of the crystallization accelerator were changed as shown in Table 2. The obtained polymer is excellent in color tone, hardly any deposits around the nozzle hole during spinning and an increase in filtration pressure are observed, and there are few yarn breaks during high-speed spinning as shown in Table 2, and the molding processability is good. The polymer.

Examples 15-28
Titanium oxide addition amount, titanium compound content, bis (2,4-di-tert-butylphenyl) instead of bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite ) Pentaerythritol-di-phosphite, tris (monononylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, bis (2,6-di-) Polyester was polymerized, spun and dyed in the same manner as in Example 1 except that the content of tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite was changed as shown in Table 3. The obtained polymer is excellent in color tone, hardly any deposits around the mouthpiece hole during spinning and an increase in filtration pressure are observed, and there are few yarn breaks during high-speed spinning as shown in Table 3, and the molding processability is good. The polymer.

Examples 29-30
Polyester was polymerized and spun in the same manner as in Example 1 except that 15 ppm of antimony trioxide (manufactured by Sumitomo Metal Mining Co., Ltd.) in terms of metal was mixed with a titanium compound and added as shown in Table 4. The polymers obtained in both Examples 29 and 30 were excellent in color tone, and deposits around the nozzle holes during spinning in Example 29 and almost no increase in filtration pressure were observed, but in Example 30, the nozzles during spinning were used. There was a slight increase in sediment and filtration pressure around the hole, but there was no problem in operation. Further, the yarn breakage during high-speed spinning was small as shown in Table 4, and the polymer was excellent in molding processability.

Examples 31-38
Polyester was polymerized and spun in the same manner as in Example 1 except that the types and contents of the cobalt compound and the color tone adjusting agent were changed as shown in Table 4. The obtained polymer was excellent in color tone, and almost no deposits around the nozzle holes and no increase in filtration pressure were observed during spinning. Further, the yarn breakage during high-speed spinning was small as shown in Table 4, and the polymer was excellent in moldability.

  In addition, the phosphorus compound 1 described in Tables 1 to 4 is bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol di-phosphite (Asahi Denka Co., Adeka Stub PEP-36), phosphorus Compound 2 is bis (2,4-di-tert-butylphenyl) pentaerythritol di-phosphite (Asahi Denka Co., ADK STAB PEP24G), and phosphorus compound 3 is tris (monononylphenyl) phosphite (Aldrich) ), Phosphorus compound 4 is 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite (Asahi Denka Co., Adeka Stub HP-10), and B1 is a blue color tone adjuster. SOLVEN BLUE 104 (manufactured by Clariant, Polysynthren Blue RBL), with R1 System toning agent SOLVENT RED 135 (manufactured by Clariant, Polysynthren Red GFP) is.

Comparative Examples 1-3
Polyester was polymerized and spun in the same manner as in Example 1 except that the addition amounts of the magnesium compound, manganese compound, and calcium compound were changed as shown in Table 5.

  In Comparative Example 1, the time until the predetermined stirring torque was reached was significantly increased, and the b value was 11.0, and the polymer was inferior in color. On the other hand, in Comparative Examples 2 and 3, the time required to reach the predetermined agitation torque was fast and the polymerization activity was good, but deposits around the nozzle holes during spinning and an increase in the filtration pressure occurred. As shown in Table 5, yarn breakage occurred frequently and spinning was impossible.

Comparative Examples 4-5
Polyester was polymerized and spun in the same manner as in Example 1 except that the addition amount and added species of the crystallization accelerator were changed as shown in Table 5. The polymer obtained in Comparative Example 4 had a temperature increase crystallization temperature of 166 ° C. and a temperature decrease crystallization temperature of 163 ° C. This polymer is excellent in color tone, and deposits around the mouthpiece hole during spinning and an increase in filtration pressure were hardly recognized, but there were many yarn breaks at 6.5 times per ton of high-speed spinning, and high-speed spinnability. There were difficulties. Further, in Comparative Example 5, deposits around the die holes and an increase in filtration pressure occurred during spinning, and yarn breakage occurred frequently during high speed spinning, making spinning impossible.

Comparative Examples 6-10
Except that the addition amount of titanium oxide, the content of titanium compound, and the addition amount of bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite were changed as shown in Table 5. Polyester was polymerized and spun as in Example 1.

  In Comparative Examples 6, 7, and 10, the polymerization activity was not sufficient, and the viscosity did not increase up to a predetermined stirring torque. On the other hand, in Comparative Examples 8 and 9, although the polymerization activity was good, deposits around the nozzle holes and an increase in filtration pressure occurred during spinning, and yarn breakage occurred frequently during high speed spinning, making spinning impossible.

Comparative Example 11
Instead of the titanium catalyst, antimony trioxide (manufactured by Sumitomo Metal Mining Co., Ltd.), 251 ppm in terms of antimony atom, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di, with respect to the obtained polyester -Phosphoric acid instead of phosphite was polymerized in the same manner as in Example 1 except that 26 ppm in terms of phosphorus atom was added to the obtained polyester and no color tone modifier was added, and melt spinning was performed. Even when the catalyst was changed, the polymerization reactivity was good and the color of the obtained polymer was good. However, the base was soiled during spinning, thread breakage occurred, and the operability was poor.

Comparative Example 12
Polyester was polymerized and spun in the same manner as in Example 1 except that the types and contents of the cobalt compound and the color tone adjusting agent were changed as shown in Table 5. Polymerization activity was good, and deposits around the mouthpiece hole during spinning and almost no increase in filtration pressure were observed, but the b value was 8.9 and the polymer was inferior in color.

  The phosphorus compound 1 listed in Table 5 is bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite (Adeka Stub PEP-36 manufactured by Asahi Denka Co., Ltd.), and B1 Is a blue color tone adjusting agent (manufactured by Clariant, Polysynthren Blue RBL).

Claims (15)

  At least one selected from the group consisting of 1 to 150 ppm in terms of titanium atoms relative to the polyester, and 0.1 to 200 ppm in terms of phosphorus atoms relative to the polyester, magnesium compounds, manganese compounds, and calcium compounds. 1 to 200 ppm as a total in terms of atoms with respect to polyester of magnesium, manganese and calcium, 1 to 1000 ppm of crystallization accelerator, and 1.5 to 7.0 wt% of titanium oxide particles. Polyester composition. The polyester composition according to claim 1, wherein the crystallization accelerator is a fatty acid metal salt represented by the following general formula or a residue thereof.

  The polyester composition according to claim 1 or 2, wherein the temperature-rising crystallization temperature is 165 ° C or lower and the temperature-falling crystallization temperature is 165 ° C or higher.   The polyester composition according to any one of claims 1 to 3, which is contained in an amount of 11 to 100 ppm in terms of atoms of the magnesium compound.   The polyester composition according to any one of claims 1 to 4, wherein the molar ratio Mg / P of magnesium atoms to the polyester and phosphorus atoms of the phosphorus compound is 0.5 to 2.5. The titanium compound has a functional group represented by the following chemical formulas 1 to 5 and is obtained by adding a titanium compound containing at least a carbonyl group, a carboxyl group or an ester group at an arbitrary point in producing the polyester. The polyester composition according to any one of claims 1 to 5, wherein:

(In Chemical Formulas 1 to 5, R _{1 to} R ₃ are each independently hydrogen, a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group, a hydroxyl group, a carbonyl group, an acetyl group, a carboxyl group, an ester group, or an amino group. Represents a hydrocarbon group of 1-30.) 7. The polyester composition according to claim 6, wherein in Chemical Formulas 2 to 4, at least one of R _{1 to} R ₃ is a hydrocarbon group having 1 to 30 carbon atoms having a carbonyl group, a carboxyl group, or an ester group. object. R _{1 in} Chemical Formula 4 is a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group having 1 to 30 carbon atoms having a hydroxyl group, a carbonyl group, an acetyl group, a carboxyl group, or an ester group. 7. The polyester composition according to 7. The polyester composition according to any one of claims 1 to 8, wherein the polyester composition is obtained by adding a phosphorus compound represented by the following chemical formula 6 at an arbitrary time when the polyester is produced.

(In the above chemical formula 6, R ₁ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a hydrocarbon group having 1 to 50 carbon atoms including an alkoxy group, and has two or more with respect to the benzene ring. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl, an aliphatic branched structure, and an aromatic ring structure such as phenyl or naphthyl, and R ₂ and R ₃ are each independently An alkoxy group that represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, or an alkoxy group and that is —OR ₂ or —OR ₃ with respect to a phosphorus atom may be used. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl, an aliphatic branched structure, and an aromatic ring structure such as phenyl or naphthyl, L + M + N = 3, and L is an integer of 1 to 3. , M and N are integers from 0 to 2 A.)   The polyester composition according to claim 9, wherein the phosphorus compound represented by Chemical Formula 6 is a compound having a ring structure of 6 or more members containing a phosphorus atom. The polyester composition according to claim 9, wherein the phosphorus compound is a compound represented by Chemical Formula 7.

(In the above chemical formula 7, R ₁ and R ₂ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxy group, and a hydrocarbon group having 1 to 50 carbon atoms. Two or more different groups may be attached to one benzene ring, and the hydrocarbon group may be an alicyclic structure such as cyclohexyl, an aliphatic branched structure, phenyl or naphthyl. An aromatic ring structure such as The polyester composition according to any one of claims 1 to 11, which is a polyester mainly composed of terephthalic acid or an ester-forming derivative thereof and ethylene glycol or a derivative thereof, wherein the following formula 1 is satisfied.

  The polyester composition according to any one of claims 1 to 12, wherein the polyester composition contains a blue-based adjusting agent and / or a red-based adjusting agent as the color tone adjusting agent. The polyester composition according to claim 13, wherein the content of the color tone adjusting agent and the cobalt compound satisfies the following formula 2.

  The color adjusting agent is a dye, and its COLOR INDEX GENERIC NAME is SOLVENT BLUE 104, SOLVENT BLUE 122, SOLVENT BLUE 45 in the blue system, and SOLVENT RED 135, SOLVENT RED 111, SOLVENT RED 111, and SOLVENT RED 17 in the red system. The polyester composition according to claim 14.