JP2002212833A - Polyester combined filament yarn - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inexpensive polyester combined filament yarn having excellent thermal stability, good operating efficiency, and excellent safety. SOLUTION: This polyester combined filament yarn is obtained by carrying out polymerization using a catalyst containing aluminum and/or its compound and a phenolic compound or a phosphorus compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester polymerization catalyst and a polyester fiber produced by using the same. More specifically, the present invention relates to a novel polyester polymerization catalyst not using germanium or an antimony compound as a main component of the catalyst, and The present invention relates to a polyester blended yarn produced using this.

[0002]

2. Description of the Related Art Polyethylene terephthalate (PE)
T), polyesters represented by polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and the like are excellent in mechanical properties and chemical properties, and depending on the properties of each polyester, for example, for clothing and Used in fibers for industrial materials. A typical example of a polyester comprising an aromatic dicarboxylic acid and an alkylene glycol as main components is, for example, in the case of polyethylene terephthalate (PET), by esterification or transesterification of terephthalic acid or dimethyl terephthalate with ethylene glycol. Screw (2-
(Hydroxyethyl) terephthalate is produced industrially, for example, by a polycondensation method in which this is polycondensed using a catalyst at high temperature and in a vacuum. Conventionally, antimony trioxide has been widely used as a polyester polymerization catalyst used at the time of such polycondensation of polyester.
Antimony trioxide is a catalyst which is inexpensive and has excellent catalytic activity.However, if this is used as a main component, that is, in an amount added so as to exhibit a practical polymerization rate, metal antimony during polycondensation is used. Has a problem that blackening or foreign matter is generated in the polyester. Under such circumstances, a polyester containing no antimony or containing no antimony as a main component of a catalyst is desired.

[0003] The above-mentioned foreign substances in polyester, particularly when used for fibers, cause the following problems at the time of spinning. Precipitation of metallic antimony causes an increase in the pressure inside the spin pack during spinning, so that the exchange cycle of the spin pack is shortened, which causes an increase in cost. In addition, the spinneret is stained, and yarn spots and breaks are likely to occur. Further, if the foreign matter is mixed into the fiber, it causes breakage of the yarn at the time of drawing and a decrease in strength. Therefore, in the production of polyester fibers, a polyester polymerization catalyst free of foreign matter is required mainly from the viewpoint of operability. As a method for solving the above problem, an attempt has been made to use antimony trioxide as a catalyst and to suppress the occurrence of darkening or foreign matter in PET. For example, Japanese Patent No. 266650
In No. 2, the use of a compound of antimony trioxide, bismuth and selenium as a polycondensation catalyst makes it possible to use PET.
The generation of black foreign matter inside is suppressed. Also, Japanese Patent Application Laid-Open
No. 291141 states that the use of antimony trioxide containing sodium and iron oxides as a polycondensation catalyst suppresses the deposition of antimony metal. However, these polycondensation catalysts cannot ultimately achieve the purpose of reducing the content of antimony in the polyester.

Japanese Patent Application Laid-Open No. 10-36495 discloses a continuous process for producing a polyester having excellent transparency using antimony trioxide, phosphoric acid and a sulfonic acid compound. However, the polyester obtained by such a method has a problem that heat stability is poor and the acetaldehyde content of the obtained hollow molded article is high. Studies have been made on polycondensation catalysts replacing antimony-based catalysts such as antimony trioxide, and titanium compounds and tin compounds represented by tetraalkoxy titanates have already been proposed. There is a problem that the polyester is susceptible to thermal deterioration during melt molding and the polyester is significantly colored. As an attempt to overcome such problems when using a titanium compound as a polycondensation catalyst, for example, Japanese Patent Application Laid-Open No.
No. 16722 proposes a method of using a tetraalkoxy titanate simultaneously with a cobalt salt and a calcium salt. JP-A-8-73581 proposes a method in which a tetraalkoxy titanate is used simultaneously with a cobalt compound as a polycondensation catalyst, and a fluorescent brightener is used. However, in these techniques, when tetraalkoxy titanate is used as a polycondensation catalyst, P
Although the coloring of ET is reduced, it has not been achieved to effectively suppress the thermal decomposition of PET. Other attempts to suppress thermal degradation during melt molding of polyesters polymerized using a titanium compound as a catalyst are disclosed in, for example,
No. 259296 discloses a method of adding a phosphorus compound after polymerizing a polyester using a titanium compound as a catalyst. However, it is not only technically difficult to effectively mix the additive into the polymer after polymerization, but also increases the cost and is not practically used.

It is known that aluminum compounds generally have poor catalytic activity. Among the aluminum compounds,
It has been reported that aluminum chelate compounds have higher catalytic activity as polycondensation catalysts than other aluminum compounds, but that they have sufficient catalytic activity compared to the above-mentioned antimony compounds and titanium compounds. In addition, there is a problem that the polyester which is polymerized for a long time using an aluminum compound as a catalyst has poor thermal stability. A technique of adding an alkali metal compound to an aluminum compound to obtain a polyester polymerization catalyst having sufficient catalytic activity is also known. The use of such a known catalyst provides a polyester having excellent thermal stability.However, a catalyst using this alkali metal compound in combination requires a large amount of addition thereof in order to obtain practical catalytic activity. As a result, at least one of the following problems occurs due to the alkali metal compound in the obtained polyester polymer.

[0006] 1) The amount of foreign matters increases, and when used for fiber applications, the yarn-forming properties and yarn physical properties deteriorate. 2) The hydrolysis resistance of the polyester polymer decreases, and the transparency decreases due to the generation of foreign substances. 3) Poor color tone of the polyester polymer, that is, a phenomenon in which the polymer is colored yellow occurs, and when used for fiber applications, there is a problem that the color tone of the obtained fiber deteriorates. 4) The filter pressure at the time of melt spinning increases due to clogging of foreign matter, and the productivity decreases. As a catalyst that provides a polyester having excellent catalytic activity other than the antimony compound and not having the above problems,
Germanium compounds have already been put into practical use.However, this catalyst is very expensive, and it is difficult to control polymerization by changing the catalyst concentration of the reaction system because it is easily distilled out of the reaction system during polymerization. And there is a problem in using it as a main component of the catalyst. Further, as a method of suppressing thermal degradation during melt molding of polyester,
There is also a method of removing the catalyst from the polyester. As a method for removing a catalyst from polyester, for example, JP-A-10-251394 discloses a method in which a polyester resin is contacted with an extractant which is a supercritical fluid in the presence of an acidic substance. However, such a method using a supercritical fluid is not preferable because it is technically difficult and leads to an increase in product cost. As described above, the polymerization catalyst containing a metal component other than antimony and germanium as a main metal component of the catalyst, has excellent catalytic activity and hardly causes thermal deterioration during melt molding. (A) Thermal stability, There is a demand for a polymerization catalyst which provides polyester fibers which are excellent in at least one of b) thermal oxidation stability and (c) hydrolysis resistance and which have a small amount of foreign matter and excellent transparency.

[0007]

SUMMARY OF THE INVENTION The present invention provides a polyester fiber obtained by melt-spinning a polyester polymer produced using a novel polyester polymerization catalyst other than an antimony compound. In addition, the present invention does not contain an antimony compound or a germanium compound as a main component of a catalyst, uses aluminum as a main metal component, has excellent catalytic activity, and does not deactivate or remove the catalyst, and thus does not cause thermal degradation during melt spinning. And a polyester fiber obtained by melt-spinning using a polyester polymer having excellent heat stability, little foreign matter generation and excellent color tone.

[0008]

Means for Solving the Problems The inventors of the present invention examined the effects of adding various antioxidants and stabilizers during polymerization with the aim of improving the thermal stability of a polyester polymerized using an aluminum compound as a catalyst. However, by combining an aluminum compound with a phenolic compound, a phosphorus compound or a phosphorus compound having a phenol moiety in the same molecule, the thermal stability of the polyester is improved, and the aluminum compound, which is originally poor in catalytic activity, is sufficiently used as a polycondensation catalyst. The present invention has been found to have an excellent activity, and has reached the present invention. Using the polycondensation catalyst of the present invention,
It is possible to obtain a polyester fiber excellent in quality without using an antimony compound.

That is, the present invention provides, as a solution to the above-mentioned problems, a polyester produced using a polyester polymerization catalyst comprising an aluminum compound and a phosphorus compound or a phenolic compound, particularly a phosphorus compound having a phenol moiety in the same molecule. Provided are a polyester fiber comprising a polymer and a method for producing the polyester fiber.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention provides a novel polycondensation catalyst other than an antimony compound, and a polyester fiber comprising a polyester polymer produced using the same. The polycondensation catalyst of the present invention is a polyester polymerization catalyst comprising an aluminum compound and a phosphorus compound or a phenolic compound, particularly a phosphorus compound having a phenol moiety in the same molecule.

As the aluminum or aluminum compound constituting the polycondensation catalyst of the present invention, known aluminum compounds can be used without limitation in addition to metallic aluminum.

Specific examples of the aluminum compound include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, and aluminum trichloroacetate. , Aluminum lactate,
Carboxylates such as aluminum citrate and aluminum salicylate; inorganic acid salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate and aluminum phosphonate; aluminum methoxide, aluminum ethoxide, and aluminum n -Propoxide, aluminum is
aluminum chelate compounds such as o-propoxide, aluminum n-butoxide, aluminum alkoxide such as aluminum t-butoxide, aluminum acetylacetonate, aluminum acetyl acetate, aluminum ethyl acetoacetate, aluminum ethyl acetoacetate di-iso-propoxide, trimethyl aluminum, Organoaluminum compounds such as triethylaluminum and partial hydrolysates thereof,
Aluminum oxide and the like can be mentioned. Of these, carboxylate, inorganic acid salt and chelate compound are preferred,
Among these, aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred.

The amount of the aluminum or aluminum compound used in the present invention is 0.001 to 0.05 mol based on the total number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the obtained polyester. %, More preferably 0.005 to 0.0%
2 mol%. If the amount used is less than 0.001 mol%, the catalytic activity may not be sufficiently exhibited. If the amount used is 0.05 mol% or more, the thermal stability and thermo-oxidation stability decrease, and aluminum is caused. In some cases, the generation of foreign matter and the increase in coloring may become a problem. As described above, even when the addition amount of the aluminum component is small, the polymerization catalyst of the present invention is greatly characterized in that it exhibits a sufficient catalytic activity. As a result, thermal stability and thermal oxidation stability are excellent, and foreign matter and coloring due to aluminum are reduced.

The phenolic compound constituting the polycondensation catalyst of the present invention is not particularly limited as long as it is a compound having a phenol structure. For example, 2,6-di-tert-butyl-4-methylphenol, 2 , 6-Di-tert-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-
tert-amyl-4-methylphenol, 2,6-di-tert-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-
n-octylphenol, 2-isopropyl-4-methyl-6-te
rt-butylphenol, 2-tert-butyl-2-ethyl-6-tert
-Octylphenol, 2-isobutyl-4-ethyl-6-tert-
Hexylphenol, 2-cyclohexyl-4-n-butyl-6-
Isopropylphenol, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, triethylene glycol-bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thiodiethylenebis [3-
(3,5-di-tert-butyl-4,4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-tert
-Butyl-4-hydroxy-hydrocinnamide), 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5- Di-tert-
Butyl-4-hydroxybenzyl) isocyanurate, 1,
3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate,
Tris (4-tert-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, tetrakis [methylene (3,5-
Di-tert-butyl-4-hydroxy) hydrocinnamate]
Methane, bis [(3,3-bis (3-tert-butyl-4-hydroxyphenyl) butyric acid) glycol ester, N, N'-bis [3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionyl] hydrazine, 2,2'-oxazamide bis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-
Methyl-6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 1,3,5-trimethyl
-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,9-bis [1,1-dimethyl2- {β- (3-t
ert-butyl-4-hydroxy-5-methylphenyl) propionyloxydiethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2-bis [4- (2- (3 , 5-di-tert-
Butyl-4-hydroxycinnamoyloxy)) ethoxyphenyl] propane, β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid alkyl ester, tetrakis- [methyl-3- (3 ′, 5 '-Di-tert-butyl-4-hydroxyphenyl) propionate] methane, octadecyl-3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-
Butylphenyl) butane, thiodiethylene-bis [3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate], ethylenebis (oxyethylene) bis [3- (5-tert-
Butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol-bis-[-3- (3 ′ -tert-butyl-4-hydroxy-5-methylphenyl)] propionate, 1,1,3-tris [2-methyl-4- [3- (3,
5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -5-tert-butylphenyl] butane. These can be used in combination of two or more at the same time. Of these, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis- [methyl-3- (3 ′, 5 ′) -Di-tert-butyl
4-Hydroxyphenyl) propionate] methane and thiodiethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] are preferred.

By adding these phenolic compounds during the polymerization of the polyester, the catalytic activity of the aluminum compound is improved, and the thermal stability of the polymerized polyester is also improved.

The phenolic compound of the present invention is used in an amount of 5 × 10 ^{-7 to} 0.01 mol per mol of all the constituent units of the carboxylic acid component such as dicarboxylic acid and polycarboxylic acid of the obtained polyester. Preferably, it is more preferably 1 × 10 ^{−6 to} 0.005 mol. In the present invention, a phosphorus compound may be used together with the phenolic compound.

The phosphorus compound constituting the polycondensation catalyst of the present invention is not particularly limited.
Phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds,
It is preferable to use one or more compounds selected from the group consisting of phosphine-based compounds because the effect of improving the catalytic activity is large. Among these, the use of one or two or more phosphonic acid compounds is particularly preferable because the effect of improving the catalytic activity is particularly large.

The phosphonic acid compound, phosphinic acid compound, phosphine oxide compound, phosphonous acid compound, phosphinous acid compound and phosphine compound referred to in the present invention are represented by the following formulas (22) to (27), respectively. Means a compound having a structure represented by

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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The phosphonic acid compounds of the present invention include, for example, dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate and the like. Can be Examples of the phosphinic acid compound of the present invention include diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate,
Phenylphosphinic acid, methyl phenylphosphinate,
And phenyl phenylphosphinate. As the phosphine oxide compound of the present invention, for example,
Examples include diphenylphosphine oxide, methyldiphenylphosphine oxide, and triphenylphosphine oxide. Among phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds, and phosphine compounds, the phosphorus compounds of the present invention are represented by the following formulas (28) to (33). Preferably, a compound is used.

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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Among the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is preferred because the effect of improving the catalytic activity is large.

As the phosphorus compound constituting the polycondensation catalyst of the present invention, the compounds represented by the following general formulas (34) to (36) are particularly preferred because the effect of improving the catalytic activity is large.

[0034]

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[0035]

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[0036]

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(In the formulas (34) to (36), R ¹ , R ⁴ , R
⁵ and R ⁶ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a halogen group, or a hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl group or an amino group. R ² and R ³ 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 alkoxyl group. However, the hydrocarbon group may contain an alicyclic structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

The phosphorus compounds constituting the polycondensation catalyst of the present invention include those represented by R ¹ , R ⁴ and R in the above formulas (34) to (36).
Compounds in which ⁵ and R ⁶ are groups having an aromatic ring structure are particularly preferred.

The phosphorus compound constituting the polycondensation catalyst of the present invention includes, for example, dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate,
Diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate, diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate,
Phenylphosphinic acid, methyl phenylphosphinate,
Phenyl phenylphosphinate, diphenylphosphine oxide, methyldiphenylphosphine oxide,
Triphenylphosphine oxide and the like.
Of these, dimethyl phenylphosphonate and diethyl benzylphosphonate are particularly preferred.

The amount of the phosphorus compound of the present invention used is based on the number of moles of all the constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the obtained polyester.
5 × 10 ^{−7 to} 0.01 mol is preferable, and 1 × 10 ⁻⁶ is more preferable.
~ 0.005 mol.

The phosphorus compound having a phenol moiety in the same molecule constituting the polycondensation catalyst of the present invention is not particularly limited as long as it is a phosphorus compound having a phenol structure. The use of one or more compounds selected from the group consisting of acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds, and phosphine compounds improves the catalytic activity. Is preferred. Among these, the use of a phosphonic acid-based compound having one or more phenol moieties in the same molecule is particularly preferred because the effect of improving the catalytic activity is particularly large. As the phosphorus compound having a phenol moiety in the same molecule constituting the polycondensation catalyst of the present invention, the compounds represented by the following general formulas (37) to (39) are preferably used because the catalytic activity is particularly improved. .

[0042]

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[0043]

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[0044]

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(In the formulas (37) to (39), R ¹ contains a substituent such as a hydrocarbon group having 1 to 50 carbon atoms including a phenol moiety, a hydroxyl group, a halogen group, an alkoxyl group or an amino group, and a phenol moiety. Represents a hydrocarbon group having 1 to 50 carbon atoms, wherein R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, a substituent such as a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group or an amino group; And R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a carbon group having 1 to 50 carbon atoms including a substituent such as a hydroxyl group or an alkoxyl group. Wherein the hydrocarbon group may contain a branched structure, an alicyclic structure such as cyclohexyl, or an aromatic ring structure such as phenyl or naphthyl. The terminals of R ² and R ⁴ are bonded to each other. May be.)

Examples of the phosphorus compound having a phenol moiety in the same molecule of the present invention include, for example, p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate,
Diphenyl hydroxyphenylphosphonate, bis (p
-Hydroxyphenyl) phosphinic acid, bis (p-hydroxyphenyl) phosphinic acid methyl, bis (p-hydroxyphenyl) phosphinic acid phenyl, p-hydroxyphenylphenylphosphinic acid, p-hydroxyphenylphenylphosphinic acid methyl, p-hydroxyphenyl Phenyl phenylphosphinate, p-hydroxyphenylphosphinic acid, methyl p-hydroxyphenylphosphinate, phenyl p-hydroxyphenylphosphinate, bis (p-hydroxyphenyl) phosphine oxide, tris (p-hydroxyphenyl) phosphine oxide, bis ( (p-hydroxyphenyl) methylphosphine oxide, and the following formulas (40) to (43)
And the like. Of these,
The compound represented by the following formula (42) and dimethyl p-hydroxyphenylphosphonate are particularly preferred.

[0047]

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[0048]

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[0049]

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[0050]

Embedded image As the compound represented by the above formula (42), SANKO-
220 (manufactured by Sanko Co., Ltd.) is available.

By adding a phosphorus compound having such a phenol moiety in the same molecule during the polymerization of the polyester, the catalytic activity of the aluminum compound is improved, and the thermal stability of the polymerized polyester is also improved.

The amount of the phosphorus compound of the present invention having a phenol moiety in the same molecule may be 5 × 5 moles of all the constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the obtained polyester. It is preferably from 10 ^{-7 to} 0.01 mol, more preferably from 1 × 10 ^{-6 to} 0.005 mol. In the present invention, it is preferable to use a phosphorus metal salt compound as the phosphorus compound. The metal salt compound of phosphorus, which is a preferred phosphorus compound constituting the polymerization catalyst of the present invention, is not particularly limited as long as it is a metal salt of a phosphorus compound, but the use of a metal salt of a phosphonic acid compound improves the catalytic activity. Is preferred. Examples of the metal salt of a phosphorus compound include a monometal salt, a dimetal salt, and a trimetal salt.

In the above-mentioned phosphorus compounds, the metal portion of the metal salt is Li, Na, K, Be, Mg, Sr,
It is preferable to use one selected from Ba, Mn, Ni, Cu, and Zn because the effect of improving the catalytic activity is large. Of these, Li, Na, and Mg are particularly preferred.

As the phosphorus metal salt compound constituting the polymerization catalyst of the present invention, it is preferable to use at least one selected from the compounds represented by the following general formula (44) because the effect of improving the catalytic activity is large.

[0055]

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(In the formula (44), R ¹ is hydrogen and has 1 to 1 carbon atoms.
Represents a hydrocarbon group having 1 to 50 carbon atoms including 50 hydrocarbon groups, hydroxyl groups, halogen groups, alkoxyl groups, or amino groups. R ² represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group having 1 to 5 carbon atoms.
Represents a hydrocarbon group of 0. R ³ is hydrogen, carbon number 1-50
Represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group, a hydroxyl group, an alkoxyl group or a carbonyl. l is an integer of 1 or more, m is 0 or an integer of 1 or more, and l + m is 4 or less. M represents a (l + m) -valent metal cation. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. As the above R ¹ , for example, phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl,
2-biphenyl and the like. Examples of R ² include hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, ter
t- butyl group, an aliphatic group of a long chain, a phenyl group, a naphthyl group, a substituted phenyl group or a naphthyl group, -CH ₂ CH ₂
And a group represented by OH. Examples of R ³ O ⁻ include a hydroxide ion, an alcoholate ion, an acetate ion and an acetylacetone ion.

Among the compounds represented by the general formula (44), it is preferable to use at least one selected from the compounds represented by the following general formula (45).

[0058]

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(In the formula (45), R ¹ is hydrogen and has 1 to 1 carbon atoms.
Represents a hydrocarbon group having 1 to 50 carbon atoms including 50 hydrocarbon groups, hydroxyl groups, halogen groups, alkoxyl groups, or amino groups. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl. l is an integer of 1 or more, m is 0 or an integer of 1 or more, and l + m is 4 or less. M represents a (l + m) -valent metal cation. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. As the above R ¹ , for example, phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl,
2-biphenyl and the like. Examples of R ³ O ⁻ include a hydroxide ion, an alcoholate ion, an acetate ion and an acetylacetone ion. Among the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the effect of improving the catalytic activity is large.

In the above formula (45), M is Li, N
a, K, Be, Mg, Sr, Ba, Mn, Ni, Cu,
It is preferable to use a material selected from Zn because the effect of improving the catalytic activity is large. Of these, Li, Na, and Mg are particularly preferred.

The phosphorus metal salt compounds of the present invention include lithium [ethyl (1-naphthyl) methylphosphonate],
Sodium [ethyl (1-naphthyl) methyl phosphonate], magnesium bis [(1-naphthyl) methyl phosphonate], potassium [ethyl (2-naphthyl) methyl phosphonate], magnesium bis [(2-naphthyl) methyl phosphonate], Lithium [ethyl benzyl phosphonate], sodium [ethyl benzyl phosphonate], magnesium bis [ethyl benzyl phosphonate], beryllium bis [ethyl benzyl phosphonate],
Strontium bis [ethyl benzylphosphonate], manganese bis [ethyl benzylphosphonate], sodium benzylphosphonate, magnesium bis [benzylphosphonic acid], sodium [ethyl (9-anthryl) methylphosphonate], magnesium bis [(9-anthryl) ) Ethyl methyl phosphonate], sodium [ethyl 4-hydroxybenzyl phosphonate], magnesium bis [ethyl 4-hydroxybenzyl phosphonate], sodium [phenyl chlorophenyl phosphonate], magnesium bis [4-chlorobenzyl phosphonate ethyl] ], Sodium [methyl 4-aminobenzylphosphonate], magnesium bis [methyl 4-aminobenzylphosphonate], sodium phenylphosphonate, magnesium bis [phenylphosphonate] Ethyl phosphate], zinc bis [phenylphosphonic acid ethyl] and the like. Among these, lithium [ethyl (1-naphthyl) methylphosphonate], sodium [ethyl (1-naphthyl) methylphosphonate], magnesium bis [(1-naphthyl) methylphosphonate], lithium [ethyl benzylphosphonate], Sodium [ethyl benzylphosphonate],
Magnesium bis [ethyl benzylphosphonate], sodium benzylphosphonate and magnesium bis [benzylphosphonic acid] are particularly preferred.

The phosphorus metal salt compound which is another preferred phosphorus compound constituting the polymerization catalyst of the present invention is at least one selected from the compounds represented by the following general formula (46).

[0063]

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((In the formula (46), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.
³ represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. R ⁴ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl. Examples of R ⁴ O ⁻ include a hydroxide ion, an alcoholate ion, an acetate ion and an acetylacetone ion. l
Represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and l + m
Is 4 or less. M represents a (l + m) -valent metal cation. n
Represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Among these, it is preferable to use at least one selected from compounds represented by the following general formula (47).

[0066]

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(In the formula (47), M ^{n +} represents an n-valent metal cation; n represents 1, 2, 3, or 4)

In the above formula (46) or (47),
M is Li, Na, K, Be, Mg, Sr, Ba, M
It is preferable to use one selected from n, Ni, Cu, and Zn because the effect of improving the catalytic activity is large. Of these, L
i, Na and Mg are particularly preferred.

The specific phosphorus metal salt compounds of the present invention include lithium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-t-t
ethyl ert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], potassium [3,5-di-tert-butyl]
-Butyl-4-hydroxybenzylphosphonate], magnesium bis [3,5-di-tert-butyl-4-]
Ethyl hydroxybenzylphosphonate], magnesium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], beryllium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate methyl], Strontium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], barium bis [3,5-
Phenyl di-tert-butyl-4-hydroxybenzylphosphonate], manganese bis [3,5-di-tert-butyl-4
-Ethyl ethyl hydroxybenzylphosphonate], nickel bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], copper bis [3,5-di-tert-butyl-4]
-Ethyl ethyl hydroxybenzylphosphonate] and zinc bis [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate]. Among them, lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [ Ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate] is particularly preferred.

Another embodiment of the present invention is a polyester polymerization catalyst comprising at least one selected from aluminum salts of phosphorus compounds. An aluminum salt of a phosphorus compound may be used in combination with another aluminum compound, a phosphorus compound, a phenol compound or the like. The aluminum salt of a phosphorus compound, which is a preferred component constituting the polymerization catalyst of the present invention, is not particularly limited as long as it is a phosphorus compound having an aluminum portion. However, the use of an aluminum salt of a phosphonic acid compound improves the catalytic activity. Is preferred. Examples of the aluminum salt of the phosphorus compound include a monoaluminum salt, a dialluminum salt, and a trialuminum salt.

Of the above-mentioned aluminum salts of phosphorus compounds, the use of a compound having an aromatic ring structure is preferred because the effect of improving the catalytic activity is large.

As the aluminum salt of the phosphorus compound constituting the polymerization catalyst of the present invention, it is preferable to use at least one selected from compounds represented by the following general formula (48) because the effect of improving the catalytic activity is large.

[0073]

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((In the formula (48), R ¹ is hydrogen, carbon number 1
Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrocarbon group of 50 to 50, a hydroxyl group, a halogen group, an alkoxyl group or an amino group. R ² is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group having 1 to 1 carbon atoms.
Represents 50 hydrocarbon groups. R ³ is hydrogen, carbon number 1-5
And represents a hydrocarbon group having 1 to 50 carbon atoms including 0 hydrocarbon group, hydroxyl group, alkoxyl group or carbonyl. l
Represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and l + m
Is 3. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

As the above R ¹ , for example, phenyl,
Examples include 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like. R above
^{As 2} , for example, hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, phenyl, naphthyl, substituted Phenyl and naphthyl groups,
And a group represented by —CH ₂ CH ₂ OH. Examples of R ³ O ⁻ include a hydroxide ion, an alcoholate ion, an ethylene glycolate ion, an acetate ion and an acetylacetone ion.

Examples of the aluminum salt of the phosphorus compound of the present invention include an aluminum salt of ethyl (1-naphthyl) methylphosphonate, an aluminum salt of (1-naphthyl) methylphosphonic acid, an aluminum salt of ethyl (2-naphthyl) methylphosphonate, and benzyl. Aluminum salt of ethyl phosphonate, aluminum salt of benzylphosphonic acid, (9
Aluminum salt of ethyl -anthryl) methylphosphonate, aluminum salt of ethyl 4-hydroxybenzylphosphonate, aluminum salt of ethyl 2-methylbenzylphosphonate, aluminum salt of phenyl 4-chlorobenzylphosphonate, methyl 4-aminobenzylphosphonate Aluminum salt of ethyl 4-methoxybenzylphosphonate, aluminum salt of ethyl phenylphosphonate, and the like. Among them, (1-
Naphthyl) aluminum salt of ethyl methylphosphonate,
Aluminum salts of ethyl benzylphosphonate are particularly preferred.

In another embodiment of the present invention, the following general formula (4)
It is a polyester polymerization catalyst comprising at least one selected from aluminum salts of phosphorus compounds represented by 9). The aluminum salt of the phosphorus compound may be used in combination with another aluminum compound, a phosphorus compound, a phenol compound, or the like. Another preferred aluminum salt of a phosphorus compound constituting the polymerization catalyst of the present invention refers to one composed of at least one selected from compounds represented by the following general formula (49).

[0078]

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((In the formula (49), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.
³ represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. R ⁴ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl. l is an integer of 1 or more, m is
Represents an integer of 0 or 1 or more, and l + m is 3. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Among these, it is preferable to use at least one selected from compounds represented by the following general formula (50).

[0081]

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(In the formula (50), R ³ is hydrogen, carbon number 1
Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrocarbon group of 50 to 50, a hydroxyl group or an alkoxyl group. R ⁴ is hydrogen,
It represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group or carbonyl. l represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and l + m is 3. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Examples of R ³ include hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, phenyl, Examples include a naphthyl group, a substituted phenyl group and a naphthyl group, and a group represented by —CH ₂ CH ₂ OH. Examples of R ⁴ O ⁻ include a hydroxide ion, an alcoholate ion, an ethylene glycolate ion, an acetate ion and an acetylacetone ion.

Examples of the aluminum salt of the phosphorus compound of the present invention include aluminum salt of ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and 3,5-di-tert-ethyl.
Aluminum salt of methyl butyl-4-hydroxybenzylphosphonate, aluminum salt of isopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,
Aluminum salts of phenyl 5-di-tert-butyl-4-hydroxybenzylphosphonate, aluminum salts of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid and the like can be mentioned. Of these, aluminum salts of ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and aluminum salts of methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.

In the present invention, it is preferable to use a phosphorus compound having at least one P-OH bond as the phosphorus compound. A phosphorus compound having at least one P-OH bond, which is a preferred phosphorus compound constituting the polymerization catalyst of the present invention,
There is no particular limitation as long as it is a phosphorus compound having at least one P-OH in the molecule. Among these phosphorus compounds,
Use of a phosphonic acid-based compound having at least one P-OH bond is preferred because the effect of improving the catalytic activity is large.

Of the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is preferred because the effect of improving the catalytic activity is large.

As the phosphorus compound having at least one P-OH bond constituting the polymerization catalyst of the present invention, when at least one selected from compounds represented by the following general formula (51) is used, the effect of improving the catalytic activity is obtained. Is preferred.

[0088]

Embedded image (In the formula (51), .R ² R ¹ is representing hydrogen, a hydrocarbon group having 1 to 50 carbon atoms containing a hydrocarbon group, a hydroxyl group or a halogen group, an alkoxyl group, or an amino group having 1 to 50 carbon atoms, Represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, n represents an integer of 1 or more, and the hydrocarbon group has an alicyclic structure such as cycloalkylhexyl or the like. It may contain a branched structure or an aromatic ring structure such as phenyl or naphthyl.) Examples of R ¹ include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl,
2-biphenyl and the like. Examples of R ² include hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, ter
t- butyl group, an aliphatic group of a long chain, a phenyl group, a naphthyl group, a substituted phenyl group or a naphthyl group, -CH ₂ CH ₂
And a group represented by OH.

Of the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is preferred because the effect of improving the catalytic activity is large.

The phosphorus compounds having at least one P-OH bond according to the present invention include ethyl (1-naphthyl) methylphosphonate, (1-naphthyl) methylphosphonic acid,
Ethyl (2-naphthyl) methylphosphonate, ethyl benzylphosphonate, benzylphosphonic acid, ethyl (9-anthryl) methylphosphonate, ethyl 4-hydroxybenzylphosphonate, ethyl 2-methylbenzylphosphonate, phenyl 4-chlorobenzylphosphonate , Methyl 4-aminobenzylphosphonate, ethyl 4-methoxybenzylphosphonate, and the like. Of these, (1
-Naphthyl) ethyl methylphosphonate and ethyl benzylphosphonate are particularly preferred.

Further, as a preferable phosphorus compound used in the present invention, a specific phosphorus compound having at least one P-OH bond can be mentioned. The specific phosphorus compound having at least one P-OH bond, which is a preferable phosphorus compound constituting the polymerization catalyst of the present invention, is at least one compound selected from the compounds represented by the following general formula (52). Say

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((In the formula (52), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.
³ represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Among these, it is preferable to use at least one selected from compounds represented by the following general formula (53).

[0094]

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(In the formula (53), R ³ is hydrogen, carbon number 1
Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrocarbon group of 50 to 50, a hydroxyl group or an alkoxyl group. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Examples of R ³ include hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, phenyl, Examples include a naphthyl group, a substituted phenyl group and a naphthyl group, and a group represented by —CH ₂ CH ₂ OH.

Specific phosphorus compounds having at least one P-OH bond according to the present invention include ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and 3,5-di-tert-butyl-ethyl. Methyl 4-hydroxybenzylphosphonate, isopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-
Phenyl hydroxybenzylphosphonate, 3,5-di-ter
Octadecyl t-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid and the like can be mentioned. Of these, ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.

A preferred phosphorus compound is represented by the following chemical formula (5)
And the phosphorus compound represented by 4).

Embedded image (In the formula (54), R ¹ represents a hydrocarbon group having ^{1 to} 49 carbon atoms, or a hydrocarbon group having ^{1 to} 49 carbon atoms including a hydroxyl group, a halogen group, an alkoxyl group, or an amino group;
R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group having 1 to 5 carbon atoms.
Represents a hydrocarbon group of 0. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure. Further, more preferably, a compound in which at least one of R ¹ , R ² , and R ^{3 in} the chemical formula (54) contains an aromatic ring structure.

Specific examples of the phosphorus compound used in the present invention are shown below.

[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

[Of 60]

The phosphorus compound used in the present invention having a large molecular weight has a large effect because it is difficult to be distilled off during polymerization.

Another phosphorus compound for which it is desirable to use the polycondensation catalyst of the present invention is at least one phosphorus compound selected from the compounds represented by the following general formula (61).

[0108]

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(In the formula (61), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.)
R ³ and R ⁴ are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, 1 to 1 carbon atoms including a hydroxyl group or an alkoxyl group.
Represents 50 hydrocarbon groups. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Of the above general formula (61), it is preferable to use at least one selected from the compounds represented by the following general formula (62) because the effect of improving the catalytic activity is high.

[0111]

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(In the above formula (62), R ³ and R ⁴ 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 alkoxyl group. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

The above R ³ and R ⁴ are, for example, short-chain aliphatic groups such as hydrogen, methyl group and butyl group, long-chain aliphatic groups such as octadecyl, phenyl group, naphthyl group and substituted phenyl group. aromatic groups such as groups or naphthyl group, -CH ₂ CH ₂
And a group represented by OH.

The specific phosphorus compound of the present invention includes 3,5
-Di-tert-butyl-4-hydroxybenzylphosphonate diisopropyl, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate di-n-butyl, 3,5-di-ter
dioctadecyl t-butyl-4-hydroxybenzylphosphonate, diphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and the like. Among these, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-
Diphenyl hydroxybenzylphosphonate is particularly preferred.

Another phosphorus compound for which it is desirable to use the polycondensation catalyst of the present invention is at least one phosphorus compound selected from the compounds represented by the chemical formulas (63) and (64).

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[0116]

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When the phosphorus compound of the present invention is used in combination, a catalyst exhibiting a sufficient catalytic effect can be obtained even if the amount of aluminum added in the polyester polymerization catalyst is small.

The amount of the phosphorus compound of the present invention to be used is preferably 0.0001 to 0.1 mol% with respect to the total number of moles of all constituent units of the polycarboxylic acid component of the obtained polyester.
More preferably, it is 0.005 to 0.05 mol%. When the addition amount of the phosphorus compound is less than 0.0001 mol%, the effect of addition may not be exhibited. When the addition amount exceeds 0.1 mol%, on the contrary, the catalytic activity as a polyester polymerization catalyst may decrease. The tendency changes depending on the amount of aluminum used and the like.

This is a technique in which an aluminum compound is used as a main catalyst component without using a phosphorus compound, and the amount of the aluminum compound used is reduced. Although there is a technique for preventing coloration due to a decrease in the property, if the cobalt compound is added to such an extent that it has a sufficient catalytic activity, the thermal stability also decreases. Therefore, it is difficult to achieve both using this technique.

According to the present invention, the use of the phosphorus compound having the above-mentioned specific chemical structure does not cause problems such as a decrease in thermal stability and the generation of foreign matters, and the addition amount of the metal-containing component as aluminum is small. However, a polymerization catalyst having a sufficient catalytic effect can be obtained, and the use of this polymerization catalyst improves the thermal stability during melt molding of polyester fibers. Even if a phosphoric acid ester such as phosphoric acid or trimethyl phosphoric acid is added in place of the phosphorus compound of the present invention, the effect of addition is not seen and it is not practical. Further, even when the phosphorus compound of the present invention is used in combination with a conventional antimony compound, a titanium compound, a tin compound, a metal-containing polyester polymerization catalyst such as a germanium compound in the range of the addition amount of the present invention, the melt polymerization reaction is promoted. No effect is observed.

It is preferable that the above-mentioned catalyst does not contain an alkali metal, an alkaline earth metal, or a compound thereof. On the other hand, in a preferred embodiment of the present invention, a small amount of at least one selected from alkali metals, alkaline earth metals and compounds thereof is coexisted as the second metal-containing component in addition to aluminum or its compound. The coexistence of such a second metal-containing component in the catalyst system increases the catalytic activity in addition to the effect of suppressing the production of diethylene glycol, and thus provides a catalyst component with a higher reaction rate, which is effective for improving productivity. .

It is known that a catalyst having sufficient catalytic activity can be obtained by adding an alkali metal compound or an alkaline earth metal compound to an aluminum compound. The use of such a known catalyst can provide a polyester having excellent thermal stability. However, the known catalyst using an alkali metal compound or an alkaline earth metal compound in combination is not suitable for obtaining a practical catalytic activity. When an alkali metal compound is used, the amount of foreign matters caused by the use of the alkali metal compound increases, and the fiber-forming properties and yarn physical properties of the fiber deteriorate. In addition, when an alkaline earth metal compound is used in combination, the thermal stability and thermal oxidative stability of the obtained polyester are reduced in order to obtain practical activity, the coloring due to heating is large, and the amount of foreign matter generated is also small. More. When an alkali metal, an alkaline earth metal and a compound thereof are added, the amount of use M (mol%) is
It is preferably from 1 × 10 ^{−6 to} less than 0.1 mol%, more preferably from 5 × 10 ^{−6 to} 0.05, based on the number of moles of all the polycarboxylic acid units constituting the polyester.
Mol%, more preferably 1 × 10 ^{−5 to} 0.03.
Mol%, particularly preferably 1 × 10 ^{−5 to} 0.01.
Mol%. Since the added amount of the alkali metal and the alkaline earth metal is small, the reaction rate can be increased without causing problems such as a decrease in thermal stability, generation of foreign matter, and coloring. Further, the reaction rate can be increased without causing a problem such as a decrease in hydrolysis resistance. When the amount M of the alkali metal, alkaline earth metal and its compound is 0.1 mol% or more, a decrease in thermal stability, an increase in generation of foreign substances and an increase in coloration, a decrease in hydrolysis resistance, and the like become problems in product processing. Cases occur. If M is less than 1 × 10 ⁻⁶ mol%, the effect is not clear even if added.

In the present invention, the alkali metal and alkaline earth metal constituting the second metal-containing component which is preferably used in addition to aluminum or its compound include Li, Na, K, Rb, Cs, Be, Mg, Ca,
It is preferably at least one selected from Sr and Ba, and more preferably an alkali metal or a compound thereof. When an alkali metal or a compound thereof is used, it is particularly preferable to use Li, Na, and K. Examples of the alkali metal or alkaline earth metal compound include, for example, saturated aliphatic carboxylate such as formic acid, acetic acid, propionic acid, butyric acid, and oxalic acid, and unsaturated aliphatic carboxylate such as acrylic acid and methacrylic acid. Aromatic carboxylate such as benzoic acid, halogen-containing carboxylate such as trichloroacetic acid, hydroxycarboxylate such as lactic acid, citric acid, salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, phosphorus Inorganic acid salts such as oxyhydrogen, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, and bromic acid; and organic sulfonic acid salts such as 1-propanesulfonic acid, 1-pentanesulfonic acid, and naphthalenesulfonic acid , Organic sulfates such as lauryl sulfate, methoxy, ethoxy, n
-Propoxy, iso-propoxy, n-butoxy, t
alkoxides such as tert-butoxy, chelate compounds with acetylacetonate and the like, hydrides, oxides,
Hydroxide and the like. Among these alkali metals, alkaline earth metals or compounds thereof, when those having strong alkalinity such as hydroxides are used, they tend to be hardly dissolved in organic solvents such as diols such as ethylene glycol or alcohols. However, it must be added to the polymerization system in an aqueous solution, which may cause a problem in the polymerization step. Furthermore, when a strong alkali such as a hydroxide is used, the polyester is liable to undergo side reactions such as hydrolysis during polymerization, and the polymerized polyester tends to be colored, and the hydrolysis resistance is also reduced. Tend to. Accordingly, the alkali metal or a compound thereof, or an alkaline earth metal or a compound thereof according to the present invention is preferably a saturated aliphatic carboxylate, an unsaturated aliphatic carboxylate, an aromatic salt of an alkali metal or an alkaline earth metal. Group carboxylate, halogen-containing carboxylate, hydroxycarboxylate, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid,
An inorganic acid salt selected from hydrobromic acid, chloric acid, and bromic acid, an organic sulfonate, an organic sulfate, a chelate compound, and an oxide. Among these, from the viewpoints of ease of handling and availability, it is preferable to use an alkali metal or alkaline earth metal saturated aliphatic carboxylate, particularly an acetate.

The polyester used in the present invention preferably has a thermal stability parameter (TS) satisfying the following formula (1). (1) TS <0.30 where TS has an intrinsic viscosity ([IV] i) of about 0.65
dl / g of PET was placed in a glass test tube and vacuum dried at 130 ° C. for 12 hours.
C. for 2 hours in a molten state ([I
V] f) is a numerical value calculated by the following equation. The non-circulating nitrogen atmosphere means a nitrogen atmosphere that does not flow,
For example, a glass test tube containing a resin chip is connected to a vacuum line, and after reducing pressure and filling nitrogen five times or more, nitrogen is sealed to 100 Torr and sealed. TS = 0.245 {[IV] f -1.47 - [IV] i
^-1.47 ｝ TS is more preferably 0.25 or less,
Particularly preferred is 20 or less. The polyester used in the present invention has a thermo-oxidative stability parameter (TO).
S) preferably satisfies the following expression (2). (2) TOS <0.10 In the above formula, TOS has a melt-polymerized IV of about 0.65d0
0.3 g was vacuum-dried at 12 ° C. for 12 hours, placed in a glass test tube, and PET resin chips of 1 / g were frozen and pulverized at 70 ° C. for 12 hours to obtain a powder of 20 mesh or less, 13 vacuum-dried, and then dried over silica gel. 230 ° C under air, 1
It is determined from the IV after heating for 5 minutes using the following formula. TOS = 0.245 ° [IV] f1 ^1.47 − [IV] i
^-1.47 ｝ [IV] i and [IV] f1 indicate the IV (dl / g) before and after the heating test, respectively. As a method of heating under air dried with silica gel, for example, a method of connecting a drying tube containing silica gel to the upper part of a glass test tube and heating under dry air can be exemplified. TOS is
More preferably 0.09 or less, still more preferably 0.09
8 or less. The polyester used in the present invention preferably has a hydrolysis resistance parameter (HS) satisfying the following formula (3). (3) HS <0.10 (HS has an intrinsic viscosity of about 0.65 d obtained by melt polymerization.
1 / g (before the test: [IV] i) PET chips were frozen and pulverized to form a powder having a size of 20 mesh or less at 130 ° C.
After vacuum drying for 2 hours, 1 g thereof was put into a beaker together with 100 ml of pure water, heated in a closed system at 130 ° C., and stirred for 6 hours under a pressurized condition to obtain an intrinsic viscosity ([IV] f).
2) is a numerical value calculated by the following equation. HS = 0.245 ｛[IV] f2 ^-1.47- [IV] i
^-1.47 i) Use a beaker that does not elute acid or alkali for the measurement of HS. Specifically, it is preferable to use a stainless beaker or a quartz beaker. HS is more preferably 0.09 or less, particularly preferably 0.085 or less. The polyester used in the present invention preferably has a solution haze value (Haze) of the polyester satisfying the following formula (4). (4) Haze <3.0 (%) In the above formula, Haze has a melt-polymerized intrinsic viscosity of about 0.6.
A 5 dl / g polyethylene terephthalate (PET) resin chip was treated with p-chlorophenol / 1,1,2,2-
The values are shown by dissolving in a 3/1 mixed solvent of tetrachloroethane (weight ratio) to make a solution of 8 g / 100 ml, and using a haze meter. The measurement of the haze was performed using a cell length of 1 cm.
The above-mentioned solution was filled using the cell of No. 1 and the measurement was performed. Haz
e is more preferably 2.0 or less, still more preferably 1.0 or less. In the present invention, TS, TOS, H
As a PET resin chip used for measuring S and Haze, a resin resin chip produced by quenching from a molten state after melt polymerization is used. The shape of the resin chip used for these measurements is, for example, about 3 mm in length and about 2 mm in diameter.
Use a mm-shaped cylinder-shaped resin tip. In the case of performing color measurement, a resin chip which is substantially amorphous and produced by quenching from a molten state after a melt polymerization step is used. As a method of obtaining a substantially amorphous resin chip, for example, when taking out the polymer from the reaction system after melt polymerization, quenching with cold water immediately after discharging the polymer from the discharge port of the reaction system, then sufficient cooling For example, a method of holding in cold water for a time and then cutting it into chips may be used. The resin chip thus obtained is transparent in appearance without whitening due to crystallization. The resin chip obtained in this way is
After air-drying on a filter paper etc. at room temperature for about 24 hours, it is used for color measurement. Even after the above-mentioned operation, the resin chip remains transparent in appearance without whitening due to crystallization.
It should be noted that no additive affecting the appearance such as titanium dioxide is used for the resin chip for color measurement. As the shape of the resin chip used for color measurement, for example,
A cylindrical resin tip having a length of about 3 mm and a diameter of about 2 mm is used. In a preferred embodiment, the polyester fiber of the present invention further contains a cobalt compound as a cobalt atom in an amount of less than 10 ppm based on the polyester.

It is known that the cobalt compound itself has a certain degree of polymerization activity. However, as described above, when the cobalt compound is added to such an extent that a sufficient catalytic effect is exhibited, the decrease in the brightness of the obtained polyester fiber and A decrease in thermal stability occurs. The polyester fiber obtained according to the present invention has good color tone and thermal stability, but can be obtained by adding a cobalt compound in such an amount that the catalytic effect by adding a small amount as described above is not clear. The coloring can be more effectively eliminated without lowering the brightness of the resulting polyester fiber. The purpose of the cobalt compound in the present invention is to eliminate coloration, and it may be added at any stage of the polymerization or after the completion of the polymerization reaction.

The cobalt compound is not particularly limited, but specific examples thereof include cobalt acetate, cobalt nitrate,
Cobalt chloride, cobalt acetylacetonate, cobalt naphthenate, and hydrates thereof are exemplified. Among them, cobalt acetate tetrahydrate is particularly preferred.

The addition amount of the cobalt compound is such that the total of the aluminum atoms and the cobalt atoms is 50 ppm or less and the cobalt atoms are 10 pp with respect to the polymer finally obtained.
It is preferably less than m. More preferably, the total of aluminum atoms and cobalt atoms is 40 ppm or less,
The cobalt atom is 8 ppm or less, more preferably the total of the aluminum atom and the cobalt atom is 25 ppm or less, and the cobalt atom is 5 ppm or less. From the viewpoint of the thermal stability of the polyester, the total of aluminum atoms and cobalt atoms is less than 50 ppm,
It is preferably at most 0 ppm. In order to have sufficient catalytic activity, the total amount of aluminum atoms and cobalt atoms is preferably more than 0.01 ppm.

The polyester polymer used for the production of the polyester fiber in the present invention can be produced by a method having a conventionally known process except that the polyester polymerization catalyst of the present invention is used as a catalyst. For example, when producing PET, after esterification of terephthalic acid and ethylene glycol, a method of polycondensation, or after performing an ester exchange reaction between an alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol, Any of the polycondensation methods can be used. The polymerization apparatus may be of a batch type or a continuous type.

The catalyst of the present invention has catalytic activity not only in a polymerization reaction but also in an esterification reaction and a transesterification reaction. For example, polymerization by transesterification of an alkyl ester of a dicarboxylic acid such as dimethyl terephthalate with a glycol such as ethylene glycol is usually carried out in the presence of a transesterification catalyst such as a titanium compound or a zinc compound. Alternatively, or in combination with these catalysts, the catalyst of the present invention can be used. In addition, the catalyst of the present invention has catalytic activity not only in melt polymerization but also in solid phase polymerization and solution polymerization, and it is possible to produce a polyester polymer suitable for producing polyester fibers by any method. It is. Further, the polyester fiber of the present invention can be produced by a conventional melt spinning method, and a method of performing spinning and drawing in two steps and a method of performing spinning and drawing in one step can be adopted. Further, all known fiber production methods such as a method for producing staples provided with crimping, heat setting and cutting steps can be applied.

The polymerization catalyst of the present invention can be added to the reaction system at any stage of the polymerization reaction. For example, it can be added to the reaction system before the start of the esterification reaction or transesterification reaction and at any stage during the reaction, immediately before the start of the polycondensation reaction, or at any stage during the polycondensation reaction. In particular, it is preferable to add aluminum or its compound immediately before the start of the polycondensation reaction.

The method of adding the polycondensation catalyst of the present invention may be a powdery or neat addition, or a slurry or solution addition of a solvent such as ethylene glycol. Not limited. Further, a mixture of aluminum metal or a compound thereof and another component, preferably a phenolic compound or a phosphorus compound of the present invention, may be added in advance, or they may be added separately. Further, the aluminum metal or its compound and another component, preferably a phenolic compound or a phosphorus compound, may be added to the polymerization system at the same time, or they may be added at different times.

The polymerization catalyst of the present invention comprises an antimony compound,
Other polymerization catalysts such as titanium compounds, germanium compounds, and tin compounds are allowed to coexist within the range of the addition amount in which the addition of these components does not cause a problem in the properties of the polyester, processability, color tone, etc. as described above. The use is advantageous and preferable in improving productivity by shortening the polymerization time.

However, as the antimony compound, as an antimony atom, a polyester obtained by polymerization is used.
It can be added in an amount of 50 ppm or less. More preferably 30 ppm
It is to be added in the following amount. The amount of antimony added
If it exceeds 50 ppm, precipitation of metallic antimony occurs, and blackening or foreign matter is generated in the polyester, which is not preferable.

The titanium compound can be added in a range of 10 ppm or less based on the polymer obtained by polymerization. More preferably 5ppm or less, more preferably 2ppm
It is to be added in the following amount. Add 10ppt titanium
If it is larger than m, the thermal stability of the obtained resin is significantly reduced.

The germanium compound can be added to the polyester obtained by polymerization in an amount of 20 ppm or less as a germanium atom. More preferably 10
It is to be added in the amount of ppm or less. If the amount of germanium added is more than 20 ppm, it is not preferable because it is disadvantageous in terms of cost.

When polymerizing a polyester using the polymerization catalyst of the present invention, one or more of an antimony compound, a titanium compound, a manium compound, and a tin compound can be used.

The antimony compound, titanium compound, germanium compound and tin compound used in the present invention are not particularly limited.

Specifically, as the antimony compound,
Examples include antimony trioxide, antimony pentoxide, antimony acetate, antimony glycooxide, and the like. Of these, antimony trioxide is preferable.

The titanium compound is tetra-n-
Propyl titanate, tetraisopropyl titanate,
Tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetracyclohexyl titanate, tetraphenyl titanate, titanium oxalate and the like.
-Butoxytitanate is preferred.

Examples of the germanium compound include germanium dioxide and germanium tetrachloride. Of these, germanium dioxide is preferable.

Examples of the tin compound include dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, triethyltin hydroxide, monobutylhydroxytin oxide, triisobutyltin acetate, diphenyltin dilaurate, monobutyltin trilaurate. Examples thereof include chloride, dibutyltin sulfide, dibutylhydroxytin oxide, methylstannoic acid, and ethylstannoic acid, and the use of monobutylhydroxytin oxide is particularly preferable.

The polyester referred to in the present invention is one or more selected from polycarboxylic acids containing dicarboxylic acids and their ester-forming derivatives and one or more selected from polyhydric alcohols containing glycol. Or those composed of hydroxycarboxylic acids and their ester-forming derivatives, or those composed of cyclic esters.

The dicarboxylic acids include oxalic acid, malonic acid,
Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,3-cyclocyclohexane Pentanedicarboxylic acid,
Saturated aliphatic dicarboxylic acids exemplified by 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid, and the like, and their ester-forming properties Derivatives, unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid and the like and ester-forming derivatives thereof, orthophthalic acid, isophthalic acid, terephthalic acid, 5- (alkali metal) sulfoisophthalic acid, diphenic acid 1,3 naphthalenedicarboxylic acid, 1,4 naphthalenedicarboxylic acid, 1,5 naphthalenedicarboxylic acid, 2,6 naphthalenedicarboxylic acid, 2,7 naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4'-biphenylsulfone dicarboxylic acid, 4,4'-biphe Aromatic dicarboxylic acids exemplified by enyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid and the like, and ester-forming derivatives thereof are exemplified.

Of these dicarboxylic acids, terephthalic acid and naphthalenedicarboxylic acid, particularly 2,6 naphthalenedicarboxylic acid, are preferred in view of the physical properties of the resulting polyester, and other dicarboxylic acids may be used as a component if necessary.

Examples of polycarboxylic acids other than these dicarboxylic acids include ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ′, 4′-biphenyltetracarboxylic acid. Examples include carboxylic acids and their ester-forming derivatives.

As the glycol, ethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2 butylene glycol, 1,3 butylene glycol, 2,3 butylene glycol, 1,4 butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,
2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,
Aliphatic glycols exemplified by 4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, etc., hydroquinone, 4,4'-dihydroxybisphenol 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis (β-hydroxyethoxyphenyl) sulfone, bis (p-hydroxyphenyl) ether, bis (p-hydroxyphenyl) sulfone, bis (p-hydroxy Phenyl) methane, 1,2-bis (p
-Hydroxyphenyl) ethane, bisphenol A, bisphenol C, 2,5 naphthalene diol, and aromatic glycols exemplified by ethylene glycol added to these glycols.

Among these glycols, ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol and 1,4-cyclohexanedimethanol are preferred.

As polyhydric alcohols other than these glycols, trimethylolmethane, trimethylolethane,
Trimethylolpropane, pentaerythritol, glycerol, hexanetriol and the like.

The hydroxycarboxylic acids include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid, Or, an ester-forming derivative thereof and the like.

Examples of the cyclic ester include ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycolide, lactide and the like.

Examples of the ester-forming derivatives of polycarboxylic acids or hydroxycarboxylic acids include their alkyl esters, acid chlorides and acid anhydrides.

The polyester used in the present invention is preferably a polyester whose main acid component is terephthalic acid or its ester-forming derivative or naphthalenedicarboxylic acid or its ester-forming derivative, and whose main glycol component is an alkylene glycol.

The polyester in which the main acid component is terephthalic acid or its ester-forming derivative or naphthalenedicarboxylic acid or its ester-forming derivative is referred to as terephthalic acid or its ester-forming derivative and naphthalenedicarboxylic acid or It is preferable that the polyester is a polyester containing at least 70 mol% of the ester-forming derivative in total, more preferably a polyester containing at least 80 mol%, more preferably
It is a polyester containing 90 mol% or more.

The polyester in which the main glycol component is an alkylene glycol is preferably a polyester containing alkylene glycol in a total amount of at least 70 mol% based on all glycol components, more preferably
It is a polyester containing 80 mol% or more, and more preferably a polyester containing 90 mol% or more. The alkylene glycol mentioned here may contain a substituent or an alicyclic structure in the molecular chain.

The naphthalenedicarboxylic acid or ester-forming derivative thereof used in the present invention includes 1,3 naphthalenedicarboxylic acid, 1,4 naphthalenedicarboxylic acid, 1,5 naphthalenedicarboxylic acid, and 2,6 naphthalenedicarboxylic acid. Acid, 2,7 naphthalene dicarboxylic acid,
Alternatively, these ester-forming derivatives are preferred.

Examples of the alkylene glycol used in the present invention include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol,
3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1.4
-Cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol,
1,12-dodecanediol and the like. Two or more of these may be used simultaneously.

The polyester of the present invention includes polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, poly (1,4-cyclohexane dimethylene terephthalate), polyethylene naphthalate, polybutylene naphthalate, polypropylene naphthalate and copolymers thereof. Of these, polyethylene terephthalate and its copolymer are particularly preferred.

The intrinsic viscosity of the polyester in the present invention is preferably from 0.4 to 1.2 dl / g.
If it is less than 0.4 dl / g, the resulting polyester mixed yarn lacks strength. Conversely, it is not preferable to produce a polymer exceeding 1.2 dl / g because the solid-phase polymerization requires a long time and the cost increases. More preferably, 0.4 to 0.1.
8 dl / g, more preferably 0.4 to 0.7 dl / g
It is.

The polyester fiber constituting at least a part of the polyester mixed fiber of the present invention can be produced by a conventional melt spinning method, and a method of performing spinning and drawing in two steps and a method of performing one step. Can be adopted. Further, the mixed yarn includes a yarn composed of at least two or more kinds of fibers having different dyeing properties, a mixed yarn composed of fibers having different finenesses, yarn cross sections, and the like. It is preferably a yarn, and more preferably a self-extended mixed fiber. All of the conventionally known fiber manufacturing methods can be applied to those manufacturing methods.

[0160]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The construction and effects of the present invention will be described below based on embodiments, but the present invention is not limited to these embodiments.

The evaluation method used in the present invention will be described below. [Evaluation method] 1) Intrinsic viscosity (IV) Polyester was dissolved in a 6/4 (weight ratio) mixed solvent of phenol / 1,1,2,2-tetrachloroethane and measured at a temperature of 30 ° C.

2) Thermal stability parameter (TS) The melt-polymerized IV was about 0.65 dl / g (before the melt test;
[IV] 1 g of PET resin chip of _i ) was placed in a glass test tube, vacuum-dried at 130 ° C. for 12 hours, and then kept in a molten state at 300 ° C. for 2 hours under a nitrogen atmosphere.
(After the melting test; IV] _f2 ), using the following formula. The formula was quoted from a previous report (Ueyama et al .: The Journal of the Rubber Society of Japan, Vol. 63, No. 8, page 497, 1990). TS = 0.245 ｛[IV] _f2 ^-1.47 − [IV] _i
^-1.47 ｝.

3) Thermal Oxidation Stability Parameter (TOS) 0.3 g of a melt-polymerized PET resin chip having an IV of about 0.65 dl / g, vacuum-dried at 130 ° C. for 12 hours after freeze-crushing, is put into a glass test tube. After vacuum drying at 70 ° C for 12 hours, 230 ° C under air dried with silica gel,
From the IV after heating for 15 minutes, it was determined using the same formula below as for TS described above. Here, [IV] _i and [IV] _f1 are the IV before and after the heating test, respectively.
(Dl / g). TOS = 0.245 ｛[IV] _f1 ^-1.47 − [IV] _i
^-1.47 ｝.

4) Hydrolysis resistance parameter (HS) The intrinsic viscosity obtained by melt polymerization is about 0.65 dl / g.
The PET resin chip (before the test; [IV] _i ) was frozen and pulverized by a conventional method, and 1 g of the PET resin chip was put into a beaker together with 100 ml of pure water. . The IV of the PET after the test was measured ([IV] _f2 ), and the hydrolysis resistance parameter (HS) was determined by the following equation. HS = 0.245 ｛[IV] _f2 ^-1.47- [IV] _i
^-1.47 ｝

5) Color delta b value parameter (Δ
b) PE having an IV of about 0.65 dl / g obtained by melt polymerization
Using a T resin chip and a color difference meter (manufactured by Tokyo Denshoku Co., Ltd.), the b value of the hunter was measured, and 0.05 mol% of antimony trioxide was used as an antimony atom with respect to the acid component of PET. The b value of PET polymerized by the above was subtracted.

6) Solution Haze Value (Haze) A melt-polymerized PET resin chip having an IV of about 0.65 dl / g was mixed with a 3/1 mixed solvent of p-chlorophenol / 1,1,2,2-tetrachloroethane (weight Ratio) to give a solution of 8 g / 100 ml, and measured at room temperature using a turbidity meter NDH2000 of Nippon Denshoku Industries Co., Ltd. The measuring method is based on JIS standard JIS-K7105, and the cell length is 1 cm.
The diffused transmitted light (DF) and the total light transmitted light (TT) of the solution were measured using the cell (1), and Haze (%) was determined from the calculation formula Haze (%) = (DF / TT) × 100.

7) Evaluation of operability during spinning, drawing and blending, operability during spinning was the number of yarn breaks during 14 days of 8 nozzles, and operability during drawing was the number of spindles below the yarn break during continuous operation. Was evaluated from. ○: Long-term continuous production possible △: Continuous production possible ×: Production impossible

8) Fiber breaking strength and breaking elongation Using Orientec Tensilon, the measurement sample length was 2
The breaking strength and the breaking elongation were determined at 0 cm and a crosshead speed of 200 mm / min, and evaluated by the average of the values measured repeatedly five times.

9) Shrinkage at 160 ° C. (SH)
D) First, a load of 1/33 (gram / decitex) is applied to the sample, and its length L0 (mm) is measured. Next, the above-mentioned load was removed, and the sample was put in a drier and dried
Dry for 0 minutes. After that, it is cooled and a load of 1/33 (gram / decitex) is applied again to the length L1 (mm).
Is measured. The dry heat shrinkage (SHD) is calculated by substituting the above L1 and L2 into the following equation. The measurement is performed five times, and the average value is defined as the dry heat shrinkage. SHD (%) = (L0−L1) / L0 × 100

Example 1 A mixture of bis (2-hydroxyethyl) terephthalate and oligomer prepared from high-purity terephthalic acid and ethylene glycol by a conventional method using a 2-liter stainless steel autoclave equipped with a heating wire heater equipped with a stirrer. On the other hand, a 2.5 g / l ethylene glycol solution of aluminum acetylacetonate as a polycondensation catalyst is 0.015 mol% as an aluminum atom with respect to the acid component in the polyester and a 10 g / l ethylene glycol solution of dimethyl phenylphosphonate. With respect to the acid component as 0.03 mol% as dimethyl phenylphosphonate, and lithium acetate dihydrate 5
0.025 mol% of a 0 g / l ethylene glycol solution as a lithium atom was added to the acid component, and the mixture was stirred at 245 ° C. for 10 minutes under a nitrogen atmosphere at normal pressure. Then 50
The pressure of the reaction system was gradually lowered while raising the temperature to 275 ° C. over a period of 1 minute to 13.3 Pa (0.1 Torr), and the polycondensation reaction was further performed at 275 ° C. and 13.3 Pa.

The polyethylene terephthalate has an IV of 0.
Polymerization time required to reach 65 dl / g (AP)
Was 80 minutes, and the polycondensation catalyst had a practical polymerization activity.

Further, polyethylene terephthalate having an IV of 0.65 dl / g obtained by the above polycondensation was formed into chips according to a conventional method. A melting test was performed using this PET resin chip to determine a thermal stability parameter (TS). TS was 0.18, and the thermal stability was good.

The chipped PET resin was pulverized according to a conventional method, and a thermal test was performed using the powder to determine a thermal oxidation stability parameter (TOS). TOS was 0.07, and PET obtained using the polycondensation catalyst of the present invention was also excellent in thermal oxidation stability.

The color b value was determined using the PET resin chipped. The color b value was 4.1. Similarly, a solution haze value (Haze) was obtained using the chipped PET resin. Haze was 0.1.

After drying the PET resin chip obtained by melt polymerization, it is supplied to a melt extruder, discharged from a spinneret having 18 orifices having a hole diameter of 0.24 mmΦ at 288 ° C., cooled and oiled according to a conventional method. It was withdrawn at 3000 m / min. The highly oriented undrawn yarn was used as a sheath yarn, followed by a preheating roller at 80 ° C. and a set temperature of 150 ° C. for 1.6 hours.
The film was drawn five times to obtain a drawn polyester yarn of 30 dtex and 18 filaments. The dry heat shrinkage of the sheath yarn was 6%. On the other hand, as a core yarn, a preheating roller is stretched to 1.65 times without heat setting at 80 ° C. and 30 dtex,
An 18 filament drawn polyester yarn was obtained. The dry heat shrinkage of the core yarn was 20%. Each yarn was aligned and interlaced and mixed at 500 m / min to obtain a polyester mixed yarn of 60 decitex and 36 filaments. The operability in spinning and drawing was very good, and the operability in blending was also good. The mechanical properties of the yarn obtained were not problematic for use in clothing applications.

Example 2 As a polycondensation catalyst, a 2.5 g / l ethylene glycol solution of aluminum acetylacetonate was used in an amount of 0.015 mol% as an aluminum atom with respect to the acid component in the polyester and cobalt (II) acetate water 0.005 mol% of an ethylene glycol solution of 50 g / l of a hydrate as a cobalt atom with respect to an acid component
In addition, the PET resin chip obtained by performing the polycondensation reaction is dried, supplied to a melt extruder, discharged at 290 ° C. from a spinneret having 18 orifices having a hole diameter of 0.18 mmΦ, cooled and oiled according to a conventional method. 3,000 m / min. The highly oriented undrawn yarn was used as a sheath yarn, and the preheated roller was kept at 80 ° C. without heat setting for 1.5 hours.
The film was drawn five times to obtain a drawn polyester yarn of 20 dtex and 18 filaments. The drawn polyester yarn is
90 ° C non-contact heater with retention time 0.06
After passing through at an overfeed ratio of 50% in seconds, the polyester mixed yarn of 60 dtex 36 filaments was obtained by interlacing with the core yarn of Example 1 just before winding. The heat shrinkage of the sheath heat-treated was -4%, indicating self-elongation. The operability in spinning and drawing was very good, and the operation of mixed fiber was also good. The mechanical properties of the yarn obtained were not problematic for use in clothing applications.

Example 3 A 2.5 g / l ethylene glycol solution of aluminum acetylacetonate was used as a polycondensation catalyst in an amount of 0.01 mol% as aluminum atoms with respect to the acid component in the polyester and 50 g of lithium acetate dihydrate. / L ethylene glycol solution was added to the acid component as a lithium atom in an amount of 0.1 mol% as a lithium atom to carry out a polycondensation reaction. The obtained PET resin chip was dried, fed to a melt extruder, and subjected to 84 dtex by a conventionally known method. Trifilament cross-section fiber with irregularity 3 of 24 filaments and 55
Loop mixed fiber was obtained by mixing different kinds of hollow fibers having a hollow rate of 20% of decitex filaments with different overfeed ratios of the trilobal section fiber and the hollow section fiber of 30% and 5%, respectively. The operability in spinning and drawing was very good, and the operability in blending was also good. The mechanical properties of the yarn obtained were not problematic for use in clothing applications.

(Comparative Example 1) The same operation as in Example 1 was carried out except that antimony trioxide was used as a catalyst in an amount of 0.05 mol% as antimony atom based on an acid component in PET. went. AP was 65 minutes, TS was 0.22, and TOS was 0.01, and these physical properties were excellent. Moreover, the yarn breakage when the obtained polyester was melt-spun and the yarn breakage ratio during stretching were inferior to those in Example 1, as in Example 1.

Further, the color b value was determined using the PET resin chipped in Comparative Example 1. The color b value was 1.1. Δb <4.0 with respect to the color b value of Examples 1 to 3.
Met.

[0180]

[Table 1]

The same effect as in the above example was obtained by using the following phosphorus compounds A and B as the polymerization catalyst and the aluminum salt of the phosphorus compound obtained by the following method. The structural formula of the phosphorus compound A is as shown below.

[0182]

Embedded image

The structural formula of the phosphorus compound A is as shown below.

[0184]

Embedded image

(Synthesis Example of Aluminum Salt of Phosphorus Compound) O-ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphon
Synthesis of aluminum salt of ate (aluminum salt A)

1.Sodium (O-ethyl 3,5-di-tert-butyl-4-h
Synthesis of ydroxybenzylphosphonate) Diethyl (3,5-di-tert-butyl-4-h) in a mixed solution of 6.5 g (84 mmol) of a 50% aqueous sodium hydroxide solution and 6.1 ml of methanol
6.1 ml of a methanol solution of 5 g (14 mmol) of ydroxybenzyl) phosphonate was added, and the mixture was heated and refluxed for 24 hours under a nitrogen atmosphere. After the reaction, 7.33 g of concentrated hydrochloric acid (7
0 mmol), and the precipitate was collected by filtration, washed with isopropanol, and the filtrate was evaporated under reduced pressure. The obtained residue was dissolved in hot isopropanol, the insoluble matter was collected by filtration, and isopropanol was distilled off under reduced pressure.
dium (O-ethyl 3,5-di-tert-butyl-4-hydroxybenzylpho
3.4g (69%) of sphonate). Shape: white powder Melting point: 294-302 ° C (decomposition) ¹ H-NMR (DMSO, δ): 1.078 (3H, t, J = 7Hz), 1.354 (18H,
s), 2.711 (2H, d), 3.724 (2H, m, J = 7Hz), 6.626 (1H,
s), 6.9665 (2H, s) Elemental analysis (theoretical values in parentheses): Na 6.36% (6.56%), P
9.18% (8.84%)

2.O-ethyl 3,5-di-tert-butyl-4-hydroxy
Synthesis of aluminum salt of benzylphosphonate (aluminum salt A) Sodium (O-ethyl 3,5-di-tert-butyl-4-
Hydroxybenzylphosphonate) 1 g (2.8 mmol) aqueous solution 7.5
5 ml of an aqueous solution of 364 mg (0.97 mmol) of aluminum nitrate nonahydrate was added dropwise to the ml. After stirring for 3 hours, the precipitate was collected by filtration, washed with water, and dried to obtain O-ethyl 3,5-di-tert-butyl-4-hydroxybe.
860 mg of aluminum salt of nzylphosphonate was obtained. Shape: white powder Melting point: 183-192 ℃

[0188]

According to the present invention, it has become possible to supply a polyester blended fiber which is excellent in heat stability and environmentally safe.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Shoichi Katamai 2-1-1 Katata, Otsu-shi, Shiga F-term in Toyobo Co., Ltd. Research Laboratory 4J029 AA01 AA02 AA03 AB04 AC01 AC02 AE02 BA02 BA03 BA04 BA05 BA07 BA08 BA09 BA10 BB05A BB09A BB10A BC05A BC06A BD03A BD04A BF09 BF18 CA02 CA03 CA04 CA05 CA06 CA09 CB04A CB05A CB06A CC03A CC05A CC06A CD03 J14 HA15 J01 EA03 EB03A 01 BB91 CC11 DD15 EE02 GG02 4L036 MA05 MA33 MA39 MA40 PA01 PA03 PA33 PA46 RA03 UA08 UA26

Claims (33)

[Claims] A polyester mixed fiber comprising at least a part of a polyester fiber polymerized by using a catalyst containing aluminum and / or a compound thereof and a phenolic compound. 2. A polyester mixed fiber comprising at least a part of a polyester fiber polymerized by using a catalyst containing aluminum and / or a compound thereof and a phosphorus compound. 3. A polyester mixed fiber yarn comprising the polyester according to claim 1, wherein a catalyst further containing a phosphorus compound is used as the catalyst. 4. The phosphorus compound is one or more selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds, and phosphine compounds. The polyester mixed fiber yarn according to claim 2 or 3, which is a compound of the following. 5. The polyester mixed fiber yarn according to claim 2, wherein the phosphorus compound is one or more phosphonic acid compounds. 6. The polyester mixed yarn according to claim 2, wherein the phosphorus compound is a compound having an aromatic ring structure. 7. The compound represented by the following general formulas (1) to (3):
The polyester mixed fiber yarn according to any one of claims 2 to 6, which is one or more selected from the group consisting of compounds represented by the following formulae. Embedded image Embedded image Embedded image (In the formulas (1) to (3), R ¹ , R ⁴ , R ⁵ , and R ⁶ each independently include hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group. Represents a hydrocarbon group having 1 to 50 carbon atoms, R ² and R ³ 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 alkoxyl group. However, the hydrocarbon group may contain an alicyclic structure or an aromatic ring structure.) 8. R ¹ , R ⁴ , R ⁵ , R ^{6 in the} formulas (1) to (3)
Is a group having an aromatic ring structure. 9. The polyester mixed fiber yarn according to claim 2, wherein the phosphorus compound has a phenol moiety in the same molecule. 10. The compound according to claim 9, wherein the phosphorus compound having a phenol moiety in the same molecule is one or more selected from the group consisting of compounds represented by the following general formulas (4) to (6). Polyester mixed yarn. Embedded image Embedded image Embedded image (In the formulas (4) to (6), R ¹ is a hydrocarbon group having 1 to 50 carbon atoms including a phenol moiety, a hydroxyl group or a halogen group or an alkoxyl group or an amino group and a carbon atom having 1 to 50 carbon atoms including a phenol moiety. R ⁴ , R ⁵ and R ⁶ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a hydrocarbon group having 1 to 50 carbon atoms including a halogen group, an alkoxyl group or an amino group; R ² and R ³ 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 alkoxyl group, provided that the hydrocarbon group has a branched structure. Or an alicyclic structure or an aromatic ring structure. The terminals of R ² and R ⁴ may be bonded to each other.) 11. The polyester mixed yarn according to claim 2, wherein the phosphorus compound is at least one kind of a metal salt compound of phosphorus. 12. The method according to claim 12, wherein the metal part of the metal salt compound of phosphorus is L
i, Na, K, Be, Mg, Sr, Ba, Mn, Ni,
12. The method according to claim 11, wherein the material is selected from Cu and Zn.
The polyester blended yarn according to 1. 13. The polyester fiber blend according to claim 11, wherein the metal salt compound of phosphorus is at least one selected from compounds represented by the following general formula (7). Embedded image (In formula (7), R ¹ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a halogen group, or a hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl group or an amino group.
R ² represents 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 alkoxyl group. R ³ is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms,
Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group, an alkoxyl group or a carbonyl. l is an integer of 1 or more, m
Represents 0 or an integer of 1 or more, and l + m is 4 or less. M
Represents a (l + m) -valent metal cation. n represents an integer of 1 or more. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure. ) 14. The polyester mixed fiber according to claim 13, wherein the phosphorus compound represented by the general formula (7) is at least one selected from compounds represented by the following general formula (8). Embedded image (In the formula (8), R ¹ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a halogen group, or a hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl group or an amino group.
R ³ is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a carbon atom having 1 to 5 carbon atoms including carbonyl.
Represents 50 hydrocarbon groups. l is an integer of 1 or more, m is 0 or an integer of 1 or more, and l + m is 4 or less. M is (l + m)
Represents a valent metal cation. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure. ) 15. The polyester fiber blend according to claim 2, wherein the phosphorus compound is at least one selected from compounds represented by the following general formula (9). Embedded image (In the formula (9), R ¹ and R ² each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R ³ represents hydrogen and 1 carbon atom.
Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrocarbon group of 50 to 50, a hydroxyl group or an alkoxyl group. R ⁴ is hydrogen,
It represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group or carbonyl. l is an integer of 1 or more, m is 0 or an integer of 1 or more, and l + m is 4 or less. M represents a (l + m) -valent metal cation. n represents an integer of 1 or more. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure. ) 16. The polyester mixed yarn according to claim 15, wherein the phosphorus compound represented by the general formula (9) is at least one selected from compounds represented by the following general formula (10). Embedded image (In the formula (10), M ^{n +} represents an n-valent metal cation.
Represents 1, 2, 3 or 4. ) 17. A polyester mixed yarn polymerized using a catalyst containing an aluminum salt of a phosphorus compound. 18. The polyester mixed yarn according to claim 17, wherein the aluminum salt of the phosphorus compound is at least one selected from compounds represented by the following general formula (11). Embedded image (In the formula (11), .R ² R ¹ is representing hydrogen, a hydrocarbon group having 1 to 50 carbon atoms containing a hydrocarbon group, a hydroxyl group or a halogen group, an alkoxyl group, or an amino group having 1 to 50 carbon atoms, 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 a hydroxyl group or an alkoxyl group, and R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. Or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl, l is an integer of 1 or more, m is 0 or an integer of 1 or more, and l + m is 3.
Represents an integer of 1 or more. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure. ) 19. A polyester mixed fiber which is polymerized using a catalyst containing at least one selected from compounds represented by the following general formula (12). Embedded image (In the formula (12), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. And R ⁴ represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a carbonyl. l represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and l + m is 3. n represents an integer of 1 or more.
The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure. ) 20. The polyester mixed yarn according to claim 19, wherein the phosphorus compound represented by the general formula (12) is at least one selected from compounds represented by the following general formula (13). Embedded image (In the formula (13), R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group having 1 to 1 carbon atoms.
Represents 50 hydrocarbon groups. R ⁴ is hydrogen, having 1 to 5 carbon atoms
And represents a hydrocarbon group having 1 to 50 carbon atoms including 0 hydrocarbon group, hydroxyl group, alkoxyl group or carbonyl. l
Represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and l + m
Is 3. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure. ) 21. The polyester mixed fiber according to claim 2, wherein the phosphorus compound is at least one selected from phosphorus compounds having at least one P-OH bond. 22. The polyester mixed yarn according to claim 21, wherein the phosphorus compound is at least one selected from compounds represented by the following general formula (14). Embedded image (In the formula (14), .R ² R ¹ is representing hydrogen, a hydrocarbon group having 1 to 50 carbon atoms containing a hydrocarbon group, a hydroxyl group or a halogen group, an alkoxyl group, or an amino group having 1 to 50 carbon atoms, Represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, and n represents an integer of 1 or more. It may contain an aromatic ring structure.) 23. The polyester mixed fiber yarn according to claim 2, wherein the phosphorus compound is at least one selected from phosphorus compounds represented by the following general formula (15). Embedded image (In the formula (15), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. And n represents an integer of 1 or more. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure.) 24. The polyester mixed fiber according to claim 23, wherein the phosphorus compound represented by the general formula (15) is at least one selected from the compounds represented by the following general formula (16). Embedded image (In the formula (16), R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group having 1 to 1 carbon atoms.
Represents 50 hydrocarbon groups. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure. ) 25. The polyester mixed yarn according to claim 2, wherein the phosphorus compound is at least one selected from phosphorus compounds represented by the following general formula (17). Embedded image (In the formula (17), R ¹ represents a hydrocarbon group having ¹ to 49 carbon atoms, or a hydrocarbon group having ¹ to 49 carbon atoms including a hydroxyl group, a halogen group, an alkoxyl group, or an amino group;
R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group having 1 to 5 carbon atoms.
Represents a hydrocarbon group of 0. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure. ) 26. The polyester mixed yarn according to claim 2, wherein the phosphorus compound is at least one selected from phosphorus compounds represented by the following general formula (18). Embedded image (In the formula (18), R ¹ and R ² each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R ³ and R ⁴ each independently represent hydrogen and a hydrocarbon group having 1 to 50 carbon atoms. , A hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group, and n represents an integer of 1 or more. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure.) 27. The polyester mixed fiber according to claim 26, wherein the phosphorus compound represented by the general formula (18) is at least one selected from the compounds represented by the following general formula (19). Embedded image (In the formula (19), R ³ and R ⁴ 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 alkoxyl group. It may contain an alicyclic structure, a branched structure, or an aromatic ring structure.) 28. The polyester mixed yarn according to claim 2, wherein the phosphorus compound has the following chemical formula (20) or (21). Embedded image Embedded image 29. The polyester mixed yarn according to any one of claims 1 to 28, wherein an amount of an antimony compound as an antimony atom is 50 ppm or less based on the polyester as a polymerization catalyst. 30. The method according to claim 1, wherein a germanium compound is added as a polymerization catalyst in an amount of not more than 20 ppm relative to the polyester as germanium atoms.
The polyester blended yarn according to any one of the above. 31. An intrinsic viscosity of 0.4 dl / g to 1.2 d
The polyester mixed fiber according to any one of claims 1 to 30, wherein the yarn is 1 / g. 32. The polyester mixed fiber yarn according to any one of claims 1 to 31, wherein the polyester mixed fiber yarn is a different shrinkage mixed fiber yarn. 33. The polyester mixed fiber yarn according to claim 32, wherein the polyester hetero-shrink mixed yarn partially includes a self-extended yarn.