JP2002249955A - Polyester stretch woven or knitted fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester stretch woven or knitted fabric excellent in fabric characteristics such as color developing property, brightness of color and tear strength even when the fabric is set at a high temperature and having good heat setting property by carrying out weaving or knitting by using a polyester fiber having heat stability and whiteness and a specific polyurethane elastic yarn. SOLUTION: This polyester stretch woven or knitted fabric is obtained by at least partially using a polyester fiber composed of a polyester polymerized by using a catalyst containing aluminum and/or its compound and a phenolic compound or a phosphorus compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyester polymerization catalyst and a polyester stretch woven / knitted fabric obtained by combining at least a part of a polyester fiber produced by using the same with a polyurethane elastic yarn. The present invention relates to a novel polyester polymerization catalyst not using germanium or an antimony compound as a main component of a catalyst, and a polyester stretch woven or knitted fabric obtained by using at least a part of a polyester fiber produced by using the same and a polyurethane elastic yarn.

[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 relates to a stretch woven or knitted fabric comprising a polyester fiber obtained by melt-spinning a polyester polymer produced using a novel polyester polymerization catalyst other than an antimony compound and a polyurethane elastic yarn. Is provided. 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. It is an object of the present invention to obtain a polyester stretch woven or knitted fabric using a polyurethane polymer yarn and a fiber made of a polyester polymer, which is effectively suppressed, has excellent thermal stability, generates less foreign matter, and has 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 stretch woven or knitted fabric composed of high quality polyester fiber and polyurethane elastic yarn without using an antimony compound.

That is, the present invention provides, as a solution to the above-mentioned problem, 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. The object is to obtain a stretch woven or knitted fabric composed of a polyester fiber made of a polymer and a polyurethane elastic yarn.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention provides a novel polycondensation catalyst other than an antimony compound, and a stretch woven / knitted fabric comprising a polyester fiber made of a polyester polymer and a polyurethane elastic yarn produced using the same. Things. 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 thereof 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 d
l / g of PET is placed in a glass test tube, and
After vacuum drying for 2 hours, 300 ° C. in a non-circulating nitrogen atmosphere
Intrinsic viscosity ([IV]) after maintaining in a molten state for 2 hours at
_f ) is a numerical value calculated by the following equation. The non-circulating nitrogen atmosphere means a nitrogen atmosphere that does not circulate. For example, a glass test tube containing a resin chip is connected to a vacuum line, and after the pressure reduction and the nitrogen sealing are repeated 5 times or more, 10 g
In this state, nitrogen is sealed so as to be 0 Torr, and the tube is 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 0.08 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 into powder having a size of 20 mesh or less at 130 ° C. for 12 minutes.
After drying for 1 hour in a vacuum, 1 g of the solution was put into a beaker together with 100 ml of pure water, heated to 130 ° C. in a closed system, and stirred for 6 hours under pressurized conditions, followed by intrinsic viscosity ([IV] _f2 ).
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 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, a cobalt compound as a cobalt atom is added to the polyester fiber used in the present invention 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 exerted, it is composed of a polyester fiber and a polyurethane elastic yarn. The brightness and thermal stability of the stretch woven or knitted fabric are reduced. According to the present invention, the obtained stretch woven or knitted fabric comprising polyester fibers and polyurethane elastic yarns has good color tone and thermal stability, but the addition of such a small amount of the cobalt compound does not clearly show a catalytic effect. By adding in an amount, the coloring can be more effectively eliminated without lowering the brightness of the obtained stretch woven or knitted fabric comprising the polyester fiber and the polyurethane elastic yarn. 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 in the production of the polyester stretch woven or knitted fabric according to the present invention can be produced by a conventionally known method 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. Also, the polymerization apparatus is a batch type,
It may be 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. Further, 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 a polyester stretch woven or knitted fabric by any method. Is possible.

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.

Examples of the hydroxycarboxylic acid 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 polyester of the present invention may contain a known phosphorus compound as a copolymer component. As the phosphorus compound, a bifunctional phosphorus compound is preferable, for example, (2-carboxylethyl) methylphosphinic acid,
(2-carboxyethyl) phenylphosphinic acid, 9,
10-dihydro-10-oxa- (2,3-carboxypropyl) -10-phosphaphenanthrene-10-oxide and the like. By including these phosphorus compounds as copolymer components, it is possible to improve the flame retardancy and the like of the obtained polyester.

As the constituent components of the polyester of the present invention,
In a preferred embodiment, a polycarboxylic acid having a sulfonate alkali metal base is used as a copolymer component in order to improve dyeability when polyester is used as a fiber.

The metal sulfonate group-containing compound used as the copolymerizable monomer is not particularly limited, but is preferably 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 5-lithium sulfoisophthalic acid, or 2-lithium sulfoisophthalic acid. Examples thereof include terephthalic acid, 5-potassium sulfoisophthalic acid, 2-potassium sulfoterephthalic acid, and lower alkyl ester derivatives thereof. In the present invention, use of 5-sodium sulfoisophthalic acid or an ester-forming derivative thereof is particularly preferred.

The amount of the metal sulfonate group-containing compound to be copolymerized is 0.3 to 10.0 with respect to the acidic components constituting the polyester.
Mol% is preferred, and more preferably 0.80 to 5.0 mol%. If the copolymerization amount is too small, the dyeability of the basic dye is inferior. If the copolymerization amount is too large, not only the spinning properties are poor, but also the fiber does not have sufficient strength due to the thickening phenomenon. The metal sulfonate-containing compound was 2.0 mol%
By copolymerizing as described above, it is also possible to impart normal pressure dyeability to the obtained modified polyester fiber. It is possible to appropriately reduce the amount of the metal sulfonate group-containing compound by selecting an appropriate dye for facilitating dyeing. Examples of the easily dyeable monomer include, but are not particularly limited to, long-chain glycol compounds represented by polyethylene glycol and polytetramethylene glycol, and aliphatic dicarboxylic acids represented by adipic acid, sebacic acid, and azelaic acid.

After the polyester is polymerized according to the method of the present invention, the thermal stability of the polyester can be further increased by removing the catalyst from the polyester or deactivating the catalyst by adding a phosphorus compound or the like. .

The polyester of the present invention may contain an organic, inorganic, or organometallic toner, a fluorescent whitening agent, and the like. Coloration such as yellowishness can be suppressed to a more excellent level. In addition, any other polymer, antistatic agent, defoamer, dyeability improver, dye,
Pigments, matting agents, optical brighteners, stabilizers, antioxidants and other additives may be included. As the antioxidant, an antioxidant such as an aromatic amine type or a phenol type can be used, and as the stabilizer, a phosphoric acid type such as phosphoric acid or a phosphoric acid ester type, a sulfur type or an amine type stabilizer can be used. Can be used.

The polyester fiber used in the polyester stretch woven or knitted fabric 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. . In the case of a long fiber, it is possible to obtain a different shrinkage mixed fiber yarn by adjusting the heat treatment temperature, the drawing conditions, etc., it may be a non-uniformly drawn thick and thin yarn, or a false twisted yarn The woven or knitted material may be configured in the form of a false twisted yarn. Taking into account the texture and mechanical properties of the woven or knitted fabric, twisting with a known twisting machine is also possible.After adding priming, multiple strands are aligned and twisted in the opposite direction to priming. It may be used as a twisted yarn. Also included is weaving and knitting as a design twist yarn such as chenille or bouclé using a special twisting machine.

The polyester stretch woven or knitted fabric of the present invention uses the above-mentioned polyester fiber in at least a part thereof and is combined with a polyurethane elastic yarn. Particularly, a drape property is required for women's clothing using long fibers. It is preferable to insert a real twist having the following number of twists into the warp and / or weft in order to improve the feeling of swelling of the fabric. 12000 / √ (D × 0.9) ≦ Tw ≦ 32000 / √
(D × 0.9) (where Tw is the actual twist number (twice / m) and D is the total fineness (dtex) of the polyester fiber to be twisted.) The twist number Tw is 12000 / √ (D If it is less than (× 0.9), the feeling of swelling is poor. , It has a paper-like texture.
If Tw exceeds 32000 / √ (D × 0.9), the touch becomes extremely dry and the twisting torque becomes too strong. Some of the strips become stiff or snare and protrude from the fabric surface, which is not preferable in terms of appearance quality.

Further, windbreakers, jackets, etc.
In the case of sports wear or casual wear, it is preferable to weave or knit polyester fibers into which no twist or the following number of twists are inserted. 700 / √ (D × 0.9) ≦ Tw ≦ 6000 / √ (D ×
0.9) (However, Tw is the actual twisted number (twice / m), and D is the total fineness (dtex) of the twisted polyester fiber.) The actual twisted insertion number is 700 / √ (D × 0 .9)
It becomes difficult to use a double twister, and it becomes a twisting machine such as a ring twisting machine, an Italian twisting machine, and other uptwisters. Although it is also in the sweet twist region, the problem of the twisting speed is rare, but the twist is biased due to extremely slight scratching, and there is a risk of deteriorating the appearance quality. Also 6000 / √
In the range exceeding (D × 0.9), the surface of the woven or knitted fabric is crumpled and impairs the appearance quality. In addition, particularly in the case of a windbreaker, the water pressure resistance is reduced, and in terms of product characteristics, it is preferable. No.

The polyurethane elastic yarn used in the polyester stretch woven or knitted fabric of the present invention is obtained by blending a compound having a nitrogen atom as an additive with a polyurethane polymer as one embodiment. Under a dry heat of 190 ° C. for 1 minute, the PSD is 50
% Or more, and under 100% elongation, from 40 ° C.
After the temperature was raised to 30 ° C for 60 minutes, the wet heat was continuously applied at 130 ° C for 60 minutes.
The PSW after the minute treatment is 75% or less. The PSD is preferably at least 55%, more preferably at least 60%, the PSW is preferably at most 70%,
More preferably, it is 68% or less.

If the PSD value is less than 50%, the heat setting property under dry heat treatment such as a pre-setting step in the post-processing step becomes poor. The setting temperature must be increased and the heat setting time must be increased, which tends to reduce the efficiency of passing through the post-processing step. When the value of PSW exceeds 75%, the heat resistance under wet heat treatment such as a dyeing step in the post-processing step becomes poor, and the cloth knitted using such elastic yarns has a high strength and elasticity of the cloth. It tends to be difficult to maintain resilience.

The PSD is measured as follows. 1 / 100th of the denier of polyurethane elastic yarn
By applying an initial load (g) of 0, the length L1 is set as the yarn length before the treatment. Next, the yarn is elongated by 100% (extended to twice L1).
After a treatment at 190 ° C. for 1 minute (equivalent to a presetting step using a thermosetter or the like), the mixture was allowed to shrink at room temperature for 10 minutes and allowed to cool. An initial load (g) of / 1000 is applied, and the length L2 is taken as the yarn length after the treatment. From L1 and L2, the PSD is calculated by the following equation. (Equation 5) PSD (%) = (L2−L1) / L1 × 100

The measurement method of PSW is performed as follows. 1 / 100th of the denier of polyurethane elastic yarn
By applying an initial load (g) of 0, the length L3 is taken as the yarn length before the treatment. Next, the yarn is elongated by 100% (extended to twice L3).
Then, the yarn is put in a water bath, and the water bath is heated up from 40 ° C. to 130 ° C. by wet heat over 60 minutes in a sealed state, and then treated continuously at 130 ° C. for 60 minutes (dyeing machine, etc.). And then allowed to cool for 10 minutes at room temperature and allowed to cool, then apply an initial load (g) of 1/1000 of the denier of the yarn before the treatment, and adjust the length L4. This is the yarn length after processing. From L3 and L4, PSW is calculated by the following equation. (Equation 6) PSW (%) = (L4−L3) / L3 × 100

In the polyurethane elastic yarn used in the polyester stretch woven or knitted fabric of the present invention, one or more compounds having a nitrogen atom are blended to obtain a polyurethane elastic yarn having good heat setting property under dry heat treatment. Can be. When a compound having a nitrogen atom is not blended into the polyurethane elastic yarn, heat resistance under wet heat treatment is good, but heat setting under dry heat treatment becomes poor,
In order to process the amount of dough according to the purpose, the heat setting temperature must be increased or the heat setting time must be increased,
It tends to reduce the efficiency of passing through the post-processing step.

The mechanism of improving the heat setting property under dry heat and wet heat treatment by compounding a compound having a nitrogen atom is as follows.
It is presumed that the compound having a nitrogen atom promotes urethane decomposition at a high temperature to such an extent that physical properties are not impaired. Generally, the dry heat treatment such as the presetting process is performed at a higher temperature in a shorter time than the wet heat treatment such as the dyeing process, and in a state where the elongation rate is higher for the polyurethane elastic yarn. It is considered that the effect of accelerating the decomposition is easier to be exerted under dry heat treatment than under wet heat treatment.

The polyurethane polymer used for the polyurethane elastic yarn used in the polyester stretch woven or knitted fabric of the present invention is an intermediate polymer composed of a polyol and an excess mole of a diisocyanate compound, both ends of which are isocyanate groups, and N, N-dimethyl. It can be obtained by dissolving in an inert organic solvent such as acetamide, N, N-dimethylformamide, dimethylsulfoxide and the like and reacting with a diamine compound.

The above polyol is not particularly limited.
For example, polymer diol and the like can be mentioned. Specifically, polyether diols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxypentamethylene glycol and polyoxypropylene tetramethylene glycol, adipic acid, sebacic acid, maleic acid,
One or more dibasic acids such as itaconic acid, azelaic acid and malonic acid and ethylene glycol, 1,2-
Propylene glycol, 1,3-propylene glycol, 2,2-dimethyl-1,3-propanediol,
Polyester diols obtained from one or more glycols such as 1,4-butanediol, 2,3-butanediol, hexamethylene glycol and diethylene glycol, polylactone diols such as poly-ε-caprolactone and polyvalerolactone; Polyesteramide diol, polyetherester diol,
Examples thereof include polycarbonate diol. The number average molecular weight of the polyol is usually about 500 to 6000,
Preferably 1000 to 5000, more preferably 10
00 to 3000. When the number average molecular weight is less than 500, the elasticity of the resulting elastic yarn tends to be insufficient, and when it exceeds 6000, the mechanical properties such as strength and elastic recovery tend to be insufficient. is there.

As the diisocyanate compound, any of aliphatic, alicyclic and aromatic diisocyanate compounds which are soluble or liquid under the reaction conditions may be used.
There is no particular limitation. For example, methylene-bis (4-phenylisocyanate), methylene-bis (3-methyl-
4-phenyl isocyanate), 1,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m
-And p-phenylene diisocyanate, m- and p-xylylene diisocyanate, methylene-bis (4
-Cyclohexyl isocyanate), 1,3- and 1,4-cyclohexylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like. Among them, methylene-bis (4-phenyl isocyanate) is preferred.

The above-mentioned reaction of the polyol with the diisocyanate compound is carried out in such a manner that the isocyanate compound is mixed in an excess mole, and the equivalent ratio of the isocyanate group to the hydroxyl group is preferably in the range of 1.5 to 3.0, more preferably. The mixing is performed in the range of 1.5 to 2.0, and the reaction is carried out at a temperature of 60 to 120 ° C., whereby an intermediate polymer having isocyanate groups at both terminals is obtained. At this time, for the polyol and the diisocyanate compound, two or more kinds can be used as long as the physical properties of the obtained polyurethane polymer are not impaired. Further, a low molecular weight diol such as a small amount of ethylene glycol, propylene glycol, or butanediol can also be used.

The diamine compound as a chain extender is not particularly limited. For example, ethylenediamine, propylenediamine, trimethylenediamine,
Hexamethylenediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, hydrazine, and the like can be given, and one or more diamines can be used.
Particularly, a polyurethane elastic yarn using only ethylenediamine as a chain extender has a higher cohesive force of a hard segment, and therefore has a high heat resistance under a wet heat treatment in a post-processing step, and is particularly preferable.

A secondary monoamine compound may be mixed with the diamine compound. As the secondary monoamine compound used in combination, for example, dimethylamine, diethylamine, diethanolamine, diisopropylamine, di-
Examples thereof include n-butylamine, methylethylamine, methyl-isopropylamine, dicyclohexylamine, and the like, and one or more monoamines can be used. Of these, diethylamine is preferred.

The inert organic solvent used in the reaction is not particularly limited as long as it can dissolve the above-mentioned various raw materials and dissolve or disperse the produced polyurethane polymer. For example, N, N-dimethylacetamide,
N, N-dimethylformamide, dimethylsulfoxide and the like can be mentioned. Preferably, it is N, N-dimethylacetamide.

The reaction between the intermediate polymer and the diamine compound is as follows:
Usually performed by cooling the intermediate polymer to 40 ° C. or lower, and reacting the amine solution in which the diamine compound is dissolved in the inert organic solvent with the intermediate polymer solution dissolved in the inert organic solvent,
A polyurethane polymer is produced. As the reaction temperature,
8-40 ° C is preferred. In the reaction, a mixed solution of a diamine compound containing an amino group in an excess equivalent to the isocyanate group in the intermediate polymer reacts with the intermediate polymer, so that the terminal group of the resulting polymer is derived from the diamine compound. It is an amino group (A) or a urea group (B) derived from a secondary monoamine compound which is a terminal stopper. The concentration of the polyurethane solution obtained by the above reaction is 30.
~ 40% by weight is preferred. The viscosity of the polyurethane solution is 1
500-5000 poise (30 ° C.), preferably 200
0 to 4000 poise (30 ° C.), and the amount ratio B / A of the polymer end groups is 0.5 to 2.0, preferably 0.7 to 1.5. It is preferable to carry out the reaction by adjusting the amounts of the organic diamine and the secondary monoamine to the isocyanate group of the above.
The viscosity of the polyurethane solution was measured by a B-type viscometer manufactured by Tokyo Keiki Co., Ltd. at a shear rate of 0.08 sec-1 at a polyurethane solution temperature of 30 ° C.

If the viscosity of the polyurethane solution is less than 1500 poise (30 ° C.) or more than 5000 poise (30 ° C.), spinning becomes difficult, and the amount ratio of polymer end groups B
When / A is less than 0.5 or more than 2.0, sufficient physical properties cannot be exhibited by heat treatment after spinning, and heat resistance in a post-processing step, particularly under wet heat treatment, tends to be poor.

A compound having a nitrogen atom is added to the polyurethane solution. Further, if desired, an organic or inorganic compounding agent having a known specific chemical structure useful for the polyurethane polymer may be added. After the addition, dry spinning is performed by a conventional method to obtain a yarn.

As the compound having a nitrogen atom, specifically, a nitrogen atom-containing compound which is a reaction product of a diisocyanate compound and a dialkylhydrazine (for example, a reaction product of methylene-bis (4-phenylisocyanate) and dimethylhydrazine) A nitrogen atom-containing polymer (for example, methylene-bis (4-phenylisocyanate) and 4-methyl-2,6-dimethyl-) which is a reaction product of a diisocyanate compound and a diol containing an excess mole of nitrogen atom.
4-azaheptanediol reaction product), a nitrogen atom-containing polymer in which a terminal isocyanate group of a reaction product of a nitrogen atom-containing diol and an excess mole of a diisocyanate compound is blocked with a monoamine and / or a dialkylhydrazine ( For example, 4-ethyl-2,
6-dimethyl-4-azaheptanediol and methylene-
Glycidyl of a reaction product of bis (4-cyclohexyl isocyanate) with a nitrogen atom-containing polymer having a terminal isocyanate group blocked with n-butylamine and dimethylhydrazine, and a compound having two phenolic hydroxyl groups with carboxylic hydrazide Nitrogen atom-containing polymers that are reactants with etherified compounds (eg,
Diglycidyl etherified product of lauryl hydrazide and bisphenol A).

Examples of the reaction product of the diisocyanate compound and the dialkylhydrazine and the diisocyanate compound used in producing the above-mentioned nitrogen-containing polymer include methylene-bis (4-phenylisocyanate) and methylene-bis (3-methyl- 4-phenyl isocyanate), 2,4-tolylene diisocyanate,
Aromatic diisocyanates such as 2,6-tolylene diisocyanate, m- and p-phenylene diisocyanate, m- and p-xylylene diisocyanate, methylene-bis (4-cyclohexyl isocyanate);
Examples thereof include aliphatic diisocyanates such as 3- and 1,4-cyclohexylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Of these, aliphatic diisocyanates are preferred. Examples of the dialkylhydrazine used for producing the nitrogen atom-containing polymer include, for example, N, N-
Dimethylhydrazine, N, N-diisopropylhydrazine, N-ethyl-N-methylhydrazine, N-methyl-
Examples thereof include N-laurylhydrazine, and among them, those having up to about 20 carbon atoms are preferable.

Examples of the nitrogen-containing diol used in producing the nitrogen-containing polymer include, for example,
N-methyldiethanolamine, N-ethyldiethanolamine, N-isopropyldiethanolamine, N-
Butyldiethanolamine, N-cyclohexyldiethanolamine, N-stearyldiethanolamine,
1,5-dimethyl-3-methyl-3-azapentanediol, 3-butyl-1,5-dimethyl-3-azapentanediol, 2,6-dimethyl-4-methyl-4-azaheptanediol, 4- Ethyl-2,6-dimethyl-4
-Azaheptanediol, 4-butyl-2,6-dimethyl-4-azaheptanediol, 4-cyclohexyl-
2,6-dimethyl-4-azaheptanediol, N, N
Compounds containing a nitrogen atom in the main chain, such as dihydroxyethylpiperazine, 2-ethyl-2-N, N-dimethylamino-1,3-dihydroxypropane, 2-ethyl-
2-N, N-diethylamino-1,3-dihydroxypropane, 2-N, N-dibutylamino-2-ethyl-
1,3-dihydroxypropane, 2-N, N-dimethylaminomethyl-2-methyl-1,3-dihydroxypropane, 2-N, N-diethylaminomethyl-2-methyl-1,3-dihydroxypropane, 2- Compounds containing a nitrogen atom in the side chain such as N, N-dibutylaminomethyl-2-methyl-1,3-dihydroxypropane;
-Dimethyl-N ', N'-dihydroxyethyl-1,3
-Diaminopropane, N, N-diethyl-N ', N'-
Dihydroxyethyl-1,3-diaminopropane, N,
N-dimethyl-N ', N'-di- (2-hydroxypropyl) -1,3-diaminopropane, N, N-dimethyl-N', N'-di- (3-hydroxy-2-methylpropyl) Compounds containing a nitrogen atom in the main chain and side chain such as -1,3-diaminopropane are exemplified. Of these, compounds containing a nitrogen atom in the main chain are preferred.

The monoamine used in producing a nitrogen atom-containing polymer in which a terminal isocyanate group of a reaction product of a nitrogen atom-containing diol and an excess mole of a diisocyanate compound is blocked with a monoamine and / or a dialkylhydrazine. Is, for example,
Secondary amines such as dimethylamine, diethylamine, diethanolamine, diisopropylamine, di-n-butylamine, methylethylamine, methyl-isopropylamine, dicyclohexylamine, ethylamine,
Primary amines such as n-butylamine and laurylamine are exemplified. Of these, primary amines and secondary amines having up to about 20 carbon atoms are preferred.

Examples of the carboxylic acid hydrazide used for producing a nitrogen atom-containing polymer which is a reaction product of a carboxylic acid hydrazide and a glycidyl etherified compound of a compound having two phenolic hydroxyl groups include, for example, acetic acid hydrazide and propionic acid hydrazide. Hydrazide, heptanoic acid hydrazide, lauric acid hydrazide, stearic acid hydrazide, and the like. Among them, those having up to about 20 carbon atoms are preferable. Examples of the glycidyl ether compound of a compound having two phenolic hydroxyl groups used in producing the nitrogen atom-containing polymer include, for example, bisphenol-A glycidyl ether compound, methylene bisphenol glycidyl ether compound, ethylidene bisphenol glycidyl ether compound, Propanediyl bisphenol glycidyl etherified product, methylene bis (2-
Examples thereof include methyl phenol) glycidyl ether and 1-methylethylidene bis (2-methyl phenol) glycidyl ether. Among them, bisphenol-A glycidyl ether compound is preferred.

Among the compounds having a nitrogen atom exemplified above, the nitrogen atom obtained by blocking the terminal isocyanate group of the reaction product of a nitrogen atom-containing diol with an excess mole of a diisocyanate compound with a monoamine and / or a dialkylhydrazine is used. The containing polymer is particularly preferred, and among them, 4-ethyl-2,6-dimethyl-4-
A nitrogen atom-containing polymer in which a reaction product of azaheptanediol and methylene-bis (4-cyclohexyl isocyanate) is terminally blocked with a terminal isocyanate group by n-butylamine and dimethylhydrazine is most preferable. Reactants and polymers produced from the compounds exemplified above are examples of compounds having a nitrogen atom and are by no means limited to these.

Examples of the organic or inorganic compounding agents include ultraviolet absorbers such as benzophenone compounds, benzotriazole compounds and hindered amine compounds, antioxidants such as hindered phenol compounds, barium sulfate, and the like.
Examples include inorganic fine particles such as magnesium silicate, calcium silicate, zinc oxide and magnesium oxide, anti-adhesive agents such as magnesium stearate, polytetrafluoroethylene and organopolysiloxane, and fungicides.

The spinning apparatus and spinning conditions used for dry spinning the polyurethane solution vary depending on the composition of the polyurethane, the thickness of the target fiber and the physical properties of the yarn.
Usually, a polyurethane solution containing additives and the like is supplied to a spinning apparatus, and a spinning temperature (hot air temperature) of 200 to 260 ° C and a spinning speed of 400 to 1000 m / min, preferably 450 to 7
Spinning is performed at 00 m / min, and the polyurethane elastic yarn is wound around a bobbin.

In the spinning step, the polyurethane elastic yarn wound around the bobbin is usually heated at a temperature of 40 to 90 ° C., preferably 40 to 60 ° C. for 2 hours or more, preferably 10 to 72 ° C.
Heat treatment for hours. By this treatment, the polyurethane polymer constituting the yarn is increased in molecular weight and has a logarithmic viscosity of 1.1 dl.
/ G or more, preferably 1.3 dl / g or more, so that physical properties such as cutting strength and elastic recovery are improved, and chemical properties such as chemical resistance are also improved. At this time, an amino group (A) derived from an organic diamine, which is a terminal group of the polymer,
And when the equivalent ratio B / A of the urea group (B) derived from the secondary monoamine as a terminal stopper is in the range of 0.5 to 2.0, preferably 0.7 to 1.5, heat treatment after spinning. Thus, sufficient physical properties can be exhibited, and heat resistance in a post-processing step, particularly under wet heat treatment, is high, which is particularly preferable.

The polyurethane elastic yarn may be used as a bare knitted fabric, and is represented by a covering yarn represented by a single covering yarn, a double covering yarn, an air covering yarn, or a plied yarn twisted with an inelastic yarn. A composite yarn such as a ply-twisted yarn or a core yarn inserted into a core during spinning may be used. In particular, when used for textiles, it is preferable to use it as a covering yarn from the viewpoint of quality and operability.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The evaluation method used in each of the examples and comparative examples will be described below.

(1) Intrinsic Viscosity (IV) Polyester is dissolved using a 6/4 (weight ratio) mixed solvent of phenol / 1,1,2,2-tetrachloroethane,
It was measured at a temperature of 30 ° C.

(2) Acid value 0.1 g of polyester was dissolved by heating in 10 ml of benzyl alcohol, and the acid value was determined by titration using a solution of 0.1N NaOH in methanol / benzyl alcohol = 1/9. (3) Diethylene glycol content (DEG) 0.1 g of the polyester was placed at 250 ° C. in 2 ml of methanol.
And then quantitatively determined by gas chromatography.

(4) Differential Scanning Calorimetry (DSC) Measurement was performed using a DSC 2920 manufactured by TA Instruments. Put 10.0mg of polyester in an aluminum pan, 50 ℃
The temperature was raised to 280 ° C. at a heating rate of / min, and after reaching 280 ° C., the temperature was maintained for 1 minute, and immediately after that, quenched in liquid nitrogen. Thereafter, the temperature is increased from room temperature by 20 ° C./min.
℃, the crystallization temperature Tc1 and the melting point T
m was determined. After the temperature was maintained at 300 ° C. for 2 minutes, the temperature was lowered at a rate of 10 ° C./minute, and the crystallization temperature Tc2 at the time of temperature decrease was determined. Tc1, Tm, and Tc2 were the temperatures of the local maximums of the respective peaks.

(5) Hue At the time when a predetermined stirring torque was reached in the melt polymerization, nitrogen was introduced into the autoclave to return the pressure to normal pressure, and the polycondensation reaction was stopped. Thereafter, the polymer was discharged into cold water in the form of strands under slight pressure and rapidly cooled. After that, the polymer was held in cold water for about 20 seconds and then cut to obtain a cylindrical resin tip having a length of about 3 mm and a diameter of about 2 mm. The resin chip thus obtained was air-dried on a filter paper at room temperature for about 24 hours, and then used for color measurement. The color measurement was performed using a PET resin chip having an IV of about 0.65 dl / g obtained by melt polymerization using a color difference meter (MODEL TC-150 manufactured by Tokyo Denshoku Co., Ltd.).
0MC-88) was used to measure the hunter's L value, a value, and b value.

(6) Thermal stability parameter (TS) The melt-polymerized IV was about 0.65 dl / g (before the melting test;
[IV] 1 g of PET resin chip of _i ) is about 14 m in inner diameter
m, placed in a glass test tube, vacuum-dried at 130 ° C. for 12 hours, set in a vacuum line, and repeatedly vacuumed and filled with nitrogen five times or more, sealed with 100 mmHg of nitrogen, and sealed.
After being immersed in a salt bath at 300 ° C. and maintained in a molten state for 2 hours, the sample was taken out, freeze-crushed and vacuum-dried.
V (after the melting test; IV] _f2 ) was measured and determined using the following formula. The ceremony is already reported (Kamiyama et al.
3, No. 8, p. 497, 1990). TS = 0.245 ｛[IV] _f2 ^-1.47 − [IV] _i
^-1.47 ｝

(7) Thermal Oxidation Stability Parameter (TOS) A PET resin chip having a melt-polymerized IV having an IV of about 0.65 dl / g was freeze-pulverized to a powder of 20 mesh or less, which was vacuum-dried at 130 ° C. for 12 hours. 300 mg is placed in a glass test tube having an inner diameter of about 8 mm and a length of about 140 mm.
After vacuum drying at 0 ° C. for 12 hours, a drying tube containing silica gel was placed on the upper portion of the test tube, and dried under air at 230 ° C.
IV after being immersed in a salt bath and heated for 15 minutes, was determined using the same formula as that for TS described above. Here, [IV] _i and [IV] _f1 indicate the IV (dl / g) before and after the heating test, respectively. For freezing and pulverization, use a freezer mill (Type 6750 manufactured by Spex, USA)
This was performed using After putting about 2 g of resin chip and dedicated impactor in the dedicated cell, set the cell in the device, fill the device with liquid nitrogen and hold for about 10 minutes, then
Milling was performed for 5 minutes with ATE10 (impacter moves around 20 times per second). TOS = 0.245 ｛[IV] _f1 ^-1.47 − [IV] _i
^-1.47 ｝

(8) Hydrolysis resistance parameter (HS) The intrinsic viscosity obtained by melt polymerization is about 0.65 dl / g.
(Before the test; the PET resin chip of [IV] _i ) was frozen and pulverized in the same manner as in 7) to obtain a powder having a size of 20 mesh or less, which was vacuum-dried at 130 ° C. for 12 hours. The hydrolysis test was performed using a mini color device (TypeMC12.EL manufactured by Texam Giken Co., Ltd.).
B). 1 g of the above-mentioned powder was put into a special stainless beaker together with 100 ml of pure water, a special stirring blade was further put therein, and a closed system was set.
The mixture was stirred for 6 hours while heating and pressurizing to 30 ° C. The PET after the test was collected by filtration with a glass filter, dried under vacuum, and then measured for IV ([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 ｝

(9) 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.

(10) ¹ H-NMR Measurement The compound was dissolved in CDCl ₃ or DMSO, and
Measured using GEMINI-200.

(11) Melting point measurement The compound was placed on a cover glass, and Yanaco MICRO MELTING
Measurement was performed at a heating rate of 1 ° C./min using POINT APPARATUS.

(12) Elemental Analysis The phosphorus was analyzed by molybdenum blue colorimetry after wet decomposition of a PET resin chip. Other metals were subjected to high-frequency plasma emission analysis and atomic absorption analysis after incineration / acid dissolution.

Measurement of PSD] Initial length 22.5 cm (L
After treating the elastic yarn of 1) at a dry heat of 190 ° C. for 1 minute under 100% elongation, the yarn length (L2) after shrinking and cooling at room temperature for 10 minutes is measured and calculated by the following equation. did. (Equation 7) PSD (%) = (L2−L1) / L1 × 100

[Measurement of PSW] Initial length 9.5 cm (L
The elastic yarn of 3) is heated from 40 ° C to 130 ° C under 100% elongation.
After heating to 130 ° C. for 60 minutes, continuously treating at 130 ° C. for 60 minutes, and then shrinking and cooling at room temperature for 10 minutes, measure the yarn length (L4), and calculate by the following formula. did. (Equation 8) PSW (%) = (L4−L3) / L3 × 100

[Measurement of logarithmic viscosity] 0.075 g of a polyurethane polymer was added to 25 ml of N, N-dimethylacetamide.
10 ml of this solution was taken in an Ostwald viscometer, and the number of drops per second was measured in a thermostat at 30 ° C., and the logarithmic viscosity (ηinh) was calculated from the following equation. In the formula, t is the number of seconds the polyurethane polymer solution falls (seconds), t0 is the number of seconds the solvent falls (seconds), and C is the concentration of the polyurethane polymer solution (g / g).
dl). (Equation 9) ηinh (dl / g) = [ln (t / t0)] / C

[Measurement of Strong Retention of Dough] 10 cm × 5
The stress at the time of 100% elongation of the dough of cm was measured by Tensilon manufactured by Toyo BOLDWIN, and the strength retention of the dough was calculated by the following formula. (Equation 10) Strong retention of fabric (%) = Strength after dyeing finish / Strength of greige × 100

[Measurement of elastic recovery rate of fabric] 10 cm × 5
cm of fabric at a time of 50% elongation in the forward path (50% elongation force) and 50% elongation in the return path (50% elongation) when the fabric is stretched once to 80% by Tensilon manufactured by Toyo BOLDWIN.
% Tightening force) was measured, and the elastic recovery rate of the fabric was calculated by the following equation. (Equation 11) Elastic recovery rate of fabric (%) = 50% tightening force / 50% elongation force × 100

(Example 1) (Synthesis example of phosphorus compound) Synthesis of phosphorus compound (phosphorus compound A) represented by the following formula (65)

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Sodium (O-ethyl 3,5-di-tert-butyl-4-hyd
Synthesis of roxybenzylphosphonate) Diethyl (3,5-di-tert-butyl-4-h)
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%)

O-ethyl 3,5-di-tert-butyl-4-hydroxyben
Synthesis of zylphosphonic acid (phosphorus compound A) Sodium (O-ethyl 3,5-di-tert-butyl-4-
Hydroxybenzylphosphonate) 1g (2.8mmol) aqueous solution 20m
1.5 g of concentrated hydrochloric acid was added to 1 and stirred for 1 hour. Water to the reaction mixture
150 ml was added, and the precipitated crystals were collected by filtration, washed with water, and dried to obtain Oe.
thyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonic a
826 mg (88%) of cid was obtained. Shape: plate-like crystal Melting point: 126-127 ° C. ¹ H-NMR (CDCl ₃ , δ): 1.207 (3H, t, J = 7 Hz), 1.436 (18H,
s), 3.013 (2H, d), 3.888 (2H, m, J = 7Hz.), 7.088 (2H, d
s), 7.679-8.275 (1H, br)

(Example of Polyester Polymerization) A high-purity terephthalic acid and a 2-fold molar amount of ethylene glycol were charged into a heating medium-circulating 2-liter stainless steel autoclave equipped with a stirrer, and triethylamine was added in an amount of 0.3 mol% based on the acid component. A mixture of bis (2-hydroxyethyl) terephthalate (BHET) and an oligomer having an esterification rate of 95% was performed for 120 minutes while distilling water out of the system at 245 ° C. under a pressure of 0.25 Mpa, and BHET mixture). To this BHET mixture, an ethylene glycol solution of 2.5 g / l of aluminum trisacetylacetonate was added in an amount of 0.015 mol% as aluminum atoms with respect to an acid component in the polyester, and 10 g / l of ethylene glycol of the phosphorus compound A was added. The solution was added with 0.04 mol% of phosphorus compound A as an acid component in the polyester, and stirred at 245 ° C. for 10 minutes under a normal pressure under a nitrogen atmosphere. Then take 50 minutes at 275 ° C
The polycondensation reaction was further performed at 275 ° C. and 0.1 Torr by gradually lowering the pressure of the reaction system to 0.1 Torr while increasing the temperature. The polymerization time required for the IV of polyethylene terephthalate to reach 0.65 dlg ^-1 was 103 minutes. In addition, polyethylene terephthalate having an IV of 0.65 dlg ⁻¹ obtained by the above polycondensation was formed into chips according to a conventional method. P obtained
Oxidation of ET resin chip is 2 eq / ton, DE
G was 2.0 mol%. Tm is 257.5.
° C, Tc1 is 164.1 and Tc2 is 18
5.4 ° C. The L value is 68.3 and the a value is-
1.1, b value is 1.9, TS is 0.16, TOS is 0.1.
Below 01, the HS was 0.04.

The above-mentioned melt polymerization was repeated until the required amount of resin for spinning evaluation was obtained. After drying the obtained PET resin chip, it was supplied to a melt extruder to obtain a pore size of 0.14.
29 from a spinneret with 108 orifices of mmΦ
After discharging at 0 ° C, cooling and oiling
It was withdrawn at 720 m / min. Continue with preheating roller 8
Stretched 2.127 times at 0 ° C and set temperature of 150 ° C to 5
A polyester drawn yarn having 0 dtex and 108 filaments was obtained. The operability in spinning and drawing was good.

On the other hand, 200 parts of polyoxytetramethylene glycol having a molecular weight of 1800 and 45 parts of methylene-bis (4-phenylisocyanate) were reacted at 80 ° C. for 3 hours to obtain an intermediate polymer having isocyanate groups at both terminals. After cooling the intermediate polymer to 40 ° C., 375 parts of N, N-dimethylacetamide was added to dissolve the intermediate polymer, and 10
Cooled to ° C. 4.0 parts of ethylenediamine and 0.4 parts of diethylamine were added to N, N-dimethylacetamide 14
A solution dissolved in 7.6 parts was prepared, and this amine solution was added at a stretch to a place where the solution of the intermediate polymer was stirred at a high speed, and the viscosity was 2500 poise (30 ° C.) and the polymer concentration was 3
A 2.3% by weight polyurethane solution was obtained. The viscous polyurethane solution thus obtained was added to a reaction product of 4-ethyl-2,6-dimethyl-4-azaheptanediol and methylenebis (4-cyclohexylisocyanate) as a compound having a nitrogen atom, n-butylamine / N. , N
-4% of dimethylhydrazine end-blocking polymer (based on polymer weight), a benzotriazole-based compound, a hindered phenol-based compound, and an antiblocking agent were added thereto, followed by mixing and stirring to obtain a spinning dope having a viscosity of 1950 poise. . After defoaming the spinning solution, the spinning solution is spun from a die having a hole diameter of 0.3 mm and 4 holes, and extruded into a spinning cylinder in which heated air at 230 ° C. is flown.
After winding at m / min, 7
Heat treatment was performed for 2 hours to obtain 40d polyurethane elastic yarn to be subjected to post-processing. The polyurethane elastic yarn has a PSD of 67%, a PSW of 68%, a terminal group ratio (B / A) of 1.0, a logarithmic viscosity of 1.4 dl / g, and a logarithmic viscosity after treatment with boiling water for 1 hour. Was 2.0 dl / g.

The obtained polyurethane elastic yarn of 44 dtex and the drawn polyester yarn of 50 dtex were used in 2 watts.
After knitting the ay-tricot knitted fabric, a relaxation treatment, a preset treatment, and a disperse dye using a conventional method were carried out.
C., a series of post-processing processes of a dyeing process for 30 minutes and a final setting process at 170 ° C. for 40 seconds are continuously performed.
Dyed fabric was obtained. For this dough, the optimum preset condition for processing to the target dough amount is 18
5 ° C. for 1 minute. The resulting fabric has a strong retention of 8
8% and the elastic recovery was 68%. Operability in knitting and processing of a knitted fabric using these fibers was very good.

(Example 2) (Synthesis example of phosphorus compound) Synthesis of magnesium salt of phosphorus compound (phosphorus compound B) represented by the following formula (66)

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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. Magnesium bis (O-ethyl 3,5-di-tert-bu
Synthesis of tyl-4-hydroxybenzylphosphonate (phosphorus compound B) Sodium (O-ethyl 3,5-di-tert-butyl-4-
Hydroxybenzylphosphonate) 500mg (1.4mmol) aqueous solution
To 4 ml, 1 ml of an aqueous solution of 192 mg (0.75 mmol) of magnesium nitrate hexahydrate was added dropwise. After stirring for 1 hour, the precipitate was collected by filtration, washed with water, and dried to remove magnesium bis (O-ethyl 3,5-di-tert-buty).
359 mg (74%) of l-4-hydroxybenzylphosphonate) was obtained. Shape: white powder Melting point:> 300 ° C ¹ H-NMR (DMSO, δ): 1.0820 (6H, t, J = 7 Hz), 1.3558 (36H,
s), 2.8338 (4H, d), 3.8102 (4H, m, J = 7Hz), 6.6328 (2
H, s), 6.9917 (4H, s)

(Example of Polyester Polymerization) A high-purity terephthalic acid and a 2-fold molar amount of ethylene glycol were charged into a heating medium circulation type 2-liter stainless steel autoclave equipped with a stirrer, and triethylamine was added at 0.3 mol% to the acid component. A mixture of bis (2-hydroxyethyl) terephthalate (BHET) and an oligomer having an esterification rate of 95% was performed for 120 minutes while distilling water out of the system at 245 ° C. under a pressure of 0.25 Mpa, and BHET mixture). For this BHET mixture, a 2.5 g / l solution of aluminum acetylacetonate in ethylene glycol was added to the acid component in the polyester in an amount of 0.01 to 0.01 as aluminum atoms.
5 mol%, the above-mentioned phosphorus compound B was added to 0.02 m
ol%, and the mixture was stirred at 245 ° C. for 10 minutes at normal pressure under a nitrogen atmosphere. Next, it took 50 minutes to gradually raise the temperature of the reaction system to 275 ° C while gradually lowering the pressure to 0.1 Torr to further increase the temperature to 275 ° C and 0.1T.
A polycondensation reaction was performed at orr. The time required for the PET IV to reach 0.65 was 39 minutes. In addition, polyethylene terephthalate having an IV of 0.65 dlg ⁻¹ obtained by the above polycondensation was formed into chips according to a conventional method. Various physical properties were measured using this PET resin chip. The oxidation of the obtained PET resin chip was 2 eq / ton. Also, Tm
Is 256.5 ° C., Tc1 is 165.6 ° C.,
Tc2 was 185.1 ° C. The L value is 66.
6, a value is -2.1, b value is 4.5, TS is 0.19,
TOS was 0.01 or less and HS was 0.06.

The above melt polymerization was repeated until the required amount of resin for spinning evaluation was obtained. The obtained PET resin chip was dried and then supplied to a melt extruder to obtain a pore size of 0.14.
29 from a spinneret with 108 orifices of mmΦ
After discharging at 0 ° C, cooling and oiling
It was withdrawn at 720 m / min. Continue with preheating roller 8
Stretched 2.127 times at 0 ° C and set temperature of 150 ° C to 5
A polyester drawn yarn having 0 dtex and 108 filaments was obtained. The operability in spinning and drawing was good.

Except that the reaction product of methylene-bis (4-phenylisocyanate) and dimethylhydrazine was changed to 2% (based on the weight of polymer) and added to the polyurethane solution obtained in Example 1 as a compound having a nitrogen atom. Was polymerized and spun under the same method and under the same conditions as in Example 1 to obtain a 44 decitex polyurethane elastic yarn to be subjected to post-processing. The polyurethane elastic yarn has a PSD of 6
5%, PSW 68%, terminal group quantitative ratio (B / A) 1.
0, the logarithmic viscosity was 1.4 dl / g, and the logarithmic viscosity after treatment with boiling water for 1 hour was 2.0 dl / g. Using the obtained yarn, post-processing was performed in the same manner and under the same conditions as in Example 1 to obtain a dyed fabric. The optimum preset condition for processing the dough to the target dough amount was 185 ° C. for 1 minute. The resulting fabric had a strength retention of 88% and an elastic recovery of 68%.
Operability in knitting and processing of a knitted fabric using these fibers was very good.

Example 3 (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 ℃

(Example of Polyester Polymerization) A high-purity terephthalic acid and a 2-fold molar amount of ethylene glycol were charged into a heating medium-circulating 2-liter stainless steel autoclave equipped with a stirrer, and 0.3 mol% of triethylamine was added to the acid component. A mixture of bis (2-hydroxyethyl) terephthalate (BHET) and an oligomer having an esterification rate of 95% was performed for 120 minutes while distilling water out of the system at 245 ° C. under a pressure of 0.25 Mpa, and BHET mixture). With respect to this BHET mixture, the above-mentioned aluminum salt A was added to the acid component in the polyester in an amount of 0.
After adding 02 mol%, the mixture was stirred at 245 ° C. for 10 minutes under a nitrogen atmosphere at normal pressure. Next, it took 50 minutes to gradually raise the temperature of the reaction system to 275 ° C. and gradually reduced the pressure of the reaction system to 0.1 Torr.
The polycondensation reaction was performed at 0.1 Torr. The polymerization time (AP) required for the IV of polyethylene terephthalate to reach 0.65 dlg ^-1 was 98 minutes. In addition, polyethylene terephthalate having an IV of 0.65 dlg ⁻¹ obtained by the above polycondensation was formed into chips according to a conventional method. When various physical properties were measured using this PET resin chip, the acid value was 1 eq / ton or less, and DS
The melting point by C is 257.1 ° C, Tc1 is 160.7 ° C, and Tc2
Was 185.1 ° C. The L value was 64.3, the a value was -1.4, the b value was 2.3, TS was 0.14, TOS was 0.01, and HS was 0.03.

The above-mentioned melt polymerization was repeated until the required amount of resin for spinning evaluation was obtained. After drying the obtained PET resin chip, it was supplied to a melt extruder to obtain a pore size of 0.14.
29 from a spinneret with 108 orifices of mmΦ
After discharging at 0 ° C, cooling and oiling
It was withdrawn at 720 m / min. Continue with preheating roller 8
Stretched 2.127 times at 0 ° C and set temperature of 150 ° C to 5
A polyester drawn yarn having 0 dtex and 108 filaments was obtained. The operability in spinning and drawing was good.

Polymerization and spinning were carried out in the same manner and under the same conditions as in Example 1 except that a mixture of 3.2 parts of ethylenediamine and 1.0 part of propylenediamine was used as the organic diamine during the polymerization of the polyurethane. A 44 decitex polyurethane elastic yarn to be subjected to post-processing was obtained. The polyurethane elastic yarn has a PSD of 70%, a PSW of 71%, a terminal group quantitative ratio (B / A) of 1.0, and a logarithmic viscosity of 1.4 dl.
/ G, and the logarithmic viscosity after treatment with boiling water for 1 hour is 2.0 d
1 / g. Using the obtained yarn, post-processing was performed in the same manner and under the same conditions as in Example 1 to obtain a dyed fabric. The optimum preset condition for processing the dough to the target dough amount was 185 ° C. for 1 minute. The obtained fabric had a strength retention of 85% and an elastic recovery of 64%. Operability in knitting and processing of a knitted fabric using these fibers was very good.

Example 4 A mixture of bis (2-hydroxyethyl) terephthalate and an oligomer prepared from a high-purity terephthalic acid and ethylene glycol according to a conventional method was mixed with 13 g of aluminum chloride as a polycondensation catalyst.
l of ethylene glycol solution with respect to the acid component in the polyester is 0.015 mol% as aluminum atom and 10 g / l of ethylene glycol solution of Irganox 1425 (manufactured by Ciba Specialty Chemicals) is 0 as Irganox 1425 with respect to the acid component. .0
245 ° C at normal pressure under nitrogen atmosphere
For 10 minutes. Then take 50 minutes to 275 ° C
The temperature of the reaction system was gradually lowered while raising the temperature to 13.3P.
a (0.1 Torr) at 275 ° C., 13.3
A polycondensation reaction was performed at Pa.

The IV obtained by the above polycondensation is 0.65
dl / g of polyethylene terephthalate was formed into chips according to a conventional method. The time (AP) required for the polycondensation reaction was 75 minutes. The intrinsic viscosity of PET after polycondensation is 0.65 dl /
g, acid value was 1.4 eq / ton, and DEG was 2.1 mol%. Further, Tm is 257.4 ° C. and Tc1 is 15
5.6 ° C. and Tc2 was 181.5 ° C. The hue was L value 68.47, a value -2.73, and b value 5.32.

Further, the thermal stability parameter (TS) of the above PET resin chip was 0.17, the hydrolysis resistance parameter (HS) was 0.05, and the thermal oxidation parameter (TOS) was less than 0.01. The haze was 0.1%.

The above-mentioned melt polymerization was repeated until the required amount of resin for spinning evaluation was obtained. After drying the obtained PET resin chip, it was supplied to a melt extruder to obtain a pore size of 0.14.
29 from a spinneret with 108 orifices of mmΦ
After discharging at 0 ° C, cooling and oiling
It was withdrawn at 720 m / min. Continue with preheating roller 8
Stretched 2.127 times at 0 ° C, set temperature 150 ° C,
A polyester drawn yarn of 7 dtex and 108 filaments, which is subjected to false twisting by a known method to give a boiling water shrinkage of 5
% Of false twisted yarn was obtained. The operability in spinning and drawing was good.

On the other hand, a method for producing polyurethane will be described below. (Synthesis of hindered amine compound) Thermometer, stirrer,
2,2,6,6-tetramethyl-4- was placed in a 500 cc branched flask equipped with a nitrogen inlet tube and a reflux condenser.
Piperidyl methacrylate (ADK STAB LA-87 /
(Asahi Denka Kogyo Co., Ltd.) 60 parts, cyclohexyl methacrylate 40 parts, and N, N'-dimethylacetamide 2
13 parts were taken and dissolved by stirring. The flask was heated in an oil bath with stirring to 60 ° C. while bubbling nitrogen through.

After reaching 60 ° C., 0.8 parts of 4,4-azoisobutyronitrile (AIBN) were added. The reaction was maintained at 60 ° C. while stirring as it was. Five hours after the initial addition of AIBN, an additional 0.2 parts of AIBN was added. The reaction was further continued at 60 ° C. for 15 hours, and then cooled to room temperature to obtain a hindered amine compound solution in which the reaction was completed. Using a rotor with a cone angle of 3 ° and a radius of 14 mm, 3
The solution viscosity measured with an E-type viscometer at 0 ° C. is 15 poise
Met. The unreacted polymerizable monomer in the solution was quantified by gas chromatography and found to be 4% by weight based on the weight of the charged polymerizable monomer. The number average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent and a refractometer as a detector was 2,700. The 1H-NMR spectrum of the obtained hindered amine compound was measured using DMSO-d6
When measured at 50 ° C. using a 1: 1 mixture of methane and CDCl 3 as a solvent, the proton of the methine carbon of the piperidyl group and the proton of the methine carbon of the cyclohexyl group were 5.0, 4,. 6 ppm, integration ratio is 5
2:48. Since this integral ratio is considered to be the molar ratio of the unit derived from 2,2,6,6-tetramethyl-4-piperidyl methacrylate and the unit derived from cyclohexyl methacrylate in the hindered amine compound, The percentage was calculated to be 60,40% by weight, which was consistent with the value determined from the charge.

Next, 175.37 parts of polytetramethylene ether glycol having a number average molecular weight of 1800,
-38.92 parts of diphenylmethane diisocyanate,
The reaction was carried out at 80 ° C. for 3 hours under a stream of N 2 to obtain a prepolymer having isocyanate groups at both ends. Prepolymer at 40 ° C
After cooling to 30%, N, N'-dimethylacetamide 30
8.36 parts were added and dissolved. It was further cooled to 10 ° C.
3.58 parts of ethylenediamine and 0.4 of diethylamine
A solution prepared by dissolving 6 parts of N, N'-dimethylacetamide in 146.86 parts was added to the prepolymer solution with high-speed stirring at one time and mixed to complete the reaction. 30 of this solution
The viscosity at 2000C was 2000 poise. The hindered amine solution 1 obtained in the above synthesis example was added to this solution.
3.42 parts, 1,3,5-tris (4
-T-butyl-3-hydroxy-2,6-dimethylbenzyl isocyanurate) (Cyanox 1790 /
Nippon Cyanamid) 2.15 parts, as an ultraviolet absorber
2- [2-hydroxy- (3,5-di-t-amyl) phenyl] benzotriazole (KEMISORB74 /
1.08 parts of Chemipro Kasei Co., Ltd.) and 0.69 parts of magnesium stearate as an antiadhesive were added and mixed by stirring to obtain a polyurethane solution. It was polymerized and spun under the same method and under the same conditions as in Example 1 to obtain a polyurethane elastic yarn of 44 dtex for post-processing.
The polyurethane elastic yarn has a PSD of 70% and a PSW of 7
1%. The obtained polyester false twisted yarn was used as a core yarn obtained by a known covering device.
The single covering yarn A was wound 600 times / m in the S twist direction while being stretched 5 times. The warp yarn is made of polyester of 84 decitex and 36 filaments, and the weft yarn is woven using the single covering yarn A.
A greige fabric having a five-sheet satin structure with 50 threads / in and 105 wefts / in was prepared. Post-processing was performed under the same temperature conditions as in Example 1 to obtain a dyed fabric. The optimum preset condition for processing the dough to the target dough amount was 185 ° C. for 1 minute. The fabric was excellent in stretchability. The weavability and the operability in processing of the fabric using these fibers were very good.

(Comparative Example 1) The same operation as in Example 4 was carried out except that antimony trioxide was used as a catalyst such that the addition amount was 0.05 mol% as antimony atoms with respect to an acid component in PET. went. The polymerization time (AP) required for the IV of polyethylene terephthalate to reach 0.65 dlg ^-1 was 65 minutes. In addition, polyethylene terephthalate having an IV of 0.65 dlg ⁻¹ obtained by the above polycondensation was formed into chips according to a conventional method. Various physical properties were measured using this PET resin chip. Oxidation of the obtained PET resin chip was 4.4 eq / ton, and DEG was 2.2 mo.
1%. Further, Tm is 256.5 ° C.
1 was 130.7 ° C and Tc2 was 209.3 ° C. L value is 55.03, a value is -0.29, b value is 1.06, TS is 0.22, TOS is 0.01 or less,
HS was 0.05. The haze was 0.4%. Further, the obtained polyester was confirmed to have thread breakage during melt spinning and stretching in the same manner as in Example 4, but was extremely inferior to those in each Example. Polymerization and spinning were carried out in the same manner and under the same conditions as in Example 1 except that the compound having a nitrogen atom was not added to the polyurethane solution obtained in Example 1, and a 44 dtex polyurethane for post-processing was used. An elastic yarn was obtained. The polyurethane elastic yarn had a PSD of 48%, a PSW of 66%, a terminal group quantitative ratio (B / A) of 1.0, and a logarithmic viscosity of 1.4 dl /.
g, and the logarithmic viscosity after treatment with boiling water for 1 hour is 2.1 dl.
/ G. Using the obtained yarn, post-processing was performed under the same method and under the same conditions as in Example 1 except for the pre-setting treatment, to obtain a dyed fabric. Although these fibers were used, the knitting operability was poor and was far from the level at which stable operation was possible.

[0236]

According to the present invention, by weaving and knitting using polyester fiber having excellent heat stability and whiteness and a specific polyurethane elastic yarn, the coloring property can be obtained even at a high temperature setting.
This makes it possible to stably produce a polyester stretch woven / knitted fabric having excellent heat setting properties and excellent fabric properties such as color clarity and tear strength.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D04B 1/18 D04B 1/18 21/00 21/00 B (72) Inventor Takahiro Nakajima Katata, Otsu City, Shiga Prefecture 2-1-1, Toyobo Co., Ltd., Research Institute (72) Inventor Shoichi 2-1-1 Katata, Otsu-shi, Shiga F-term, Toyobo Co., Ltd. Research Laboratory F-term (reference) BA01 BA02 BA03 BA04 BA05 BA07 BA08 BA09 BA10 BB05A BB10A BB12A BB13A BC05A BD03A BD04A BD06A BD07A BF09 BF18 BF19 BF25 BH02 CA01 CA02 CA03 CA04 CA05 EC06 CB05 DB02 CB10A03 CB10A02 EH03 FC02 FC03 FC04 FC05 FC08 FC12 FC14 FC35 FC36 GA13 GA14 GA17 JA061 JA091 JA121 JA261 JB131 JB171 JB191 JB231 JC121 JC131 JC281 JC341 JC4 51 JC461 JC471 JC551 JC561 JC571 JC591 JC601 JC621 JC641 JC751 JF021 JF031 JF041 JF071 JF121 JF131 JF151 JF181 JF221 JF361 JF471 JF541 JF561 KE02 KE03 KE06 KE07 4A002 AA01A07A04A07A04A07A04A07A AC14 CA04 DA01

Claims (38)

[Claims] The present invention is characterized in that at least a part of a polyester fiber made of a polyester polymerized by using a catalyst containing aluminum and / or a compound thereof and a phenolic compound is used and combined with a polyurethane elastic yarn. Polyester stretch woven and knitted fabric. 2. A polyester stretch woven or knitted fabric characterized by using at least a portion of polyester fibers made of polyester polymerized using a catalyst containing aluminum and / or a compound thereof and a phosphorus compound. 3. The polyester stretch woven or knitted fabric 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 stretch woven or knitted fabric according to claim 2 or 3, which is a compound of the following. 5. The polyester stretch woven or knitted fabric according to claim 2, wherein the phosphorus compound is one or more phosphonic acid compounds. 6. The polyester stretch woven or knitted fabric 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 stretch woven or knitted fabric 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 stretch woven or knitted fabric 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 stretch woven and knitted fabric. 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 stretch woven or knitted fabric according to claim 2, wherein the phosphorus compound is at least one 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.
Polyester stretch woven or knitted fabric according to 1. 13. The polyester stretch woven or knitted fabric 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 stretch woven or knitted fabric according to claim 13, wherein the phosphorus compound represented by the general formula (7) is at least one selected from the 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 stretch woven or knitted fabric 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 or a hydrocarbon group having 1 to 30 carbon atoms. R ³ represents hydrogen or 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 stretch woven or knitted fabric according to claim 15, wherein the phosphorus compound represented by the general formula (9) is at least one selected from the 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 stretch woven or knitted fabric comprising at least a portion of polyester fibers made of a polyester produced using a catalyst containing an aluminum salt of a phosphorus compound. 18. The polyester stretch woven or knitted fabric 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 obtained by using at least a portion of a polyester fiber made of a polyester produced using a catalyst containing at least one selected from compounds represented by the following general formula (12): Stretch woven knit. 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 stretch woven or knitted fabric 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 stretch woven or knitted fabric 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 stretch woven or knitted fabric 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 stretch woven or knitted fabric according to claim 2, wherein the phosphorus compound is at least one selected from the 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 stretch woven or knitted fabric 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 stretch woven or knitted fabric according to claim 2, wherein the phosphorus compound is at least one selected from the 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 stretch woven or knitted fabric according to claim 2, wherein the phosphorus compound is at least one selected from the 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 stretch woven or knitted fabric 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 stretch woven or knitted fabric according to claim 2, wherein the phosphorus compound has the following chemical formula (20) or (21). Embedded image Embedded image 29. The method according to claim 1, wherein one or more metals and / or metal compounds selected from the group consisting of alkali metals or compounds thereof, alkaline earth metals or compounds thereof coexist. 28
A polyester stretch woven or knitted fabric comprising at least a portion of a polyester fiber made of a polyester polymerized using the catalyst according to any one of the above. 30. The polyester stretch woven or knitted fabric according to any one of claims 1 to 29, wherein an amount of an antimony compound as an antimony atom is 50 ppm or less based on polyester as a polymerization catalyst. 31. The method according to claim 1, wherein a germanium compound as a polymerization catalyst is added in an amount of 20 ppm or less to the polyester as germanium atoms.
The polyester stretch woven or knitted fabric according to any one of the above. 32. The polyester according to any one of claims 1 to 32, wherein polyurethane elastic yarns satisfying the following conditions (1) and (2) are used at least in part. Stretch woven knit. (1) Dry heat set rate (PSD) after treatment at 190 ° C. for 1 minute under 100% elongation (Equation 1) PSD (%) = (L2−L1) / L1 × 100 (where L1 is L2 represents the yarn length before the treatment, and L2 represents the yarn length after the treatment). (2) After heat-up from 40 ° C. to 130 ° C. by wet heat over 60 minutes under 100% elongation, the wet heat set rate (PSW) after continuous treatment at 130 ° C. for 60 minutes (Expression 2) %) = (L4−L3) / L3 × 100 (where L3 represents the yarn length before the treatment and L4 represents the yarn length after the treatment) is 75% or less. 33. The polyester stretch woven / knitted fabric according to claim 32, wherein the polyurethane elastic yarn contains a compound having a nitrogen atom. 34. A nitrogen atom-containing compound which is a reaction product of a diisocyanate compound and a dialkylhydrazine, a nitrogen atom-containing polymer which is a reaction product of a diisocyanate compound and a diol containing an excess mole of nitrogen atom, A nitrogen-containing polymer in which a terminal isocyanate group of a reaction product of an atom-containing diol and an excess mole of a diisocyanate compound is blocked with a monoamine and / or dialkylhydrazine; and a carboxylic acid hydrazide and two phenolic hydroxyl groups The polyester stretch woven / knitted fabric according to claim 33, which is at least one compound selected from a nitrogen atom-containing polymer which is a reaction product of the compound with a glycidyl etherified product. 35. A polyurethane elastic yarn comprising a polyurethane polymer obtained by reacting a diamine compound with an intermediate polymer having terminal isocyanate groups obtained from a polyol and an excess mole of a diisocyanate compound. Item 35. The polyester stretch woven or knitted fabric according to any one of Items 32 to 34. 36. The polyurethane elastic yarn according to claim 35, wherein the diamine compound is ethylenediamine.
The described polyester stretch woven or knitted fabric. 37. The polyester stretch woven or knitted fabric according to claim 35, wherein the diamine compound of the polyurethane elastic yarn contains a secondary monoamine compound. 38. The polyurethane polymer of the polyurethane elastic yarn has an amino group (A) as a terminal group and a urea group (B) derived from a secondary monoamine which is a terminal terminator, and an equivalent ratio of both terminal groups. The polyester stretch woven or knitted fabric according to any one of claims 35 to 37, wherein (B / A) is 0.5 to 2.0.