JP2001098418A - Polyester fiber for industrial material and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester fiber for an industrial material, comprising a resin obtained by using a polymerization catalyst except an antimony compound and a germanium compound, containing no foreign matter causing the reduction of the strength of the fiber, and hardly soiling a spinneret when spinning the resin, and suitable for a rubber-reinforcing use such as a tire cord and a V-belt. SOLUTION: This polyester fiber for the industrial material is obtained by polymerizing the polyester by using a catalyst satisfying specific parameters without using the antimony compound and the germanium compound, and forming the obtained polyester into the objective fiber: (1) an activity parameter(AP) satisfying the inequality AP(min)<T(min)×2 (AP is a time required for polymerizing a polyethylene terephthalate having 0.5 dlg-1 intrinsic viscosity by using a prescribed catalyst at 275 deg.C at 0.1 Torr reduced pressure degree; T is the AP by using antimony trioxide as the catalyst with the proviso that the proportion of the added antimony trioxide is 0.05 mol% expressed in terms of antimony atom based on the acid components in the formed polyethylene terephthalate); (2) a thermostability indicator (TD) satisfying the inequality TD<25 (%) (TD is the decreasing rate (%) of the intrinsic viscosity when inserting 1 g PET having 0.6 dlg-1 intrinsic viscosity in a glass test tube, vacuum-drying the resultant PET at 130 deg.C for 12 h, and melting the dried PET in nitrogen atmosphere at 300 deg.C for 2 h).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester fiber suitable for industrial materials and a method for producing the same. In particular, it does not contain foreign matter that reduces the strength in the fiber,
An object of the present invention is to provide a polyester fiber for industrial materials suitable for rubber reinforcement applications such as tire cords and V-belts, which have a small stain on a spinneret during spinning, and a method for producing the same.

[0002]

2. Description of the Related Art Polyester high-strength yarns represented by polyester tire cords are organic fibers having an excellent balance in physical properties and cost, and are widely and widely used as fibers for industrial materials.

[0003] Polyester fibers for industrial materials are particularly required to be free of foreign matter that causes a decrease in strength in the fibers and to have a small amount of spinneret contamination during spinning. It is known that most of these problems are caused by antimony compounds which are polycondensation catalysts for polyesters. Patent publication 26
No. 66502 proposes a method for improving spinneret staining during yarn production by using an antimony trioxide containing a specific bismuth and selenium as a catalyst. In the present situation, the foreign matter that is generated is not completely removed. JP-A-2-182914 proposes a method in which a specific amount of a germanium compound is used without using an antimony compound as a polycondensation catalyst. However, although such a method can certainly reduce foreign matter in the fiber, this catalyst is not only disadvantageous in that it is very expensive, but also easily distills out of the reaction system during polymerization, so that the catalyst concentration in the reaction system is low. However, there is a problem that the polymerization is difficult to control the polymerization. On the other hand, as a polymerization catalyst having excellent catalytic activity other than the antimony compound and the germanium compound, titanium compounds and tin compounds represented by tetraalkoxytitanate have already been proposed,
Polyester fibers produced using these materials are susceptible to thermal degradation during melt molding and have the problem of being markedly colored.

As described above, the conventional method does not include any foreign matter,
Polyester fibers for industrial materials which can be industrially produced with less spinneret contamination during spinning have not yet been obtained.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to a polyester for industrial materials suitable for rubber reinforcing applications such as tire cords and V-belts, which do not contain foreign matter which causes a decrease in fiber strength in the resin and which has a small stain on a spinneret during spinning. The present invention provides a fiber and a method for producing the fiber.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies with the aim of solving the above problems, and as a result, have found that a catalyst having the following characteristics, that is, an antimony compound or a germanium compound is used. If it is a catalyst that satisfies the activity parameter represented by the following formula (1), and if the polyethylene terephthalate polymerized using the catalyst satisfies the thermal stability index represented by the following formula (2), It has been found that thermal degradation during melt molding of a polyester polymerized using the catalyst can be effectively suppressed.

Further, alkali metals, alkaline earth metals, Group 5A metals, Group 6A metals, Group 7A metals, Group 8 metals, Group 1B metals, Group 2B metals, Group 3B metals, lead, bismuth, tellurium, silicon, Boron, zirconium, hafnium, scandium,
The coexistence of a specific compound such as yttrium, a lanthanoid metal or a compound thereof, which originally has a low catalytic activity for polyester polymerization, surprisingly has sufficient activity as a polymerization catalyst. The catalyst is a catalyst satisfying the properties of the formulas (1) and (2) without using any antimony compound or germanium compound.
The present inventors have found that the resin does not contain any foreign matter that causes a decrease in fiber strength, and that it is suitable for polyester fibers for industrial materials with less spinneret stain during spinning. (1) Activity parameter (AP): AP (min) <T (min) * 2 (In the above formula, AP has a specific viscosity of 0.5 dlg ⁻¹ at 275 ° C. under a reduced pressure of 0.1 Torr using a predetermined catalyst. The time (min) required to polymerize polyethylene terephthalate is indicated by T. T indicates AP when antimony trioxide is used as a catalyst, where antimony trioxide is converted to an antimony atom with respect to the acid component in the produced polyethylene terephthalate. (2) Thermal stability index (TD): TD <25 (%) (In the above formula, ¹ g of PET having an intrinsic viscosity of 0.6 dlg ^-1 is placed in a glass test tube and placed at 130 ° C. for 12 hours. After vacuum drying, the intrinsic viscosity decreases (%) when melted under nitrogen atmosphere at 300 ° C for 2 hours
Indicates)

[0008] That is, the present invention provides a solution to the above-mentioned problems as an alkali metal, alkaline earth metal, group 5A metal, group 6A metal, group 7A metal, group 8 metal, group 1B metal, group 2B metal, group 3B metal. Has little or no activity as a polymerization catalyst, such as lead, bismuth, tellurium, silicon, boron, zirconium, hafnium, scandium, yttrium, lanthanoid metals or compounds thereof. Provided is a polyester fiber for industrial materials, which comprises a polyester polymerized by using a catalyst obtained by combining a metal compound and a specific compound, and a method for producing the same.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention does not include, in a resin, a foreign matter which causes a reduction in fiber strength, which is obtained by spinning a polyester comprising a polycondensation catalyst other than an antimony compound and a germanium compound. An object of the present invention is to provide a small amount of polyester fiber for industrial materials and a method for producing the same.

An alkali metal, an alkaline earth metal, a group 5A metal, a group 6A metal, a group 7A metal, a group 8 metal, a group 1B metal constituting a polymerization catalyst used for producing the polyester fiber for industrial materials of the present invention. , Group 2B metals, Group 3B metals, lead, bismuth, tellurium, silicon, boron, zirconium, hafnium, scandium, yttrium, lanthanoid metals,
Or as those compounds, alkali metals, alkaline earth metals, Group 5A metals, Group 6A metals, Group 7A metals, Group 8 metals, Group 1B metals, Group 2B metals, Group 3B metals, lead, bismuth, tellurium, silicon , Boron, zirconium, hafnium, scandium, yttrium, lanthanoid metal, in addition to one or more compounds selected from these compounds is not particularly limited, for example, these formic acid, acetic acid, propionic acid, Butyric acid, saturated aliphatic carboxylate such as oxalic acid, acrylic acid, unsaturated aliphatic carboxylate such as methacrylic acid, aromatic carboxylate such as benzoic acid, halogen-containing carboxylate such as trichloroacetic acid,
Lactic acid, citric acid, hydroxycarboxylic acid salts such as salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, hydrogen phosphate, hydrogen sulfate, sulfurous acid, thiosulfuric acid, hydrochloric acid,
Inorganic acid salts such as hydrobromic acid, chloric acid, and bromic acid, 1-propanesulfonic acid, 1-pentanesulfonic acid, organic sulfonates such as naphthalenesulfonic acid, organic sulfates such as lauryl sulfate, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, alkoxides such as t-butoxy, chelate compounds such as acetylacetonate, oxides, hydroxides and the like, among which saturated aliphatic carboxylate is preferable, Further, acetate is particularly preferred. Also, alkali metals, alkaline earth metals, group 5A metals, group 6A metals, group 7A metals, group 8 metals, group 1B metals, group 2B metals, group 3B metals, lead, bismuth, tellurium, silicon, boron, zirconium, Hafnium, scandium, yttrium, lanthanoid metals, or among these compounds, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Cr, Mn, Fe, Ru, Co, N
i, Pd, Cu, Ag, Zn, In, Tl, Pb, Bi, Zr, Hf, Sc, Y, La, Ce, Sm, Eu, G
d or compounds thereof are preferred.

These alkali metals, alkaline earth metals,
Group 5A metal, Group 6A metal, Group 7A metal, Group 8 metal, Group 1B metal, 2
Group B metal, Group 3B metal, lead, bismuth, tellurium, silicon, boron, zirconium, hafnium, scandium, yttrium, lanthanoid metal or their compounds, the amount of the dicarboxylic acid or polycarboxylic acid of the resulting polyester, etc. relative number of moles of all the structural units of the carboxylic acid component 1 × 10 ^- is preferably ^{from 6} to 0.1 mols, is that more preferably in the range of 5 × 10 ^-6 to 0.05 moles.

The specific compound constituting the polymerization catalyst used for polymerizing the polyester used for the polyester fiber for industrial materials of the present invention is a compound having a structure represented by the following general formula (1) and / or (2): A compound selected from the group consisting of

[0013]

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[0014]

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(In the formulas (1) and (2), Ar represents an aryl group.)

The specific compound constituting the polymerization catalyst used for polymerizing the polyester used for the polyester fiber for industrial materials of the present invention is, for example, an aminophenol compound having both the general formulas (1) and (2). Or a compound in which both N and O are bonded to an aromatic compound or a derivative thereof.

The compound having the structure of the general formula (1) and / or (2) used as the specific compound in the polymerization catalyst used for polymerizing the polyester used for the polyester fiber for industrial materials of the present invention includes: More specifically, one or more compounds selected from the group consisting of compounds having the structures of the following general formulas (3) and / or (4) are preferred.

[0018]

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[0019]

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(In the formulas (3) to (4), X ¹ , X ² and X ³ each independently represent a group containing hydrogen, a hydrocarbon group, an acyl group, a sulfonyl group,
For example, a group containing phosphoryl, such as a sulfonic acid group or a sulfonate group, such as a phosphonic acid group or a phosphonate group,
Or a hydrocarbon group having an ether bond, etc .;
Represents an aryl group exemplified by the following general formulas (5) to (12). )

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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Ar is Ar-OX ¹ or Ar represented by the general formula (5)
Examples of the compound having a structure of -N (-X ² ) -X ³ include, for example, linear phenol compounds represented by the following general formulas (13) and (14), linear aniline compounds and derivatives thereof, Branched linear phenol compounds, branched linear aniline compounds and derivatives thereof represented by the following general formulas (15) and (16), or the following general formulas (17) and (1)
Examples include the cyclic phenol compounds, cyclic aniline compounds and derivatives thereof represented by 8), among which linear phenol compounds, linear aniline compounds, or cyclic phenol compounds and derivatives thereof are preferable. Further, among linear phenol compounds or cyclic phenol compounds and their derivatives,
2,2′-bisphenol represented by the following formula (45),
6) 2-aminobiphenyl, 2,2′-dihydroxydiphenyl ether represented by the following formula (47), the following formula (48)
2,2'-thiobis (4-tert-octylphenol) represented by the following formula (49) and 2,2'-methylenebis (6-ter
t-butyl-p-cresol), a methylene-bridged linear phenol compound represented by the following formula (50) (a mixture of 2 to 100 mer), and a methylene-bridged linear p-formula represented by the following formula (51)
tert-butylphenol compound (a mixture of 2 to 100 mer), calix [4] arene represented by the following formula (52), calix [6] arene represented by the following formula (53), and the following formula (54) Calix [8] arene represented by the following formula (5
5) p-tert-butyl calix [4] arene represented by the following formula (56), p-tert-butyl calix [6] arene represented by the following formula (56), or p-tert represented by the following formula (57) -Butylcalix [8] arene and derivatives thereof are particularly preferred.

[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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(In the formulas (13) to (18), each R ¹ is the same or different and is a hydrocarbon group of C1 to C20, a halogen group, a carboxyl group or an ester thereof, a formyl group, an acyl group,
A group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituent thereof, a hydroxyl group,
An alkoxyl group, an alkylthio group, a group containing a sulfonyl, such as a sulfonic acid group or a sulfonate group, a group containing a phosphoryl group, such as a phosphonic acid group or a phosphonate group, a nitro group, a cyano group, a thiocyano group, etc.
R ² is the same or different and is hydrogen, a C1 to C20 hydrocarbon group, a halogen group, a carboxyl group or an ester thereof,
Formyl group, acyl group, group represented by (acyl) -O-, amino group, mono- or dialkylamino group, amide group or a substitute thereof, hydroxyl group, alkoxyl group, alkylthio group, group containing sulfonyl, for example, sulfonic acid Groups or sulfonate groups, such as a phosphoryl group, such as a phosphonic acid group or a phosphonate group, such as a nitro group, a cyano group, or a thiocyano group; each X is the same or different, hydrogen, C
1 to C20 hydrocarbon group, an acyl group, a group containing a sulfonyl, such as a sulfonic acid group or a sulfonate group, a group containing a phosphoryl, such as a phosphonic acid group or a phosphonate group, or a hydrocarbon group having an ether bond. , Each Y is the same or different, a direct bond, a C1-C10 alkylene group,-(alkylene) -O-,-(alkylene) -S-,
-O -, - S -, - SO 2 -, - CO -, - COO- represent like, each n are the same or different, represent an integer from 1 to 100, a is an integer from 1 to 3, b represents 0 or an integer of 1 to 3, each c is the same or different, and represents an integer of 1 to 3, each d is the same or different, and represents an integer of 0 or 1 to 3. Where 1
≦ a + b ≦ 5, 1 ≦ c + d ≦ 4. The hydrocarbon group here represents an alkyl group, an aryl group, or the like, and may include a substituent such as a hydroxyl group or a halogen group in the molecular chain. )

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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(In the formula (50), n represents an arbitrary integer from 1 to 99.)

[0044]

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(In the formula (51), n represents an arbitrary integer from 1 to 99.)

[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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Ar is Ar-OX ¹ or Ar represented by the general formula (5)
Other examples of the compound having a structure of -N (-X ² ) -X ³ include coumarin derivatives represented by the following general formulas (19) and (20), and the following general formulas (21) and (22) ), A dihydrocoumarin derivative represented by the following general formulas (23) and (24), a general formula (25) and
Chromanone derivative represented by (26), the following general formula (2
Isochromanone derivatives as represented by 7) and (28),
Examples include chroman derivatives represented by the following general formulas (29) and (30), and heterocyclic compounds such as isochroman derivatives represented by the following general formulas (31) and (32),
Of these, coumarin derivatives, chromone derivatives, and chroman derivatives are preferred. Among coumarin derivatives, chromone derivatives, and chroman derivatives, the following formula (58)
Esculetin represented by the following formula (59), 7-amino-4-methylcoumarin represented by the following formula (60), chrysin represented by the following formula (60), morin represented by the following formula (61), ), Epicatechin represented by the following formula (63), epigallocatechin gallate represented by the following formula (64), and derivatives thereof are particularly preferred.

[0053]

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[0054]

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[0055]

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[0056]

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(In the formulas (19) to (22), each R is the same or different and is a C1 to C20 hydrocarbon group, a halogen group, a carboxyl group or an ester thereof, a formyl group, an acyl group,
A group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituent thereof, a hydroxyl group,
An alkoxyl group, an alkylthio group, a group containing a sulfonyl, such as a sulfonic acid group or a sulfonate group, a group containing a phosphoryl group, such as a phosphonic acid group or a phosphonate group, a nitro group, a cyano group, a thiocyano group, etc.
X is the same or different and is hydrogen, a hydrocarbon group of C1 to C20, an acyl group, a group containing a sulfonyl group such as a sulfonic acid group or a sulfonate group, a group containing a phosphoryl group such as a phosphonic acid group or a phosphonate group, or an ether Represents a hydrocarbon group having a bond, and j and b are 0 or 1
Represents an integer of from 1 to 3, and m and d represent 0 or an integer of from 1 to 2. However, 0 ≦ j + b ≦ 4, 0 ≦ m + d ≦ 2, and 1 ≦ j + m ≦ 5. The hydrocarbon group here represents an alkyl group, an aryl group, or the like, and may include a substituent such as a hydroxyl group or a halogen group in the molecular chain. )

[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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(In the formulas (23) to (28), each R is the same or different and represents a C1 to C20 hydrocarbon group, a halogen group, a carboxyl group or an ester thereof, a formyl group, an acyl group,
A group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituent thereof, a hydroxyl group,
An alkoxyl group, an alkylthio group, a group containing a sulfonyl, such as a sulfonic acid group or a sulfonate group, a group containing a phosphoryl group, such as a phosphonic acid group or a phosphonate group, a nitro group, a cyano group, a thiocyano group, etc.
X is the same or different and is hydrogen, a hydrocarbon group of C1 to C20, an acyl group, a group containing a sulfonyl group such as a sulfonic acid group or a sulfonate group, a group containing a phosphoryl group such as a phosphonic acid group or a phosphonate group, or an ether Represents a hydrocarbon group having a bond, etc., a represents an integer of 1 to 3, b represents 0 or an integer of 1 to 3, and c and d represent 0 or an integer of 1 to 2. Where 1 ≦ a + b ≦ 4, 0 ≦ c + d
≦ 2. The hydrocarbon group here represents an alkyl group, an aryl group, or the like, and may include a substituent such as a hydroxyl group or a halogen group in the molecular chain. )

[0065]

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[0066]

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[0067]

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[0068]

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(In the formulas (29) to (32), each R is the same or different and represents a C1 to C20 hydrocarbon group, a halogen group, a carboxyl group or an ester thereof, a formyl group, an acyl group,
A group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituent thereof, a hydroxyl group,
An alkoxyl group, an alkylthio group, a group containing a sulfonyl, such as a sulfonic acid group or a sulfonate group, a group containing a phosphoryl group, such as a phosphonic acid group or a phosphonate group, a nitro group, a cyano group, a thiocyano group, etc.
X is the same or different and is hydrogen, a hydrocarbon group of C1 to C20, an acyl group, a group containing a sulfonyl group such as a sulfonic acid group or a sulfonate group, a group containing a phosphoryl group such as a phosphonic acid group or a phosphonate group, or an ether Represents a hydrocarbon group having a bond, etc., a represents an integer of 1 to 3, b represents 0 or an integer of 1 to 3, and c and d represent 0 or an integer of 1 to 3. Where 1 ≦ a + b ≦ 4, 0 ≦ c + d
≦ 3. The hydrocarbon group here represents an alkyl group, an aryl group, or the like, and may include a substituent such as a hydroxyl group or a halogen group in the molecular chain. )

[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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Ar is Ar-OX ¹ or Ar represented by the general formula (6)
Examples of the compound having a structure of -N (-X ² ) -X ³ include, for example, naphthalene derivatives represented by the following general formulas (33) and (34), or the following general formulas (35) and (36) Among them, bisnaphthyl derivatives and the like, among these, 4,5-dihydroxynaphthalene represented by the following formula (65)
Disodium 2,7-disulfonate, 1,8-diaminonaphthalene represented by the following formula (66), naphthol AS represented by the following formula (67), 1,1 represented by the following formula (68) '-Bi-2-naphthol, or 1,1'-binaphthyl-2,2' represented by the following formula (69)
-Diamines and their derivatives are preferred, and among these, disodium 4,5-dihydroxynaphthalene-2,7-disulfonate or 1,8-diaminonaphthalene and their derivatives are particularly preferred.

[0078]

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[0079]

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(In the formulas (33) to (34), each R is the same or different, and represents a C1 to C20 hydrocarbon group, a halogen group, a carboxyl group or an ester thereof, a formyl group, an acyl group,
A group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituent thereof, a hydroxyl group,
An alkoxyl group, an alkylthio group, a group containing a sulfonyl, such as a sulfonic acid group or a sulfonate group, a group containing a phosphoryl group, such as a phosphonic acid group or a phosphonate group, a nitro group, a cyano group, a thiocyano group, etc.
X is the same or different and is hydrogen, a hydrocarbon group of C1 to C20, an acyl group, a group containing a sulfonyl group such as a sulfonic acid group or a sulfonate group, a group containing a phosphoryl group such as a phosphonic acid group or a phosphonate group, or an ether Represents a hydrocarbon group having a bond, and j, b, c, and d are
Represents 0 or an integer from 1 to 3. Where 0 ≦ j + b ≦ 4, 0 ≦ c
+ d ≦ 4 and 1 ≦ j + c ≦ 6. The hydrocarbon group here represents an alkyl group, an aryl group, or the like, and may include a substituent such as a hydroxyl group or a halogen group in the molecular chain. )

[0081]

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[0082]

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(In the formulas (35) to (36), each R is the same or different, and represents a C1 to C20 hydrocarbon group, a halogen group, a carboxyl group or an ester thereof, a formyl group, an acyl group,
A group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituent thereof, a hydroxyl group,
An alkoxyl group, an alkylthio group, a group containing a sulfonyl, such as a sulfonic acid group or a sulfonate group, a group containing a phosphoryl group, such as a phosphonic acid group or a phosphonate group, a nitro group, a cyano group, a thiocyano group, etc.
X is the same or different and is hydrogen, a hydrocarbon group of C1 to C20, an acyl group, a group containing a sulfonyl group such as a sulfonic acid group or a sulfonate group, a group containing a phosphoryl group such as a phosphonic acid group or a phosphonate group, or an ether It represents such a hydrocarbon group having a bond, Y is a direct bond, an alkylene group from C1 to C10, - (alkylene) -O -, - (alkylene) -S -, - O -, - S -, - SO 2 - , -CO-, -COO-, etc.
j, b, c, d, e, f, g, and h represent 0 or an integer of 1 to 3. Where 0 ≦ j + b ≦ 4, 0 ≦ c + d ≦ 3, 0 ≦ e + f ≦ 4, 0
≦ g + h ≦ 3, 1 ≦ j + c + e + g ≦ 12. The hydrocarbon group here represents an alkyl group, an aryl group, or the like, and may include a substituent such as a hydroxyl group or a halogen group in the molecular chain. )

[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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Ar-OX represented by the general formula (7) or (8)
Examples of the compound having the structure of ¹ or Ar-N (-X ² ) -X ³ include:
For example, anthracene derivatives represented by the following general formulas (37) and (38) and the like, among these,
Anthrarobin represented by the following formula (70), 9,10-dimethoxyanthracene represented by the following formula (71), or the following formula (7
2-aminoanthracene represented by 2) and derivatives thereof are preferable, and among these, anthralobin and derivatives thereof are particularly preferable.

[0090]

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[0091]

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(In the formulas (37) to (38), each R is the same or different, and represents a C1 to C20 hydrocarbon group, a halogen group, a carboxyl group or an ester thereof, a formyl group, an acyl group,
A group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituent thereof, a hydroxyl group,
An alkoxyl group, an alkylthio group, a group containing a sulfonyl, such as a sulfonic acid group or a sulfonate group, a group containing a phosphoryl group, such as a phosphonic acid group or a phosphonate group, a nitro group, a cyano group, a thiocyano group, etc.
X is the same or different and is hydrogen, a hydrocarbon group of C1 to C20, an acyl group, a group containing a sulfonyl group such as a sulfonic acid group or a sulfonate group, a group containing a phosphoryl group such as a phosphonic acid group or a phosphonate group, or an ether Represents a hydrocarbon group having a bond, and j, b, e, and f are
Represents an integer of 0 or 1 to 3, and p and q are 0 or 1 to 2
Represents an integer. Where 0 ≦ j + b ≦ 4, 0 ≦ p + q ≦ 2, 0 ≦ e + f
≦ 4, 1 ≦ j + p + e ≦ 8. The hydrocarbon group here represents an alkyl group, an aryl group, or the like, and may include a substituent such as a hydroxyl group or a halogen group in the molecular chain. )

[0093]

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[0094]

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[0095]

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Ar is Ar-OX ¹ or Ar represented by the general formula (9)
Examples of the compound having a structure of -N (-X ² ) -X ³ include benzoquinone derivatives represented by the following general formulas (39) and (40). (73)
2,5-dihydroxybenzoquinone and its derivatives represented by

[0097]

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[0098]

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(In the formulas (39) to (40), each R is the same or different, and represents a C1 to C20 hydrocarbon group, a halogen group, a carboxyl group or an ester thereof, a formyl group, an acyl group,
A group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituent thereof, a hydroxyl group,
An alkoxyl group, an alkylthio group, a group containing a sulfonyl, such as a sulfonic acid group or a sulfonate group, a group containing a phosphoryl group, such as a phosphonic acid group or a phosphonate group, a nitro group, a cyano group, a thiocyano group, etc.
X is the same or different and is hydrogen, a hydrocarbon group of C1 to C20, an acyl group, a group containing a sulfonyl group such as a sulfonic acid group or a sulfonate group, a group containing a phosphoryl group such as a phosphonic acid group or a phosphonate group, or an ether Represents a hydrocarbon group having a bond, and k, l, p, and q are
Represents 0 or an integer from 1 to 2. Where 0 ≦ k + l ≦ 2, 0 ≦ p
+ q ≦ 2, 1 ≦ k + p ≦ 4. The hydrocarbon group here represents an alkyl group, an aryl group, or the like, and may include a substituent such as a hydroxyl group or a halogen group in the molecular chain. )

[0100]

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Ar is an Ar-O represented by the general formula (10) or (11)
Examples of the compound having the structure of -X ¹ or ^{Ar-N (-X 2) -X} 3, for example, naphthoquinone derivatives as represented by the following general formula (41) and (42), with these Among them, 5,8-dihydroxy-1,4-naphthoquinone represented by the following formula (74), 2-aminonaphthoquinone represented by the following formula (75) and derivatives thereof are preferable.

[0102]

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[0103]

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(In the formulas (41) to (42), each R is the same or different, and represents a C1 to C20 hydrocarbon group, a halogen group, a carboxyl group or an ester thereof, a formyl group, an acyl group,
A group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituent thereof, a hydroxyl group,
An alkoxyl group, an alkylthio group, a group containing a sulfonyl, such as a sulfonic acid group or a sulfonate group, a group containing a phosphoryl group, such as a phosphonic acid group or a phosphonate group, a nitro group, a cyano group, a thiocyano group, etc.
X is the same or different and is hydrogen, a hydrocarbon group of C1 to C20, an acyl group, a group containing a sulfonyl group such as a sulfonic acid group or a sulfonate group, a group containing a phosphoryl group such as a phosphonic acid group or a phosphonate group, or an ether Represents a hydrocarbon group having a bond, and k and l are 0 or 1
Represents an integer from 1 to 2, and c and d represent 0 or an integer from 1 to 3. However, 0 ≦ k + 1 ≦ 2, 0 ≦ c + d ≦ 4, and 1 ≦ k + c ≦ 5. The hydrocarbon group here represents an alkyl group, an aryl group, or the like, and may include a substituent such as a hydroxyl group or a halogen group in the molecular chain. )

[0105]

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[0106]

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Ar is Ar-OX ¹ or A represented by the general formula (12)
Examples of the compound having the structure of rN (-X ² ) -X ³ include, for example,
Examples include anthraquinone derivatives represented by the following general formulas (43) and (44).
Quinalizarin represented by (76), alizarin represented by the following formula (77), quinizarin represented by the following formula (78),
Anthralphine represented by 9), emodin represented by the following formula (80), 1,4-diaminoanthraquinone represented by the following formula (81), 1,8-diamino represented by the following formula (82) -4,5-dihydroxyanthraquinone or Acid Blue 25 represented by the following formula (83) and derivatives thereof are preferable, and among these, quinalizarin, 1,4-diaminoanthraquinone and derivatives thereof are particularly preferable.

[0108]

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[0109]

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(In the formulas (43) to (44), each R is the same or different, and represents a C1 to C20 hydrocarbon group, a halogen group, a carboxyl group or an ester thereof, a formyl group, an acyl group,
A group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituent thereof, a hydroxyl group,
An alkoxyl group, an alkylthio group, a group containing a sulfonyl, such as a sulfonic acid group or a sulfonate group, a group containing a phosphoryl group, such as a phosphonic acid group or a phosphonate group, a nitro group, a cyano group, a thiocyano group, etc.
X is the same or different and is hydrogen, a hydrocarbon group of C1 to C20, an acyl group, a group containing a sulfonyl group such as a sulfonic acid group or a sulfonate group, a group containing a phosphoryl group such as a phosphonic acid group or a phosphonate group, or an ether Represents a hydrocarbon group having a bond, and j, b, c, and d are
Represents 0 or an integer from 1 to 3. Where 0 ≦ j + b ≦ 4, 0 ≦ c
+ d ≦ 4 and 1 ≦ j + c ≦ 6. The hydrocarbon group here represents an alkyl group, an aryl group, or the like, and may include a substituent such as a hydroxyl group or a halogen group in the molecular chain. )

[0111]

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[0112]

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[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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The amount of such a specific compound to be used may be, for example, coexisting alkali metal, alkaline earth metal, group 5A metal, group 6A metal, group 7A metal, group 8 metal, group 1B metal, group 2B metal, 3B Group metal, lead, bismuth, tellurium, silicon, boron, zirconium, hafnium, scandium, yttrium, lanthanoid metal or a compound thereof, preferably in the range of 0.01 to 100 mol, more preferably 0.05 to 100 mol. In the range of 50 moles.

The present invention also relates to a polyester fiber for industrial materials comprising a polyester produced using a catalyst substantially having catalytic activity consisting of two or more compounds having substantially no catalytic activity for polyester polymerization, It is intended to provide a manufacturing method. It is preferable that at least one kind of the compound having substantially no catalytic activity in the polyester polymerization of the present invention is a metal or a compound thereof. It is preferable that at least one other compound having substantially no catalytic activity in the polyester polymerization of the present invention is an organic compound.

The metal or compound having substantially no catalytic activity for polyester polymerization used for producing the polyester fiber for industrial materials of the present invention is Na, K, Rb, Cs, Be, Ca, S
It is a metal such as r, Si, V, Cr, Ru, Rh, Pd, Te, Cu or a compound thereof, preferably Na, K, Rb, Cs, Be, Si, Cu or a compound thereof. The compounds of these metals are not particularly limited. For example, formic acid, acetic acid,
Propionic acid, butyric acid, saturated aliphatic carboxylate such as oxalic acid, acrylic acid, unsaturated aliphatic carboxylate such as methacrylic acid, aromatic carboxylate such as benzoic acid, halogen-containing carboxylate such as trichloroacetic acid, Hydroxycarboxylic acid salts such as lactic acid, citric acid, salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, hydrogen phosphate, hydrogen sulfate, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, Inorganic acid salts such as bromate, 1-propanesulfonic acid, 1-pentanesulfonic acid, organic sulfonates such as naphthalenesulfonic acid, organic sulfates such as lauryl sulfate, methoxy, ethoxy, n-propoxy, iso-propoxy, alkoxides such as n-butoxy and t-butoxy,
Chelating compounds such as acetylacetonate, oxides,
Hydroxides and the like can be mentioned, and among them, saturated aliphatic carboxylate is preferable, and acetate is particularly preferable.

The organic compound having substantially no catalytic activity for polyester polymerization described in the present invention is a compound selected from the group consisting of compounds having the structures of the above-mentioned general formulas (1) and / or (2). Is preferred.

The catalyst used for the polymerization of the polyester used for the polyester fiber for industrial materials of the present invention has catalytic activity not only in the polycondensation reaction but also in the esterification reaction and the transesterification reaction. Further, it has catalytic activity not only in melt polymerization but also in solid phase polymerization and solution polymerization. The polymerization of the polyester in the present invention can be carried out by a conventionally known method. For example, in the case of polyethylene terephthalate, a method of esterifying terephthalic acid and ethylene glycol followed by polycondensation, or a polycondensation reaction after an ester exchange reaction between an alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol is performed. It can be performed by any of the following methods. The polymerization apparatus may be of a batch type or a continuous type.

The catalyst used for the polymerization of the polyester used for the polyester fiber for industrial materials of the present invention is preferably added before the start of the polycondensation reaction, but before the start of the esterification or transesterification and during the reaction. It can be added to the reaction system at any stage. The method of adding the catalyst used in the polymerization of the polyester in the present invention may be in the form of a powder or a slurry or a solution of a solvent such as ethylene glycol, and is not particularly limited. Alkali metals, alkaline earth metals, Group 5A metals, Group 6A metals, Group 7A metals, Group 8 metals, 1
A group B metal, a group 2B metal, a group 3B metal, lead, bismuth, tellurium, silicon, boron, zirconium, hafnium, scandium, yttrium, a lanthanoid metal or a mixture thereof and a compound in which a specific compound is previously mixed is added. Or these may be added separately.

The polyester used for the polyester fiber for industrial materials of the present invention may be polymerized by using an antimony compound or a germanium compound in combination. However, the antimony compound is preferably added in an amount of 50 ppm or less as an antimony atom to a polyester obtained by polymerization. More preferably, it is added in an amount of 30 ppm or less. If the added amount of antimony is 50 ppm or more, foreign substances are generated in the polyester, which is not preferable. The germanium compound is preferably added to the polyester obtained by polymerization in an amount of 20 ppm or less as a germanium atom. More preferably, it is added in an amount of 10 ppm or less. Germanium added to 20
If it is more than ppm, it is not preferable because it is disadvantageous in cost. As the antimony compound used in the present invention, antimony trioxide, antimony pentoxide, antimony acetate,
Examples include antimony glycooxide, and among these, antimony trioxide is preferable. Examples of the germanium compound include germanium dioxide and germanium tetrachloride, among which germanium dioxide is preferable.

Further, the catalyst used for the polymerization of the polyester used for the polyester fiber for industrial materials used in the present invention is different from other polymerization catalysts such as a titanium compound, a tin compound and a cobalt compound in impairing the thermal stability and color tone of the polyester. It is possible to coexist in a range that does not exist.

The polyester used for the polyester fiber for industrial materials used in the present invention contains terephthalic acid or naphthalenedicarboxylic acid as a main acid component, and is selected from at least one glycol, preferably ethylene glycol, trimethylene glycol or tetramethylene glycol. And polyesters containing at least one alkylene glycol as a main glycol component. Further, a polyester in which a part of a terephthalic acid component or a naphthalenedicarboxylic acid component is replaced with another difunctional carboxylic acid component may be used, and / or a part of the glycol component may be a glycol other than the main component. May be replaced with a diol component.

As the dicarboxylic acid, 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, 4,7′-biphenyldicarboxylic acid, 4,4'-biphenylsulfone dicarboxylic acid, 4,4'-biphe Aromatic dicarboxylic acids exemplified by phenyl 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, and these dicarboxylic acids Of these, terephthalic acid and naphthalenedicarboxylic acid, particularly 2,6 naphthalenedicarboxylic acid, are preferred.

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 glycols obtained by adding ethylene oxide to these glycols, and the like. Among these glycols, ethylene glycol and 1 ,
4-butylene glycol is 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.

In the present invention, in the polyester composed of the above dicarboxylic acid component and diol component, it is particularly preferred that 80 mol% or more of the repeating units are ethylene terephthalate units or ethylene naphthalate.

The polymerization of PET using a catalyst for polymerization of polyester used for the polyester fiber for industrial materials used in the present invention can be carried out by a conventionally known method.
That is, terephthalic acid and a 2-fold molar amount of ethylene glycol were charged into a batch-type autoclave equipped with a stirrer, and the esterification reaction was carried out at 245 ° C. under a pressure of 2.5 kgcm ⁻² while distilling off generated water out of the system. To produce bis (2-hydroxyethyl) terephthalate. The pressure is released when the esterification rate reaches 95%, calculated from the amount of water distilled off. The catalyst was added thereto, and the pressure was increased to 245 at normal pressure under a nitrogen atmosphere.
Stir for at least 10 minutes at ° C. Continue for 50 minutes 27
While raising the temperature to 5 ° C, gradually reduce the pressure of the reaction system to 0.1 Torr.
Further, PET with an intrinsic viscosity of 0.5 dlg ^-1 or more by performing a polycondensation reaction while stirring at a constant speed at 275 ° C and 0.1 Torr
Is polymerized. The time required for the polycondensation reaction is called the polymerization time.

The catalyst for polymerization of polyester used for the polyester fiber for industrial materials used in the present invention has an activity parameter (AP) satisfying AP (min) <T (min) * 2. Preferably, AP (min) <T (min) * 1.5, and more preferably, AP (min) <T (min). However, AP
Indicates the time (min) required to polymerize PET having an intrinsic viscosity of 0.5 dlg ^-1 by the above method. T indicates AP when antimony trioxide is used as a catalyst. However, antimony trioxide is commercially available diantimony trioxide, for example, ALDRICH
Antimony (III) oxide, purity 99.999%, which is added to ethylene glycol to a concentration of about 10 gl ^-1
A solution obtained by stirring and dissolving at 0 ° C. for about 1 hour is added so that the acid component in the produced PET becomes 0.05 mol% as an antimony atom.

The PET polymerized using the polyester polymerization catalyst used in the polyester fiber for industrial materials used in the present invention must have a thermal stability index (TD) satisfying TD <25%. However, TD has an intrinsic viscosity of 0.6 dlg ^-1
The reduction rate (%) of the intrinsic viscosity when 1 g of PET is placed in a glass test tube, vacuum dried at 130 ° C. for 12 hours, and then melted at 300 ° C. for 2 hours in a nitrogen atmosphere. Preferably TD <22%, more preferably TD <18%. If the catalyst has a TD of 25% or more, the polyester polymerized using this catalyst is susceptible to thermal deterioration during melt molding, resulting in significant coloring. The compound having substantially no catalytic activity for polyester polymerization referred to in the present invention is a compound having a limiting activity parameter (LP) satisfying LP (min)> T (min) * 2. However, LP is the time required for polymerizing polyethylene terephthalate having an intrinsic viscosity of 0.3 dlg ^-1 by the method described above (mi
n). The catalyst having substantially the catalytic activity of the polyester polymerization referred to in the present invention has an activity parameter (AP).
AP (min) <T (min) * 2. Preferably, A
P (min) <T (min) * 1.5, more preferably AP (mi
n) <T (min).

Further, a small amount of other optional polymers and stabilizers, antioxidants, antistatic agents, dye improvers, dyes, pigments, matting agents, fluorescent brighteners, and inert fine particles are contained in the polyester. Other additives may be contained. In particular, when adding inert fine particles, any of the external precipitation method and the internal precipitation method can be adopted.

As a method for obtaining such a polyester,
It is not necessary to employ special polymerization conditions, and it can be synthesized by any method employed when polycondensing a reaction product of a dicarboxylic acid and / or an ester-forming derivative thereof and a glycol into a polyester. it can. It is, of course, preferable to further improve the degree of polymerization of the polyester by a step such as solid phase polymerization after the melt polymerization.

In the production of the polyester fiber of the present invention, ordinary spinning conditions can be adopted, but the spinning speed is 150.
0 to 5000 m / min, preferably 2000 to 5000 m
/ Min. If the spinning speed is 1500 m / min or less, the productivity is low and the cost is high, which is not practical.

Although spinning at 5000 m / min or more is preferable in view of theoretical productivity, problems that must be solved engineeringly, such as the control of the accompanying flow, which occur during spinning, are increased. Unless the apparatus is modified, the yarn breakage during spinning frequently occurs, which is not preferable.

The spun yarn thus obtained may be once wound and then subjected to a drawing step, or may be continuously drawn without being once wound and used as a drawn yarn.

In any case, if the draw ratio is 1.3 times or less, sufficient strength usable for industrial materials cannot be obtained. In addition, it is difficult to stably perform a stretching of 3.5 times or more in a normal stretching step.

6 g of polyester fiber for industrial materials
/ D or more and preferably 12% or more, more preferably 7 g / d or more.

[0146]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. In addition, the evaluation method of various characteristics followed the following method.

Intrinsic viscosity: Parachlorophenol / tetrachloroethane = 6 / at a concentration of 0.4 g / dl.
Dissolved in 4 mixed solvents and measured at 30 ° C.

Foreign matter amount: Polyester was formed into a 0.1 mm biaxially stretched film, and the amount of foreign matter per 1 g of the film was visually observed and expressed as the number per 1 g of the film.

Example 1 Bis (2-hydroxyethyl)
To terephthalate, a polycondensation catalyst of 5 g / l concentration of lithium acetate in ethylene glycol was added to the acid component in an amount of 0.3 mol% as a lithium atom and alizarin was added to the acid component in an amount of 0.2 mol% at normal pressure under a nitrogen atmosphere. At 245 ° C for 10 minutes. Then, the temperature of the reaction system was gradually decreased while raising the temperature to 275 ° C. over 50 minutes to 0.1 Torr to further increase the pressure to 275 ° C.
The polycondensation reaction was performed at 0.1 ° C. and 0.1 Torr. The polymerization time required until the IV of polyethylene terephthalate reaches 0.5 dlg ^-1 is shown in Table 1. In addition, IV is 0.6 dlg ^{-1 by the} above method.
Was polymerized to determine the thermal stability index (TD). Table 1 shows the values of IV and TD after the melting test.
Shown in When the IV of the polymer reached 0.63, the polymer was formed into chips according to a conventional method.
Solid phase polymerization was performed under a vacuum of mmHg to obtain a polyester chip having an IV of 1.0. When this was spun at a spinning temperature of 310 ° C., almost no die stain was observed and the spinning property was good. The number of foreign substances was 0 / g.

Examples 2 to 26 and Comparative Example 1 The same operation as in Example 1 was performed except that the catalyst was changed. Tables 1, 2, 3, 4, and 5 show the catalyst composition used, the polymerization time required for the PET IV to reach 0.5 dlg ^-1 , and the IV and TD values after the melt test. However, the added amount is a value based on the acid component in the PET. The addition amount of the metal catalyst is the addition amount as a metal atom. When the IV of the polymer reached 0.63, the polymer was formed into chips according to a conventional method.
The solid phase polymerization was carried out at 0 ° C. under a vacuum of 0.01 mmHg, and IV
1.0 polyester chips were obtained. Spinning temperature 3
When spun at 10 ° C., almost no die stain was observed, and the spinning property was also good. Tables 1, 2, 3, 4, and 5 show the number of confirmed foreign substances. Comparative Example 1 has a disadvantage that the polymerization time is long.

(Comparative Examples 2 and 3) The same operation as in Example 1 was performed except that the catalyst was changed. The results are shown in Table 5, and the IV did not reach 0.5 even after polymerization for 180 minutes or more.

(Comparative Example 4) The same operation as in Example 1 was performed except that the catalyst was changed to antimony trioxide. Antimony trioxide was added in an amount of 0.05 mol% as antimony atoms with respect to the acid component in the PET. Polymerization time required for IV of PET to reach 0.5 dlg ^-1 , IV and TD after melt test
Are shown in Table 5. When the IV of the polymer reached 0.63, the polymer was chipped according to a conventional method, and further 230
Performed solid-state polymerization under vacuum of 0.01 mmHg
1.0 polyester chips were obtained. Spinning temperature 3
When spun at 10 ° C., a considerable amount of die stain was observed, and the spinning property was poor. In addition, the resin was darkened, and foreign substances were also considerably observed.

Comparative Example 5 Polymerization of PET was carried out in the same manner as in Example 2 except that quinalizarin was not added. Table 6 shows the time required for the IV of PET to reach 0.3 dlg ^-1 .

Comparative Example 6 Polymerization of PET was carried out in the same manner as in Example 2 except that sodium acetate was not added. Table 6 shows the time required for the IV of PET to reach 0.3 dlg ^-1 .

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[Table 1]

[0156]

[Table 2]

[0157]

[Table 3]

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[Table 4]

[0159]

[Table 5]

[0160]

[Table 6]

[0161]

Industrial Applicability According to the present invention, a polyester fiber for an industrial material which is suitable for rubber reinforcing applications such as tire cords and V-belts, which does not contain foreign matter which causes a decrease in fiber strength in the resin and has a small stain on spinnerets at the time of spinning, and its use. A manufacturing method can be obtained.

Continued on the front page F term (reference) 4J029 AA02 AA03 AC01 AD01 AD10 AE02 BA02 BA04 BA05 CB06A CC06A HA01 HB01 JA011 JA061 JA091 JA121 JA161 JA201 JA261 JA281 JA301 JB111 JB131 JB141 JB151 JB1 1 JF081 JF091 JF121 JF131 JF141 JF151 JF161 JF181 JF191 JF201 JF221 JF231 JF241 JF251 JF261 JF281 JF331 JF341 JF361 JF381 JF421 JF431 JF441 JF471 JF481 JF511 JF531 JF541 JF05 GG01 KE05 KE05 KE05 KE01 KE 010 KE

Claims (50)

[Claims] (1) A polyethylene terephthalate polymerized by using a catalyst satisfying an activity parameter represented by the following formula (1) without using an antimony compound or a germanium compound and represented by the following formula (2): Polyester fibers for industrial materials polymerized using a polyester polymerization catalyst that satisfies the thermal stability index. (1) Activity parameter (AP): AP (min) <T (min) * 2 (In the above formula, AP has a specific viscosity of 0.5 dlg ⁻¹ at 275 ° C. under a reduced pressure of 0.1 Torr using a predetermined catalyst. The time (min) required to polymerize polyethylene terephthalate is indicated by T. T indicates AP when antimony trioxide is used as a catalyst, where antimony trioxide is converted to an antimony atom with respect to the acid component in the produced polyethylene terephthalate. (2) Thermal stability index (TD): TD <25 (%) (In the above formula, ¹ g of PET having an intrinsic viscosity of 0.6 dlg ^-1 is placed in a glass test tube and placed at 130 ° C. for 12 hours. After vacuum drying, the intrinsic viscosity decreases (%) when melted under nitrogen atmosphere at 300 ° C for 2 hours
Indicates) 2. A catalyst comprising at least one metal and / or metal compound and at least one compound selected from the group consisting of compounds having the structures of the following general formulas (1) and / or (2): 2. The method according to claim 1, wherein the method is performed.
Polyester fibers for industrial materials as described. Embedded image Embedded image (In the formulas (1) and (2), Ar represents an aryl group.) 3. The metal and / or metal compound is an alkali metal and / or a compound thereof or an alkaline earth metal and / or a compound thereof.
Polyester fibers for industrial materials as described. 4. An alkali metal and / or a compound thereof or an alkaline earth metal and / or a compound thereof selected from the group consisting of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr and Ba. 4. The polyester fiber for industrial materials according to claim 3, which is a compound thereof. 5. The method according to claim 1, wherein the metal and / or the metal compound is Al, Ga, T
The polyester fiber for industrial materials according to claim 2, which is a metal selected from l, Pb, and Bi and / or a compound thereof. 6. The method according to claim 1, wherein the metal and / or the metal compound is Tl, Pb, Bi.
The polyester fiber for industrial materials according to claim 2, which is a metal and / or a compound thereof selected from the group consisting of: 7. The method according to claim 1, wherein the metal and / or the metal compound is Sc, Y, Zr,
The polyester fiber for industrial materials according to claim 2, which is a metal selected from Hf and V and / or a compound thereof. 8. The method according to claim 1, wherein the metal and / or metal compound is Sc, Y, Zr,
3. The polyester fiber for industrial materials according to claim 2, which is a metal selected from Hf and / or a compound thereof. 9. The method according to claim 1, wherein the metal and / or the metal compound is Cr, Ni, M
The polyester fiber for industrial materials according to claim 2, which is a metal selected from o, Tc, and Re and / or a compound thereof. 10. The method according to claim 1, wherein the metal and / or the metal compound is Cr, Ni.
The polyester fiber for industrial materials according to claim 2, which is a metal and / or a compound thereof selected from the group consisting of: 11. The method according to claim 11, wherein the metal and / or metal compound is Ru, Rh,
The polyester fiber for industrial materials according to claim 2, which is a metal selected from Pd, Os, Ir, and Pt and / or a compound thereof. 12. The method according to claim 12, wherein the metal and / or the metal compound is Ru, Pd.
The polyester fiber for industrial materials according to claim 2, which is a metal and / or a compound thereof selected from the group consisting of: 13. The method according to claim 1, wherein the metal and / or metal compound is Cu, Ag,
The polyester fiber for industrial materials according to claim 2, which is a metal selected from Au, Cd, and Hg and / or a compound thereof. 14. The metal and / or metal compound is Cu, Ag
The polyester fiber for industrial materials according to claim 2, which is a metal and / or a compound thereof selected from the group consisting of: 15. The polyester fiber for industrial materials according to claim 2, wherein the metal and / or the metal compound is a metal selected from lanthanoids and / or a compound thereof. 16. The method according to claim 16, wherein the metal and / or metal compound is La, Ce,
The polyester fiber for industrial materials according to claim 2, which is a metal selected from Sm, Eu, and Gd and / or a compound thereof. 17. The polyester fiber for industrial materials according to claim 2, wherein the metal and / or the metal compound is indium and / or a compound thereof. 18. The method according to claim 18, wherein the metal and / or the metal compound is Mn, Co,
The polyester fiber for industrial materials according to claim 2, which is a metal selected from Zn and / or a compound thereof. 19. The method according to claim 19, wherein the metal and / or the metal compound is Fe, Nb,
The polyester fiber for industrial materials according to claim 2, which is a metal selected from Ta and W and / or a compound thereof. 20. The polyester fiber for industrial materials according to claim 2, wherein the metal and / or the metal compound is Fe and / or a compound thereof. 21. The polyester fiber for industrial materials according to claim 2, wherein the metal and / or the metal compound is tellurium, silicon, boron and / or a compound thereof. 22. A compound having the structure of the general formula (1) and / or (2) is a compound represented by the following general formula (3) and / or (4):
The polyester fiber for industrial materials according to any one of claims 2 to 21, which is a compound having a structure represented by the following formula: Embedded image Embedded image (In the formulas (3) to (4), Ar represents an aryl group, X ¹ , X ² , and X ³ each independently represent a hydrogen-containing group, a hydrocarbon group, an acyl group, a sulfonyl-containing group, a phosphoryl-containing group, or Represents a hydrocarbon group having an ether bond.) 23. Ar in the general formulas (3) and (4) is represented by the following general formula:
23. The polyester fiber for industrial materials according to claim 22, which is selected from the group consisting of (5) to (12). Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image 24. A compound having a structure represented by the general formula (3) and / or (4) is a linear phenol compound or a linear aniline represented by the following general formulas (13) and (14). The polyester fiber for industrial materials according to claim 22, which is a compound selected from the group consisting of a compound and a derivative thereof. Embedded image Embedded image (In the formulas (13) to (14), each R ¹ is the same or different and has 1 to 20 carbon atoms, a hydroxyl group or a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, a halogen group. ,
A carboxyl group or an ester thereof, a formyl group, an acyl group, a group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituted product thereof, a hydroxyl group, an alkoxyl group, an alkylthio group, and a sulfonyl group. Represents a group containing, phosphoryl-containing group, nitro group, cyano group, thiocyano group, each R ² is the same or different, hydrogen,
A hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, a halogen group, a carboxyl group or an ester thereof, a formyl group, an acyl group, (acyl) -O- Represented groups, amino groups,
A mono- or dialkylamino group, an amide group or a substituted form thereof, a hydroxyl group, an alkoxyl group, an alkylthio group, a group containing a sulfonyl, a group containing a phosphoryl group, a nitro group, a cyano group, a thiocyano group, and each X is the same or different; Hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, an acyl group, a group containing a sulfonyl, a group containing a phosphoryl, or a hydrocarbon having an ether bond Represents the group
Y is the same or different and is a direct bond, having 1 to 1 carbon atoms
0 alkylene group,-(alkylene) -O-,-(alkylene)-
S -, - O -, - S -, - SO 2 -, - CO -, - COO- represent, n represents from 1 10
Represents an integer of 0, a and c represent an integer of 1 to 3, b and d represent 0 or an integer of 1 to 3. Where 1 ≦ a + b ≦
5, 1 ≦ c + d ≦ 4. Each d may be the same or different. ) 25. A compound having a structure represented by the general formulas (3) and / or (4) is a branched linear phenol compound represented by the following general formulas (15) and (16): 23. A compound selected from the group consisting of linear aniline compounds and their derivatives.
Polyester fibers for industrial materials as described. Embedded image Embedded image (In the formulas (15) to (16), each R ¹ is the same or different and has 1 to 20 carbon atoms, a hydroxyl group or a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, a halogen group. ,
A carboxyl group or an ester thereof, a formyl group, an acyl group, a group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituted product thereof, a hydroxyl group, an alkoxyl group, an alkylthio group, and a sulfonyl group. Represents a group containing, phosphoryl-containing group, nitro group, cyano group, thiocyano group, each R ² is the same or different, hydrogen,
A hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, a halogen group, a carboxyl group or an ester thereof, a formyl group, an acyl group, (acyl) -O- Represented groups, amino groups,
A mono- or dialkylamino group, an amide group or a substituted form thereof, a hydroxyl group, an alkoxyl group, an alkylthio group, a group containing a sulfonyl, a group containing a phosphoryl group, a nitro group, a cyano group, a thiocyano group, and each X is the same or different; Hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, an acyl group, a group containing a sulfonyl, a group containing a phosphoryl, or a hydrocarbon having an ether bond Represents the group
Y is the same or different and is a direct bond, having 1 to 1 carbon atoms
0 alkylene group,-(alkylene) -O-,-(alkylene)-
S -, - O -, - S -, - SO 2 -, - CO -, - COO- represent, each n are the same or different, represent an integer of 1 to 100, each c is the same or different, Represents an integer from 1 to 3, each d being the same or different and representing 0 or an integer from 1 to 3; Where 1 ≦ c +
d ≦ 4. Each d may be the same or different. ) 26. A compound having a structure represented by the general formulas (3) and / or (4) is a cyclic phenol compound, a cyclic aniline compound represented by the following general formulas (17) and (18): The polyester fiber for industrial materials according to claim 22, which is a compound selected from the group consisting of derivatives thereof. Embedded image Embedded image (In the formulas (17) to (18), each R ¹ is the same or different and includes a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, a halogen group. ,
A carboxyl group or an ester thereof, a formyl group, an acyl group, a group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituted product thereof, a hydroxyl group, an alkoxyl group, an alkylthio group, and a sulfonyl group. Represents a group containing, a group containing phosphoryl, a nitro group, a cyano group, a thiocyano group, each X is the same or different, hydrogen,
A hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, an acyl group, a group containing a sulfonyl, a group containing a phosphoryl, or a hydrocarbon group having an ether bond. And each Y is the same or different and represents a direct bond, an alkylene group having 1 to 10 carbon atoms,-(alkylene) -O-,-(alkylene) -S-, -O-,-
_{S -, - SO 2 -,} - CO -, - COO- represent, n represents an integer of 1 to 100, c is an integer of from 1 to 3, d is an integer of from 0 or 1 3. However, 1 ≦ c + d ≦ 4. Each d may be the same or different. ) 27. A compound having a structure represented by the general formula (3) and / or (4) is a coumarin derivative represented by the following general formula (19) or (20) or a compound represented by the following general formula ( twenty one)
And a compound selected from the group consisting of chromone derivatives represented by (22).
Polyester fibers for industrial materials as described. Embedded image Embedded image Embedded image Embedded image (In the formulas (19) to (22), each R is the same or different and has 1 to 20 carbon atoms, a hydroxyl group or a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, a halogen group,
A carboxyl group or an ester thereof, a formyl group, an acyl group, a group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituted product thereof, a hydroxyl group, an alkoxyl group, an alkylthio group, and a sulfonyl group. Represents a group containing, a group containing phosphoryl, a nitro group, a cyano group, a thiocyano group, each X is the same or different, hydrogen,
A hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, an acyl group, a group containing a sulfonyl, a group containing a phosphoryl, or a hydrocarbon group having an ether bond. And j and b are 0
Or represents an integer of 1 to 3, and m and d are 0 or 1 to 2
Represents an integer. Where 0 ≦ j + b ≦ 4, 0 ≦ m + d ≦ 2, 1 ≦ j + m
≦ 5. ) 28. A compound having a structure represented by the general formula (3) and / or (4) is a dihydrocoumarin derivative represented by the following general formula (23) or (24): Two
5) A compound selected from the group consisting of a chromanone derivative represented by (26) or an isochromanone derivative represented by the following general formulas (27) and (28): 23. The polyester fiber for an industrial material according to 22. Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image (In the formulas (23) to (28), each R is the same or different and has 1 to 20 carbon atoms, a hydroxyl group or a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, a halogen group,
A carboxyl group or an ester thereof, a formyl group, an acyl group, a group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituted product thereof, a hydroxyl group, an alkoxyl group, an alkylthio group, and a sulfonyl group. Represents a group containing, a group containing phosphoryl, a nitro group, a cyano group, a thiocyano group, each X is the same or different, hydrogen,
A hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, an acyl group, a group containing a sulfonyl, a group containing a phosphoryl, or a hydrocarbon group having an ether bond. Represents a represents an integer of 1 to 3, b represents 0 or an integer of 1 to 3, p and q
Represents 0 or an integer of 1 to 2. Where 1 ≦ a + b ≦ 4,0
≦ p + q ≦ 2. ) 29. A compound having a structure represented by the general formula (3) and / or (4) is a chroman derivative represented by the following general formula (29) or (30), or a compound represented by the following general formula ( 3. A compound selected from the group consisting of isochroman derivatives represented by (31) and (32).
2. The polyester fiber for industrial materials according to 2. Embedded image Embedded image Embedded image Embedded image (In the formulas (29) to (32), each R is the same or different and has 1 to 20 carbon atoms, a hydroxyl group or a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, a halogen group,
A carboxyl group or an ester thereof, a formyl group, an acyl group, a group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituted product thereof, a hydroxyl group, an alkoxyl group, an alkylthio group, and a sulfonyl group. Represents a group containing, a group containing phosphoryl, a nitro group, a cyano group, a thiocyano group, each X is the same or different, hydrogen,
A hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, an acyl group, a group containing a sulfonyl, a group containing a phosphoryl, or a hydrocarbon group having an ether bond. Represents a represents an integer of 1 to 3, b represents 0 or an integer of 1 to 3, c and d
Represents 0 or an integer of 1 to 3. Where 1 ≦ a + b ≦ 4,0
≦ c + d ≦ 3. ) 30. A compound having a structure represented by the general formula (3) and / or (4) is a naphthalene derivative represented by the following general formula (33) or (34), or a compound represented by the following general formula ( Three
23. The polyester fiber for industrial materials according to claim 22, which is a compound selected from the group consisting of bisnaphthyl derivatives represented by 5) and (36). Embedded image Embedded image (In formulas (33) to (34), each R is the same or different and has 1 to 20 carbon atoms, a hydroxyl group or a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, a halogen group,
A carboxyl group or an ester thereof, a formyl group, an acyl group, a group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituted product thereof, a hydroxyl group, an alkoxyl group, an alkylthio group, and a sulfonyl group. Represents a group containing, a group containing phosphoryl, a nitro group, a cyano group, a thiocyano group, each X is the same or different, hydrogen,
A hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, an acyl group, a group containing a sulfonyl, a group containing a phosphoryl, or a hydrocarbon group having an ether bond. And j, b, c, and d represent 0 or an integer of 1 to 3. Where 0 ≦ j + b ≦
4, 0 ≦ c + d ≦ 4, 1 ≦ j + c ≦ 6. ) Embedded image (In the formulas (35) to (36), each R is the same or different and has 1 to 20 carbon atoms, a hydroxyl group or a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, a halogen group,
A carboxyl group or an ester thereof, a formyl group, an acyl group, a group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituted product thereof, a hydroxyl group, an alkoxyl group, an alkylthio group, and a sulfonyl group. Represents a group containing, a group containing phosphoryl, a nitro group, a cyano group, a thiocyano group, each X is the same or different, hydrogen,
A hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, an acyl group, a group containing a sulfonyl, a group containing a phosphoryl, or a hydrocarbon group having an ether bond. represents, Y is a direct bond, an alkylene group having 1 to 10 carbon atoms, - (alkylene) -O -, - (alkylene) -S -, - O -, - S -, - SO 2 -, - CO-,
-COO-, wherein j, b, c, d, e, f, g, and h are 0 or
Represents an integer from 1 to 3. However, 0 ≦ j + b ≦ 4, 0 ≦ c + d ≦ 3,
0 ≦ e + f ≦ 4, 0 ≦ g + h ≦ 3, 1 ≦ j + c + e + g ≦ 12. ) 31. The compound having a structure represented by the general formulas (3) and / or (4) is selected from the group consisting of anthracene derivatives represented by the following general formulas (37) and (38): The polyester fiber for industrial materials according to claim 22, which is a compound. Embedded image Embedded image (In the formulas (37) to (38), each R is the same or different, and has 1 to 20 carbon atoms, a hydroxyl group or a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, a halogen group,
A carboxyl group or an ester thereof, a formyl group, an acyl group, a group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituted product thereof, a hydroxyl group, an alkoxyl group, an alkylthio group, and a sulfonyl group. Represents a group containing, a group containing phosphoryl, a nitro group, a cyano group, a thiocyano group, each X is the same or different, hydrogen,
A hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, an acyl group, a group containing a sulfonyl, a group containing a phosphoryl, or a hydrocarbon group having an ether bond. J, b, e, and f represent 0 or an integer of 1 to 3, and p and q represent 0 or an integer of 1 to 2. However, 0 ≦ j + b ≦ 4, 0 ≦ p + q ≦
2, 0 ≦ e + f ≦ 4, 1 ≦ j + p + e ≦ 8. ) 32. The compound having a structure represented by the general formulas (3) and / or (4) is selected from the group consisting of benzoquinone derivatives represented by the following general formulas (39) and (40): The polyester fiber for industrial materials according to claim 22, which is a compound. Embedded image Embedded image (In the formulas (39) to (40), each R is the same or different and has 1 to 20 carbon atoms, a hydroxyl group or a 1 to 20 carbon atoms having a hydroxyl group or a halogen group, a halogen group,
A carboxyl group or an ester thereof, a formyl group, an acyl group, a group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituted product thereof, a hydroxyl group, an alkoxyl group, an alkylthio group, and a sulfonyl group. Represents a group containing, a group containing phosphoryl, a nitro group, a cyano group, a thiocyano group, each X is the same or different, hydrogen,
A hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, an acyl group, a group containing a sulfonyl, a group containing a phosphoryl, or a hydrocarbon group having an ether bond. And k, l, p, and q represent 0 or an integer of 1 to 2. Where 0 ≦ k + l ≦
2, 0 ≦ p + q ≦ 2, 1 ≦ k + p ≦ 4. ) 33. The compound having a structure represented by the general formulas (3) and / or (4) is selected from the group consisting of naphthoquinone derivatives represented by the following general formulas (41) and (42) The polyester fiber for industrial materials according to claim 22, which is a compound. Embedded image Embedded image (In the formulas (41) to (42), each R is the same or different and has 1 to 20 carbon atoms, a hydroxyl group or a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, a halogen group,
A carboxyl group or an ester thereof, a formyl group, an acyl group, a group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituted product thereof, a hydroxyl group, an alkoxyl group, an alkylthio group, and a sulfonyl group. Represents a group containing, a group containing phosphoryl, a nitro group, a cyano group, a thiocyano group, each X is the same or different, hydrogen,
A hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, an acyl group, a group containing a sulfonyl, a group containing a phosphoryl, or a hydrocarbon group having an ether bond. Where k and l are 0
Or represents an integer of 1 to 2, and c and d are 0 or 1 to 3
Represents an integer. However, 0 ≦ k + l ≦ 2, 0 ≦ c + d ≦ 4, 1 ≦ k + c
≦ 5. ) 34. The compound having a structure represented by the general formula (3) and / or (4) is selected from the group consisting of anthraquinone derivatives represented by the following general formulas (43) and (44) The polyester fiber for industrial materials according to claim 22, which is a compound. Embedded image Embedded image (In the formulas (43) to (44), each R is the same or different and has 1 to 20 carbon atoms, a hydroxyl group or a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, a halogen group,
A carboxyl group or an ester thereof, a formyl group, an acyl group, a group represented by (acyl) -O-, an amino group, a mono- or dialkylamino group, an amide group or a substituted product thereof, a hydroxyl group, an alkoxyl group, an alkylthio group, and a sulfonyl group. Represents a group containing, a group containing phosphoryl, a nitro group, a cyano group, a thiocyano group, each X is the same or different, hydrogen,
A hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a halogen group, an acyl group, a group containing a sulfonyl, a group containing a phosphoryl, or a hydrocarbon group having an ether bond. And j, b, c, and d represent 0 or an integer of 1 to 3. Where 0 ≦ j + b ≦
4, 0 ≦ c + d ≦ 4, 1 ≦ j + c ≦ 6. ) 35. A compound having a structure represented by the general formula (3) and / or (4) is selected from the group consisting of 2,2′-bisphenol represented by the following formula (45) and a compound represented by the following formula (46). 23. The polyester fiber for industrial materials according to claim 22, which is a compound selected from the group consisting of 2-aminobiphenyl and derivatives thereof. Embedded image Embedded image 36. A compound having a structure represented by the general formula (3) and / or (4) is a compound represented by the following formula (47): 2,2′-dihydroxydiphenyl ether represented by the following formula (48): Be done
Selected from the group consisting of 2,2'-thiobis (4-tert-octylphenol) or 2,2'-methylenebis (6-tert-butyl-p-cresol) represented by the following formula (49) and derivatives thereof 23. The polyester fiber for industrial materials according to claim 22, which is a compound to be produced. Embedded image Embedded image Embedded image 37. A compound having a structure represented by the general formula (3) and / or (4) is a methylene-bridged linear phenol compound represented by the following formula (50) (a mixture of 2 to 100 mer) ) Or a methylene-bridged linear compound represented by the following formula (51)
The polyester fiber for industrial materials according to claim 22, which is a compound selected from the group consisting of a p-tert-butylphenol compound (a mixture of 2 to 100 mer) and a derivative thereof. Embedded image (In the formula (50), n represents an arbitrary integer from 1 to 99.) (In the formula (51), n represents any integer from 1 to 99.) 38. A compound having a structure represented by the general formula (3) and / or (4) is a calix [4] arene represented by the following formula (52) and a compound represented by the following formula (53): Calix [6] arene, calix [8] arene represented by the following formula (54), p-tert-butylcalix [4] represented by the following formula (55)
Arene, p-tert-butyl calix [6] arene represented by the following formula (56), or p-tert- represented by the following formula (57)
23. The polyester fiber for industrial materials according to claim 22, which is a compound selected from the group consisting of butyl calix [8] arene and derivatives thereof. Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image 39. The compound having a structure represented by the general formula (3) and / or (4) is an esculetin represented by the following formula (58) or a 7-amino acid represented by the following formula (59): 23. The polyester fiber for industrial materials according to claim 22, which is a compound selected from the group consisting of -4-methylcoumarin and derivatives thereof. Embedded image Embedded image 40. A compound having a structure represented by the general formula (3) and / or (4) is selected from the group consisting of chrysin represented by the following formula (60), morin represented by the following formula (61), and 23. The polyester fiber for industrial materials according to claim 22, which is a compound selected from the group consisting of 2-aminochromone represented by the formula (62) and derivatives thereof. Embedded image Embedded image Embedded image 41. The compound having a structure represented by the general formula (3) and / or (4) is an epicatechin represented by the following formula (63) or an epigallo represented by the following formula (64): The polyester fiber for industrial materials according to claim 22, which is a compound selected from the group consisting of catechin gallate and derivatives thereof. Embedded image Embedded image 42. A compound having a structure represented by the general formula (3) and / or (4) is a disodium 4,5-dihydroxynaphthalene-2,7-disulfonate represented by the following formula (65): ,
1,8-diaminonaphthalene represented by the following formula (66), the following formula
Naphthol AS represented by (67), 1, represented by the following formula (68)
1'-bi-2-naphthol, or 1,1 'represented by the following formula (69)
23. The polyester fiber for industrial materials according to claim 22, which is a compound selected from the group consisting of -binaphthyl-2,2'-diamine and derivatives thereof. Embedded image Embedded image Embedded image Embedded image Embedded image 43. A compound having a structure represented by the general formulas (3) and / or (4) is an anthralobin represented by the following formula (70) or a compound represented by the following formula (71): 23. The polyester fiber for industrial materials according to claim 22, which is a compound selected from the group consisting of -dimethoxyanthracene or 2-aminoanthracene represented by the following formula (72) and derivatives thereof. Embedded image Embedded image Embedded image 44. The compound having a structure represented by the general formula (3) and / or (4) is selected from the group consisting of 2,5-dihydroxybenzoquinone represented by the following formula (73) and derivatives thereof: The polyester fiber for industrial materials according to claim 22, which is a compound. Embedded image 45. A compound having a structure represented by the general formula (3) and / or (4) is selected from the group consisting of 5,8-dihydroxy-1,4-naphthoquinone represented by the following formula (74) and 75. A compound selected from the group consisting of 2-aminonaphthoquinone represented by the formula (75) and derivatives thereof.
2. The polyester fiber for industrial materials according to 2. Embedded image Embedded image 46. A compound having a structure represented by the general formula (3) and / or (4) is a quinalizarin represented by the following formula (76), an alizarin represented by the following formula (77), Quinizarin represented by (78), anthralphine represented by the following formula (79), emodin represented by the following formula (80), 1,4-diaminoanthraquinone represented by the following formula (81), (82) represented by 1,8-diamino-4,5-dihydroxyanthraquinone, or a compound selected from the group consisting of Acid Blue 25 represented by the following formula (83) and derivatives thereof, 23. The polyester fiber for industrial materials according to claim 22. Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image 47. A polyester fiber for industrial materials produced by using a catalyst substantially having catalytic activity consisting of two or more compounds having substantially no catalytic activity for polyester polymerization. 48. A method for producing a polyester fiber for industrial materials according to any one of claims 1 to 47. 49. When producing a polyester, an antimony compound is converted to an antimony atom with respect to the polyester.
49. The method according to claim 48, wherein the addition is performed in an amount of 50 ppm or less.
2. The method for producing a polyester fiber for industrial materials according to item 1. 50. The method according to claim 48, wherein a germanium compound is added as a germanium atom in an amount of 20 ppm or less to the polyester when the polyester is produced.