JP2001089552A - Copolyester of cyclohexanedimethanol and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cyclohexanedimethanol copolyester having excellent thermal stability and polymerized in the presence of a catalyst except an antimony compound and a germanium compound, and to provide a method for producing the cyclohexanedimethanol copolyester. SOLUTION: When the cyclohexanedimethanol copolyester is produced, an antimony compound or a germanitun compound is not used, and a catalyst is used. The catalyst satisfies a specific parameter and gives polyethylene terephthalate satisfying a specific thermal stability index, when the polyethylene terephthalate is produced in the presence of the catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copolyester of cyclohexane dimethanol which is hardly thermally degraded during melt molding and has excellent thermal stability and a method for producing the same. More specifically, the present invention relates to a compound other than an antimony compound and a germanium compound. The present invention relates to a copolyester of cyclohexanedimethanol which is polymerized by using a polymerization catalyst of the formula (1) and has excellent thermal stability and a method for producing the same.

[0002]

2. Description of the Related Art Cyclohexanedimethanol-modified polyethylene terephthalate (hereinafter referred to as CHDM-modified PET)
Is excellent in impact resistance, transparency, gas barrier properties, chemical resistance, recyclability, etc., and is therefore used for various molded articles such as sheets.

[0003] CHDM-modified PET produces low molecular weight oligomers by esterification of terephthalic acid with ethylene glycol and cyclohexane dimethanol, or transesterification of dimethyl terephthalate with ethylene glycol and cyclohexane dimethanol, which are then heated at high temperatures. It is obtained by polycondensation using a catalyst under vacuum. As a catalyst used at the time of polycondensation, a catalyst such as an antimony compound is used. Antimony trioxide
It is a catalyst that is inexpensive, has excellent catalytic activity, and gives a polyester with excellent thermal stability.However, since metal antimony precipitates during polycondensation, there is a problem that blackening and foreign matter are generated in the polyester. ing. In addition, environmental issues have recently raised concerns about the safety of antimony. Under such circumstances, a polyester containing no antimony or containing only a very small amount is desired.

[0004] Attempts have been made to use antimony trioxide as a polycondensation catalyst and to suppress the occurrence of blackening and foreign matters of polyester. For example, in Japanese Patent No. 2666502, the use of a compound of antimony trioxide, bismuth and selenium as a polycondensation catalyst suppresses the formation of black foreign matter in polyethylene terephthalate. JP-A-9-291141 states that the use of antimony trioxide containing sodium and iron oxides as a polycondensation catalyst suppresses the deposition of antimony metal. However, these polycondensation catalysts cannot ultimately achieve the purpose of reducing the content of antimony.

[0005] Germanium compounds have already been put into practical use as catalysts which provide polyesters having excellent catalytic activity and excellent thermal stability, other than antimony compounds, but this catalyst is very expensive. In addition, there is a problem in that the catalyst concentration in the reaction system changes due to easy distilling out of the reaction system during the polymerization, and it becomes difficult to control the polymerization.

[0006] Under such circumstances, a polymerization catalyst which is a polymerization catalyst other than the antimony compound and the germanium compound and which provides a polyester having excellent catalytic activity and excellent heat stability which hardly causes thermal deterioration during melt molding is desired. I have.

[0007] As polymerization catalysts having excellent catalytic activity other than antimony compounds and germanium compounds, titanium compounds and tin compounds represented by tetraalkoxy titanates have already been proposed. There is a problem that the polyester is susceptible to thermal deterioration during melt molding and the polyester is significantly colored.

As an attempt to suppress the thermal degradation during melt molding of a polyester polymerized using a titanium compound as a catalyst, for example, Japanese Patent Application Laid-Open No. 10-259296 discloses a method in which a polyester compound is polymerized using a titanium compound as a catalyst and then a phosphorus compound is added. A method of adding is disclosed. As typified by this technology, it is possible to improve the thermal stability of the polyester by adding a stabilizer such as a phosphorus compound to deactivate the catalyst, but it is possible to improve the polymer after polymerization. At present, it is not only practically difficult to mix the additives effectively, but also to increase the cost and has not been put to practical use. Further, the use of the additive itself is not preferable because it leads to an increase in cost.

Further, as a method for suppressing thermal deterioration during melt molding of polyester, there is a method of removing a catalyst from polyester. As a method for removing a catalyst from polyester, for example, JP-A-10-251394 discloses a method in which a polyester resin is contacted with an extractant which is a supercritical fluid in the presence of an acidic substance. However, such a method using a supercritical fluid is not preferable because it is technically difficult and leads to an increase in cost.

[0010] Polymerization which is excellent in catalytic activity except for an antimony compound or a germanium compound, and which has excellent heat stability without effectively deactivating or removing the catalyst without heat deactivation during melt molding. No catalyst has been developed so far, and it is possible to obtain a copolyester of cyclohexanedimethanol with excellent thermal stability that hardly undergoes thermal deterioration during melt molding, which is polymerized using a polymerization catalyst other than an antimony compound or a germanium compound. I didn't.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a copolymer of cyclohexanedimethanol which has been polymerized using a polymerization catalyst other than an antimony compound and a germanium compound and which has little heat deterioration during melt molding and has excellent heat stability. An object of the present invention is to provide a polyester and a method for producing the same.

[0012]

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 the copolyester of cyclohexanedimethanol polymerized using the catalyst can effectively suppress the thermal deterioration during melt molding. Furthermore, 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,
Surprisingly, the coexistence of certain compounds such as bismuth, tellurium, silicon, boron, zirconium, hafnium, scandium, yttrium, lanthanoid metals, or those compounds originally having low catalytic activity for polyester polymerization. The catalyst has sufficient activity as a polymerization catalyst.Furthermore, this catalyst becomes 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 a copolyester of cyclohexanedimethanol can effectively suppress thermal deterioration during melt molding, and have reached the present invention. (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, TD is 1 g of polyethylene terephthalate having an intrinsic viscosity of 0.6 dlg ^{-1 in} a glass test tube at 130 ° C.) Shows the reduction rate (%) of the intrinsic viscosity when melted at 300 ° C for 2 hours in a nitrogen atmosphere after vacuum drying for 12 hours)

[0013] 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 To provide a cyclohexanedimethanol copolyester with excellent thermal stability that hardly undergoes thermal deterioration during melt molding produced using a catalyst in which a specific metal compound is combined with a specific compound, and a method for producing the same. The present invention also provides a cyclohexane dimethanol copolyester produced using a catalyst having substantially catalytic activity consisting of two or more compounds having substantially no catalytic activity for polyester polymerization, and a method for producing the same. .

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a copolyester of cyclohexanedimethanol which is polymerized using a polymerization catalyst other than an antimony compound and a germanium compound and has little heat degradation during melt molding and has excellent heat stability and its production. It provides a method. The polymerization catalyst used for producing the cyclohexane dimethanol copolyester of the present invention is 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, a group 2B metal, Group 3B metal, lead, bismuth, tellurium, silicon, boron, zirconium, hafnium, scandium,
A catalyst in which a specific compound is combined with a metal compound having little activity as a polymerization catalyst, such as yttrium, a lanthanoid metal, or a compound thereof, or having sufficient activity as a polymerization catalyst.

An alkali metal, an alkaline earth metal, a group 5A metal, a group 6A metal, a group 7A metal, a group 8 metal, and a group 1B metal constituting the polymerization catalyst used for producing the cyclohexanedimethanol copolyester of the present invention. , Group 2B metals, Group 3B metals, lead, bismuth, tellurium, silicon, boron, zirconium, hafnium, scandium, yttrium, lanthanoid metals, or compounds thereof as alkali metals, alkaline earth metals, Group 5A metals, 6A Group 7 metal, Group 7A metal, Group 8 metal, Group 1B metal, Group 2B metal, Group 3B metal, lead, bismuth, tellurium, silicon, boron, zirconium, hafnium, scandium, yttrium, lanthanoid metal, and these compounds The compound is not particularly limited as long as it is one or two or more compounds selected from, for example, formic acid, acetic acid, and propionic acid. Saturated aliphatic carboxylate such as butyric acid and oxalic acid, unsaturated aliphatic carboxylate such as acrylic acid and methacrylic acid, aromatic carboxylate such as benzoic acid, halogen-containing carboxylate such as trichloroacetic acid, lactic acid, citric acid Hydroxycarboxylic acid salts such as acid and 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, bromic acid, etc. Inorganic acid salts, such as 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 And alkoxides such as t-butoxy, chelate compounds such as acetylacetonate, oxides and hydroxides. Preferred are aliphatic carboxylate salts, and particularly preferred are acetate salts. 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,
Among yttrium, lanthanoid metals, or compounds thereof, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Cr, Mn, Fe,
Ru, Co, Ni, Pd, Cu, Ag, Zn, In, Tl, Pb, Bi, Zr, Hf, Sc, Y, La, Ce,
Sm, Eu, Gd, 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 the amount of these compounds used, as the acid component of the obtained cyclohexanedimethanol copolyester 1 × 10 ^{-6 to} 0.1
It is preferably in a molar range, more preferably 5 × 1
0 ^-6 is that 0.05 in the range of mole.

The specific compound constituting the polymerization catalyst used in producing the cyclohexanedimethanol copolyester of the present invention is defined by the group consisting of compounds having the structures of the following general formulas (1) and / or (2). The compound of choice.

[0018]

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[0019]

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

The specific compound constituting the polymerization catalyst used in producing the cyclohexanedimethanol copolyester of the present invention is a compound having both the general formulas (1) and (2), such as aminophenols and the like. A compound in which both N and O are bonded to an aromatic compound or a derivative thereof may be used.

The general formula (1) used as a specific compound in the polymerization catalyst used in producing the cyclohexanedimethanol copolyester of the present invention and / or
Specifically, the compound having the structure of (2) is preferably one or more compounds selected from the group consisting of compounds having the structures of the following general formulas (3) and / or (4).

[0023]

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[0024]

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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). )

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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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.

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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(In the formulas (13) to (18), each R ¹ is the same or different and is a hydrocarbon group having 1 to 20 carbon atoms, 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. Groups, such as sulfonic acid groups and sulfonate groups, phosphoryl-containing groups, such as phosphonic acid groups and phosphonate groups, such as nitro groups, cyano groups, thiocyano groups, etc., each R ² is the same or different, hydrogen, carbon 1 atom
20 hydrocarbon groups, halogen groups, carboxyl groups or esters thereof, formyl groups, acyl groups, groups represented by (acyl) -O-, amino groups, mono- or dialkylamino groups, amide groups or substituted products thereof, hydroxyl groups , 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,
For example, nitro groups such as phosphonic acid groups and phosphonate groups,
Represents a cyano group, a thiocyano group or the like, and each X is the same or different and includes hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, an acyl group, a group containing a sulfonyl group, for example, a phosphoryl group such as a sulfonic acid group or a sulfonate group. A group such as a phosphonic acid group or a phosphonate group, or a hydrocarbon group having an ether bond, wherein each Y is the same or different, a direct bond, an alkylene group having 1 to 10 carbon atoms,-
(Alkylene) -O-,-(alkylene) -S-, -O-, -S-, -SO
_2- , -CO-, -COO-, etc., each n is the same or different and represents an integer from 1 to 100, a represents an integer from 1 to 3, b
Represents 0 or an integer from 1 to 3, each c is the same or different, represents an integer from 1 to 3, each d is the same or different,
Represents 0 or an integer from 1 to 3. However, 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. )

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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

[0049]

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

[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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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.

[0058]

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[0059]

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[0060]

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[0061]

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(In the formulas (19) to (22), each R is the same or different and is a hydrocarbon group having 1 to 20 carbon atoms, 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. Groups, such as sulfonic acid groups and sulfonate groups, phosphoryl-containing groups, such as phosphonic acid groups and phosphonate groups, such as nitro groups, cyano groups, thiocyano groups, etc., each X is the same or different, hydrogen, carbon atom Number 1
20 hydrocarbon groups, acyl groups, sulfonyl-containing groups, such as sulfonic acid groups and sulfonate groups, and phosphoryl-containing groups, such as phosphonic acid groups and phosphonate groups, and hydrocarbon groups having an ether bond; And b represents 0 or an integer of 1 to 3, and m and d represent 0 or an integer of 1 to 2. However, 0 ≦ j + b ≦ 4, 0 ≦ m + d ≦
2, 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. )

[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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(In the formulas (23) to (28), each R is the same or different and is a hydrocarbon group having 1 to 20 carbon atoms, 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. Groups, such as sulfonic acid groups and sulfonate groups, phosphoryl-containing groups, such as phosphonic acid groups and phosphonate groups, such as nitro groups, cyano groups, thiocyano groups, etc., each X is the same or different, hydrogen, carbon atom Number 1
20 hydrocarbon groups, an acyl 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, or a hydrocarbon group having an ether bond; Is 1
Represents an integer from to 3, b represents 0 or an integer from 1 to 3, c
And d represents 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. )

[0070]

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[0071]

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[0072]

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[0073]

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(In the formulas (29) to (32), each R is the same or different and is a hydrocarbon group having 1 to 20 carbon atoms, 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. Groups, such as sulfonic acid groups and sulfonate groups, phosphoryl-containing groups, such as phosphonic acid groups and phosphonate groups, such as nitro groups, cyano groups, thiocyano groups, etc., each X is the same or different, hydrogen, carbon atom Number 1
20 hydrocarbon groups, an acyl 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, or a hydrocarbon group having an ether bond; Is 1
Represents an integer from to 3, b represents 0 or an integer from 1 to 3, c
And d represents 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. )

[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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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.

[0083]

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[0084]

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(In formulas (33) to (34), each R is the same or different and is a hydrocarbon group having 1 to 20 carbon atoms, 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. Groups, such as sulfonic acid groups and sulfonate groups, phosphoryl-containing groups, such as phosphonic acid groups and phosphonate groups, such as nitro groups, cyano groups, thiocyano groups, etc., each X is the same or different, hydrogen, carbon atom Number 1
20 hydrocarbon groups, acyl groups, sulfonyl-containing groups, such as sulfonic acid groups and sulfonate groups, and phosphoryl-containing groups, such as phosphonic acid groups and phosphonate groups, and hydrocarbon groups having an ether bond; ,
b, c, and d represent 0 or an integer of 1 to 3. However,
0 ≦ j + b ≦ 4, 0 ≦ c + d ≦ 4, 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. )

[0086]

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[0087]

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(In the formulas (35) to (36), each R is the same or different and is a hydrocarbon group having 1 to 20 carbon atoms, 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. Groups, such as sulfonic acid groups and sulfonate groups, phosphoryl-containing groups, such as phosphonic acid groups and phosphonate groups, such as nitro groups, cyano groups, thiocyano groups, etc., each X is the same or different, hydrogen, carbon atom Number 1
20 represents a 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, and the like. is a direct bond, an alkylene group having 1 to 10 carbon atoms, - (alkylene) -O -, - (alkylene) -S -, - O -, - S -, - SO 2 -, - CO
-, -COO-, etc., where j, b, c, d, e, f, g, and h are
Represents 0 or an integer from 1 to 3. Where 0 ≦ j + b ≦ 4, 0 ≦ c
+ d ≦ 3, 0 ≦ e + f ≦ 4, 0 ≦ g + h ≦ 3, and 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. )

[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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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.

[0095]

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[0096]

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(In the formulas (37) to (38), each R is the same or different and is a hydrocarbon group having 1 to 20 carbon atoms, 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. Groups, such as sulfonic acid groups and sulfonate groups, phosphoryl-containing groups, such as phosphonic acid groups and phosphonate groups, such as nitro groups, cyano groups, thiocyano groups, etc., each X is the same or different, hydrogen, carbon atom Number 1
20 hydrocarbon groups, acyl groups, sulfonyl-containing groups, such as sulfonic acid groups and sulfonate groups, and phosphoryl-containing groups, such as phosphonic acid groups and phosphonate groups, and hydrocarbon groups having an ether bond; ,
b, e, and f represent 0 or an integer of 1 to 3, p and q
Represents 0 or an integer of 1 to 2. 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. )

[0098]

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[0099]

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[0100]

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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

[0102]

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[0103]

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(In the formulas (39) to (40), each R is the same or different and is a hydrocarbon group having 1 to 20 carbon atoms, 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. Groups, such as sulfonic acid groups and sulfonate groups, phosphoryl-containing groups, such as phosphonic acid groups and phosphonate groups, such as nitro groups, cyano groups, thiocyano groups, etc., each X is the same or different, hydrogen, carbon atom Number 1
20 hydrocarbon groups, 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, and the like; ,
l, p, and q represent 0 or an integer of 1 to 2. However,
0 ≦ k + 1 ≦ 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. )

[0105]

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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.

[0107]

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[0108]

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(In the formulas (41) to (42), each R is the same or different and includes a hydrocarbon group having 1 to 20 carbon atoms, 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. Groups, such as sulfonic acid groups and sulfonate groups, phosphoryl-containing groups, such as phosphonic acid groups and phosphonate groups, such as nitro groups, cyano groups, thiocyano groups, etc., each X is the same or different, hydrogen, carbon atom Number 1
20 hydrocarbon groups, 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, and the like; And l represents 0 or an integer of 1 to 2, and c and d represent 0 or an integer of 1 to 3. However, 0 ≦ k + l ≦ 2, 0 ≦ c + d ≦
4, 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. )

[0110]

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[0111]

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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.

[0113]

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[0114]

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(In the formulas (43) to (44), each R is the same or different and is a hydrocarbon group having 1 to 20 carbon atoms, 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. Groups, such as sulfonic acid groups and sulfonate groups, phosphoryl-containing groups, such as phosphonic acid groups and phosphonate groups, such as nitro groups, cyano groups, thiocyano groups, etc., each X is the same or different, hydrogen, carbon atom Number 1
20 hydrocarbon groups, acyl groups, sulfonyl-containing groups, such as sulfonic acid groups and sulfonate groups, and phosphoryl-containing groups, such as phosphonic acid groups and phosphonate groups, and hydrocarbon groups having an ether bond; ,
b, c, and d represent 0 or an integer of 1 to 3. However,
0 ≦ j + b ≦ 4, 0 ≦ c + d ≦ 4, 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. )

[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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The amount of such a specific compound to be used is, 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 preferably in the range of 0.01 to 100 moles relative to the number of moles of the compound,
More preferably, it is in the range of 0.05 to 50 mol.

The present invention also relates to a copolyester of cyclohexanedimethanol produced using a catalyst substantially having catalytic activity consisting of two or more compounds having substantially no catalytic activity for polyester polymerization and a method for producing the same. Is provided.

It is preferred that at least one of the compounds 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 its compound having substantially no catalytic activity for the polyester polymerization of the present invention is Na, K, Rb, Cs, B
e, Ca, Sr, Si, V, Cr, Ru, Rh, Pd, Te, a metal such as Cu or a compound thereof, preferably Na, K, Rb, Cs, Be, Si, Cu
Or those compounds. The compounds of these metals are not particularly limited, but 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, hydroxycarboxylate 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, thiosulfate, 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.

The organic compound having substantially no catalytic activity for polyester polymerization constituting the polycondensation catalyst of the present invention comprises the compound having the structure of the above-mentioned general formula (1) and / or (2). Compounds selected from the group are preferred.

The production of the cyclohexanedimethanol copolyester according to the present invention can be carried out by a conventionally known method. For example, in the case of CHDM-modified PET, a method of esterifying terephthalic acid with ethylene glycol and cyclohexane dimethanol followed by polycondensation, or an ester of an alkyl ester of terephthalic acid such as dimethyl terephthalate with ethylene glycol and cyclohexane dimethanol. After the exchange, any method of polycondensation can be used. The polymerization apparatus may be of a batch type or a continuous type.

The polymerization catalyst used for producing the copolyester of cyclohexanedimethanol of the present invention has catalytic activity not only in polycondensation reaction but also in esterification reaction and transesterification reaction. The transesterification of an alkyl ester of terephthalic acid such as dimethyl terephthalate with ethylene glycol and cyclohexanedimethanol is usually performed in the presence of a transesterification catalyst such as a manganese compound or a zinc compound. Alternatively, the present polymerization catalyst can be used in the presence of these catalysts. Further, the present polymerization catalyst has catalytic activity not only in melt polymerization but also in solid phase polymerization and solution polymerization, and a copolyester of cyclohexanedimethanol can be produced by these polymerization methods.

The time for adding the polymerization catalyst used for producing the cyclohexanedimethanol copolyester of the present invention is preferably before the start of the polycondensation reaction, but may be any time before the start of the esterification or transesterification and during the reaction. Can be added to the reaction system at the stage.

The method of adding the polymerization catalyst used in producing the cyclohexane dimethanol copolyester of the present invention may be a powder or a slurry or solution of a solvent such as ethylene glycol. May be used, and there is no particular limitation. 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 a mixture thereof in advance with a specific compound may be added, or they may be added separately.

When polymerizing a copolyester of cyclohexanedimethanol according to the method of the present invention, an antimony compound or a germanium compound may be used in combination. However, the antimony compound is preferably added in an amount of 50 ppm or less as an antimony atom to a copolyester of cyclohexanedimethanol 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, precipitation of antimony metal occurs, and blackening or foreign matter is generated in the copolyester of cyclohexanedimethanol, which is not preferable. As the germanium compound, it is preferable to add a germanium atom in an amount of 20 ppm or less to a copolyester of cyclohexanedimethanol obtained by polymerization. More preferably, it is added in an amount of 10 ppm or less. It is not preferable to add germanium in an amount of 20 ppm or more, since it is disadvantageous in terms of cost.

Examples of the antimony compound used in the present invention include antimony trioxide, antimony pentoxide, antimony acetate, antimony glycoside, and the like. Of these, antimony trioxide is preferable. Examples of the germanium compound include germanium dioxide and germanium tetrachloride, among which germanium dioxide is preferable.

When polymerizing a cyclohexane dimethanol copolyester according to the method of the present invention, other polymerization catalysts such as a titanium compound, a tin compound, and a cobalt compound are added to the thermal stability and color tone of the cyclohexane dimethanol copolyester. Can coexist within a range that does not impair.

The copolyester of cyclohexanedimethanol referred to in the present invention is a copolyester containing terephthalic acid or an ester-forming derivative thereof as a main acid component and ethylene glycol or cyclohexanedimethanol as a main glycol component. The copolyester whose main acid component is terephthalic acid or an ester-forming derivative thereof is a copolyester containing terephthalic acid or an ester-forming derivative thereof in a total amount of 90 mol% or more based on the total acid components. The copolyester in which the main glycol component is ethylene glycol or cyclohexanedimethanol is a glycol component in the copolyester containing 90 to 5 mol% of ethylene glycol and 10 to 95 mol% of cyclohexanedimethanol, and ethylene glycol and It is a copolyester containing 10 mol% or less of glycols other than cyclohexanedimethanol.

The cyclohexane dimethanol used in the present invention is preferably 1,2-cyclohexane dimethanol, 1,3-cyclohexane dimethanol, or 1,4-cyclohexane dimethanol. Of these,
1,4-Cyclohexanedimethanol is particularly preferred.

The copolyester of cyclohexanedimethanol of the present invention contains oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid as acid components other than terephthalic acid or its ester-forming derivative. , Sebacic acid, decanedicarboxylic acid,
Dodecane dicarboxylic acid, tetradecane dicarboxylic acid,
Hexadecane dicarboxylic acid, 1,3-cyclobutane dicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2
-Cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,
Saturated aliphatic dicarboxylic acids exemplified by 2,5-norbornanedicarboxylic acid, dimer acid and the like and ester-forming derivatives thereof, unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid and the like, or these Ester-forming derivatives, orthophthalic acid, isophthalic acid, terephthalic acid, 1,3 naphthalenedicarboxylic acid, 1,4 naphthalenedicarboxylic acid, 1,5 naphthalenedicarboxylic acid, 2,6 naphthalenedicarboxylic acid, 2,2
7-naphthalenedicarboxylic acid, 5- (alkali metal) sulfoisophthalic acid, diphenic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenylsulfonedicarboxylic acid, 4,4′-biphenylether dicarboxylic acid,
Aromatic dicarboxylic acids exemplified by 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid and the like or ester-forming derivatives thereof, ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid , Pyromellitic acid, trimellitic acid, trimesic acid, polycarboxylic acids exemplified by 3,4,3 ′, 4′-biphenyltetracarboxylic acid, and ester-forming derivatives thereof as copolymer components. Can be. Also, lactic acid, citric acid,
Examples of hydroxycarboxylic acids or ester-forming derivatives thereof exemplified by malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid and the like Can also be included. Also,
ε-caprolactone, β-propiolactone, β-methyl-
Cyclic esters exemplified by β-propiolactone, δ-valerolactone, glycolide, lactide and the like can also be included. Two or more of these may be used simultaneously.

Examples of ester-forming derivatives of dicarboxylic acids, polycarboxylic acids or hydroxycarboxylic acids include:
These alkyl esters, acid chlorides, acid anhydrides and the like can be mentioned.

The copolyester of cyclohexanedimethanol of the present invention contains 1,1 as a glycol component other than ethylene glycol and cyclohexanedimethanol.
2-propylene glycol, 1,3-propylene 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, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol Aliphatic glycols exemplified by diethylene glycol, triethylene glycol, 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-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol C,
Aromatic glycols, such as 2,5 naphthalene diol, glycols obtained by adding ethylene oxide to these glycols, and the like, trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, hexanetriol, and the like. A polyhydric alcohol or the like can be contained as a copolymer component. Two or more of these may be used simultaneously.

The copolyester of cyclohexanedimethanol of the present invention may contain a known phosphorus compound as a copolymer component. As the phosphorus compound, a bifunctional phosphorus compound is preferable. For example, dimethyl phenylphosphonate, diphenyl phenylphosphonate, (2-carboxylethyl) methylphosphinic acid, (2-carboxylethyl) phenylphosphinic acid, (2-methoxy (Carboxyethyl) methyl phenylphosphinate, methyl (4-methoxycarbonylphenyl) phenylphosphinate, [2- (β-hydroxyethoxycarbonyl) ethyl]
Ethylene glycol ester of methylphosphinic acid,
(1,2-dicarboxyethyl) dimethylphosphine oxide, 9,10-dihydro-10-oxa- (2,3-carboxypropyl) -10-phosphaphenanthrene-10-oxide and the like. By including these phosphorus compounds as copolymer components, it is possible to improve the flame retardancy and the like of the obtained copolyester of cyclohexanedimethanol.

The polymerization of polyethylene terephthalate using the polymerization catalyst used in producing the cyclohexanedimethanol copolyester of 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 at 245 ° C. under a pressure of 2.5 kgcm ⁻²
An esterification reaction is carried out 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 is added thereto, and the mixture is stirred at 245 ° C. for 10 minutes or more at normal pressure under a nitrogen atmosphere. Subsequently, the temperature of the reaction system was gradually reduced to 0.1 Torr while raising the temperature to 275 ° C. over 50 minutes, and further increased to 275 ° C. and 0.1 Torr.
A polycondensation reaction is carried out while stirring at a constant speed to polymerize polyethylene terephthalate. The time required for the polycondensation reaction is called the polymerization time.

The polymerization catalyst used for producing the cyclohexanedimethanol copolyester of 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). Here, AP indicates the time (min) required to polymerize polyethylene terephthalate having an intrinsic viscosity of 0.5 dlg ^-1 by the above method. T
Shows AP when antimony trioxide is used as a catalyst. However, antimony trioxide is a commercially available diantimony trioxide, for example, ALDRICH Antimony (III) oxide, purity 99.
Using 999%, a solution obtained by stirring and dissolving this in ethylene glycol at 150 ° C. for about 1 hour so as to have a concentration of about 10 gl ⁻¹ was added as an antimony atom to the acid component in the produced polyethylene terephthalate by 0.05 as an antimony atom. mol%.

The polyethylene terephthalate polymerized by using the polymerization catalyst used for producing the cyclohexanedimethanol copolyester of the present invention must have a thermal stability index (TD) satisfying TD <25%. However, TD
Is the intrinsic viscosity reduction rate (%) when 1 g of polyethylene terephthalate having an intrinsic viscosity of 0.6 dlg ^-1 was placed in a glass test tube, vacuum-dried at 130 ° C. for 12 hours, and then melted under nitrogen atmosphere at 300 ° C. for 2 hours. . Preferably TD <22%, more preferably TD <18%. If the catalyst has a TD of 25% or more, the copolyester of cyclohexane dimethanol polymerized using this catalyst is susceptible to thermal degradation during melt molding, resulting in extremely low strength of the resulting fibers and films, etc. It causes coloring.

The compound having substantially no catalytic activity for polyester polymerization as 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).

The cyclohexane dimethanol copolyester of the present invention may contain phosphorus-based, sulfur-based, amine-based stabilizers and phenol-based, aromatic amine-based antioxidants, etc. By containing two or more kinds, the thermal stability of the cyclohexanedimethanol copolyester can be further enhanced. Phosphorus stabilizers include phosphoric acid and phosphoric acid esters such as trimethyl phosphate, phosphorous acid, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-diphenyl) -tert-butylphenyl) 4,4 '
-Phosphites such as biphenylenediphosphite,
Examples thereof include phosphonite such as distearylpentaerythritol diphosphite, phosphonic acid such as methylphosphonic acid and phenylphosphonic acid, and mono- or dialkyl esters of phosphonic acid. Phenolic antioxidants include tetrakis- [methyl-3- (3 ', 5'-
Di-tert-butyl-4-hydroxyphenyl) propionate] methane, 4,4'-butylidenebis- (3-methyl-6-tert-butylphenol) and the like.

After the copolyester of cyclohexanedimethanol is polymerized according to the method of the present invention, the catalyst is removed from the copolyester or the catalyst is deactivated by the addition of a phosphorus compound or the like, whereby the heat stability of the copolyester is reduced. Properties can be further enhanced.

In the copolyester of cyclohexanedimethanol of the present invention, other optional polymers, stabilizers, antioxidants, antistatic agents, defoamers, dye improvers, dyes, pigments, matting agents, A fluorescent whitening agent and other additives may be contained.

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, lead, bismuth, tellurium, silicon, boron, zirconium , Hafnium, scandium, yttrium, lanthanoid metals, or their compounds originally have insufficient catalytic activity, but by coexisting with the specific compound of the present invention, they have sufficient activity as a polymerization catalyst and can be melted. It is possible to obtain a cyclohexanedimethanol copolyester having excellent thermal stability which hardly causes thermal deterioration during molding.

[0150]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In each of the examples and comparative examples, the physical properties of the polyester were measured as follows.

Intrinsic viscosity (IV) and reduced viscosity: using a 6/4 mixed solvent (weight ratio) of p-chlorophenol / 1,1,2,2-tetrachloroethane, concentration: 400 mg / 100 ml (reduced viscosity: 200 mg / 100ml) at a temperature of 30 ° C.

Thermal stability index (TD): 1 g of polyethylene terephthalate having an IV of 0.6 dlg ^-1 was placed in a glass test tube at 130 ° C.
After vacuum drying for 12 hours at 300 ° C. for 2 hours in a nitrogen atmosphere.

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

To 38 parts by weight of dimethyl terephthalate, 54 parts by weight of ethylene glycol and 23 parts by weight of 1,4-cyclohexanedimethanol, 0.038 parts by weight of manganese acetate tetrahydrate was added as a transesterification catalyst, and 190 Stirring was started at 0 ° C, and methanol as a by-product was distilled off while increasing the temperature to 220 ° C. After 120 minutes, 0.026 parts by weight of trimethyl phosphoric acid was added to terminate the transesterification reaction. Next, the above polycondensation catalyst was added, and the mixture was added at normal pressure under a nitrogen atmosphere.
After stirring at 0 ° C for 15 minutes, it takes 75 minutes to raise the temperature from 240 ° C.
While raising the temperature to 275 ° C, gradually reduce the pressure of the reaction system to 0.1
A polycondensation reaction was further performed at 275 ° C. and 0.1 Torr for 70 minutes as Torr. Table 2 shows the physical property values of the obtained copolyester of cyclohexanedimethanol.

Reference Example 1 The same operation as in Example 1 was performed except that the polycondensation 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 polyester. Table 7 shows the polymerization time required for the IV of polyethylene terephthalate to reach 0.5 dlg- ¹ and the values of IV and TD after the melt test.
Shown in

(Examples 2 to 28 and Comparative Example 1) The same operation as in Example 1 was performed except that the polycondensation catalyst was changed. Table 1, Table 3, Table 5, Table 7, Table 9 show the catalyst composition used, the polymerization time required for the IV of polyethylene terephthalate to reach 0.5 dlg- ¹ , and the IV and TD values after the melting test. . In addition, Table 2, Table 4, Table 6, Table 8, and Table 10 show the polycondensation time required for polymerizing the cyclohexanedimethanol copolyester and the physical properties of the obtained cyclohexanedimethanol copolyester. However, the addition amount of the metal catalyst is the addition amount as a metal atom.

(Example 29) 100 parts by weight of terephthalic acid
A reactor was charged with 52 parts by weight of ethylene glycol and 32 parts by weight of 1,4-cyclohexane dimethanol, and was loaded with 2.5 kgcm ^-2.
The water produced as a by-product was distilled off while stirring at 240 ° C. under pressure. After 105 minutes, the pressure was released when the water by-product substantially stopped. Then, the same polycondensation catalyst as in Example 1 was added, and the mixture was stirred at 240 ° C. for 15 minutes under a normal pressure under a nitrogen atmosphere. Then, the reaction system was heated while increasing the temperature from 240 ° C. to 275 ° C. over 75 minutes. 275 ° C, 0.1To
A polycondensation reaction was performed at rr for 65 minutes. The reduced viscosity of the obtained copolyester of cyclohexanedimethanol is 0.77 dlg.
It was ^-1 .

(Comparative Example 2) Alizarin was not added.
Except that the polyethylene terephthalate was prepared in the same manner as in Example 1.
Tried to polymerize the sheet. The polycondensation reaction was performed for 180 minutes
0.5 dlg at IV ^-1Polymerization was stopped because the
I made sure. Further, cyclohexanediene was prepared in the same manner as in Example 1.
The copolyester of methanol was polymerized. Polycondensation time
Copolyester of cyclohexanedimethanol obtained
Table 10 shows the physical property values of

Comparative Example 3 Polyethylene terephthalate was polymerized in the same manner as in Example 1 except that an ethylene glycol solution of lithium acetate was not added.
When the polycondensation reaction was carried out for 180 minutes, the IV had not reached 0.5 dlg ⁻¹ , so the polymerization was abandoned. Further, a copolyester of cyclohexanedimethanol was polymerized in the same manner as in Example 1. Table 10 shows the polycondensation time and the physical properties of the obtained copolyester of cyclohexanedimethanol.

Comparative Example 4 Polyethylene terephthalate was polymerized in the same manner as in Example 2 except that quinalizarin was not added. Table 11 shows the polymerization time required until the IV of polyethylene terephthalate reached 0.3 dlg ^{- 1} .

Comparative Example 5 Polymerization of polyethylene terephthalate was attempted in the same manner as in Example 2 except that sodium acetate was not added. Table 11 shows the polymerization time required for the IV of polyethylene terephthalate to reach 0.3 dlg ^-1 .

[0162]

[Table 1]

[0163]

[Table 2]

[0164]

[Table 3]

[0165]

[Table 4]

[0166]

[Table 5]

[0167]

[Table 6]

[0168]

[Table 7]

[0169]

[Table 8]

[0170]

[Table 9]

[0171]

[Table 10]

[0172]

[Table 11]

[0173]

According to the present invention, there is provided a copolyester of cyclohexanedimethanol which is polymerized using a polymerization catalyst other than an antimony compound and a germanium compound and has excellent thermal stability, and a method for producing the same. The copolyester of cyclohexanedimethanol of the present invention can be applied to sheets for foods, credit cards, cosmetics, various films for food packaging, and various molded articles such as electronic parts.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08J 5/00 CFD C08J 5/00 CFD 5/18 CFD 5/18 CFD C08L 67/02 C08L 67/02 F term (reference) ) 4F071 AA44X AA45 AA45X AA46 AA46X AA76 AF45 AH04 AH12 BA01 BC01 4J002 CF041 CF051 4J029 AA03 AB04 AC02 AD01 AE01 AE03 BA03 BD06A BD07A CB06A HA01 HB01 HB02 JB201 JC051 JF011 JF021 JF031 JF041 JF121 JF131 JF141 JF151 JF161 JF221 JF231 JF251 JF261 JF281 JF331 JF341 JF381 JF481 JF511 JF531 JF561 JF581

Claims (53)

[Claims] 1. A copolyester comprising terephthalic acid or an ester-forming derivative thereof as a main acid component and ethylene glycol or cyclohexanedimethanol as a main glycol component, wherein a copolyester having the following formula (1) is used without using an antimony compound or a germanium compound. Is a catalyst that satisfies the activity parameter represented by, and characterized in that polyethylene terephthalate polymerized using the catalyst is produced using a catalyst that satisfies the thermal stability index represented by the following formula (2). Copolyester. (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, TD is 1 g of polyethylene terephthalate having an intrinsic viscosity of 0.6 dlg ^{-1 in} a glass test tube at 130 ° C.) Shows the reduction rate (%) of the intrinsic viscosity when melted at 300 ° C for 2 hours in a nitrogen atmosphere after vacuum drying for 12 hours) 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.
A copolyester of the described cyclohexanedimethanol. 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.
A copolyester of the described cyclohexanedimethanol. 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. Or a copolyester of cyclohexanedimethanol 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 copolyester of cyclohexanedimethanol 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 copolyester of cyclohexanedimethanol 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 copolyester of cyclohexanedimethanol 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,
The copolyester of cyclohexanedimethanol 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 copolyester of cyclohexanedimethanol 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 copolyester of cyclohexanedimethanol 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 copolyester of cyclohexanedimethanol 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 copolyester of cyclohexanedimethanol 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 cyclohexanedimethanol copolyester 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 copolyester of cyclohexanedimethanol according to claim 2, which is a metal and / or a compound thereof selected from the group consisting of: 15. The copolyester of cyclohexanedimethanol according to claim 2, wherein the metal and / or 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 copolyester of cyclohexanedimethanol according to claim 2, which is a metal selected from Sm, Eu, and Gd and / or a compound thereof. 17. The copolyester of cyclohexanedimethanol 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 cyclohexanedimethanol copolyester 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 cyclohexanedimethanol copolyester according to claim 2, which is a metal selected from Ta and W and / or a compound thereof. 20. The copolyester of cyclohexanedimethanol according to claim 2, wherein the metal and / or the metal compound is Fe and / or a compound thereof. 21. The copolyester of cyclohexanedimethanol 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 copolyester of cyclohexanedimethanol 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:
The copolyester of cyclohexanedimethanol 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 formulas (3) and / or (4) is a linear phenol compound or a linear aniline represented by the following general formulas (13) and (14). The copolyester of cyclohexanedimethanol 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.
A copolyester of the described cyclohexanedimethanol. 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 copolyester of cyclohexanedimethanol 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).
A copolyester of the described cyclohexanedimethanol. 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 copolyester of cyclohexanedimethanol 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).
3. The copolyester of cyclohexane dimethanol 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 cyclohexanedimethanol copolyester 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): 23. The copolyester of cyclohexanedimethanol 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): 23. The copolyester of cyclohexanedimethanol 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) 23. The copolyester of cyclohexanedimethanol 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) 23. The copolyester of cyclohexanedimethanol 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 copolyester of cyclohexanedimethanol 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 copolyester of cyclohexanedimethanol according to claim 22, which is a compound obtained by the following method. 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 copolyester of cyclohexanedimethanol 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 copolyester of cyclohexanedimethanol 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): The copolyester of cyclohexanedimethanol 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 The copolyester of cyclohexanedimethanol 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 copolyester of cyclohexanedimethanol 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 copolyester of cyclohexanedimethanol 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 copolyester of cyclohexanedimethanol 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: 23. The copolyester of cyclohexanedimethanol 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.
3. The copolyester of cyclohexane dimethanol 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 copolyester of cyclohexanedimethanol according to claim 22. Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image 47. A copolyester of cyclohexanedimethanol produced using a catalyst substantially having catalytic activity consisting of two or more compounds having substantially no catalytic activity for polyester polymerization. 48. A process for producing a copolyester of cyclohexanedimethanol according to any one of claims 1 to 47. 49. The method according to claim 48, wherein the antimony compound is added as an antimony atom in an amount of 50 ppm or less to the copolyester of cyclohexanedimethanol when the copolyester of cyclohexanedimethanol is produced. A method for producing a copolyester of cyclohexanedimethanol. 50. The method according to claim 48, wherein when producing the copolyester of cyclohexanedimethanol, the germanium compound is added as a germanium atom in an amount of 20 ppm or less to the copolyester of cyclohexanedimethanol. A method for producing a copolyester of cyclohexanedimethanol. 51. A molded article obtained by molding the copolyester of cyclohexanedimethanol according to any one of claims 1 to 47. 52. A sheet obtained by molding the copolyester of cyclohexanedimethanol according to any one of claims 1 to 47. 53. A film obtained by molding the copolyester of cyclohexanedimethanol according to any one of claims 1 to 47.