WO2002072665A1

WO2002072665A1 - Polyester and process for producing polyester

Info

Publication number: WO2002072665A1
Application number: PCT/JP2001/007723
Authority: WO
Inventors: Ken-Ichi Tukamoto; Takahiro Nakajima; Shoichi Gyobu
Original assignee: Toyo Boseki Kabushiki Kaisha
Priority date: 2001-03-09
Filing date: 2001-09-06
Publication date: 2002-09-19

Abstract

A polyester produced with a catalyst comprising as the main component(s) one or more ingredients which are neither antimony compounds nor germanium compounds. It is excellent in thermal stability, color tone, and hydrolytic resistance. The polyester may be one which is produced with a catalyst comprising an aluminum compound and a cobalt compound and contains an aluminum compound and a cobalt compound in specific amounts.

Description

Description Polyester and method for producing polyester

[Technical field]

The present invention relates to a polyester and a method for producing a polyester. More specifically, the present invention relates to a polyester produced by using a component other than an antimony compound and a germanium compound as a main component of a catalyst, and has a ripening stability, a color tone, and a resistance to ripening. The present invention relates to a polyester having excellent hydrolytic properties and a method for producing the polyester.

[Background technology]

Polyester, especially polyethylene terephthalate (hereinafter abbreviated as PET), has excellent mechanical and chemical properties, and can be used for a variety of applications, such as textiles for clothing and industrial materials, packaging and Applications are being made to various films and sheets for magnetic tapes, and molded products such as bottles and engineering plastics.

In the industrial production of PET, bis (2-hydroxyethyl) terephthalate is industrially produced by esterification or transesterification of terephthalic acid or dimethyl terephthalate with ethylene glycol, and is produced at high temperature and in a vacuum using a catalyst. It is obtained by condensation. Antimony trioxide is widely used as a catalyst for polycondensation. Antimony trioxide is a catalyst that is inexpensive and has excellent catalytic activity, but has the problem that blackening and foreign matter are generated in PET because metal antimony precipitates during polycondensation. Under these circumstances, polyesters containing no or only a small amount of antimony have been desired.

Attempts have been made to use antimony trioxide as a polycondensation catalyst and to suppress the occurrence of darkening and foreign matter in PET. For example, in Japanese Patent No. 2666502, by using a compound of antimony trioxide and bismuth selenium as a polycondensation catalyst,

The formation of black foreign substances in PET is suppressed. Also, in JP-A-9-291141,

1 Replacement form (Rule 26) It is stated 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 attain the purpose of a polyester containing no antimony after all.

Studies have been made on polycondensation catalysts that can replace antimony trioxide. In particular, titanium compounds typified by tetraalkoxy titanate have already been proposed, but the PET produced using this compound has problems that it is extremely colored and that thermal decomposition easily occurs.

In an attempt to overcome such problems when using a tetraalkoxy titanate as a polycondensation catalyst, for example, Japanese Patent Application Laid-Open No. 552-17222 discloses a method in which tedraalkoxy titanate is used simultaneously with a cobalt salt and a calcium salt. Proposed. JP-A-8-73581 proposes a method in which a tetraalkoxythiocyanate is used simultaneously with a cobalt compound as a polycondensation catalyst, and a fluorescent whitening agent is used. However, in these proposals, although the coloring of PET is reduced when tetraalkoxy titanate is used as a polycondensation catalyst, it has not been achieved to effectively suppress the thermal decomposition of PET.

Germanium compounds have been put to practical use as a polycondensation catalyst that can replace antimony trioxide and that overcomes problems such as those that occur when using tetraalkoxy titanate. However, they have a problem that they are very expensive and a problem that since the catalyst distills out of the reaction system during the polymerization, the catalyst concentration in the reaction system changes and it becomes difficult to control the polymerization. '

It is known that aluminum compounds generally have poor catalytic activity. Among aluminum compounds, aluminum chelate compounds are known to have higher catalytic activity as polycondensation catalysts than other aluminum compounds, but have sufficient catalytic activity compared to the above-mentioned antimony compounds and titanium compounds. Could not be said to have. Furthermore, polyesters conventionally polymerized using an aluminum compound as a catalyst could not sufficiently avoid problems such as poor thermal stability and odors and coloring derived from the aluminum compound. In response to such problems, for example, US Pat. No. 5,512,340 and Japanese Patent Application Laid-Open No. 10-324741 disclose an aluminum compound such as aluminum hydroxide, aluminum chloride or aluminum acetyl acetonate with a cobalt compound. It has been proposed that when used in combination, the catalyst activity is excellent and the coloring derived from the aluminum compound is improved. However, polyesters polymerized by using an aluminum compound and a cobalt compound as catalysts described in the publication are inferior in heat stability, color tone and hydrolysis resistance, and the polyesters are dark and the appearance of molded articles is inferior. It was a thing. [Disclosure of the Invention]

The present invention relates to a polyester produced using a component other than an antimony compound and a germanium compound as a main component of the catalyst, and a polyester which has solved the above-mentioned problems concerning heat stability, color tone, and hydrolysis resistance. It is intended to provide a method for producing a polyester.

The inventors of the present invention have conducted intensive studies with the aim of solving the above problems, and as a result, when producing a polyester using an aluminum compound and a cobalt compound as a catalyst, the halo of the aluminum compound and the cobalt compound is within a specific range. It has been found that a polyester having excellent heat stability and control, and furthermore, excellent hydrolysis resistance can be obtained by using the polyester.

That is, the present invention relates to a polyester produced by using an aluminum compound and a cobalt compound as a catalyst, wherein the amounts of the aluminum compound and the cobalt compound in the polyester are as follows. A polyester containing an amount satisfying the formulas (1) and (2) is provided.

0.01 (p pm) ≤A 1 + C o≤ (5 Oppm) (1)

Co (1 Oppm) (2) ''

(In the formulas (1) and (2), A 1 and Co represent the content (ppm) of aluminum atoms and cobalt atoms contained in the polyester, respectively.)

Further, the present invention solves both the thermal stability and the color tone of the polyester, which are the above-mentioned problems. As a method for preparing a polyester produced using an aluminum compound and a cobalt compound as a catalyst, the amounts of the aluminum compound and the cobalt compound in the polyester satisfy the following formulas (3) and (4). Provide polyester containing.

A 1 go 400 (p pm) (3)

Co / (A 1 + C o) ≤0. 05 (4)

(In the formulas (3) and (4), A 1 and Co represent the content (ppm) of aluminum atoms and cobalt atoms contained in the polyester, respectively.)

Further, the present invention provides a method for solving the above-mentioned problems of thermal stability, color tone and hydrolysis resistance of polyester, which is a polyester produced by using an aluminum compound and a cobalt compound as a catalyst, Provided is a polyester in which the amounts of the compound and the cobalt compound satisfy the following formulas (5) and (6).

C o≤4 (ppm) (5)

0.5≤A 1 / C o≤45 (6)

(Equation (5), (in 6) shows the content of A 1 Contact ¹ Preliminary C o is Miniumu atoms respectively contained in the polyester and cobalt atoms (ppm).)

The present invention also provides a method for producing a polyester by using an aluminum compound and a cobalt compound as a catalyst so that the content of the aluminum compound and the cobalt compound in the polyester falls within the above range.

The present invention also provides a catalyst system for maintaining high catalytic activity even when the aluminum compound and the cobalt compound are within the above specific ranges.

[Best mode for carrying out the invention] '

The aluminum compound that can be used in the present invention is not particularly limited. Examples thereof include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, and benzoic acid. Aluminum, Trichloride Aluminum acetate, Aluminum lactate, Aluminum citrate, Salicylate Carboxylates such as luminum, aluminum chloride, aluminum hydroxide, hydroxide chloride, aluminum carbonate, aluminum phosphate, inorganic acid salts such as aluminum phosphonate, aluminum methoxide, aluminum ethoxide, aluminum n-Propoxide, aluminum iso-propoxide, aluminum n-butoxide, aluminum t-butoxide, etc.Aluminum alkoxide, aluminum acetyl acetate, aluminum acetyl acetate, aluminum acetyl acetate, aluminum ethyl acetate Aluminum chelate compounds such as aluminum ethyl acetate acetate iso-propoxide, and organic aluminum compounds such as trimethyl aluminum dimethyl and triethyl aluminum Partial hydrolyzate of aluminum oxide, and metal aluminum. Of these, carboxylate, inorganic acid salt and chelate compound are preferable, and among these, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetyl acetonate are particularly preferable.

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

In the polyester of the present invention, in order to solve the problem of thermal stability, the total of the aluminum atom and the cobalt atom in the polyester is at least 0.1 ppm and not more than 50 ppm, and the cobalt atom is less than 10 ppm. It is necessary. More preferably, the sum of the aluminum atom and the copartite atom is 0.1 ppm or more, 40 ppm or less, and the cobalt atom is about 8 ppm or less, and further preferably, the total of the aluminum atom and the cobalt atom is 1 ppm or more, 25 ppm And the cobalt atom is below 5 ppm.

If the sum of the aluminum and cobalt atoms is greater than 50 ppm, or if the cobalt atom is greater than 10 ppm, the resulting polyester becomes prematurely unstable. Also, if the total amount of aluminum Yasuko and cobalt atoms is less than 0.1 ppm Sufficient catalytic activity cannot be obtained.

On the other hand, in another polyester of the present invention, in order to solve both the thermal stability and the color tone of the polyester, the aluminum content in the polyester is less than 400 ppm as an aluminum atom and the above formula ( 4) The value on the left side of is not more than 0.05. Preferably, the aluminum atom is less than 2 OOppm and the value on the left side of the above formula (4) is 0.005 to 0.04, more preferably less than 100 ppm as the aluminum atom, and the value on the left side of the above formula (4) Is from 0.01 to 0.03.

When the aluminum content is 400 pm or more, the obtained polymer has a problem that thermal stability is reduced and foreign matters are generated. For example, this causes productivity loss such as yarn breakage and back pressure increase during spinning. Further, when the value on the left side of the above formula (4) exceeds 0.05, the obtained polymer has a problem that the thermal stability is reduced and the color tone of the polymer is inferior to the dark appearance. If the value on the left side of the above equation (4) is smaller than 0.005, the color tone of the polymer becomes yellow, which is not desirable in practical use. In another polyester of the present invention, the cobalt content in the polyester of the present invention is 4 ppm or less as a cobalt atom in order to solve the problems of thermal stability, color tone, and hydrolysis resistance of the polyester. And the content ratio of aluminum atoms to cobalt atoms must be 0.5 to 45. Preferably, the content ratio of aluminum atoms to cobalt atoms is 2.0 to 25, more preferably 2 ppm or less as cobalt atoms, and the content ratio of aluminum atoms to cobalt atoms is 3 ppm or less as a cobalt atom. 3.0 to 15. If the added amount of cobalt atoms is more than 4 ppm, the resulting polyester will have reduced thermal stability and hydrolysis resistance. If the content ratio of aluminum atoms to cobalt atoms is less than 0.5, the color tone of the polymer becomes dark. If the content ratio of aluminum atoms to cobalt atoms is larger than 45, the color tone of the polymer becomes yellow. In addition, the aluminum content in polyester is 1 as aluminum atom.

It is preferably 20 ppm or less, more preferably 80 ppm or less. 1 added

If the content is more than 20 ppm, the thermal stability of the obtained polyester will be reduced, and May be decomposed or markedly colored.

The present invention also relates to a method for producing a polyester by using an aluminum compound and a cobalt compound as a catalyst such that the content of the aluminum compound and the cobalt compound in the polyester is in the above-mentioned range.

When the specific phosphorus compound is contained in the polyester of the present invention, in addition to improving the thermal stability of the polyester, the specific amounts of the aluminum compound and the cobalt compound as described above are reduced. It is preferable to use a specific phosphorus compound when polymerizing the polyester by using the compound because the catalytic activity can be improved.

The specific phosphorus compound is at least one selected from the phosphorus compounds represented by the following general formulas (Formula 3) and (Formula 4).

(Chemical Formula 3) Ph-P (= 0) (OR ¹ ) (0R ² X

'(In the formula (Ich 3),, each independently represents hydrogen, an alkyl group having 1 to 50 carbon atoms, or an aryl group.)

(Formula 4) Me-P (= 0) (0R ³ ) (0R ⁴ )

(In the formula (I-Dai 4), R ³ , each independently represents hydrogen, an alkyl group having 1 to 50 carbon atoms, or an aryl group.)

The compound represented by the above (Chemical Formula 3) or (Idani 4) is preferably at least one selected from dimethyl phenylphosphonate and diphenyl methylphosphonate, and the use of dimethyl phenylphosphonate is particularly preferred.

Phosphorus compounds are generally well known as antioxidants, but they are not known to greatly promote melt polymerization even when used in combination with conventional metal-containing polyester polymerization catalysts. When the polyester is melt-polymerized using an antimony compound, a titanium compound, a tin compound, or a germanium compound, which is a typical catalyst for polyester polymerization, as a polymerization catalyst, the specific phosphorus compound of the present invention is added. However, it is not recognized that the polymerization is promoted to a substantially useful level.

The amount of the phosphorus compound of the present invention to be used is preferably 0.000 to 0.1 mol%, and more preferably 0.005 to 0.1 mol% based on the total number of moles of the constituent units of the polycarboxylic acid component of the obtained polyester. More preferably, it is 0.05 mol%.

By using the phosphorus compound of the present invention in combination, a sufficient catalytic effect can be obtained even when the amount of aluminum and cobalt compounds added to the polyester is small. In addition, the heat stability and the low hydrolysis resistance inherent in the polyester containing the cobalt compound are improved by the combined use of the phosphorus compound of the present invention. If the added amount of the phosphorus compound is less than 0.0001 mol%, the effect of the addition may not be exhibited. If the added amount exceeds 0.1 mol%, the catalytic activity as a polyester polymerization catalyst may be reduced. Yes, its tendency to decrease depends on the amount of aluminum used.

When the polyester of the present invention contains one or more metals or group II compounds selected from the group consisting of alkali metals and their compounds, and alkaline earth metals and their compounds, the polyester This is preferable because physical properties such as thermal stability of the polymer are improved. Further, for example, in the case of PET, one or more metals or metal compounds selected from the group consisting of alkaline metal and their compounds, and alkaline earth metals and their compounds are used in the production of ethylene to produce ethylene. It is preferable because it can reduce the by-product of diethylene glycol (DEG), which is a dimer of glycol, and suppress the copolymerization of DEG into polyester, so that deterioration in the physical properties such as lowering of the softening point of the polyester can be eliminated. In addition, when polymerizing the polyester using the specific amounts of the aluminum compound and the cobalt compound as described above, it is selected from the group consisting of alkali metals and their compounds, and alkaline earth metals and their compounds. It is preferable to add one or more metals or metal compounds to improve the catalytic activity. Furthermore, it is preferable to use the above-mentioned specific phosphorus compound in combination, because the catalytic activity can be further improved.

The alkali metal or the compound thereof or the alkaline earth metal or the compound thereof of the present invention includes, in addition to the alkali metal or the alkaline earth metal,

The compound is not particularly limited as long as it is one or more compounds selected from Li. Na. K. Rb, Cs. Be, Mg, Ca, and Sr. Ba. For example, for example, formic acid, acetic acid, and propion of these metals Saturated aliphatic carboxylate such as acid, butyric acid, oxalic acid, acrylic acid, methacrylic acid, etc. Unsaturated aliphatic carboxylate, aromatic carboxylate such as benzoic acid, halogen-containing carboxylate such as trichloroacetic acid, hydroxycarboxylate such as lactic acid, cunic acid, salicylic acid, carbonic acid, sulfuric acid, nitric acid, Inorganic acid salts such as phosphoric acid, phosphonic acid, hydrogen carbonate, hydrogen phosphate, hydrogen sulfate, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, bromic acid, etc., 1-propanesulfonic acid, toppentanesulfonic acid Organic sulfonates such as naphthalene sulfonate, organic sulfates such as lauryl sulfate, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, t-butoxy, etc., acetyl acetate, etc. Chelate compounds, oxides, hydroxides and the like. Of these, saturated aliphatic carboxylate is preferable, and vinegar is more preferable. Salt is particularly preferred.

When adding an alkali metal, alkaline earth metals and their compounds, its amount M (mol%), relative to number of moles of all the polycarboxylic acids units constituting the polyester, 1 x 10- ⁶ or 0. It is preferably less than 1 mol%, more preferably 5 xl (T ^{6 to} 0.05 mol%, still more preferably lxi (T ⁵ to 0.03 mol%, particularly preferably 1 × 10 5 — ⁵ to 0.01% by mole Addition of a small amount of alkali metal or alkaline earth metal reduces the reaction rate without causing problems such as reduced thermal stability, generation of foreign matter, and coloring. When the amount of alkali metal, alkaline earth metal or its compound exceeds 0.1 mol%, thermal stability is reduced, foreign matter is generated, and coloring is increased. If occurs. in Μ is less than IX 10- ^6, added The effect is not clear also.

The production of the polyester according to the present invention can be carried out by a conventionally known method. For example, when producing PET, a method of esterifying terephthalic acid with ethylene glycol followed by polycondensation, or a transesterification reaction between an alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol is performed. Any method of polycondensation can be used. The polymerization apparatus may be of a batch type or a continuous type.

The polyester of the present invention may be produced not only by melt polymerization but also by solid phase polymerization or solution polymerization. The catalyst used in the production of the polyester of the present invention can be added to the reaction system at any stage of the polymerization reaction. For example, addition to the reaction system before the start of the esterification reaction or the transesterification reaction and at any stage during the reaction or immediately before the start of the polycondensation reaction and at any stage during the reaction is exemplified. In particular, aluminum or its compound is preferably added immediately before the start of the polycondensation reaction.

The method of adding the additive such as a catalyst used in the production of the polyester of the present invention may be in the form of powder or neat, or may be in the form of a slurry or a solution of a solvent such as ethylene glycol. Not limited. Further, a mixture obtained by previously mixing an aluminum compound and a cobalt compound may be added, or these may be added separately. In addition, these compounds may be added in advance with a phosphorus compound, and a premix of Z or an alkali metal or a compound thereof, or an alkaline earth metal or a compound thereof, or may be added separately. May be. Further, these compounds may be added at the same time or at different times.

When an aluminum compound and a cobalt compound are used as a catalyst for producing the polyester of the present invention, the catalyst has catalytic activity not only in a polycondensation reaction but also in an esterification reaction and a transesterification reaction. For example, polymerization by transesterification of an alkyl ester of a dicarboxylic acid such as dimethyl terephthalate with a glycol such as ethylene glycol is usually carried out in the presence of a transesterification catalyst such as a titanium compound or a zinc compound. Alternatively, or in the presence of these catalysts, the catalysts can be used. Further, the catalyst has catalytic activity not only in melt polymerization but also in solid phase polymerization and solution polymerization, and it is possible to produce polyester by any method.

When producing a polyester according to the method of the present invention, other polymerization catalysts such as an antimony compound, a titanium compound, and a germanium compound may be added to a product having the above-described properties, processability, and color tone of the polyester by adding these components. The coexistence within the range of the addition amount that does not cause a problem is advantageous and preferable in improving the productivity by shortening the polymerization time. However, the content of the antimony compound in the polyester is defined as antimony atoms.

An amount of 50 ppm or less is preferred. It is more preferably at most 30 ppm. If the content of antimony is more than 50 ppm, precipitation of metallic antimony occurs, and blackening or foreign matter is generated in the polyester, which is not preferable. The content of the titanium compound in the polyester is preferably lOppni or less as a titanium atom. More preferably, it is 5 ppm or less, more preferably, 2 ppm or less. When the content of titanium is more than 10 ppm, the thermal stability of the obtained resin is significantly reduced. The content of the germanium compound in the polyester is preferably 20 ppm or less as a germanium atom. More preferably, it is less than 10 ppm. If the content of germanium is more than 20 ppm, it is not preferable because it is disadvantageous in terms of cost.

When producing a polyester according to the method of the present invention, two or three kinds of antimony compounds, titanium compounds and germanium compounds may be used in combination. However, it is preferable that the total content of antimony, titanium, and germanium atoms in the polymer be 50 ppm or less. More preferably, the total content is 40 ppm or less, and still more preferably, the total content is 30 ppm or less. If the total content of antimony, titanium, and germanium atoms in the polyester exceeds 50 ppm, problems such as darkening and foreign matter in the polyester and a decrease in thermal stability may occur.

The antimony compound, titanium compound, and germanium compound used in the present invention are not particularly limited. Specifically, examples of the antimony compound include antimony trioxide, antimony pentoxide, antimony acetate, antimony glycoxide, and the like. Of these, antimony trioxide is preferable. Examples of the titanium compound include tetra-n-butoxytitanate and titanium oxalate. Of these, tetra-n-butoxytitanate is preferred. Examples of the germanium compound include germanium dioxide and germanium tetrachloride. Of these, germanium dioxide is preferable.

Further, when producing a polyester according to the method of the present invention, another polymerization catalyst such as a tin compound is allowed to coexist within a range that does not impair the thermal stability and color tone of the polyester. It is possible to

As used herein, the term "polyester" refers to one or more selected from multivalent rubonic acids containing dicarboxylic acids and ester-forming derivatives thereof, or one or more selected from polyhydric alcohols containing glycol and glycols. It is composed of two or more kinds, or composed of hydroxycarboxylic acid and their ester-forming derivatives, or composed of cyclic ester.

The dicarboxylic acids include oxalic acid, malonic acid, conodic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, and hexadecanedicarboxylic acid Acid, 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2, Saturated aliphatic dicarboxylic acids or ester-forming derivatives thereof such as 5-norbornanedicarboxylic acid and dimeric acid; unsaturated aliphatic dicarboxylic acids or esters thereof such as fumaric acid, maleic acid and itaconic acid Forming derivatives, orthophthalic acid, isophthalic acid, terephthalic , 5- (alkali metal) sulfoisophthalic acid, diphenic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid rubonic acid, 2,6-naphthalenedicarboxylic acid, 2 , 7-Naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-biphenylsulfondicarboxylic acid, 4,4'-biphenyletherdicarboxylic acid, 1,2-bis (phenoxy) ethane- ,, Ρ '—Aromatic dicarboxylic acids such as dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid and the like and their esdell-forming derivatives. Among these dicarboxylic acids, terephthalic acid and naphthalenedicarboxylic acid are particularly preferred.

2,6-Naphthalenedicarboxylic acid is preferred.

Polycarboxylic acids other than these dicarboxylic acids include ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3, 4, 3 ', and 4'-piphenyl. And tetracarboxylic acids, and their ester-forming derivatives. Examples of glycols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, and 2,3-butylene glycol. 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4 1-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene Glycol, 1, 12—dodecanediol, polyethylene glycol, polytrimethylene glycol, Aliphatic glycols exemplified by lithetamethylene glycol, hydroquinone, 4,4'-dihydroxybisphenol, 1,4-bis (] 3-hydroxyethoxy) benzene, 1,4-bis (/ 3-hydroxy Edoxyphenyl) sulfone, bis (p-'hydroxyphenyl) ether, bis (p-hydroxyphenyl) sulfone, bis (ρ-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane , Bisphenol A, bisphenol C, 2,5-naphthalene diol, glycols obtained by adding ethylene oxide to these glycols, and the like, and aromatic glycols such as ethylene glycol and 1, 4 One Petite Render Recall is preferred. .

Examples of polyhydric alcohols other than these glycols include trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, and hexanetriol.

Hydroxycarboxylic acids include lactic acid, cunic acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, P-hydroxybenzoic acid, ρ- (2-hydroxyethoxy) benzoic acid, and 4-hydroxycyclohexanecarboxylic acid Or ester-forming derivatives thereof.

Cyclic esters include ε-force prolactone,) 3-propiolatatatone, / 3-methyl

-ι6-Propiolataton, <5-Valerolactone, glycolide, lactide, etc. It is.

'' Ester-forming derivatives of polycarboxylic acids or hydroxycarboxylic acids include these alkyl esters, acid chlorides, acid anhydrides and the like. The polyester used in the present invention is preferably a polyester in which the main acid component is terephthalic acid or an ester-forming derivative thereof or naphthalenedicarboxylic acid or an ester-forming derivative thereof, and the main glycol component is an alkylene glycol. Polyester whose main acid component is terephthalic acid or its ester-forming derivative or naphthalenedicarboxylic acid or its ester-forming derivative is defined as terephthalic acid or its ester-forming derivative and naphthalate with respect to all the acid components. Preferably, the polyester contains at least 70 mol% of a total of a range carboxylic acid or an ester-forming derivative thereof, more preferably at least 80 mol%, even more preferably at least 90 mol%. It is. The polyester in which the main glycol component is alkylenedaricol is preferably a polyester containing at least 70 mol% of alkylene glycol in total with respect to all glycol components, more preferably a polyester containing at least 80 mol%. And more preferably a polyester containing 90 mol% or more. The alkylene glycol mentioned here may contain a substituent or an alicyclic structure in the molecular chain.

The naphthalenedicarboxylic acid or ester-forming derivative thereof used in the present invention includes 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid,

Preferred are 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and ester-forming derivatives thereof.

As the alkylenedaricol used in the present invention, ethylenedalicol, 1,

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, 1,2-cyclohexanedim Tanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethyleneglycol, 1,12-dodecanediol, etc. Yes. Two or more of these may be used at the same time.

The polyester of the present invention includes terephthalic acid or an ester-forming derivative thereof, naphthalenedicarbo: / acid or oxalic acid, malonic acid, succinic acid, daltaric acid, adipic acid, pimelic acid , Suberic acid, Azelaic acid, Sebacic acid, Decanedicarboxylic acid, Dodecanedicarboxylic acid, Tetradecanedicarboxylic acid, Hexadecandicarboxylic acid, 1,3-Ciglobutanedicarboxylic acid, 1,3-Cyclopentanedicarboxylic acid, 1 Saturated aliphatics exemplified by 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norpolnandicarboxylic acid, dimeric acid, etc. Dicarboxylic acid or their ester-forming derivatives, fumaric acid, maleic acid, itaconic acid Unsaturated aliphatic dicarboxylic acids or ester-forming derivatives thereof, such as orthophthalic acid, isophthalic acid, 5- (alkali metal) sulfoisophthalic acid, diphenic acid, 4,4'-biphenyldicarboxylic acid, 4, 4'-Biphenylsulfonic dicarboxylic acid, 4,4'-Pipenyl ether dicarboxylic acid, 1,2-bisphenoxy) ρ, ρ '-Dicarboxylic acid,' Pamoic acid, Anthrazine dicarboxylic acid Aromatic dicarboxylic acids or their ester-forming derivatives, e.g., ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3, 4, 3 ' Polyvalent carboxylic acids exemplified by 4'-biphenyltetracarboxylic acid and their ester-forming induction Can be included as a copolymer component. Examples include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, ρ-hydroxybenzoic acid, ρ- (2-hydroxyethoxy) benzoic acid, and 4-hydroxycyclohexacarboxylic acid. Or an ester-forming derivative thereof. Also, £ -force prolactone, j3-propiolactone, β-methyl-propiolactone, (5-valerolatatatone, glycolide, LA It may also contain a cyclic ester exemplified by a tide and the like.

The polyester of the present invention includes, as glycol components other than the alkylene glycol, aliphatic glycols, hydroquinones, and 4,4 'as exemplified by diethylene glycol, triethylene glycol, polyethylene glycol, polytrimethylene glycol, polytetramethylene dalicol, and the like. Dihydroxybisbuenol, 1,4-bis () 3-hydroxyethoxy) benzene, 1,4-bis (i3-hydroxyethoxyphenyl) sulfone, bis (p-hydroxyphenyl) ether, bis (p-hydroxyphenyl) Enyl) sulfone, bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxy ciphenyl) ethane, bisphenol A, bisphenol (3,2,5-naphthalenediol) Oxide added Include glycols, aromatic exemplified in such Darikoru, trimethylol methane, trimethylol E Tan, trimethylol propane, and the like polyhydric alcohols exemplified such as hexane triol Pentaerisuri tall _Λ glycerol to as copolymerization composite spectral Can be '

Examples of the polyester of the present invention include polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, poly (1,4-cycloxandimethylene terephthalate), polyethylene naphthalate, polybutylene naphthalate, polypropylene naphthalate and copolymers thereof. Among them, polyethylene terephthalate and its copolymer are particularly preferred.

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

As a component of the polyester of the present invention, in order to improve the dyeability when polyester is used as a fiber, a polycarboxylic acid having a metal salt of a sulfonate is used. It is a preferred embodiment to use an acid as a copolymer component.

'' The metal sulfonate group-containing compound used as the copolymerization monomer is not particularly limited. However, 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 5-lithium sulfoisophthalic acid, and 2-lithium sulfo Examples thereof include terephthalic acid, 5-potassium sulfoisophthalic acid, 2-potassium sulfoterephthalic acid, and lower alkyl ester derivatives thereof. In the present invention, it is particularly preferable to use 5-sodium sulfoisophthalic acid or an ester-forming derivative thereof. ,

The copolymerization amount of the metal sulfonate group-containing compound constitutes the polyester. The amount is preferably 0.3 to 10.0 mol%, more preferably 0.80 to 5.0 mol%, based on the acid content.

If the copolymerization amount is too small, the dyeability of the basic dye is poor, and if the copolymerization amount is too large, not only the spinning properties are poor, but also the fiber does not have sufficient strength due to the thickening phenomenon. Further, when 2.0 mol% or more of the metal sulfonate-containing compound is copolymerized, it is possible to impart normal pressure dyeability to the obtained modified polyester fiber. In addition, it is possible to appropriately reduce the amount of the metal sulfonate group-containing compound by selecting an appropriate 5 easy dyeing monomer. Examples of the easily dyeable monomer include, but are not particularly limited to, long-chain glycol compounds represented by polyethylene glycol and polytetramethylene glycol, and aliphatic dicarboxylic acids represented by adipic acid, sebacic acid, and azelaic acid. No.

After the polyester is polymerized according to the method of the present invention, the catalyst may be removed from the polyester or the catalyst may be deactivated by adding a phosphorus compound or the like to further increase the thermal stability of the polyester.

The polyester of the present invention may include organic, inorganic, and organometallic toners, and a fluorescent whitening agent. Coloring such as yellowing can be suppressed to a more excellent level. Also, any other polymer may contain antistatic agents, antifoaming agents, dyeing improvers, dyes, pigments, anti-glazing agents, optical brighteners, stabilizers, antioxidants, and other additives. Good. Antioxidants include antioxidants such as aromatic amines and phenols As the stabilizer, phosphorus-based stabilizers such as phosphoric acid and phosphate esters, zeolite-based and amine-based stabilizers can be used.

[Example]

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In each of the examples and comparative examples, the intrinsic viscosity (IV) of the polyester was measured as follows. The measurement was performed at a temperature of 30 ° C using a 6/4 mixed solvent (weight ratio) of phenol / 1,1,1,2,2-tetrachloroethane.

Analysis of metal content: The metal content was determined by dissolving the polymer in ashing acid, followed by high-frequency plasma emission analysis and atomic absorption analysis.

Evaluation method of thermal stability (used in Examples 1 to 15 and Comparative Examples 1 and 2): PETlg was placed in a glass test tube, dried under vacuum at 130 ° C for 12 hours, and then heated to 300 ° C under a nitrogen atmosphere. C. Visually determine the change in color after maintaining the molten state for 3 hours. The index of the change in color is indicated by the following symbols.

◎: almost no coloring, 〇: slight coloring

△: Slightly colored, X: markedly colored.

Evaluation method of thermal stability (used in Examples 16 to 22 and Comparative Examples 3 and 4): 2.5 g of PET was placed in a glass test tube, vacuum dried at 130 ° C for 12 hours, and then dried under a nitrogen atmosphere. After maintaining the molten state at ° C for 5 hours, it was cooled at room temperature and the treated PET was taken out. Next, the removed PET was formed into a film by a heat press machine. The obtained film was cut into a test piece having a length of 8 cm and a width of 4 cm, and the obtained film was pulled in the length direction and evaluated based on the easiness of the cut. Those that were hard to cut were evaluated as good. The evaluation index is represented by the following symbols.

@: Very good, 〇: Good

Δ: somewhat poor, X: poor

Evaluation method of thermal stability (used in Examples 23 to 29 and Comparative Examples 5 to 7): 2.5 g of PET was placed in a glass test tube, vacuum dried at 130 ° C for 12 hours, and then dried under a nitrogen atmosphere. After maintaining the molten state at ° C for 5 hours, it was cooled at room temperature and the treated PET was taken out. next, The removed PET was formed into a film by a heat press. The obtained film was cut into a test piece having a length of 8 cm and a width of 4 cm, and the obtained film was stretched in the length direction and evaluated based on the easiness of the cut. Those that were hard to cut were evaluated as good. The evaluation index is represented by the following symbols.

5 ◎: extremely good, 〇: good

△: Somewhat bad, X: Bad

'Color evaluation method (used in Examples 16 to 22 and Comparative Examples 3 and 4): The degree of coloring (yellowish and darkened) of the polyester resin chip obtained by polymerization was visually confirmed. The color index is represented by the following symbols. '

10 ◎: almost no coloring, 〇: slight coloring

△: slightly colored, X: markedly colored

Evaluation method of color tone (used in Examples 23 to 29 and Comparative Examples 5 to 7): polyester resin chips obtained by polymerization are formed into a film by a heat press machine, and then polyester is colored (yellowish and blackish). ) Was visually checked. The color index is represented by the symbol 15 below.

◎: almost no coloring, 〇: slight coloring

△: slightly colored, X: markedly colored

'Method for evaluating hydrolysis resistance: PET was formed into a film by a heat press machine, and the obtained film was cut into a test piece of 8 cm in length and 4 cm in width. The obtained film 20 and 100 ml of water were placed in a cylindrical container having an inner diameter of 6 cni and a height of 11 cm, sealed, and heat-treated with an EG bath at 140 ° C for 6 hours. Then, the film taken out was dried under reduced pressure at 80 ° (for 12 hours), and then the film was pulled in the length direction to evaluate the hydrolysis resistance by the easiness of the cut. The evaluation indicators are represented by the following symbols.

25 ◎: Very good, 〇: Good

△: Somewhat bad, X: Bad

(Example 1)

Bis (2-hydroxyethyl) terephthalate and oligomer produced by a conventional method 3 g / l ethylene dalicol solution of aluminum chloride as a catalyst was added to the resulting mixture of 2 Op pm as aluminum atoms to the final polymer, and 1 Og / 1 of cobalt acetate tetrahydrate was added. An ethylene glycol solution was added at 2.5 ppm as a cobalt atom to the finally obtained polymer, and then a 10 g / 1 ethylene glycol solution of dimethyl phenylphosphonate was added at 0.02 mol% based on the acid component in the polyester. Further, a 5 g / 1 ethylene glycol solution of lithium acetate dihydrate was added to the polyester in an amount of 0.02 mol% based on the acid content, and the mixture was stirred at 245 ° C. for 10 minutes at normal pressure. Then, the pressure of the reaction system was gradually reduced to 13.3 Pa while raising the temperature to 275 ° C in 50 minutes, and the polycondensation reaction was further performed at 275 ° C and 13.3 Pa for 3 hours. Table 1 shows the physical properties of the obtained polymer, the metal content in the polymer, and the evaluation results of thermal stability. ,-

(Examples 2 to 15 and Comparative Examples 1 and 2)

Table 1 shows the physical properties of the polymer obtained by polymerizing the polyester _{c in} exactly the same manner as in Example 1 except that the catalyst was changed, the metal content in the polymer, and the evaluation results of thermal stability.

(Example 16)

For a mixture of bis (2-hydroxyethyl) terephthalate and an oligomer prepared by a conventional method, a catalyst containing a 3 g solution of aluminum chloride in ethylene dalicol was used as a catalyst, and an aluminum atom was added to the resulting polymer. 300 ppm, and a 1 Og / 1 ethylene glycol solution of cobalt acetate tetrahydrate is added to the final polymer at 10 ppm as cobalt atoms, and then 10 g of dimethyl phenylphosphonate / 1 ethylene glycol solution Was added to the acid component in the polyester in an amount of 0.2 mol%, and the mixture was stirred at normal pressure at 245 ° C. for 10 minutes. Then, over 50 minutes, the pressure of the reaction system was gradually lowered while the temperature was raised to 275 ° C to 13.3 Pa, and the polycondensation reaction was further performed at 275 ° C and 13.3 Pa for 3 hours. Table 2 shows the physical properties of the obtained polymer, the metal content in the polymer, the thermal stability, and the evaluation results of color tone.

(Examples 17 to 22 and Comparative Examples 3, 4)

The polyester was polymerized in exactly the same manner as in Example 16 except that the catalyst was changed. Was. Table 2 shows the physical properties of the obtained polymer, the metal content in the polymer, and the evaluation results of thermal stability and color tone. ,

(Example 23)

For a mixture of bis (2-hydroxyethyl) terephthalate and an oligomer produced by a conventional method, a 3 g / l ethylene glycol solution of aluminum chloride was used as a catalyst as an aluminum atom for the finally obtained polymer. ppm, followed by a 1 Og / 1 solution of cobalt acetate tetrahydrate in ethylene glycol added to the final polymer at 3 ppm as cobalt atoms, followed by a 10 g / 1 solution of dimethyl dimethylphosphonate in ethylene dalicol Was added to the acid component in the polyester at 0.01 mol%, and a 5 gZ1 ethylene glycol solution of lithium acetate dihydrate was added at 0.025 mol% to the acid content in the polyester. Then, the mixture was stirred at 245 ° C for 10 minutes under normal pressure. Then, over 50 minutes, the pressure of the reaction system was gradually lowered while raising the temperature to 275 ° C to 13.3 Pa, and the polycondensation reaction was further performed at 275 ° C and 13.3 Pa for 3 hours. Table 3 shows the physical properties of the obtained polymer, the metal content in the polymer, and the evaluation results of thermal stability, color tone, and hydrolysis resistance.

(Examples 24 to 29 and Comparative Examples 5 to 7)

A polyester was polymerized in exactly the same manner as in Example 23 except that the catalyst was changed. Table 3 shows the physical properties of the obtained polymer, the metal content in the polymer, and the evaluation results of thermal stability, color tone, and hydrolysis resistance. .

[Industrial applicability]

According to the present invention, a polyester obtained by polymerizing a compound other than an antimony compound and a germanium compound as a main component of a catalyst and having excellent heat stability, a mako is a polyester having both heat stability and excellent color tone, The present invention provides a polyester having excellent heat stability, color tone and hydrolysis resistance. The polyester of the present invention can be applied to clothing fibers, industrial material fibers, various films, sheets, various molded products such as bottles and engineering plastics, and paints and adhesives. TJP01 / 07723

t

Claims

The scope of the claims

1. A polyester containing aluminum and / or a compound thereof and cobalt and / or a compound thereof, and having a content satisfying the following formulas (1) and (2).

0.01 (p pm) ≤A 1 + Co≤50 (p pm) (1)

C o <1 0 (p pm) (2)

2. A polyester containing aluminum and / or its compound, cobalt and / or its compound, and having a content satisfying the following formulas (3) and (4). ,

A 1 <400 (p pm) (3)

C o / (A 1 + C o) ≤0. 05 (4)

(In the formulas (3) and (4), A 1 and Co indicate the contents (ppm) of aluminum atoms and cobalt atoms contained in the polyester, respectively.)

3. A polyester containing aluminum and / or a compound thereof, cobalt and / or a compound thereof, and having a content satisfying the following formulas (5) and (6).

C o≤4 (ppm) (5)

0.5≤A 1 / C o≤45 (6)

(In the formulas (5) and (6), A 1 and Co indicate the content (ppm) of aluminum atoms and cobalt atoms contained in the polyester, respectively.)

4. The polyester according to any one of claims 1 to 3, containing at least one compound represented by the following general formulas (Chemical Formula 1) and (Chemical Formula 2). (Formula 1) Ph-P (= 0) (OR ¹ ) (OR ² )

(In the formula, R ^1. Independently represents hydrogen, an alkyl group having 1 to 50 carbon atoms, or an aryl group.)

(Formula 2) Me-P (= 0) (0R ³ ) (0R ⁴ )

(In the formula, R ³ , independently represents hydrogen, an alkyl group having 1 to 50 carbon atoms, or an aryl group.)

5. One or more metals and / or metal compounds selected from the group consisting of alkali metal and their compounds, and earth metal and their compounds. The polyester according to any one of 1 to 4.

6. The polyester according to any one of claims 1 to 5, comprising antimony, titanium and germanium in amounts satisfying the following formulas (7) to (10).

Sb≤50 (p pm) (7)

T i≤ 10 (ρ pm) (8)

Ge≤20 (ρ pm) (9)

S b + T i + Ge≤50 (p pm) (10)

(Sb, Ti, and Ge represent the contents (ppm) of antimony, titanium, and germanium atoms contained in the polyester, respectively.)

7. A method for producing a polyester, comprising using the substance and the amount described in the claim contained in the polyester according to any one of claims 1 to 6 as a polymerization catalyst.