JP2002322254A - Polyester and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide both a polyester produced by using a polymerization catalyst comprising a metal component other than antimony and germanium as a main metal component of the catalyst with reduced filter clogging, etc., during molding and a method for producing the polyester. SOLUTION: This polyester comprises specific amounts of at least one kind selected from the group consisting of an alkali metal and its compounds and an alkaline earth metal and its compounds, at least one kind selected from the group consisting of aluminum and its compounds and at least one kind selected from phosphorus compounds.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester and a method for producing the same, and more particularly, to a polyester having improved filter clogging during molding and a method for producing the same.

[0002]

2. Description of the Related Art Polyester, especially polyethylene terephthalate (hereinafter abbreviated as PET) has excellent mechanical properties and chemical properties, and is applicable to various uses, for example, fibers for clothing and industrial materials, and packaging. It is applied to various films and sheets for tapes and magnetic tapes, and molded products such as bottles and engineering plastics.

[0003] PET industrially produces bis (2-hydroxyethyl) terephthalate by esterification or transesterification of terephthalic acid or dimethyl terephthalate with ethylene glycol, which is heated at a high temperature.
It is obtained by polycondensation using a catalyst under vacuum. As a catalyst used in the polycondensation, antimony trioxide is widely used. Antimony trioxide is a catalyst that is inexpensive and has excellent catalytic activity, but has a problem that blackening or foreign matter is generated in PET because metal antimony precipitates during polycondensation. In such circumstances,
A polyester that does not contain antimony at all or does not contain antimony as a main component of a catalyst is desired.

[0004] The above-mentioned foreign substances in polyester cause the following problems, for example.

(1) In polyester for film, the precipitation of antimony metal becomes a foreign matter in the polyester and causes not only stains on a die at the time of melt extrusion but also surface defects on the film. In addition, when a raw material such as a hollow molded article is used, it is difficult to obtain a hollow molded article having excellent transparency.

(2) The foreign matter in the polyester for the fiber is
It becomes a foreign substance that causes a decrease in strength in the fiber, causing stains in a spinneret during yarn production and an increase in filter filtration pressure. In the production of polyester fibers, a polyester polymerization catalyst free of foreign matter is required mainly from the viewpoint of operability.

[0007] 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 Patent No. 2666502,
The use of a compound of antimony trioxide, bismuth and selenium as a polycondensation catalyst suppresses the formation of black foreign substances in PET. Also, in JP-A-9-291141,
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 ultimately achieve the purpose of reducing the content of antimony.

As polycondensation catalysts other than the antimony compound, titanium compounds and tin compounds have already been proposed. However, polyesters produced using these compounds are susceptible to thermal deterioration during melt molding, and the polyesters are markedly colored. There is a problem that.

As an attempt to overcome such problems when using a titanium compound as a polycondensation catalyst, for example, JP-A-55-116722 discloses a method in which a tetraalkoxy titanate is used simultaneously with a cobalt salt and a calcium salt. Has been proposed. Also, Japanese Patent Application Laid-Open No. 8-735
No. 81 proposes a method in which a tetraalkoxy titanate is used simultaneously with a cobalt compound as a polycondensation catalyst and a fluorescent whitening agent is used. However, in these techniques, although the coloring of PET is reduced when tetraalkoxy titanate is used as a polycondensation catalyst, the P
Effective suppression of thermal decomposition of ET has not been achieved.

On the other hand, Japanese Patent Publication No. 46-41031 discloses that excellent catalytic activity is exhibited when an alkali metal or a compound thereof and a chelate compound of aluminum coexist. Polyester polymerized according to the method described in the publication, although excellent in thermal stability, a lot of foreign matter insoluble in the polyester is generated, filter clogging due to the foreign matter occurs during polyester molding, and when used for fibers Thread breakage during spinning frequently occurs, and when used for a film, there is a problem that the film properties and the like are deteriorated, which is not suitable for practical use.

Although there is a technique of adding an alkaline earth metal compound to an aluminum compound to obtain a catalyst having a sufficient catalytic activity, a large amount of the alkaline earth metal compound is required to obtain a practical catalytic activity. As a result, the thermal stability and thermal oxidation stability of the resulting polyester are reduced, the coloring by heating is large, and the amount of foreign matters insoluble in the polyester is increased.

[0012] Germanium compounds have already been put to practical use as catalysts which provide polyesters having excellent catalytic activity other than the antimony compounds and not having the above-mentioned problems, but this catalyst is very expensive. And
Since it is easy to distill out of the reaction system during polymerization, the catalyst concentration in the reaction system changes, making it difficult to control the polymerization, and there is a problem in using it as the main component of the catalyst.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyester produced by using a polymerization catalyst containing a metal component other than antimony and germanium as a main metal component of the catalyst, and a filter clogging during molding. And a method for producing the same.

[0014]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies with the aim of solving the above problems, and as a result, have found that polymerization using a catalyst in which an alkali metal compound or an alkaline earth metal compound and an aluminum compound coexist is carried out. The foreign matter insoluble in the polyester produced by the process was found to be mainly due to alkali metal compounds and alkaline earth metal compounds, and as a result of further investigation, these foreign materials were effectively reduced by the coexistence of phosphorus compounds. By further reducing the content of the metal compound and the phosphorus compound in the polyester to a specific range, the generation of foreign matter insoluble in the polyester is effectively suppressed, and clogging of the filter when molding the polyester, etc. The present inventors have found that the above problem has been improved, and arrived at the present invention.

That is, the present invention provides, as a solution to the above problems, at least one selected from the group consisting of alkali metals and their compounds and alkaline earth metals and their compounds, and the group consisting of aluminum and its compounds. At least one, and at least one selected from the group consisting of phosphorus compounds,
And a polyester characterized by containing them in an amount satisfying the following formulas (1) to (3).

(1) 0.1 ≦ M ≦ 150 (2) M / Al ≦ 40 (3) P / Al ≧ 0.01 (In the formulas (1) to (3), M represents an alkali metal atom contained in the polyester and an alkali metal. The total amount (ppm) of earth metal atoms is shown, and Al and P are the amounts (ppm) of aluminum atoms and phosphorus atoms contained in the polyester, respectively.) Provided is a polyester produced by using as a catalyst and a method for producing the same.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester of the present invention has a total of at least one selected from the group consisting of alkali metals and their compounds and alkaline earth metals and their compounds as a metal atom in the polyester in a total amount of 0.1.
It must be contained in an amount of 1 ppm or more and 150 ppm or less. When the content is more than 150 ppm, many foreign matters insoluble in the polyester are generated, and as a result, a problem occurs that yarn breakage at the time of spinning and filter clogging at the time of molding frequently occur. In addition, the coloring of the resin becomes remarkable, causing a problem that the appearance of the molded article is impaired, and a problem that the thermal stability and hydrolysis resistance of the resin are reduced. Content is 0.1ppm
If the amount is smaller than this, a problem occurs that the thermal stability of the resin becomes poor, and a problem occurs that the catalytic activity is remarkably reduced when the resin is used as a catalyst. A more preferable range of the content is 1 ppm or more and 100 ppm or less, and further preferably 5 ppm or more and 50 ppm or less.

The polyester of the present invention comprises at least one selected from the group consisting of aluminum and its compounds in addition to at least one selected from the group consisting of the above-mentioned alkali metals and their compounds and alkaline earth metals and their compounds. Must be included. Further, the content of at least one selected from the group consisting of alkali metals and their compounds and alkaline earth metals and their compounds and at least one selected from the group consisting of aluminum and its compounds is defined as an alkali metal atom in the polyester. It is necessary that the ratio of the total content (ppm) of alkaline earth metal atoms to the content (ppm) of aluminum atoms be 40 or less. This ratio is preferably at least 0.05. Ratio 40
If it exceeds, a lot of foreign matter insoluble in polyester occurs,
As a result, there arises a problem that yarn breakage during spinning and filter clogging during molding frequently occur. Further, when used as a catalyst, there is a problem that the catalytic activity is significantly reduced. If the ratio is less than 0.05, a large amount of foreign matters insoluble in the polyester due to the aluminum compound is generated, and the thermal stability of the polyester is also undesirably reduced. A more preferable range of the ratio is 0.1 or more and 20 or less, and further preferably 0.5 or more and 10 or less.

The polyester of the present invention comprises a phosphorus compound in addition to at least one selected from the group consisting of alkali metals and their compounds and alkaline earth metals and their compounds and at least one selected from the group consisting of aluminum and its compounds. At least one selected from the group consisting of: Further, the content of at least one selected from the group consisting of phosphorus compounds and aluminum and at least one selected from the group consisting of the compounds, the content of phosphorus atoms in the polyester (ppm) and the content of aluminum atoms (ppm) Is required to be 0.01 or more. This ratio is preferably 30 or less. If the ratio is less than 0.01, there arises a problem that a large amount of foreign matters insoluble in the polyester caused by the aluminum compound and a problem that the thermal stability of the polyester is reduced. If the ratio exceeds 30, a large amount of foreign matter insoluble in the polyester is generated, and when used as a catalyst, there is a problem that the catalytic activity is remarkably reduced. A more preferable range of the ratio is 0.1 or more and 20 or less, and further preferably 1 or more and 10 or less.

In the polyester, at least one selected from the group consisting of alkali metals and their compounds and alkaline earth metals and their compounds, at least one selected from the group consisting of aluminum and its compounds, and the group consisting of phosphorus compounds When the content of at least one selected from the above is in the above range, the generation of foreign matters insoluble in polyester is effectively suppressed, and problems such as yarn breakage during spinning and filter clogging during molding are improved.

Further, the aluminum and the compound thereof in the present invention are preferably contained in the polyester in an amount of 0.5 ppm or more and 500 ppm or less as aluminum atoms. If the content of the aluminum atom exceeds 500 ppm, it is not preferable because a large amount of foreign matters insoluble in the polyester due to the aluminum compound is generated and the thermal stability of the polyester is lowered. The content of aluminum atoms is
If the amount is less than 0.5 ppm, a large amount of foreign matter due to the alkali metal compound or the alkaline earth metal compound is generated, or the catalytic activity is significantly reduced when used as a catalyst, which is not preferable. More preferably, it is in the range of 5 ppm or more and 70 ppm or less, and still more preferably in the range of 10 ppm or more and 30 ppm or less.

The phosphorus compound in the present invention is preferably contained in the polyester in a range of 1 ppm to 1000 ppm as a phosphorus atom. If the phosphorus atom content is less than 1 ppm, the effect of suppressing the formation of foreign matter insoluble in the polyester is poor, and the thermal stability of the polyester is undesirably reduced. Phosphorus atom content is 10
If it exceeds 00 ppm, it is not preferable because a large amount of foreign matter insoluble in polyester is generated. More preferably, it is in the range of 10 ppm or more and 200 ppm or less, and still more preferably in the range of 20 ppm or more and 100 ppm or less.

The polyester of the present invention needs to contain at least one selected from the group consisting of alkali metals and their compounds and alkaline earth metals and their compounds. Among these, lithium and sodium It is preferable to contain at least one selected from the group consisting of potassium, magnesium, calcium, and compounds thereof from the viewpoint of reducing foreign substances in the polyester and reducing coloring of the polyester. Among these, it is preferable to contain at least one selected from the group consisting of lithium, calcium and compounds thereof because the polyester has excellent thermal stability. Further, it is preferable to contain at least one selected from the group consisting of calcium and their compounds from the viewpoint of reducing the coloring of the polyester.

It is preferable that the polyester of the present invention does not use a polymerization catalyst such as an antimony compound, a germanium compound, a titanium compound, and a tin compound.

On the other hand, the polyester of the present invention comprises an antimony compound, a germanium compound, a titanium compound,
The use of a polymerization catalyst such as a tin compound in such an amount that the addition of these components does not cause a problem in the product such as the properties, processability, and color tone of the polyester described above coexists to use the polymerization catalyst. When it is used, it is effective and preferable in improving productivity by shortening the polymerization time.

It is preferable that the content of antimony atoms in the polyester of the present invention is 50 ppm or less based on the amount of the polyester, because blackening of the polyester and generation of foreign matter are suppressed. It is more preferably at most 30 ppm, further preferably at most 10 ppm. On the other hand, the polyester of the present invention preferably does not contain an antimony atom.

It is preferable that the content of germanium atoms in the polyester of the present invention is not more than 20 ppm based on the amount of the polyester, so that the cost is not disadvantageous. It is more preferably at most 10 ppm, further preferably at most 5 ppm. On the other hand, it is preferable that the polyester of the present invention does not contain a germanium atom.

It is preferable that the content of titanium atoms in the polyester of the present invention is 5 ppm or less relative to the polyester, because the polyester has excellent heat stability and color tone. More preferably 3 ppm or less,
More preferably, it is 1 ppm or less. On the other hand, the polyester of the present invention preferably does not contain a titanium atom.

The polyester of the present invention preferably further contains cobalt or a compound thereof from the viewpoint of reducing the coloring of the polyester. However, as the content of cobalt or its compound in the polyester,
It is preferable to contain the cobalt atom in an amount of less than 10 ppm based on the polyester. More preferably 5 pp
m, more preferably 3 ppm or less.

It is known that the cobalt compound itself has a certain degree of catalytic activity. However, if the cobalt compound is added to such an extent that a sufficient catalytic effect is exerted, the resulting polyester polymer will have a reduced brightness and a lower thermal stability. Decrease occurs. In the present invention, by adding the cobalt compound in such a small amount that the catalytic effect of the addition is not clear as described above, the coloring can be further improved without lowering the brightness and thermal stability of the obtained polyester. Can be effectively erased. The purpose of the cobalt compound in the present invention is to eliminate coloration, and it may be added at any stage of the polymerization or after the completion of the polymerization reaction.

On the other hand, it is preferable that the polyester of the present invention does not contain a cobalt atom.

The present invention also relates to a polyester produced using the above-mentioned metal and compound as a catalyst and a method for producing the same. As the addition amount of the metal and the compound,
It is necessary that the content of metal atoms and phosphorus atoms in the finally obtained polyester be as described above.
By this method, the generation of foreign matters insoluble in polyester is effectively suppressed, and problems such as yarn breakage during spinning and filter clogging during molding are improved.

The alkali metals and their compounds and the alkaline earth metals and their compounds used as the polymerization catalyst in the present invention include Li, Na, K,
At least one metal or a compound thereof selected from Rb, Cs, Be, Mg, Ca, Sr, and Ba is preferable. When an alkali metal or a compound thereof is used, foreign matters insoluble in polyester are reduced, It is more preferable because the polyester has excellent thermal stability. When an alkali metal or its compound is used, Li, N
It is preferable to use a, K or a compound thereof. Of these, use of Li or a compound thereof is particularly preferable because foreign matter insoluble in polyester is further reduced. As a compound of an alkali metal or an alkaline earth metal, for example,
Saturated aliphatic carboxylate such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, unsaturated aliphatic carboxylate such as acrylic acid and methacrylic acid, aromatic carboxylate such as benzoic acid, and trichloroacetic acid of these metals Halogen-containing carboxylate, hydroxycarboxylate such as lactic acid, citric acid, salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, odor Inorganic acid salts such as hydrofluoric acid, chloric acid, and bromic acid; organic sulfonates such as 1-propanesulfonic acid, 1-pentanesulfonic acid, and naphthalenesulfonic acid; organic sulfates such as lauryl sulfate; methoxy, ethoxy, n
-Propoxy, iso-propoxy, n-butoxy, t
alkoxides such as tert-butoxy, chelate compounds with acetylacetonate and the like, hydrides, oxides,
Hydroxide and the like.

When strong alkalis such as hydroxides are used among these alkali metals, alkaline earth metals or their compounds, they tend not to be easily dissolved in diols such as ethylene glycol or organic solvents such as alcohols. Therefore, an aqueous solution must be added to the polymerization system, which may cause a problem in the polymerization step. Further, when a strong alkali such as a hydroxide is used, the polyester is liable to undergo side reactions such as hydrolysis during polymerization, and the polymerized polyester tends to be easily colored, and the hydrolysis resistance is also reduced. Tend to. Accordingly, the alkali metal or a compound thereof or an alkaline earth metal or a compound thereof suitable for the present invention is preferably a saturated aliphatic carboxylate, an unsaturated aliphatic carboxylate, or an aromatic salt of an alkali metal or an alkaline earth metal. Group carboxylate, halogen-containing carboxylate, hydroxycarboxylate, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid,
It is an inorganic acid salt selected from chloric acid and bromic acid, an organic sulfonate, an organic sulfate, a chelate compound, and an oxide. Among these, from the viewpoints of ease of handling and availability, it is preferable to use an alkali metal or alkaline earth metal saturated aliphatic carboxylate, particularly an acetate.

The aluminum or a compound thereof used as a polymerization catalyst in the present invention is not particularly limited. In addition to metal aluminum, for example, aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, acrylic acid Aluminum carboxylate such as aluminum phosphate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, aluminum lactate, aluminum citrate, aluminum salicylate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, phosphorus Inorganic acid salts such as aluminum phosphate, aluminum phosphonate, aluminum methoxide, aluminum ethoxide, aluminum
n-propoxide, aluminum iso-propoxide,
Aluminum chelate compounds such as aluminum alkoxide, aluminum acetylacetonate, aluminum acetyl acetate, aluminum ethyl acetoacetate, aluminum ethyl acetoacetate di-iso-propoxide, aluminum n-butoxide, aluminum t-butoxide, trimethyl aluminum, triethyl aluminum, etc. Organic aluminum compounds and partial hydrolysates thereof, aluminum oxide and the like can be mentioned. 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 acetylacetonate are particularly preferable.

The phosphorus compound used in the present invention includes:
Although not particularly limited, phosphoric acid and a phosphoric acid ester such as trimethylphosphoric acid, triethylphosphoric acid, phenylphosphoric acid, triphenylphosphoric acid, phosphorous acid and trimethylphosphite, triethylphosphite, triphenylphosphite, tris ( Examples include phosphites such as 2,4-di-tert-butylphenyl) phosphite and tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylenediphosphite.

On the other hand, examples of the phosphorus compound used in the present invention include phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds. Can be By using these phosphorus compounds together with the aluminum compound of the present invention during the polymerization of the polyester, an effect of improving the catalytic activity can be obtained. Among these, the use of a phosphonic acid-based compound is preferred because the effect of improving the catalytic activity is large.

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

[0039]

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Embedded image Examples of the phosphonic acid compound of the present invention include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate, and the like. Examples of the phosphinic acid compound of the present invention include diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate, phenylphosphinic acid, methyl phenylphosphinate, phenyl phenylphosphinate and the like. Examples of the phosphine oxide-based compound of the present invention include diphenylphosphine oxide, methyldiphenylphosphine oxide, triphenylphosphine oxide, and the like.

Among the phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds and phosphine compounds, the phosphorus compounds of the present invention are represented by the following formulas (28) to (33). It is preferred to use the compounds represented.

[0041]

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

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

[0043]

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Embedded image (In the formulas (34) to (36), R ¹ , R ⁴ , R ⁵ , and R ⁶ each independently include hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group. .R ² representing a hydrocarbon group having 1 to 50 carbon atoms,
R ³ each independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group having 1 to 50 carbon atoms.
Represents a hydrocarbon group. However, the hydrocarbon group may contain an alicyclic structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. As the phosphorus compound constituting the polycondensation catalyst of the present invention, a compound in which R ¹ , R ⁴ , R ⁵ and R ⁶ are groups having an aromatic ring structure in the above formulas (34) to (36) is particularly preferred. .

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

As the phosphorus compound constituting the polycondensation catalyst of the present invention, it is preferable to use a phosphorus compound having a phenol moiety in the same molecule. The phosphorus compound having a phenol moiety in the same molecule is not particularly limited as long as it is a phosphorus compound having a phenol structure, but a phosphonic acid-based compound, a phosphinic acid-based compound, and a phosphine oxide-based compound having a phenol moiety in the same molecule. It is preferable to use one or more compounds selected from the group consisting of compounds, phosphonous acid compounds, phosphinous acid compounds, and phosphine compounds because the effect of improving the catalytic activity is large. Among these, the use of a phosphonic acid-based compound having one or more phenol moieties in the same molecule is particularly preferred because the effect of improving the catalytic activity is particularly large.

When a compound represented by the following general formulas (37) to (39) is used as the phosphorus compound having a phenol moiety in the same molecule constituting the polycondensation catalyst of the present invention, the catalytic activity is particularly improved. Is preferred.

[0047]

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Embedded image (In the formulas (37) to (39), R ¹ represents a hydrocarbon group having 1 to 50 carbon atoms including a phenol moiety, a hydroxyl group, a halogen group, a substituent such as an alkoxyl group or an amino group, and 1 carbon atom including a phenol moiety. Represents a hydrocarbon group of 50 to 50. R ⁴ , R ⁵ , and R ⁶ each independently represent hydrogen or a carbon atom of 1
And represents a hydrocarbon group having 1 to 50 carbon atoms including a substituent such as a hydrocarbon group, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group. R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a substituent such as a hydroxyl group or an alkoxyl group. However, the hydrocarbon group may include a branched structure, an alicyclic structure such as cyclohexyl, or an aromatic ring structure such as phenyl or naphthyl. The terminals of R ² and R ⁴ may be bonded to each other. Examples of the phosphorus compound of the present invention having a phenol moiety in the same molecule include p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, and p-hydroxyphenylphosphonic acid.
Diethyl hydroxyphenylphosphonate, diphenyl p-hydroxyphenylphosphonate, bis (p-hydroxyphenyl) phosphinic acid, methyl bis (p-hydroxyphenyl) phosphinate, phenyl bis (p-hydroxyphenyl) phosphinate, p-hydroxyphenyl Phenylphosphinic acid, methyl p-hydroxyphenylphenylphosphinate, phenyl p-hydroxyphenylphenylphosphinate, p-hydroxyphenylphosphinate, methyl p-hydroxyphenylphosphinate, phenyl p-hydroxyphenylphosphinate, bis (p-hydroxy Phenyl) phosphine oxide,
Examples thereof include tris (p-hydroxyphenyl) phosphine oxide, bis (p-hydroxyphenyl) methylphosphine oxide, and compounds represented by the following formulas (40) to (43). Among these, a compound represented by the following formula (42) and dimethyl p-hydroxyphenylphosphonate are particularly preferred.

[0048]

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

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

In the present invention, it is preferable to use a metal salt compound of phosphorus as the phosphorus compound. The metal salt compound of phosphorus is not particularly limited as long as it is a metal salt of a phosphorus compound, but the use of a metal salt of a phosphonic acid-based compound is preferred because the effect of improving the catalytic activity is large. Examples of the metal salt of a phosphorus compound include a monometal salt, a dimetal salt, and a trimetal salt.

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

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

[0053]

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

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

[0055]

Embedded image (In the formula (45), R ¹ is .R ³ representing hydrogen, a hydrocarbon group having 1 to 50 carbon atoms containing a hydrocarbon group, a hydroxyl group or a halogen group, an alkoxyl group, or an amino group having 1 to 50 carbon atoms, Hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl, wherein l is an integer of 1 or more, and m is
Represents 0 or an integer of 1 or more, and l + m is 4 or less. M
Represents a (l + m) -valent metal cation. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. As the above R ¹ , for example, phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl,
2-biphenyl and the like. Examples of R ³ O ⁻ include a hydroxide ion, an alcoholate ion, an acetate ion and an acetylacetone ion.

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

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

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

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

[0060]

Embedded image (In the formula (46), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. And R ⁴ represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a carbonyl. Examples of R ⁴ O ⁻ include a hydroxide ion, an alcoholate ion, an acetate ion, an acetylacetone ion, etc. l is an integer of 1 or more,
m represents 0 or an integer of 1 or more, and l + m is 4 or less. M represents a (l + m) -valent metal cation. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. Among these, it is preferable to use at least one selected from compounds represented by the following general formula (47).

[0061]

Embedded image (In the formula (47), M ^{n +} represents an n-valent metal cation.
Represents 1, 2, 3 or 4. In the above formula (46) or (47), M is Li,
Na, K, Be, Mg, Sr, Ba, Mn, Ni, C
It is preferable to use one selected from u and Zn because the effect of improving the catalytic activity is large. Of these, Li, Na, M
g is particularly preferred.

The specific phosphorus metal salt compounds of the present invention include lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate] and sodium [3,5-di-tert-butyl-4ethyl]. Ethyl-hydroxybenzylphosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], potassium [3,5-di-
Ethyl tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [3,5-di-tert-butyl-4]
Ethyl-hydroxybenzylphosphonate], magnesium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], beryllium bis [3,5-di-tert-
Methyl butyl-4-hydroxybenzylphosphonate],
Strontium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], barium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate phenyl], manganese bis [3,5 -Di-tert-
Ethyl butyl-4-hydroxybenzylphosphonate],
Nickel bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], copper bis [3,5-di-te
ethyl rt-butyl-4-hydroxybenzylphosphonate], zinc bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate] and the like. Among them, lithium [3,5-di-tert-butyl-4-]
Ethyl hydroxybenzylphosphonate], sodium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [3,5-di-tert]
-Butyl-4-hydroxybenzylphosphonate ethyl]
Is particularly preferred.

As the phosphorus compound of the present invention, it is preferable to use at least one selected from aluminum salts of phosphorus compounds.

The aluminum salt of the phosphorus compound is not particularly limited as long as it is a phosphorus compound having an aluminum portion. However, the use of an aluminum salt of a phosphonic acid compound is preferred because the effect of improving the catalytic activity is large. Examples of the aluminum salt of the phosphorus compound include a monoaluminum salt, a dialluminum salt, and a trialuminum salt.

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

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

[0067]

Embedded image (In the formula (48), .R ² R ¹ is representing hydrogen, a hydrocarbon group having 1 to 50 carbon atoms containing a hydrocarbon group, a hydroxyl group or a halogen group, an alkoxyl group, or an amino group having 1 to 50 carbon atoms, Represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group, and R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. Or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl, l represents an integer of 1 or more, m represents 0 or an integer of 1 or more, l + m is 3. n represents an integer of 1 or more. The hydrocarbon group may include an alicyclic structure or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl.) As the above R ¹ , for example, phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl ,
2-biphenyl and the like. As the above R ² , for example, hydrogen, methyl group, ethyl group, n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
tert-butyl group, long-chain aliphatic group, phenyl group, naphthyl group, substituted phenyl group or naphthyl group, -CH ₂
And a group represented by CH ₂ OH. R ³ above
Examples of O ^- include a hydroxide ion, an alcoholate ion, an ethylene glycolate ion, an acetate ion and an acetylacetone ion.

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

As the phosphorus compound of the present invention, it is preferable to use at least one selected from aluminum salts of phosphorus compounds represented by the following general formula (49).

[0070]

Embedded image (In the formula (49), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. And R ⁴ represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a carbonyl. l is an integer of 1 or more, m is 0 or an integer of 1 or more, l + m is 3. n is an integer of 1 or more, and the hydrocarbon group is an alicyclic structure such as cycloalkylhexyl, a branched structure, or phenyl. Or an aromatic ring structure such as naphthyl.) Among them, it is preferable to use at least one selected from compounds represented by the following general formula (50).

[0071]

Embedded image (In the formula (50), R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group having 1 to 1 carbon atoms.
Represents 50 hydrocarbon groups. R ⁴ is hydrogen, having 1 to 5 carbon atoms
And represents a hydrocarbon group having 1 to 50 carbon atoms including 0 hydrocarbon group, hydroxyl group, alkoxyl group or carbonyl. l
Represents an integer of 1 or more; m represents 0 or an integer of 1 or more;
m is 3. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. The above R ³ is, for example, hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, se
c-butyl group, tert-butyl group, long-chain aliphatic group,
Phenyl, naphthyl, substituted phenyl and naphthyl, and a group defined as -CH ₂ CH ₂ OH and the like. Examples of R ⁴ O ⁻ include a hydroxide ion, an alcoholate ion, an ethylene glycolate ion, an acetate ion and an acetylacetone ion.

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

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

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

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

[0076]

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

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

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

The preferred phosphorus compound used in the present invention is a specific phosphorus compound having at least one P-OH bond. The specific phosphorus compound having at least one P-OH bond refers to at least one compound selected from compounds represented by the following general formula (52).

[0080]

Embedded image (In the formula (52), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. And n represents an integer of 1 or more, and the hydrocarbon group may have an alicyclic structure such as cycloalkylhexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. Among these, it is preferable to use at least one selected from compounds represented by the following general formula (53).

[0081]

Embedded image (In the formula (53), R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group having 1 to 1 carbon atoms.
Represents 50 hydrocarbon groups. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. The above R ³ is, for example, hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, se
c-butyl group, tert-butyl group, long-chain aliphatic group,
Phenyl, naphthyl, substituted phenyl and naphthyl, and a group defined as -CH ₂ CH ₂ OH and the like.

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

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

[0084]

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

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

[0086]

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image Further, the phosphorus compound used as a polycondensation catalyst in the present invention has a large effect and is preferably large in molecular weight because it is difficult to be distilled off during polymerization.

Another phosphorus compound desirably used in the present invention is at least one phosphorus compound selected from the compounds represented by the following general formula (61).

[0088]

Embedded image (In the above formula (61), R ¹ and R ² each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R ³ and R ⁴ each independently represent hydrogen and a hydrocarbon group having 1 to 50 carbon atoms. Represents a hydrocarbon group having 1 to 50 carbon atoms, including a group, a hydroxyl group or an alkoxyl group, n represents an integer of 1 or more, and the hydrocarbon group is an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring such as phenyl or naphthyl. The structure may be included.) Of the above general formula (61), it is preferable to use at least one selected from the compounds represented by the following general formula (62) because the effect of improving the catalytic activity is high.

[0089]

Embedded image (In the above formula (62), R ³ and R ⁴ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. May contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl.) As the above R ³ and R ⁴ , for example, hydrogen, a methyl group, a short chain such as a butyl group, etc. Examples include an aliphatic group, a long-chain aliphatic group such as octadecyl, an aromatic group such as a phenyl group, a naphthyl group, a substituted phenyl group or a naphthyl group, and a group represented by —CH ₂ CH ₂ OH.

The specific phosphorus compounds of the present invention include 3,5
-Di-tert-butyl-4-hydroxybenzylphosphonate diisopropyl, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate di-n-butyl, 3,5-di-
dioctadecyl tert-butyl-4-hydroxybenzylphosphonate; diphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate; Among these, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and diphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.

Another phosphorus compound desirably used in the present invention is at least one phosphorus compound selected from the compounds represented by the chemical formulas (63) and (64).

[0092]

Embedded image

Embedded image Compounds represented by the above chemical formula (63) include I
rganox1222 (manufactured by Ciba Specialty Chemicals) is commercially available, and as the compound represented by the chemical formula (64), Irganox1425 (manufactured by Ciba Specialty Chemicals) is commercially available and can be used.

When an alkali metal, alkaline earth metal or aluminum salt is used in the above-mentioned phosphorus compound, the content of the metal or phosphorus atom in the finally obtained polyester is determined as follows. It is necessary to be as described above. By this method, the generation of foreign matters insoluble in polyester is effectively suppressed, and problems such as yarn breakage during spinning and filter clogging during molding are improved.

As the antimony compound which can be added as a polymerization catalyst in the present invention, suitable compounds include antimony trioxide, antimony pentoxide, antimony acetate and antimony glycoside, and the use of antimony trioxide is particularly preferable. Examples of the germanium compound include germanium dioxide and germanium tetrachloride, with germanium dioxide being particularly preferred.

Further, other polymerization catalysts such as a titanium compound and a tin compound include tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate and tetra-butyl titanate.
Examples thereof include tert-butyl titanate, tetracyclohexyl titanate, tetraphenyl titanate, and tetrabenzyl titanate, and the use of tetrabutyl titanate is particularly preferred. Further, as the tin compound, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, triethyltin hydroxide, monobutylhydroxytin oxide, triisobutyltin acetate, diphenyltin dilaurate, monobutyltin trichloride, dibutyltin sulfide, Examples thereof include dibutylhydroxytin oxide, methylstannoic acid and ethylstannoic acid, and the use of monobutylhydroxytin oxide is particularly preferable.

The cobalt compound that can be added in the present invention is not particularly limited, but specific examples thereof include cobalt acetate, cobalt nitrate, cobalt chloride, cobalt acetylacetonate, cobalt naphthenate and hydrates thereof. No. Among them, cobalt acetate tetrahydrate is particularly preferred.

It is preferable to add a phenolic compound during the production of the polyester according to the method of the present invention, because the thermal stability of the polyester is effectively improved. Also,
Addition of a phenolic compound also has the effect of improving the catalytic activity.

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

The amount of the phenolic compound of the present invention to be used is 5 × 10 ^-5 mol per mol of all the constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the polyester obtained by polymerization. % To 1 mol%, more preferably 1 × 10 ⁻⁴ mol% to 0.5 mol%.

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, Any of the polycondensation methods can be used. Also,
The polymerization apparatus may be a batch type or a continuous type.

The catalyst 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 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 zinc. Then, the catalyst of the present invention can be used. Further, the catalyst of the present invention has catalytic activity not only in melt polymerization but also in solid phase polymerization and solution polymerization,
The polyester can be produced by any of the methods.

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

The method for adding the polymerization catalyst of the present invention may be in the form of powder or neat, or may be in the form of slurry or solution of a solvent such as ethylene glycol.
There is no particular limitation. Further, a component obtained by previously mixing the components of the polymerization catalyst of the present invention may be added, or these components may be added separately. Further, the components of the polymerization catalyst of the present invention may be added to the polymerization system at the same addition time, or each component may be added at a separate addition time.

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

As the dicarboxylic acid, oxalic acid, malonic acid,
Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,3-cyclo Pentanedicarboxylic acid,
Saturated aliphatic dicarboxylic acids exemplified by 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid and the like, and their ester-forming properties Derivatives, unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid and the like and ester-forming derivatives thereof, orthophthalic acid, isophthalic acid, terephthalic acid, 5- (alkali metal) sulfoisophthalic acid, diphenic acid 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5
-Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-
Biphenyldicarboxylic acid, 4,4'-biphenylsulfonedicarboxylic acid, 4,4'-biphenyletherdicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p '
Aromatic dicarboxylic acids exemplified by dicarboxylic acids, pamoic acids, anthracene dicarboxylic acids and the like and ester-forming derivatives thereof, and among these dicarboxylic acids, terephthalic acid and naphthalenedicarboxylic acid, particularly 2,6-naphthalenedicarboxylic acid Is preferred.

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

As the glycol, ethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 1, 5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2
-Cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol,
1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, polytrimethylene glycol,
Aliphatic glycols exemplified by 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, 2,5-naphthalenediol,
Aromatic glycols, such as glycols obtained by adding ethylene oxide to these glycols, and the like, are exemplified. Of these glycols, ethylene glycol and 1,4-butylene glycol are preferable.

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

Examples of hydroxycarboxylic acids include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, and 4-hydroxycyclohexanecarboxylic acid. Or ester-forming derivatives thereof.

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

Further, the polyester of the present invention can contain a known phosphorus compound as a copolymerization 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 (Carboxylethyl) methyl phenylphosphinate, methyl (4-methoxycarbonylphenyl) phenylphosphinate, [2- (β-hydroxyethoxycarbonyl) ethyl] ethylene glycol ester of methylphosphinic acid, (1,2-dicarboxyethyl) dimethyl Examples include phosphine oxide and 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.

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

The polyester used in the present invention is preferably a polyester whose main acid component is terephthalic acid or its ester-forming derivative or naphthalenedicarboxylic acid or its ester-forming derivative, and whose main glycol component is an alkylene glycol. The polyester in which the main acid component is terephthalic acid or an ester-forming derivative thereof or naphthalenedicarboxylic acid or an ester-forming derivative thereof is referred to as terephthalic acid or an ester-forming derivative thereof and naphthalenedicarboxylic acid or an ester thereof with respect to all the acid components. It is preferable that the polyester contains a total of 70 mol% or more of the active derivative, more preferably a polyester containing 80 mol% or more, and further preferably a polyester containing 90 mol% or more. The polyester in which the main glycol component is an alkylene glycol is preferably a polyester containing 70 mol% or more of alkylene glycol in total with respect to all glycol components, more preferably a polyester containing 80 mol% or more, More preferably, it is 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 its ester-forming derivative used in the present invention includes 1,3-
Preferred are naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, or ester-forming derivatives thereof.

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

The polyester of the present invention contains oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, as acid components other than terephthalic acid or its ester-forming derivative, naphthalenedicarboxylic acid or its ester-forming derivative. Suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid,
1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer Saturated aliphatic dicarboxylic acids exemplified by acids and the like and ester-forming derivatives thereof, fumaric acid, maleic acid, unsaturated aliphatic dicarboxylic acids exemplified by the examples of itaconic acid and ester-forming derivatives thereof, orthophthalic acid, isophthalic acid Acid, 5- (alkali metal) sulfoisophthalic acid, diphenic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-biphenylsulfondicarboxylic acid, 4,4'-biphenyletherdicarboxylic acid, 1,2-bis ( Phenoxy) ethane-p, p'-
Dicarboxylic acid, pamoic acid, aromatic dicarboxylic acids exemplified by anthracene dicarboxylic acid or ester-forming derivatives thereof, ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ',
Polycarboxylic acids exemplified by 4′-biphenyltetracarboxylic acid and the like and ester-forming derivatives thereof can be contained as copolymer components. Also, hydroxycarboxylic acids exemplified by lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid and the like An acid or an ester-forming derivative thereof can also be included.
Also, ε-caprolactone, β-propiolactone, β
-Methyl-β-propiolactone, δ-valerolactone, glycolide, lactide and the like can also be included.

In the polyester of the present invention, as glycol components other than alkylene glycol, 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-hydroxy Phenyl) ethane, bisphenol A, bisphenol C, 2,5-naphthalene diol, aromatic glycols exemplified by ethylene glycol added to these glycols, trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol , Glycerol, polyhydric alcohols exemplified by hexanetriol and the like can be contained as a copolymerization component.

The polyester of the present invention may contain a known phosphorus compound as a copolymer component. As the phosphorus compound, a bifunctional phosphorus compound is preferable. For example, dimethyl phenylphosphonate, diphenyl phenylphosphonate, (2-carboxylethyl) methylphosphinic acid, (2-carboxylethyl) phenylphosphinic acid, (2-methoxy (Carboxylethyl) methyl phenylphosphinate, methyl (4-methoxycarbonylphenyl) phenylphosphinate, [2- (β-hydroxyethoxycarbonyl) ethyl] ethylene glycol ester of methylphosphinic acid, (1,2-dicarboxyethyl) dimethyl Examples include phosphine oxide and 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.

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

The polyester of the present invention can contain an antioxidant such as a phenolic or aromatic amine.
By containing one or more of these,
For example, the thermal stability of polyester can be improved.

The polyester of the present invention may contain a bluing agent, an organic, inorganic or organometallic dye or pigment, a fluorescent whitening agent, and the like. By doing so, coloring such as yellowing of the polyester can be suppressed.

In the polyester of the present invention, other optional polymers, stabilizers, antioxidants, antistatic agents, defoamers, dyeing improvers, dyes, pigments, matting agents and other additives are contained. It may be contained.

[0123]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

The analysis method and the evaluation method in the present invention are described below.

(1) Content of Metal and Phosphorus in Polymer (1-1) The content of phosphorus, antimony, magnesium and germanium was measured by a fluorescent X-ray method. The polyester as a measurement sample is put into a stainless steel ring having a height of 5 mm and a diameter of 40 mm placed on a photographic ferrotype plate, and is heated in an oven at 300 ° C. for 10 minutes to be melted. After being taken out of the oven and cooled, a molded sample was taken out of a stainless steel ring, and a smooth surface was measured.

Separately, several polyesters whose content was confirmed by a chemical analysis method were molded by the above method, and the fluorescent X-ray intensity was measured. A calibration curve was created. The content of phosphorus, antimony, magnesium, and germanium in each measurement sample was calculated from the fluorescent X-ray intensity data of the polyester as the measurement sample based on the calibration curve. (1-2) Other metals were measured by high-frequency plasma emission analysis and atomic absorption analysis. First, 1.0 g of a polyester as a measurement sample was weighed and carbonized, then incinerated at 550 ° C. in an electric furnace, and cooled to room temperature. The obtained ash was subjected to 6N hydrochloric acid (hydrofluoric acid / hydrochloric acid in Ti measurement).
And evaporated to dryness, and then dissolved in 1.2N hydrochloric acid to obtain a measurement sample solution. High frequency plasma analysis was performed for Al, Ca, Co, and Ti, and atomic absorption analysis was performed for Na, Li, and K. High frequency plasma analysis is ICP
S-2000 (manufactured by Shimadzu Corporation) was used for atomic absorption analysis, and AA-640-12 (manufactured by Shimadzu Corporation) was used for atomic absorption analysis. Separately, using a commercially available standard solution for atomic absorption analysis for each metal to be measured, a solution for preparing a calibration curve in a concentration range of 0.01 to 30 mg / l was prepared, and a calibration curve was prepared. Based on this calibration curve, the metal content in the polyester was calculated from the analysis data of the individual measurement sample liquids described above.

(2) Intrinsic Viscosity of Polyester (IV) Polyester was heated and dissolved in a 6/4 mixed solvent (weight ratio) of phenol / 1,1,2,2-tetrachloroethane at 80 to 100 ° C. 30 ° C using a viscometer
Was measured. The measurement was performed using a solution having several concentrations centered at 4 g / l, and the reduced viscosity was obtained by extrapolating a straight line obtained by plotting the obtained reduced viscosity with respect to the concentration to the concentration = 0. Was defined as the intrinsic viscosity (IV).

(3) Acid value The polyester is freeze-pulverized and vacuum-dried at 130 ° C. for 12 hours or more. 0.1 g of the dried polyester is precisely weighed in an Erlenmeyer flask, and 10 ml of benzyl alcohol is added to dissolve it. After dissolution, the mixture was cooled in a water bath, 10 ml of chloroform was added, and N / 10-NaOH (MeOH / benzyl alcohol 1) using phenolphthalein as an indicator.
/ 9 (volume ratio) mixed solvent solution). The same measurement is performed on the blank without the polyester sample. The acid value (eq / ton) was calculated by the following equation. Acid value = (AB) × 0.1 × f × 1000 / W A = titration constant (ml), B = blank titration (ml),
f = factor of NaOH solution, W = weight of sample (g)
It is.

(4) Diethylene glycol content (DE
G) 0.1 g of polyester in 250 ml of methanol at 250 ° C.
And then quantitatively determined by gas chromatography. GC-14B (manufactured by Shimadzu Corporation) was used as a measuring device, and a column packed with PEG-HT (manufactured by GL Sciences) was used as a measuring column.

(5) Differential Scanning Calorimetry (DSC) The measurement was performed using a DSC 2920 manufactured by TA Instruments. 10.0 mg of polyester is sealed in an aluminum pan for exclusive use of the company's autosampler, heated to 280 ° C. at a heating rate of 50 ° C./min, and after holding at 280 ° C. for 1 minute, immediately in liquid nitrogen. Quenched with Thereafter, the temperature was raised from room temperature to 300 ° C. at a rate of 20 ° C./min, and the crystallization temperature Tc1 and the melting point Tm at the time of temperature rise were determined. After holding at 300 ° C for 2 minutes, 10 ° C
/ Min, and the crystallization temperature Tc2 at the time of cooling was determined. Tc
1, Tm and Tc2 were the temperatures of the local maximums of the respective peaks.

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

(7) Evaluation of increase in filtration pressure during spinning and breakage of yarn during stretching The PET resin chip obtained by melt polymerization was dried and supplied to a melt extruder. A filter having a pore size of 20 μm was used. It was discharged at 290 ° C. from a spinneret having 108 orifices of 0.14 mmΦ, cooled and oiled according to a conventional method, and then taken out at 1720 m / min. Subsequently, at a preheating roller of 80 ° C. and a set temperature of 150 ° C.
The film was drawn 127 times to obtain a polyester drawn yarn of 47 dtex and 108 filaments.

Evaluation was made as follows according to the degree of increase in the filtration pressure during spinning.

：: Little increase in filtration pressure was observed. Δ: Slight increase in filtration pressure was observed. X: Filtration pressure was significantly increased. Evaluation was made as follows according to the frequency of yarn breakage during stretching.

：: Little thread break occurs. Δ: Little thread break occurs. X: Many thread breaks occur. (8) ¹ H-NMR Measurement of Synthesized Phosphorus Compound The compound is dissolved in CDCl ₃ or d6-DMSO. Va at room temperature
Measured using rian GEMINI-200.

(9) Measuring Melting Point of Synthesized Phosphorus Compound The compound was placed on a cover glass, and the sample was put on a Yanaco MICRO MELTING.
Measurement was performed at a heating rate of 1 ° C./min using POINT APPARATUS.

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

Example 1 A mixture of bis (2-hydroxyethyl) terephthalate and an oligomer produced from high-purity terephthalic acid and ethylene glycol according to a conventional method was mixed with 2.5 g / a of aluminum trisacetylacetonate as a polycondensation catalyst. l of an ethylene glycol solution and a 10 g / l ethylene glycol solution of Irganox 1425 ((Chemical formula 43), manufactured by Ciba Specialty Chemicals) were added. These compounds were added so that the contents of metal and phosphorus in the polymer finally obtained were as shown in Table 1. Since the metal component in the catalyst added during the polymerization hardly volatilizes during the polymerization and during the molding, the value obtained from the analysis result is almost the charged amount,
Since the phosphorus component volatilizes during polymerization and molding, it is added in a larger amount than the analysis result. After the addition of the above solution, the mixture was stirred at 245 ° C. for 10 minutes at normal pressure under a nitrogen atmosphere. Then, the temperature of the reaction system was gradually lowered while raising the temperature to 275 ° C. over 50 minutes to 0.1 Torr, and the pressure was further increased to 275 ° C. and 0.1 Torr.
A polycondensation reaction was performed at r. Table 1 shows the polymerization time required for the IV of polyethylene terephthalate to reach 0.65 dl / g. In addition, I obtained by the above polycondensation
Polyethylene terephthalate having a V of 0.65 dl / g was formed into chips according to a conventional method. That is, when a predetermined torque corresponding to an intrinsic viscosity of 0.65 is reached by melt polymerization, nitrogen is introduced into the reaction vessel to return to normal pressure, the polycondensation reaction is stopped, and then the molten polymer is pressed under a pressure of about 0.1 MPa. Was continuously extruded into a strand of cold water from a discharge nozzle provided at the lower part of the reaction vessel and rapidly cooled, and was then made into a cylindrical resin chip having a length of about 3 mm and a diameter of about 2 mm by a cutter. The holding time in cold water was about 20 seconds. The physical properties of PET were measured using this resin chip. The result is that the IV is 0.65 dl / g, the acid value is 6 eq / ton, DEG
Was 2.1 mol%, Tm was 256.3 ° C, and Tc2 was 186.2 ° C. The L value was 68.9, the a value was -2.56, and the b value was 5.49. The L, a, and b values were improved values as compared with the comparative example.

The PET resin chip was used to evaluate the increase in filtration pressure during spinning and the evaluation of yarn breakage during stretching. Table 1 shows the evaluation results.

(Examples 2 to 9, Comparative Examples 1 to 3) A polyester was polymerized in the same manner as in Example 1 except that the catalyst was changed. Table 1 shows the compounds used as catalysts in each of the examples and comparative examples. These compounds have a metal and phosphorus content in the final polymer of Table 1
Was added so as to have the amount shown in FIG. In the ninth embodiment,
Antimony trioxide was used in combination as a catalyst. Antimony trioxide was added so that the content of antimony atoms in the polymer finally obtained was 50 ppm. Table 1 shows the polymerization results of the examples and the comparative examples, and the evaluation results of the increase in the filtration pressure during spinning and the yarn breakage during stretching. Irganox14
25 was manufactured by Ciba Specialty Chemicals, and phosphorus compound A was synthesized by the following method.

(Synthesis Example of Phosphorus Compound) A phosphorus compound represented by the following formula (65) (phosphorus compound A)
Synthesis of

Embedded image Sodium (O-ethyl 3,5-di-tert-butyl-4-hydroxybenzylph
Synthesis of diethyl (3,5-di-tert-butyl-4-) in a mixed solution of 6.5 g (84 mmol) of a 50% aqueous sodium hydroxide solution and 6.1 ml of methanol.
Hydroxybenzyl) phosphonate (Irganox1222 (manufactured by Ciba Specialty Chemicals)) (5 ml, 14 mmol) in a methanol solution (6.1 ml) was added, and the mixture was heated under reflux in a nitrogen atmosphere for 24 hours. After the reaction, concentrated hydrochloric acid 7.
33 g (70 mmol) was added, the precipitate was collected by filtration, washed with isopropanol, and the filtrate was evaporated under reduced pressure. The obtained residue was dissolved in hot isopropanol, the insoluble matter was collected by filtration, the isopropanol was distilled off under reduced pressure, the residue was washed with hot heptane, and dried to obtain Sodium (O-ethyl 3,5-di-tert-butyl- 4-hydroxyben
3.4 g (69%) of zylphosphonate) were obtained.

Shape: white powder Melting point: 294-302 ° C. (decomposition) ¹ H-NMR (d6-DMSO, δ): 1.078 (3H, t, J = 7 Hz), 1.354 (1
8H, s), 2.711 (2H, d), 3.724 (2H, m, J = 7Hz), 6.626 (1
H, s), 6.9665 (2H, s) Elemental analysis (theoretical values in parentheses): Na 6.36% (6.56%), P
9.18% (8.84%).

O-ethyl 3,5-di-tert-butyl-4-hydroxyben
Synthesis of zylphosphonic acid (phosphorus compound A) Sodium (O-ethyl 3,5-di-tert-butyl-4-
Hydroxybenzyl-phosphonate) 1g (2.8mmol) aqueous solution
1.5 g of concentrated hydrochloric acid was added to 20 ml, and the mixture was stirred for 1 hour. 150 ml of water was added to the reaction mixture, and the precipitated crystals were collected by filtration, washed with water, and dried to dry O-ethyl 3,5-di-tert-butyl-4-hydroxybenzylphospho.
826 mg (88%) of nic acid were obtained.

Shape: plate-like crystal Melting point: 126-127 ° C. ¹ H-NMR (CDCl ₃ , δ): 1.207 (3H, t, J = 7 Hz), 1.436 (18H,
s), 3.013 (2H, d), 3.888 (2H, m, J = 7Hz.), 7.088 (2H, d
s), 7.679-8.275 (1H, br).

[0145]

[Table 1] As is clear from the above Examples and Comparative Examples, those in which the contents of metal and phosphorus in the polyester are within the scope of the claims of the present invention are excellent in the operability of spinning and drawing, while those of the present invention. Those which are out of the scope of the claims described above result in a remarkable increase in the filtration pressure during spinning, and frequent breakage of yarn during stretching, resulting in poor operability.

[0146]

According to the present invention, a polyester produced using a polymerization catalyst containing a metal component other than antimony and germanium as a main metal component of the catalyst, and filter clogging during molding is improved. A polyester and a method of making the same are provided. The polyester of the present invention is a fiber for clothing, a fiber for industrial materials, various films,
It can be applied to various molded products such as sheets, bottles and engineering plastics, as well as paints and adhesives.

Continued on the front page (72) Inventor Shoichi Katamai 2-1-1 Katata, Otsu City, Shiga Prefecture Inside Toyobo Co., Ltd. Research Laboratory (72) Inventor Mitsuhiro Kuwata 2-1-1 Katata, Otsu City, Shiga Prefecture Inside Toyobo Co., Ltd. (72) Inventor Nobuo Moriyama 2-1-1 Katata, Otsu-shi, Shiga F-term inside Toyobo Co., Ltd. (Ref.) 4J029 AE01 AE02 AE03 AE11 AE13 BA02 BA03 BA04 BA05 BB05A BB10A BB12A BB13A BB15A BC05A BD03A BF03 BF08 BF09 BF18 BF25 BH02 CA02 CA03 CA04 CA05 CA06 CB04A CB05A CB06A CB10A CB12A CC05A CC06A CC09 CD03 CF03 J02 CH03 DB02 DB12 DC04 DC05 DC06 EA02 EB02 FC03 FC02 FC03 J02 JC551 JC561 JC571 JC601 JF221 JF361 JF371 JF411 JF471 JF571 KH08

Claims (9)

[Claims] At least one selected from the group consisting of alkali metals and their compounds and alkaline earth metals and their compounds, at least one selected from the group consisting of aluminum and its compounds, and the group consisting of phosphorus compounds A polyester characterized by containing at least one selected from them and containing them in an amount satisfying the following formulas (1) to (3). (1) 0.1 ≦ M ≦ 150 (2) M / Al ≦ 40 (3) P / Al ≧ 0.01 (In the formulas (1) to (3), M is an alkali metal atom contained in the polyester. Total amount of alkaline earth metal atoms (p
pm), and Al and P indicate the amounts (ppm) of aluminum atoms and phosphorus atoms contained in the polyester, respectively. ) 2. The polyester according to claim 1, wherein the content of aluminum and its compound satisfies the following formula (4). (4) 0.5 ≦ Al ≦ 500 (In the formula (4), Al indicates the amount (ppm) of aluminum atoms contained in the polyester.) 3. The polyester according to claim 1, wherein the content of the phosphorus compound satisfies the following formula (5). (5) 1 ≦ P ≦ 1000 (In the formula (5), P indicates the amount (ppm) of phosphorus atoms contained in the polyester.) 4. The polyester according to claim 1, further comprising antimony or a compound thereof, and in an amount of 50 ppm or less as antimony atoms. 5. The polyester according to claim 1, further comprising germanium or a compound thereof and containing germanium atoms in an amount of 20 ppm or less. 6. The polyester according to claim 1, further comprising titanium or a compound thereof, and in an amount of 5 ppm or less as a titanium atom. 7. The polyester according to claim 1, further comprising cobalt or a compound thereof and containing less than 10 ppm as a cobalt atom. 8. At least one selected from the group consisting of alkali metals and their compounds, alkaline earth metals and their compounds, at least one selected from the group consisting of aluminum and its compounds, and the group consisting of phosphorus compounds A polyester produced using at least one selected as a catalyst,
A polyester characterized by containing them in an amount satisfying the following formulas (1) to (3). (1) 0.1 ≦ M ≦ 150 (2) M / Al ≦ 40 (3) P / Al ≧ 0.01 (In the formulas (1) to (3), M is an alkali metal atom contained in the polyester. Total amount of alkaline earth metal atoms (p
pm), and Al and P indicate the amounts (ppm) of aluminum atoms and phosphorus atoms contained in the polyester, respectively. ) 9. At least one selected from the group consisting of alkali metals and their compounds, and alkaline earth metals and their compounds, at least one selected from the group consisting of aluminum and its compounds, and the group consisting of phosphorus compounds A method for producing a polyester using at least one selected as a catalyst,
A method according to claim 1, wherein the polyester contains the polyester in an amount satisfying the following formulas (1) to (3). (1) 0.1 ≦ M ≦ 150 (2) M / Al ≦ 40 (3) P / Al ≧ 0.01 (In the formulas (1) to (3), M is an alkali metal atom contained in the polyester. Total amount of alkaline earth metal atoms (p
pm), and Al and P indicate the amounts (ppm) of aluminum atoms and phosphorus atoms contained in the polyester, respectively. )