JP2003212982A - Method for producing polyester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve the productivity in molding fibers (filtration pressure rise and fiber breakage), films, and bottles by finely dividing deposited particles caused mainly by a metallic atom such as aluminum which deposits in the polyester polycondensation step in using an aluminum compound as the major metal component of a catalyst which is free of an antimony compound or a germanium compound as the catalyst major component. <P>SOLUTION: In polycondensing a product obtained by the esterification or transesterification of an aromatic dicarboxylic acid or its ester-forming derivative with a diol or its ester-forming derivative with the use of an aluminum compound and a phosphorus compound as the polycondensation catalyst to produce a polyester, 5-5,000 ppm, based on the aluminum atom of the aluminum compound of the constituting component of the catalyst, inorganic particles having an average particle diameter of 1-1,000 nm which are insoluble or difficultly soluble in the reaction system are added. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polyester using a polycondensation catalyst composed of an aluminum compound and a phosphorus compound, in which foreign matter (precipitated particles) mainly caused by the polycondensation catalyst is made finer. Manufacturing method.

[0002]

2. Description of the Related Art Polyethylene terephthalate (PE
T), polyesters represented by polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and the like are excellent in mechanical properties and chemical properties, and depending on the properties of each polyester, for example, for clothing or It is used in a wide range of fields such as fibers for industrial materials, industrial films and sheets such as packaging and Jikitape, bottles that are hollow molded products, casings of electric and electronic parts, and other engineering plastic molded products.

Conventionally, antimony or germanium compounds have been widely used as polyester polycondensation catalysts used in such polycondensation of polyesters. Antimony trioxide is a catalyst that is inexpensive and has excellent catalytic activity. However, when it is used as a main component, that is, in an amount added so that a practical polymerization rate is exhibited, metal antimony is produced during polycondensation. As a result, the dark spots and granular substances are generated on the polyester, which also causes surface defects of the film. Further, when used as a raw material for a hollow molded article or the like, it is difficult to obtain a hollow molded article having excellent transparency.

Attempts have been made to use antimony trioxide as a catalyst and suppress the darkening of PET and the generation of particulate matter. For example, in Japanese Patent No. 2666502, by using a compound of antimony trioxide, bismuth and selenium as a polycondensation catalyst, generation of black particulate matter in PET is suppressed. In addition, JP-A-9-2911
No. 41 states that the use of antimony trioxide containing oxides of sodium and iron as a polycondensation catalyst suppresses the deposition of metallic antimony. However, these polycondensation catalysts cannot eventually achieve the purpose of reducing the amount of antimony particles precipitated in the polyester.

Germanium compounds have already been put to practical use as catalysts which give polyesters having excellent catalytic activity other than antimony compounds and which do not have the above problems. However, this catalyst is very expensive. In addition, there is a problem that the catalyst concentration in the reaction system changes and the control of the polymerization becomes difficult because it is easy to distill out of the reaction system during the polymerization, and there is a problem in using it as the main component of the catalyst. is there. Polycondensation catalysts that replace antimony-based or germanium-based catalysts have also been studied, and titanium compounds and tin compounds represented by tetraalkoxy titanates have already been proposed, but polyesters produced using these are the above-mentioned polyesters. Although the problem of foreign matter is alleviated, it has the problems that it is susceptible to thermal deterioration during melt molding and that the polyester is markedly colored.

In addition, there is also known a technique of adding an alkali metal compound to an aluminum compound to obtain a polyester polymerization catalyst having sufficient catalytic activity. When such a known catalyst is used, a polyester having excellent thermal stability can be obtained.
In order to obtain a practical catalytic activity, it is necessary to add a large amount of them, and as a result, at least one of the following problems occurs due to the alkali metal compound in the obtained polyester polymer.

1) The amount of foreign matter becomes large, so that when it is used as a fiber, the threading properties and thread properties are deteriorated, and when it is used as a film, the film properties are deteriorated. 2) The hydrolysis resistance of the polyester polymer decreases, and the transparency decreases due to the generation of foreign matter. 3) Poor color tone of the polyester polymer, that is, a phenomenon in which the polymer is colored yellow, and when used in a film, a hollow bottle, or the like, the color tone of a molded product deteriorates. 4) The filter pressure at the time of melting to produce a molded product increases due to the clogging of foreign matter, and the productivity also decreases.

Due to the above-mentioned circumstances, it is a polymerization catalyst having a metal component other than antimony and germanium, which are conventional catalysts, as a main metal component of the catalyst, has excellent catalytic activity, and hardly causes thermal deterioration during melt molding. There is a demand for a method for producing a polyester having a small amount of foreign matter and excellent transparency.

[0009]

The object of the present invention is to perform polycondensation of polyester in the case where the above-mentioned disadvantageous antimony compound or germanium compound is not contained as a catalyst main component and an aluminum compound is used as a main catalyst metal component. It is intended to provide a method for producing a polyester, which is capable of refining foreign matters mainly resulting from a metal element such as aluminum which precipitates in a process.

[0010]

The object of the present invention is to provide a product obtained by an esterification reaction or transesterification reaction with an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof with aluminum. In the method of producing a polyester by polycondensing a compound and a phosphorus compound as a polycondensation catalyst, an aluminum compound aluminum which is a constituent component of the catalyst is an inorganic particle having an average particle size of 1 to 1,000 nm and insoluble or hardly soluble in the reaction system. It is achieved by a method for producing a polyester, which is characterized by adding 5 to 5,000 ppm per atom.

That is, in order to solve the above problems, the present inventors added a small amount of inorganic particles having a specific average particle size and substantially insoluble or hardly soluble in the polyester production process in the production step of polyester. By doing so, the inventors have found that it is possible to reduce the size of the particles that are deposited mainly in the polycondensation reaction system and are mainly due to a metal element such as aluminum.

DETAILED DESCRIPTION OF THE INVENTION

The polyester used in the present invention can be produced by a conventionally known production method. That is, in the case of PET, a direct esterification method in which terephthalic acid, ethylene glycol and other copolymerization components are directly reacted to distill water to esterify it, and then polycondensate under reduced pressure, or It is produced by a transesterification method in which dimethyl terephthalate is reacted with ethylene glycol and, if necessary, other copolymerization components to distill off methyl alcohol for transesterification, and then polycondensate under reduced pressure. The above-mentioned polymerization process is a batch system, a semi-continuous system,
Either continuous method may be used.

The above-mentioned inorganic particles that can be used in the present invention have an average particle size of 1 to 1,000 nm, more preferably 5 to 500 nm.
Is. If the thickness is less than 1 nm, the effect of the crystal nucleating agent is lowered because the inorganic fine particles are extremely fine, and therefore the effect of refining the foreign matters generated in the polycondensation reaction system is low. On the other hand, if it exceeds 1,000 nm, the effect of refining foreign matter is hardly recognized.

The average particle size as used in the present invention is determined from the particle size distribution measured by, for example, an argon laser dynamic light scattering method using water or ethylene glycol as a medium.

In the present invention, the amount of the above-mentioned inorganic particles added to the polyester is 5 to 5,000 ppm with respect to the amount of aluminum element derived from the catalyst added to the polyester,
It is preferably 10 to 1,000 ppm. If it is less than 5 ppm, no refining effect on foreign matter is observed, and even if added in excess of 5,000 ppm, no improvement in the refining effect on foreign matter is observed, and the inert inorganic particles added are finally It is not preferable because the transparency of the obtained polyester is impaired.

The inorganic particles preferably used in the present invention are 70% by weight of at least one compound selected from the group consisting of titanium, aluminum, silicon, calcium, magnesium, barium and bismuth atoms. % Or more is required. Specifically, it is preferable to use the above-mentioned metal oxides, carbonates, silicates, sulfates, and aluminates.

More specifically, metal oxides such as titanium dioxide, alumina, alumino-silica gel, silicon dioxide, calcium oxide, magnesium oxide, barium oxide and bismuth oxide, calcium carbonate, magnesium carbonate,
Carbonates such as barium carbonate, calcium silicate, magnesium silicate, aluminum silicate, barium silicate,
Silicates such as bismuth silicate, aluminum sulfate, calcium sulfate, magnesium sulfate, barium sulfate, sulfates such as bismuth sulfate, calcium aluminate, magnesium aluminate, barium aluminate, aluminates such as bismuth aluminate, etc. Bismuth selenate,
Examples thereof include, but are not limited to, bismuth compounds such as bismuth antimonate.

These inorganic particles are slurried with glycols and then mechanically dispersed by a medium agitation disperser such as a sand grinder, attritor, or ultrasonic wave, and an alkali metal compound, an ammonium compound or a phosphorus compound is added to disperse the particles. It is more preferable to add after improving. The timing of adding the above-mentioned inorganic particles is not particularly limited,
In a preferred embodiment, a glycol solution of an aluminum compound and a phosphorus compound, which is the catalyst of the present invention, or a slurry thereof is added and then added to the polyester reaction system.

As the aluminum or aluminum compound that constitutes the polycondensation catalyst of the present invention, in addition to metallic aluminum, known aluminum compounds can be used without limitation.

Specific examples of the aluminum compound include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, and aluminum trichloroacetate. , Aluminum lactate,
Carboxylates such as aluminum citrate and aluminum salicylate, inorganic salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate, aluminum phosphonate, aluminum methoxide, aluminum ethoxide, aluminum n -Propoxide, aluminum is
Aluminum chelate compounds such as o-propoxide, aluminum n-butoxide, aluminum t-butoxide and other aluminum alkoxides, aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, aluminum ethylacetoacetate diiso-propoxide, trimethylaluminum, Organoaluminum compounds such as triethylaluminum and partial hydrolysates thereof are included.

Of these, carboxylic acid salts, inorganic acid salts and chelate compounds are preferable, and among these, aluminum acetate, basic aluminum acetate, aluminum lactate, aluminum chloride, aluminum hydroxide, basic aluminum chloride, polyaluminum chloride and Aluminum acetylacetonate is particularly preferred.

As the aluminum or aluminum compound constituting the polycondensation catalyst of the present invention, the amount of aluminum atom as an aluminum atom relative to the total number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid or polyvalent carboxylic acid of the obtained polyester is 0. 001 to 0.05 mol% is preferable, and 0.005 to 0.02 mol% is more preferable.
If the amount used is less than 0.001 mol%, the catalytic activity may not be sufficiently exhibited, and if the amount used is 0.05 mol% or more, the thermal stability and the thermal oxidative stability are deteriorated and aluminum is caused. Occurrence of foreign matter and increase in coloring sometimes become a problem.

The phosphorus compound used in combination with the aluminum compound of the present invention is not particularly limited,
Phosphoric acid and trimethyl phosphoric acid, triethyl phosphoric acid,
Phosphoric acid esters such as phenylphosphoric acid and triphenylphosphoric acid, phosphorous acid and trimethylphosphite, triethylphosphite, triphenylphosphite, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2 , 4-di-tert-butylphenyl) 4,4'-biphenylenediphosphite and other phosphites.

The more preferred phosphorus compound of the present invention is at least one selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds and phosphine compounds. Is a phosphorus compound. In addition to the effect of improving the physical properties such as thermal stability of the polyester by containing these phosphorus compounds, during the polymerization of polyester,
When these phosphorus compounds are used together with the aluminum compound of the present invention, the effect of improving the catalytic activity can be seen. Among these, it is preferable to use a phosphonic acid compound because the effect of improving the physical properties and the effect of improving the catalytic activity are large. Among the above-mentioned phosphorus compounds, it is preferable to use a compound having an aromatic ring structure because the effect of improving the physical properties and the effect of improving the catalytic activity are large.

The phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds referred to in the present invention are represented by the following formulas (Formula 1) to (Formula 1) It refers to a compound having a structure represented by 6).

[0026]

[Chemical 1]

[0027]

[Chemical 2]

[0028]

[Chemical 3]

[0029]

[Chemical 4]

[0030]

[Chemical 5]

[0031]

[Chemical 6]

Examples of the phosphonic acid compounds of the present invention include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate and diethyl benzylphosphonate. To be Examples of the phosphinic acid compound of the present invention include diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate,
Phenylphosphinic acid, methyl phenylphosphinate,
Examples include phenyl phenylphosphinate and the like. Examples of the phosphine oxide compound of the present invention include:
Examples thereof include diphenylphosphine oxide, methyldiphenylphosphine oxide and triphenylphosphine oxide.

Among the phosphinic acid type compounds, phosphine oxide type compounds, phosphonous acid type compounds, phosphinic acid type compounds and phosphine type compounds, the phosphorus compounds of the present invention are represented by the following formulas (formula 7) to (formula 12). The compound represented by these is preferable.

[0034]

[Chemical 7]

[0035]

[Chemical 8]

[0036]

[Chemical 9]

[0037]

[Chemical 10]

[0038]

[Chemical 11]

[0039]

[Chemical 12]

Among the above-mentioned phosphorus compounds, it is preferable to use a compound having an aromatic ring structure because the effect of improving the physical properties and the effect of improving the catalytic activity are great.

As the phosphorus compound of the present invention, the compounds represented by the following general formulas (Chemical formula 13) to (Chemical formula 15) are preferably used because the effect of improving the physical properties and the effect of improving the catalytic activity are particularly large.

[0042]

[Chemical 13]

[0043]

[Chemical 14]

[0044]

[Chemical 15]

(In the formulas (formula 13) to (formula 15), R ¹ ,
R ⁴ , R ⁵ and R ⁶ are each independently hydrogen and 1 to 50 carbon atoms.
Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrocarbon group, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group. R ² and R ³ are each independently hydrogen and have 1 to 1 carbon atoms.
It represents a hydrocarbon group of 50, a hydrocarbon group of 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. However, the hydrocarbon group may contain an alicyclic structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

As the phosphorus compound of the present invention, a compound in which R ¹ , R ⁴ , R ⁵ and R ⁶ in the above formulas (Formula 13) to (Formula 15) are groups having an aromatic ring structure is particularly preferable.

Examples of the phosphorus compound of the present invention include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenylphenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate, diphenylphosphinic acid, Methyl diphenylphosphinate,
Examples thereof include phenyl diphenylphosphinate, phenylphosphinic acid, methyl phenylphosphinate, phenyl phenylphosphinate, diphenylphosphine oxide, methyldiphenylphosphine oxide, and triphenylphosphine oxide. Of these, dimethyl phenylphosphonate and diethyl benzylphosphonate are particularly preferable.

Among the above-mentioned phosphorus compounds, a metal salt compound of phosphorus is particularly preferable as the phosphorus compound in the present invention. 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 has the effect of improving the physical properties of the polyester and the catalytic activity of the polyester, which is the subject of the present invention. Greatly preferred. Examples of metal salts of phosphorus compounds include monometal salts, dimetal salts, trimetal salts and the like.

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

As the phosphorus metal salt compound of the present invention, it is preferable to use at least one compound selected from the compounds represented by the following general formula (Formula 16) because the effect of improving the physical properties and the effect of improving the catalytic activity are large.

[0051]

[Chemical 16]

(In the formula (Formula 16), R ¹ is hydrogen and has 1 carbon atom.
Represents a hydrocarbon group having 50 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group and having 1 to 50 carbon atoms. R ² is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, and 1 to 1 carbon atoms.
It represents 50 hydrocarbon groups. R ³ is hydrogen, having 1 to 5 carbon atoms
It represents a hydrocarbon group of 0, a hydroxyl group, an alkoxyl group, or a carbonyl-containing hydrocarbon group of 1 to 50 carbon atoms. l
Is an integer of 1 or more, m is 0 or an integer of 1 or more, 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 such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. )

Examples of R ¹ are phenyl,
Examples thereof include 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl and 2-biphenyl. R above
Examples of ² include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, long-chain aliphatic group, phenyl group, naphthyl group, and substituted Phenyl and naphthyl groups,
Examples thereof include a group represented by —CH ₂ CH ₂ OH. R ³
Examples of O ⁻ include hydroxide ion, alcoholate ion, acetate ion and acetylacetone ion.

Among the compounds represented by the above general formula (Formula 16), it is preferable to use at least one selected from the compounds represented by the following general formula (Formula 17).

[0055]

[Chemical 17]

(In the formula (Formula 17), R ¹ is hydrogen and has 1 carbon atom.
Represents a hydrocarbon group having 50 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group and having 1 to 50 carbon atoms. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group, or a hydrocarbon group having 1 to 50 carbon atoms containing carbonyl. l represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and l + m is 4 or less. M represents a (l + m) -valent metal cation. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. )

Examples of R ¹ are phenyl,
Examples thereof include 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl and 2-biphenyl. Examples of R ³ O ⁻ include hydroxide ion, alcoholate ion,
Examples thereof include acetate ion and acetylacetone ion.

Among the above-mentioned phosphorus compounds, it is preferable to use a compound having an aromatic ring structure because the effect of improving the physical properties and the effect of improving the catalytic activity are great.

In the above formula (Formula 17), 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 phosphorus metal salt compound of the present invention includes lithium [(1-naphthyl) methylphosphonate ethyl],
Sodium [(1-naphthyl) methylphosphonate], magnesium bis [(1-naphthyl) methylphosphonate], potassium [(2-naphthyl) methylphosphonate], magnesium bis [(2-naphthyl) methylphosphonate], Lithium [ethyl benzyl phosphonate], sodium [ethyl benzyl phosphonate], magnesium bis [ethyl benzyl phosphonate], beryllium bis [ethyl benzyl phosphonate],
Strontium bis [ethyl benzyl phosphonate], manganese bis [ethyl phosphonate], sodium benzyl phosphonate, magnesium bis [benzyl phosphonate], sodium [(9-anthryl) methyl phosphonate], magnesium bis [(9-anthryl) ) Ethyl methylphosphonate], sodium [ethyl 4-hydroxybenzylphosphonate], magnesium bis [ethyl 4-hydroxybenzylphosphonate], sodium [phenyl chlorobenzylphosphonate], magnesium bis [ethyl 4-chlorobenzylphosphonate] ], Sodium [methyl 4-aminobenzylphosphonate], magnesium bis [methyl 4-aminobenzylphosphonate], sodium phenylphosphonate, magnesium bis [phenylphosphine] Ethyl phosphate], zinc bis [phenylphosphonic acid ethyl] and the like. Among these, lithium [(1-naphthyl) methylphosphonate ethyl], sodium [(1-naphthyl) methylphosphonate ethyl], magnesium bis [(1-naphthyl) methylphosphonate ethyl], lithium [benzylphosphonate ethyl], Sodium [ethyl benzylphosphonate],
Particularly preferred are magnesium bis [ethyl benzylphosphonate], sodium benzylphosphonate and magnesium bis [benzylphosphonate].

Among the above-mentioned phosphorus compounds, phosphorus compounds having at least one P—OH bond are particularly preferable as the phosphorus compound in the present invention. In addition to the effect of improving the physical properties of the polyester being particularly enhanced by containing these phosphorus compounds, the effect of improving the catalytic activity can be obtained by using these phosphorus compounds together with the aluminum compound of the present invention during the polymerization of polyester. Seen greatly. A phosphorus compound having at least one P-OH bond means P- in the molecule.
There is no particular limitation as long as it is a phosphorus compound having at least one OH. Among these phosphorus compounds, it is preferable to use a phosphonic acid compound having at least one P—OH bond because the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity are large.

Among the above-mentioned phosphorus compounds, it is preferable to use a compound having an aromatic ring structure because the effect of improving the physical properties and the effect of improving the catalytic activity are large.

As the phosphorus compound having at least one P—OH bond of the present invention, at least one selected from the compounds represented by the following general formula (Formula 18) is used to improve the physical properties and catalytic activity. Is greatly preferable.

[0064]

[Chemical 18]

(In the formula (Formula 18), R ¹ is hydrogen and has 1 carbon atom.
Represents a hydrocarbon group having 50 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group and having 1 to 50 carbon atoms. R ² is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, and 1 to 1 carbon atoms.
It represents 50 hydrocarbon groups. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. )

Examples of R ¹ are phenyl,
1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like can be mentioned. R above
Examples of ² include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, long-chain aliphatic group, phenyl group, naphthyl group, and substituted Phenyl and naphthyl groups,
Examples thereof include a group represented by —CH ₂ CH ₂ OH.

Among the above-mentioned phosphorus compounds, it is preferable to use a compound having an aromatic ring structure because the effect of improving the physical properties and the effect of improving the catalytic activity are large.

Examples of the phosphorus compound having at least one P—OH bond of the present invention include ethyl (1-naphthyl) methylphosphonate, (1-naphthyl) methylphosphonic acid,
Ethyl (2-naphthyl) methylphosphonate, ethyl benzylphosphonate, benzylphosphonic acid, ethyl (9-anthryl) methylphosphonate, ethyl 4-hydroxybenzylphosphonate, ethyl 2-methylbenzylphosphonate, phenyl 4-chlorobenzylphosphonate , Methyl 4-aminobenzylphosphonate, ethyl 4-methoxybenzylphosphonate and the like. Among these, (1
Ethyl-naphthyl) methylphosphonate, ethyl benzylphosphonate are particularly preferred.

Examples of preferable phosphorus compounds of the present invention include phosphorus compounds represented by the chemical formula (Formula 19).

[0070]

[Chemical 19]

(Wherein R ¹ represents a hydrocarbon group having ¹ to 49 carbon atoms, or a hydroxyl group, a halogen group, an alkoxyl group, or an amino group-containing hydrocarbon group having 1 to 49 carbon atoms; ² and R ³ are independently hydrogen and carbon number 1
It represents a hydrocarbon group of ˜50, a hydrocarbon group of 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrocarbon group may contain an alicyclic structure, a branched structure or an aromatic ring structure. )

Further preferably, the chemical formula (Formula 19)
At least one of R ¹ , R ² and R ³ therein is a compound containing an aromatic ring structure.

Specific examples of these phosphorus compounds are shown below.

[0074]

[Chemical 20]

[0075]

[Chemical 21]

[0076]

[Chemical formula 22]

[0077]

[Chemical formula 23]

[0078]

[Chemical formula 24]

[0079]

[Chemical 25]

Further, the phosphorus compound of the present invention having a larger molecular weight is preferable because the effect is large because it is hard to be distilled off during the polymerization.

The phosphorus compound of the present invention is preferably a phosphorus compound having a phenol moiety in the same molecule. In addition to the effect of improving the physical properties of polyester by containing a phosphorus compound having a phenol moiety in the same molecule, the effect of increasing the catalytic activity by using a phosphorus compound having a phenol moiety in the same molecule during polyester polymerization Is larger, and thus the productivity of polyester is excellent.

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 compound, a phosphinic acid compound having a phenol moiety in the same molecule, It is preferable to use one or more compounds selected from the group consisting of phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds because the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity are large. . Among these, it is particularly preferable to use a phosphonic acid compound having one or two or more phenol moieties in the same molecule because the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity are particularly large.

The phosphorus compounds having a phenol moiety in the same molecule of the present invention include the following general formulas (Formula 26) to (Formula 2)
The compound represented by 8) is preferable.

[0084]

[Chemical formula 26]

[0085]

[Chemical 27]

[0086]

[Chemical 28]

In the formulas (Formula 26) to (Formula 28), R ¹ is a hydrocarbon group having 1 to 50 carbon atoms including a phenol moiety, a substituent such as a hydroxyl group, a halogen group, an alkoxyl group or an amino group, and a phenol moiety. Represents a hydrocarbon group having 1 to 50 carbon atoms including R ⁴ , R ⁵ and R ⁶ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, an amino group or the like. Represents a hydrocarbon group having 1 to 50 carbon atoms containing a substituent, R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, and a carbon number 1 containing a substituent such as a hydroxyl group or an alkoxyl group; represents the 50 hydrocarbon group. However, end each other hydrocarbon groups branched structure or cyclohexyl alicyclic structure or a phenyl or naphthyl aromatic ring structure that may contain .R ² and R ⁴ of the coupling May be )

Examples of the phosphorus compound having a phenol moiety in the same molecule of the present invention include p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate and p.
-Diphenyl hydroxyphenylphosphonate, bis (p
-Hydroxyphenyl) phosphinic acid, methyl bis (p-hydroxyphenyl) phosphinate, phenyl bis (p-hydroxyphenyl) phosphinate, p-hydroxyphenylphenylphosphinic acid, methyl p-hydroxyphenylphenylphosphinate, p-hydroxyphenyl Phenyl phenylphosphinate, p-hydroxyphenylphosphinic acid, methyl p-hydroxyphenylphosphinate, phenyl p-hydroxyphenylphosphinate, bis (p-hydroxyphenyl) phosphine oxide, tris (p-hydroxyphenyl) phosphine oxide, bis ( p-hydroxyphenyl) methylphosphine oxide, and the following formulas (formula 29) to (formula 3)
Examples thereof include compounds represented by 2). Among these, a compound represented by the following formula (Formula 31) and dimethyl p-hydroxyphenylphosphonate are particularly preferable.

[0089]

[Chemical 29]

[0090]

[Chemical 30]

[0091]

[Chemical 31]

[0092]

[Chemical 32]

As the compound represented by the above formula (Formula 31), SANKO-220 (manufactured by Sanko Co., Ltd.) can be used.

Among the phosphorus compounds having the phenol moiety in the same molecule of the present invention, at least one selected from the specific phosphorus metal salt compounds represented by the following general formula (Formula 33) is particularly preferable.

[0095]

[Chemical 33]

(In the formula (Formula 33), 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 hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. R ⁴ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms containing a hydroxyl group or an alkoxyl group or carbonyl. As R ⁴ O ⁻ , for example,
Examples thereof include hydroxide ion, alcoholate ion, acetate ion and acetylacetone ion. l is 1
An integer greater than or equal to m, 0 is an integer greater than or equal to 1, and l + m is 4
It is the following. M represents a (l + m) -valent metal cation. n is 1
Represents the above integers. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. )

Among these, at least one selected from the compounds represented by the following general formula (Formula 34) is preferable.

[0098]

[Chemical 34]

(In the formula (Formula 34), M ^{n +} represents an n-valent metal cation, and n represents 1, 2, 3 or 4.)

In the above formula (Formula 33) or (Formula 34), M is Li, Na, K, Be, Mg, Sr, Ba,
It is preferable to use one selected from Mn, Ni, Cu, and Zn because the effect of improving the catalytic activity is large. Of these,
Li, Na and Mg are particularly preferable.

Specific phosphorus metal salt compounds of the present invention include lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-t-
ert-Butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], potassium [3,5-di-tert.
-Butyl-4-hydroxybenzylphosphonate ethyl], magnesium bis [3,5-di-tert-butyl-4-
Ethyl hydroxybenzylphosphonate], magnesium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], beryllium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], 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-butyl-4]
-Hydroxybenzylphosphonate], nickel bis [3,5-di-tert-butyl-4-ethyl ethyl hydroxybenzylphosphonate], copper bis [3,5-di-tert-butyl-4]
-Ethyl hydroxybenzylphosphonate], zinc bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate] and the like. Among these, lithium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], magnesium bis [ethyl Ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate] is particularly preferred.

Among the phosphorus compounds having the phenol moiety of the present invention in the same molecule, at least one selected from the specific phosphorus compounds having at least one P—OH bond represented by the following general formula (Formula 35) is used. Especially preferred.

[0103]

[Chemical 35]

(In the formula (Formula 35), 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 hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. )

Among these, at least one selected from the compounds represented by the following general formula (Formula 36) is preferable.

[0106]

[Chemical 36]

In the formula (Formula 36), R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group, and the hydrocarbon group is cyclohexyl. May contain an alicyclic structure or branched structure such as or an aromatic ring structure such as phenyl or naphthyl.)

Examples of R ³ include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, long-chain aliphatic group, phenyl group, Examples thereof include a naphthyl group, a substituted phenyl group, a naphthyl group, and a group represented by —CH ₂ CH ₂ OH.

Specific phosphorus compounds having at least one P-OH bond of the present invention include ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and 3,5-di-tert-butyl- Methyl 4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-isopropyl 4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-
Phenyl hydroxybenzylphosphonate, 3,5-di-ter
Octadecyl t-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid and the like can be mentioned. Among these, ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferable.

Among the phosphorus compounds having the phenol moiety in the same molecule of the present invention, at least one phosphorus compound selected from the specific phosphorus compounds represented by the following general formula (Formula 37) is preferable.

[0111]

[Chemical 37]

(In the formula (Formula 37), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.
³ , R ⁴ are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, and 1 to 5 carbon atoms.
Represents a hydrocarbon group of 0. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl and naphthyl. )

Among the above general formulas (Formula 37), it is preferable to use at least one selected from the compounds represented by the following general formula (Formula 38) because the effect of improving the physical properties of the polyester and the effect of improving the catalyst activity are high.

[0114]

[Chemical 38]

(In the above formula (Formula 38), R ³ and R ⁴ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

Examples of R ³ and R ⁴ include hydrogen, methyl group, butyl group and other short chain aliphatic groups, octadecyl and other long chain aliphatic groups, phenyl group, naphthyl group and substituted phenyl. aromatic groups such as groups or naphthyl group, -CH ₂ CH ₂
Examples thereof include a group represented by OH.

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-ter
Dioctadecyl t-butyl-4-hydroxybenzylphosphonate, diphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and the like can be mentioned. Among these, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-
Diphenyl hydroxybenzylphosphonate is particularly preferred.

Among the phosphorus compounds having the phenol moiety in the same molecule of the present invention, the compound particularly desirable in the present invention is at least one phosphorus compound selected from the compounds represented by the chemical formulas (Formula 39) and (Formula 40). Is.

[0119]

[Chemical Formula 39]

[0120]

[Chemical 40]

As the compound represented by the chemical formula (Formula 39), Irganox 1222 (manufactured by Ciba Specialty Chemicals) is commercially available, and as the compound represented by the chemical formula (Formula 40), Irgano.
x1425 (Ciba Specialty Chemicals)
Is commercially available and can be used.

Phosphorus compounds have been known as heat stabilizers for polyesters, but it has hitherto been known that the use of these compounds in combination with conventional metal-containing polyester polymerization catalysts greatly accelerates melt polymerization. It wasn't done. Actually, even when the phosphorus compound of the present invention is added when melt-polymerizing polyester using a typical catalyst for polyester polymerization, that is, an antimony compound, a titanium compound, a tin compound or a germanium compound as a polymerization catalyst, it is substantially useful. It is not observed that the polymerization is accelerated to a certain level.

The amount of the phosphorus compound used when the polyester is produced according to the method of the present invention is 0.0001 to 0.1 mol% based on the number of moles of all the constituent units of the polycarboxylic acid component of the obtained polyester. Preferably 0.
More preferably, it is 005 to 0.05 mol%.

By using the phosphorus compound of the present invention in combination, a catalyst exhibiting a sufficient catalytic effect can be obtained even if the amount of aluminum added in the polyester polymerization catalyst is small. If the addition amount of the phosphorus compound is less than 0.0001 mol%, the addition effect may not be exhibited,
On the contrary, when the amount added exceeds mol%, the catalytic activity as a polyester polymerization catalyst may decrease, and the decreasing tendency changes depending on the amount of aluminum used and the like.

The catalyst of the present invention preferably does not contain an alkali metal, an alkaline earth metal, or a compound thereof.

On the other hand, in a preferred embodiment of the present invention, in addition to aluminum or its compound, a small amount of at least one selected from alkali metal, alkaline earth metal and its compound is allowed to coexist as the second metal-containing component. is there. The coexistence of such a second metal-containing component in the catalyst system is effective for improving the productivity, since the catalyst component has an effect of suppressing the production of diethylene glycol and the catalytic activity is enhanced, and thus the reaction rate is further enhanced. .

A technique for adding an alkali metal compound or an alkaline earth metal compound to an aluminum compound to obtain a catalyst having sufficient catalytic activity is known. When such a known catalyst is used, a polyester having excellent thermal stability can be obtained, but a known catalyst in which an alkali metal compound or an alkaline earth metal compound is used in combination is added in an amount such that a practical catalytic activity is required. Is required, and when the alkali metal compound is used, the hydrolysis resistance of the resulting polyester is reduced and the amount of foreign matter due to the alkali metal compound is increased, and when used for fibers, the spinnability and yarn physical properties are Further, when used in a film, the physical properties of the film deteriorate. When an alkaline earth metal compound is used in combination, the thermal stability of the obtained polyester decreases when it is attempted to obtain practical activity, the coloring due to heating is large, the amount of foreign matter is increased, and the hydrolysis resistance increases. Degradability is also reduced.

When an alkali metal, an alkaline earth metal or a compound thereof is added, the amount M (mol%) to be used is
It is preferably 1 × 10 ⁻⁶ or more and less than 0.1 mol%, more preferably 5 × 10 ^{−6 to} 0.05 with respect to the total number of polycarboxylic acid units constituting the polyester.
Mol%, more preferably 1 × 10 ^{−5 to} 0.03
Mol%, particularly preferably 1 × 10 ^{−5 to} 0.01
Mol%. Since the addition amount of alkali metal or alkaline earth metal is small, it is possible to increase the reaction rate without causing problems such as deterioration of thermal stability, generation of foreign matter, coloring, and deterioration of hydrolysis resistance. is there. When the amount M of the alkali metal, alkaline earth metal or its compound used is 0.1 mol% or more, the thermal stability decreases, the generation of foreign substances and the increase in coloration, and the hydrolysis resistance decrease become problems in the processing of the product. There are cases. If M is less than 1 × 10 ⁻⁶ , the effect is not clear even if added.

In the present invention, as the alkali metal or alkaline earth metal constituting the second metal-containing component which is preferably used in addition to aluminum or its compound, Li, Na, K, Rb, Cs, Be, Mg, Ca,
At least one selected from Sr and Ba is preferable, and at least one selected from Li, Na, Mg and compounds thereof is more preferably used.
Examples of the alkali metal or alkaline earth metal compound include, for example, formic acid, acetic acid, propionic acid, butyric acid of these metals,
Saturated aliphatic carboxylates such as oxalic acid, unsaturated aliphatic carboxylates such as acrylic acid and methacrylic acid, aromatic carboxylates such as benzoic acid, halogen-containing carboxylates such as trichloroacetic acid, lactic acid, citric acid, Hydroxycarboxylic acid salts such as salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, bromic acid, etc. Acid salts, organic sulfonates such as 1-propanesulfonic acid, 1-pentanesulfonic acid and naphthalenesulfonic acid, organic sulfates such as laurylsulfate, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert. -Alkoxides such as butoxy, chelate compounds with acetylacetonate, hydrides,
Examples thereof include oxides and hydroxides.

Of these alkali metals, alkaline earth metals or their compounds, when strongly alkaline ones such as hydroxides are used, these tend to be insoluble in diols such as ethylene glycol or organic solvents such as alcohols. Therefore, it must be added to the polymerization system as an aqueous solution, which may cause a problem in the polymerization process. Furthermore, when a highly alkaline substance such as a hydroxide is used, the polyester is likely to undergo a side reaction such as hydrolysis during polymerization, and the polymerized polyester tends to be colored, and the hydrolysis resistance is also lowered. Tend to do. Therefore, as the alkali metal or the compound thereof or the alkaline earth metal or the compound thereof of the present invention, a saturated aliphatic carboxylic acid salt, an unsaturated aliphatic carboxylic acid salt or an aromatic metal salt of an alkaline metal or an alkaline earth metal is preferable. Group carboxylic acid salts, halogen-containing carboxylic acid salts, hydroxycarboxylic acid salts, 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, it is more preferable to use a saturated aliphatic carboxylic acid salt of an alkali metal or an alkaline earth metal, particularly an acetic acid salt, from the viewpoints of easy handling and availability.

The polycondensation catalyst of the present invention contains other polycondensation catalysts such as an antimony compound, a germanium compound and a titanium compound, and the addition of these components causes problems in the product such as the characteristics of polyester, processability and color tone as described above. The coexistence and use within the range of the addition amount that does not generate is effective in improving the productivity by shortening the polymerization time, and is preferable.

The antimony compound is preferably added in an amount of 50 ppm or less as antimony atom with respect to the polyester obtained by polymerization. A more preferable addition amount is 30 ppm or less. The amount of antimony added is 50
If it is more than ppm, metal antimony will be deposited,
It is not preferable because darkening and foreign matter are generated on the polyester.

The germanium compound has a germanium atom content of 20 pp with respect to the polyester obtained by polymerization.
It is preferably added in an amount of m or less. A more preferable addition amount is 10 ppm or less. When the addition amount of germanium is 20 ppm or more, it becomes disadvantageous in terms of cost, which is not preferable.

The titanium compound is preferably added in an amount of 5 ppm or less in terms of titanium atom with respect to the polyester obtained by polymerization. More preferable addition amount is 3 ppm
It is below, and more preferably below 1 ppm. When the amount of titanium added is 5 ppm or more, the polyester obtained is significantly colored, and the thermal stability is significantly reduced, which is not preferable.

The antimony compound that can be used in the present invention is not particularly limited, but preferred compounds include antimony trioxide, antimony pentoxide, antimony acetate, antimony glycoxide and the like, and the use of antimony trioxide is particularly preferable. Is preferred. The germanium compound is not particularly limited, but examples thereof include germanium dioxide and germanium tetrachloride, and germanium dioxide is particularly preferable. Both crystalline and amorphous germanium dioxide can be used.

The titanium compound usable in the present invention is not particularly limited, but tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n
-Butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetracyclohexyl titanate, tetraphenyl titanate, tetrabenzyl titanate, lithium oxalate titanate, potassium oxalate titanate, ammonium titanate oxalate, titanium oxide,
Complex oxides of titanium with silicon, zirconium, alkali metals, alkaline earth metals, etc., titanium orthoesters or condensed orthoesters, reaction products of titanium orthoesters or condensed orthoesters and hydroxycarboxylic acids, titanium ortho Reaction product consisting of ester or condensed orthoester, hydroxycarboxylic acid and phosphorus compound, reaction product consisting of titanium orthoester or condensed orthoester and polyhydric alcohol having at least two hydroxyl groups, 2-hydroxycarboxylic acid and base Examples thereof include a complex oxide of titanium and silicon, a complex oxide of titanium and magnesium, a reaction product of a titanium orthoester or a condensed orthoester, a hydroxycarboxylic acid and a phosphorus compound.

As the tin compound, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditinoxide, triethyltin hydroxide, monobutylhydroxytin oxide, triisobutyltin acetate, diphenyltin dilaurate, monobutyltin trichloride, Examples thereof include dibutyltin sulfide, dibutylhydroxytin oxide, methylstannonic acid and ethylstannonic acid, and the use of monobutylhydroxytin oxide is particularly preferable.

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

The polycondensation catalyst of the present invention may be added in the form of powder or neat, or may be added in the form of a slurry or solution of a solvent such as ethylene glycol. Not limited. Further, aluminum metal or its compound and other components, for example, the phosphorus compound of the present invention may be added in advance as a mixture, or these may be added separately. Further, the aluminum metal or its compound and the other component, for example, the phosphorus compound may be added to the polymerization system at the same addition timing, or the respective components may be added at different addition timings. Further, the whole amount of the catalyst may be added at once or may be added in plural times.

In order to improve the color tone of the polyester of the present invention, it is a preferred embodiment to add the cobalt compound as a cobalt atom in an amount of less than 10 ppm with respect to the polyester. It is more preferably 5 ppm or less, still more preferably 3 ppm or less.

The cobalt compound in the present invention is for the purpose of eliminating coloration, and may be added at any stage of the polymerization or after the completion of the polymerization reaction. It does not matter at any stage of the process.

The cobalt compound is not particularly limited, but specifically, for example, cobalt acetate, cobalt nitrate,
Examples thereof include cobalt chloride, cobalt acetylacetonate, cobalt naphthenate and their hydrates. Among them, cobalt acetate tetrahydrate is particularly preferable.

The polyester of the present invention may contain organic, inorganic, and organometallic toners, fluorescent brightening agents, and the like. By containing one or more of these, the polyester Coloring such as yellowing can be suppressed to an even more excellent level. In addition, any other polymer, antistatic agent, defoaming agent, dyeability improving agent, dye,
Pigments, matting agents, optical brighteners, stabilizers, antioxidants, and other additives may be contained. As the antioxidant, aromatic amine-based and phenol-based antioxidants can be used, and as the stabilizer, phosphoric acid and phosphoric ester-based stabilizers such as phosphorus-based, sulfur-based and amine-based stabilizers can be used. Can be used.

These additives can be added during or after the polymerization of the polyester, or at any stage during the molding of the polyester. Which stage is suitable depends on the characteristics of the compound and the requirements of the polyester molded product. Different depending on the performance.

The polyester referred to in the present invention includes one or more selected from polycarboxylic acids containing dicarboxylic acids and ester-forming derivatives thereof and one or more selected from polyhydric alcohols containing glycol. Or a hydroxycarboxylic acid and an ester-forming derivative thereof, or a cyclic ester.

Examples of the dicarboxylic acid include oxalic acid, malonic acid,
Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,3-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 ester-forming properties thereof Unsaturated aliphatic dicarboxylic acids exemplified by derivatives, fumaric acid, maleic acid, itaconic acid or the like, or 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'-biphenyl sulfone dicarboxylic acid, 4,4'-biphe Examples thereof include aromatic dicarboxylic acids such as nyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid, and ester-forming derivatives thereof.

Of these dicarboxylic acids, terephthalic acid and naphthalenedicarboxylic acid, especially 2,6 naphthalenedicarboxylic acid, are preferred in view of the physical properties of the resulting polyester, and other dicarboxylic acids are used as constituents, if necessary.

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

As glycol, ethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,
2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,
Aliphatic glycols such as 4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, polytrimethylene glycol and polytetramethylene glycol, hydroquinone, and 4,4′-dihydroxybisphenol 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis (β-hydroxyethoxyphenyl) sulfone, bis (p-hydroxyphenyl) ether, bis (p-hydroxyphenyl) sulfone, bis (p-hydroxy) Phenyl) methane, 1,2-bis (p
-Hydroxyphenyl) ethane, bisphenol A, bisphenol C, 2,5-naphthalene diol, and aromatic glycols such as glycols obtained by adding ethylene oxide to these glycols.

Of these glycols, ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol and 1,4-cyclohexanedimethanol are preferable.

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

As the hydroxycarboxylic acid, lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid, Alternatively, ester-forming derivatives thereof and the like can be mentioned.

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

Examples of the ester-forming derivative of polyvalent carboxylic acid or hydroxycarboxylic acid 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 naphthalene dicarboxylic acid or its ester-forming derivative, and whose main glycol component is alkylene glycol.

A polyester whose main acid component is terephthalic acid or its ester-forming derivative or naphthalenedicarboxylic acid or its ester-forming derivative means terephthalic acid or its ester-forming derivative and naphthalenedicarboxylic acid or A polyester containing 70 mol% or more of the ester-forming derivatives in total is preferable, more preferably a polyester containing 80 mol% or more, and further preferably
It is a polyester containing 90 mol% or more.

The polyester whose main glycol component is alkylene glycol is preferably a polyester containing 70 mol% or more of alkylene glycol in total with respect to all glycol components, and more preferably
A polyester containing 80 mol% or more, and more preferably a polyester containing 90 mol% or more. The alkylene glycol referred to herein may have a substituent or an alicyclic structure in the molecular chain.

Examples of the naphthalenedicarboxylic acid or its ester-forming derivative used in the present invention include 1,3 naphthalenedicarboxylic acid, 1,4 naphthalenedicarboxylic acid, 1,5 naphthalenedicarboxylic acid, and 2,6 naphthalenedicarboxylic acid. Acid, 2,7 naphthalene dicarboxylic acid,
Alternatively, ester-forming derivatives thereof are preferable.

As the alkylene glycol used in the present invention, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,
3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-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 at the same time.

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 copolymers thereof are particularly preferable.

[0161]

The present invention will be described in detail below with reference to examples. The characteristic evaluation was carried out by the following method. Intrinsic viscosity (IV: dl / g) 0.1 g of polyester is dissolved in 25 ml of 6/4 mixed solvent in the weight ratio of phenol / 1,1,2,2-telorachloroethane, and the temperature is 30 ° C. using an Ubbelohde viscometer. Measured. Average particle size (nm) of inorganic particles Sample preparation: 1 wt% fine water dispersion of inorganic particles which had been ultrasonically treated for about 30 minutes in advance was used as a sample for particle size measurement. The particle diameter was measured at 25 ° C. by using DSL-7000 manufactured by Otsuka Electronics Co., Ltd. and using an argon laser as a light source. Number of particles in polymer (particles / mg) Resin chips were sandwiched between two cover glasses, melt-pressed and cooled. Using an image analyzer and a phase-contrast microscope, the number of particles of 5 μ or more present in 1 mg of polymer was evaluated, and 10 particles / polymer of 1 mg or less were regarded as acceptable.

The degree of increase in filtration pressure during spinning and the degree of increase in filtration pressure during spinning were evaluated as follows. Evaluation of increase in filtration pressure ◯: No increase in filtration pressure is observed. Δ: Increase in filtration pressure is recognized. X: Significant increase in filtration pressure is observed. Evaluation of Frequency of Thread Breakage The frequency of thread breakage during drawing was evaluated as follows. ◯: Thread breakage hardly occurs. Δ: Some yarn breakage occurs. X: Thread breakage occurs frequently.

Example 1 A slurry of high-purity terephthalic acid and ethyl glycol was continuously fed to a first esterification reactor containing a reactant in advance and stirred at about 250 ° C. The reaction was carried out at 0.5 kg / cm ² G with an average residence time of about 3 hours. This reaction product was sent to the second esterification reactor and stirred at about 260 ° C. and 0.05 kg / cm ² G
The reaction was carried out up to the prescribed degree of reaction. A 15 g / l ethylene glycol solution of basic aluminum acetate prepared by adding ethylene glycol to a basic aluminum acetate aqueous solution as a polycondensation catalyst and heating to distill off water was used as an aluminum atom for the acid component in the polyester. 014 m
A 10 g / l ethylene glycol solution of ol% and Irganox 1425 (manufactured by Ciba Specialty Chemicals) was continuously supplied to the second esterification reactor at 0.02 mol% as Irganox 1425 with respect to the acid component. Further, as inorganic particles, 2.0 × 10 ⁻⁴ parts of colloidal silica having an average particle size of about 15 nm, 5.0 × 10 ⁻⁷ parts of magnesium acetate and 1.0 part of ethylene glycol are used.
A slurry prepared by subjecting x10 ^-3 parts to a dispersion treatment was continuously supplied to the second esterification reactor in an amount of 50 ppm as colloidal silica with respect to aluminum atoms. The esterification reaction product was continuously fed to the first polycondensation reactor and stirred at about 265 ° C. at 25 torr for about 1 hour, and then stirred at the second polycondensation reactor at about 265 ° C. at 3 torr. Approximately 275 for about 1 hour with stirring in the final polycondensation reactor
Polycondensation was carried out at 0.5 ° C. and 0.5 to 1 torr for about 2 hours.

Table 1 shows the evaluation results of IV of polyethylene terephthalate obtained by the above polycondensation, the number / mg of foreign matters (precipitated particles) having a size of 5 μm or more existing in the polymer, and the spinnability.

Example 2 Polycondensation was carried out in the same manner as in Example 1 except that colloidal silica having an average particle diameter of about 40 nm was used in an amount of 450 ppm with respect to aluminum atoms. Table 1 shows the IV of the obtained polyethylene terephthalate, the number / mg of foreign matters (precipitated particles) having a size of 5 μm or more present in the polymer, and the spinnability.

(Examples 3 to 6) and (Comparative Examples 1 to 5) Except that polycondensation was carried out with or without adding an inorganic particle slurry of ethylene glycol composed of inorganic particles shown in Table 1 to the reaction system. It carried out like Example 1. Table 1 shows the IV of the obtained polyethylene terephthalate, the number / mg of foreign matters (precipitated particles) having a size of 5 μm or more present in the polymer, and the spinnability.

[0167]

[Table 1]

[0168]

According to the present invention, the product obtained by the esterification reaction or the transesterification reaction with the aromatic dicarboxylic acid or the ester-forming derivative thereof and the diol or the ester-forming derivative thereof is converted into an aluminum compound and a phosphorus compound. In the method of producing a polyester by polycondensing as a polycondensation catalyst, the size of the precipitated particles mainly resulting from metal atoms such as aluminum precipitated in the production process of the polyester is miniaturized, so that fibers (filtration pressure increase, yarn breakage) ), Films and bottles and the like have improved moldability.

Continued front page    F term (reference) 4J029 AA01 AB04 AC01 AD01 AE01                       AE02 AE03 BA01 BA02 BA03                       BA04 BA05 BA08 BA09 BA10                       BB05A BB12A BB13A BC05A                       BD03A BD04A BH02 CA01                       CA02 CA03 CA04 CA05 CA06                       CA09 CB04A CB05A CB06A                       CB09A CB10A CC05A CC06A                       CD00 DB07 DB10 GA01 GA13                       GA14 GA17 JA061 JA063                       JA091 JA121 JA123 JA201                       JA203 JA231 JA261 JB011                       JB131 JB171 JB173 JC631                       JC713 JD01 JF133 JF143                       JF163 JF221 JF223 JF323                       KE02 KE05

Claims (5)

[Claims] 1. A product obtained by an esterification reaction or transesterification reaction with an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof is used as a polycondensation catalyst using an aluminum compound and a phosphorus compound as polycondensation catalysts. In the method for producing a polyester to be condensed, the average particle diameter is 1 to 1,000 nm, and inorganic particles insoluble or hardly soluble in the reaction system are used in an amount of 5 to 5,000 with respect to the aluminum atom of the aluminum compound which is a constituent component of the catalyst.
A method for producing a polyester, which comprises adding ppm. 2. At least one of the compounds whose inorganic particles contain at least one of titanium, aluminum, silicon, calcium, magnesium, barium and bismuth atoms.
The method for producing a polyester according to claim 1, wherein the content of the seed compound is 70% by weight or more. 3. The method for producing a polyester according to claim 1, wherein the inorganic particles are metal oxides, carbonates, silicates, aluminates and sulfates. 4. The aluminum compound which is a constituent of the catalyst is aluminum acetate, basic aluminum acetate,
4. The polyester according to claim 1, which is at least one selected from aluminum lactate, aluminum chloride, aluminum hydroxide, basic aluminum chloride, polyaluminum chloride and aluminum acetylacetonate. Method. 5. The phosphorus compound which is a constituent component of the catalyst is selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds and phosphine compounds. The method for producing a polyester according to any one of claims 1 to 4, wherein the polyester is at least one kind.