JP3460709B2 - Polyester polymerization catalyst, polyester produced using the same, and method for producing polyester - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester polymerization catalyst, a polyester produced by using the same, and a method for producing the polyester. More specifically, the present invention relates to a novel polyester containing no germanium or antimony compound as a catalyst main component. The present invention relates to a polymerization catalyst, a polyester produced using the same, and a method for producing a polyester.

[0002]

2. Description of the Related Art Polyesters, especially polyethylene terephthalate (hereinafter abbreviated as PET), have excellent mechanical and chemical properties, and have a wide range of applications, such as fibers for clothing and industrial materials, and packaging. It has been applied to various films and sheets for magnetic tapes, magnetic tapes, and molded products such as bottles and engineering plastics.

PET is industrially used to produce bis (2-hydroxyethyl) terephthalate by esterification or transesterification of terephthalic acid or dimethyl terephthalate with ethylene glycol, and using bis (2-hydroxyethyl) terephthalate at a high temperature under a vacuum with a catalyst. Obtained by polycondensation.

Antimony trioxide is widely used as a catalyst for polycondensation. Antimony trioxide is a catalyst that is inexpensive and has excellent catalytic activity,
Since metal antimony precipitates during polycondensation, there is a problem that darkening and foreign matter occur in PET. Under such circumstances, polyesters containing no antimony or only a very small amount thereof are desired.

Attempts have been made to use antimony trioxide as a polycondensation catalyst and to suppress the darkening of PET and the generation of foreign matter. For example, in Japanese Patent No. 2666502, by using a compound of antimony trioxide and bismuth and selenium as a polycondensation catalyst, generation of black foreign matter in PET is suppressed. Further, JP-A-9-291141 describes that when antimony trioxide containing an oxide of sodium and iron is used as a polycondensation catalyst, precipitation of metallic antimony is suppressed. However, these polycondensation catalysts cannot eventually achieve the purpose of polyester containing no antimony.

Studies have also been conducted on polycondensation catalysts that replace antimony trioxide. In particular, titanium compounds typified by tetraalkoxy titanates have already been proposed, but the PET produced using them has the problems of being markedly colored and easily causing thermal decomposition.

As an attempt to overcome such problems when using tetraalkoxy titanate as a polycondensation catalyst, for example, in JP-A-55-116722, tetraalkoxy titanate is used simultaneously with a cobalt salt and a calcium salt. A method has been proposed. In addition, JP-A-8-7358
According to No. 1, a method is proposed in which a tetraalkoxy titanate is used as a polycondensation catalyst at the same time as a cobalt compound and an optical brightener is used. However, although these proposals reduce the coloring of PET when using tetraalkoxy titanate as a polycondensation catalyst,
Effective suppression of thermal decomposition of PET has not been achieved.

A germanium compound has been put into practical use as a polycondensation catalyst which is an alternative to antimony trioxide and which overcomes the problems when tetraalkoxy titanate is used. There are problems that it is very expensive and that it is easy to distill out of the reaction system during the polymerization and the catalyst concentration in the reaction system changes, making it difficult to control the polymerization.

Aluminum compounds are generally known to have poor catalytic activity. Among aluminum compounds,
It has been reported that an aluminum chelate compound has higher catalytic activity as a polycondensation catalyst than other aluminum compounds, but it is said that it has sufficient catalytic activity as compared with the above-mentioned antimony compound or titanium compound. Not to mention, the polyester polymerized over a long period of time using an aluminum compound as a catalyst had a problem that the thermal stability was poor.

[0010]

DISCLOSURE OF THE INVENTION The present invention does not contain an antimony compound or a germanium compound as a catalyst main component, contains aluminum as a main metal component, has excellent catalytic activity, and is capable of deactivating or removing the catalyst, Provided is a polyester polymerization catalyst which effectively suppresses thermal deterioration during melt molding and provides a polyester having excellent thermal stability. The present invention also provides a film using the above catalyst,
Improved thermal stability when performing melt molding of hollow molded products such as bottles and fibers, and excellent quality even if virgin resin is used or waste generated during molding is reused. And a method for producing a polyester using the polyester polymerization catalyst.

Another object of the present invention is to use a polyester polymerization catalyst which gives a polyester excellent in heat aging resistance and hydrolysis resistance, a polyester excellent in heat aging resistance and hydrolysis resistance, and the above polyester polymerization catalyst. To provide a method for producing the polyester.

[0012]

Means for Solving the Problems As a result of intensive studies aimed at solving the above problems, the authors of the present invention use an aluminum compound and a specific phosphorus compound although the aluminum compound originally has poor catalytic activity. It was found that a polyester having excellent catalytic activity, thermal stability, thermal oxidation stability, and hydrolysis resistance can be obtained.

That is, the present invention provides a polyester polymerization catalyst, which comprises at least one selected from aluminum and its compounds as a metal-containing component and at least one metal salt compound of phosphorus. And a polyester produced using the same, and a method for producing the polyester.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The metal salt compound of phosphorus constituting the polymerization catalyst of the present invention is not particularly limited as long as it is a metal salt of a phosphorus compound. The improvement effect is large and preferable. Examples of metal salts of phosphorus compounds include monometal salts, dimetal salts, trimetal salts and the like.

The phosphonic acid compound referred to in the present invention means a compound having a structure represented by the following formula (3).

[0016]

[Chemical 3]

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

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 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 (1) because the catalytic activity improving effect is large.

[0020]

[Chemical 4]

(In the formula (1), R ¹ is hydrogen and has 1 to 5 carbon atoms.
It represents a hydrocarbon group having 0, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and a hydrocarbon group 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 50 carbon atoms.
Represents a hydrocarbon group of. 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 is 1
Is 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. ) As R ¹ above, for example, phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl,
2-biphenyl etc. are mentioned. Examples of R ² include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, ter.
t- butyl group, an aliphatic group of a long chain, a phenyl group, a naphthyl group, a substituted phenyl group or a naphthyl group, -CH ₂ CH ₂
Examples thereof include a group represented by OH. Examples of R ³ O ⁻ include hydroxide ion, alcoholate ion, acetate ion and acetylacetone ion.

Among the compounds represented by the above general formula (1), it is preferable to use at least one selected from the compounds represented by the following general formula (2).

[0023]

[Chemical 5]

(In the formula (2), R ¹ is hydrogen and has 1 to 5 carbon atoms.
It represents a hydrocarbon group having 0, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and a hydrocarbon group 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. ) As R ¹ above, for example, phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl,
2-biphenyl etc. are mentioned. Examples of R ³ O ⁻ include hydroxide ion, alcoholate ion, acetate ion and acetylacetone ion. Among the above phosphorus compounds, it is preferable to use a compound having an aromatic ring structure because the effect of improving the catalytic activity is large.

In the above formula (2), M is Li, N
a, K, Be, Mg, Sr, Ba, Mn, Ni, Cu,
It is preferable to use one selected from Zn because the effect of improving the catalytic activity is large. Of these, Li, Na and Mg are particularly preferable. Examples of the metal salt compound of phosphorus of the present invention include lithium [(1-naphthyl) methylphosphonate ethyl], sodium [(1-naphthyl) methylphosphonate ethyl], magnesium bis [(1-naphthyl) methylphosphonate ethyl], potassium [ (2-naphthyl) methylphosphonate ethyl], magnesium bis [(2-naphthyl) methylphosphonate ethyl], lithium [ethyl benzylphosphonate], sodium [ethyl benzylphosphonate], magnesium bis [ethyl benzylphosphonate], beryllium bis [Ethyl benzylphosphonate],
Strontium bis [ethyl benzylphosphonate], manganese bis [ethyl benzyl phosphonate], sodium benzyl phosphonate, magnesium bis [benzyl phosphonate], sodium [(9-anthryl) methyl phosphonate ethyl], 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].

By using a phosphorus compound having such a specific structure, an antimony compound or a germanium compound is not contained as a catalyst main component, and aluminum is used as a main metal component, which is excellent in catalytic activity and deactivates the catalyst. It is possible to obtain a polyester polymerization catalyst capable of effectively suppressing thermal deterioration at the time of melt-molding and having excellent thermal stability, and also having excellent thermal oxidation stability and hydrolysis resistance without removing the polyester.

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.

The phosphorus compound of the present invention is preferably used in an amount of 0.0001 to 0.1 mol% based on the number of moles of all constituent units of the polycarboxylic acid component of the polyester obtained.
It is more preferably 0.005 to 0.05 mol%. If the addition amount of the phosphorus compound is less than 0.0001 mol%, the addition effect may not be exhibited, and if added in excess of 0.1 mol%, the catalytic activity as a polyester polymerization catalyst may be decreased, and The tendency changes depending on the amount of aluminum used and the like.

A technique in which an aluminum compound is used as a main catalyst component without using a phosphorus compound, and the amount of the aluminum compound used is reduced, and when a cobalt compound is added to make the aluminum compound a main catalyst, thermal stability is obtained. Although there is a technique for preventing coloration due to a decrease in property, thermal stability also decreases when a cobalt compound is added to an extent having sufficient catalytic activity. Therefore, it is difficult to make both compatible with this technique.

According to the present invention, the use of the phosphorus compound having the above-mentioned specific chemical structure does not cause problems such as deterioration of thermal stability and generation of foreign matters, and the addition amount of the metal-containing component as aluminum is small. However, a polymerization catalyst having a sufficient catalytic effect is obtained, and the use of this polymerization catalyst improves the thermal stability of polyester films, hollow molded articles such as bottles, fibers and engineering plastics during melt molding. Even if a phosphoric acid ester such as phosphoric acid or trimethyl phosphoric acid is added in place of the phosphorus compound of the present invention, the effect of addition is not seen and it is not practical. Further, when the phosphorus compound of the present invention is used in combination with a conventional metal-containing polyester polymerization catalyst such as an antimony compound, a titanium compound, a tin compound and a germanium compound within the addition amount range of the present invention, the melt polymerization reaction is promoted. No effect is observed.

As the aluminum or aluminum compound constituting 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 tartrate, aluminum citrate and aluminum salicylate, inorganics such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, polyaluminum chloride, aluminum nitrate, aluminum sulfate, aluminum carbonate, aluminum phosphate, aluminum phosphonate Acid salts, aluminum methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum iso-propoxide, aluminum n-butoxide, aluminum t-butoxide and other aluminum alkoxides, aluminum acetylacetonate, aluminum acetylacetate,
Aluminum chelate compounds such as aluminum ethyl acetoacetate and aluminum ethyl acetoacetate diiso-propoxide, organoaluminum compounds such as trimethylaluminum and triethylaluminum, or their partial hydrolysates, alkoxides of aluminum and aluminum chelate compounds and hydroxycarboxylic acids Examples thereof include reaction products, aluminum oxide, ultrafine aluminum oxide, aluminum silicate, and complex oxides of aluminum with titanium, silicon, zirconium, alkali metals, alkaline earth metals, or the like. Of these, carboxylates, inorganic acid salts and chelate compounds are preferable, and among these, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferable. The basic aluminum acetate may be stabilized with an additive such as boric acid.

The amount of the aluminum or aluminum compound used in the present invention is 0.001 to 0.05 mol relative to the total number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the obtained polyester. % Is preferable, and 0.005-0.0 is more preferable.
It is 2 mol%. When the amount used is less than 0.001 mol%, the catalytic activity may not be sufficiently exhibited, and when the amount used exceeds 0.05 mol%, thermal stability and thermal oxidation stability are deteriorated and aluminum is caused. Occurrence of foreign matter and increase in coloring sometimes become a problem. As described above, the polymerization catalyst of the present invention has a great feature in that it exhibits sufficient catalytic activity even if the addition amount of the aluminum component is small. As a result, the thermal stability and the thermal oxidation stability are excellent, and the foreign substances and coloring caused by aluminum are reduced.

In the polyester polymerization catalyst of the present invention, the activity parameter (AP) satisfies the following formula (1), and polyethylene terephthalate (PET) polymerized using this polyester polymerization catalyst has a thermal stability parameter (TS).
Is the thermal oxidation stability parameter (TO
It is desirable that S) satisfy the following formula (3) and the hydrolysis resistance parameter (HS) satisfy the following formula (4).

(1) AP (min) <2T (min) (In the above equation, the activity parameter AP is the intrinsic viscosity (IV) at a pressure reduction degree of 275 ° C. and 13.3 Pa (0.1 Torr) using a predetermined amount of catalyst. Represents the time (min) required to polymerize 0.65 dl / g of polyethylene terephthalate, T represents AP when antimony trioxide is used as a catalyst, where antimony trioxide is present in the produced polyethylene terephthalate. 0.05 mol% as an antimony atom is added to the acid component.) As the antimony trioxide used for comparison in the present invention, antimony trioxide having a purity of 99% or more is used. For example, Antimony (III) oxide manufactured by ALDRICH and a purity of 99.999% are used.

(2) TS <0.30 (where TS is melt-polymerized polyethylene terephthalate (PE) having an intrinsic viscosity (IV) of about 0.65 dl / g)
T) 1 g of the resin chip was placed in a glass test tube and vacuum-dried at 130 ° C. for 12 hours, and then 300 ° C. in a non-circulating nitrogen atmosphere.
It is determined by measuring the IV after maintaining the molten state at ℃ for 2 hours and using the following calculation formula. TS = 0.245 {[IV] _f2 ^-1.47- [IV] _i
^-1.47 } [IV] _i and [IV] _f2 refer to IV (dl / g) before the melting test and after the melting test, respectively. )

The non-circulating nitrogen atmosphere means a non-circulating nitrogen atmosphere. For example, a glass test tube containing a resin chip is connected to a vacuum line, and decompression and nitrogen filling are performed.
It is a state in which nitrogen is sealed and sealed so that the pressure becomes 100 Torr after repeating more than once.

(3) TOS <0.10 (In the above formula, TOS has a melt-polymerized IV of about 0.65 d.
1 / g PET resin chips were freeze-pulverized into powder of 20 mesh or less, which was vacuum dried at 130 ° C for 12 hours. 0.3g was put in a glass test tube and vacuum dried at 70 ° C for 12 hours. 230 under dry air
It is determined by measuring the IV after heating for 15 minutes at ℃ and using the following calculation formula. TOS = 0.245 {[IV] _f1 ^-1.47- [IV] _i
^-1.47 } [IV] _i and [IV] _f1 refer to IV (dl / g) before and after the heating test, respectively. )

As a method of heating under dry air with silica gel, for example, a method of attaching a drying tube containing silica gel to the upper part of a glass test tube and heating under dry air can be used.

(4) HS <0.10 (HS has an intrinsic viscosity of about 0.65 d obtained by melt polymerization.
1 / g (before the test; [IV] _i ) PET chips were freeze-pulverized into powder of 20 mesh or less and dried under vacuum at 130 ° C. for 12 hours. 1 g was put in a beaker together with 100 ml of pure water, and a closed system was prepared. Intrinsic viscosity ([IV] _f2 ) after heating to 130 ° C and stirring for 6 hours under pressure
Is a value calculated by the following formula. HS = 0.245 {[IV] _f2 ^-1.47- [IV] _i
^-1.47 })

The beaker used for measuring HS is
Use one that does not elute acid or alkali. Specifically, it is preferable to use a stainless beaker or a quartz beaker.

With this structure, thermal deterioration during melt molding is effectively suppressed without deactivating or removing the catalyst, and the thermal stability is excellent, the thermal oxidation stability is excellent, and further the hydrolysis resistance is high. A polyester polymerization catalyst which gives excellent polyesters, has excellent catalytic activity, and therefore has high polyester productivity, and polyesters polymerized using the catalysts are preferable.

AP is more preferably 1.5 T or less, further preferably 1.3 T or less,
It is particularly preferably 0T or less. TS is more preferably 0.25 or less, and particularly preferably 0.20 or less. The TOS is more preferably 0.09 or less, and particularly preferably 0.08 or less.
Further, HS is more preferably 0.09 or less,
It is particularly preferably 0.085 or less.

The AP measuring method is specifically as follows. 1) (BHET manufacturing process) Using terephthalic acid and twice its molar amount of ethylene glycol, the esterification rate is 95%.
% Bis (2-hydroxyethyl) terephthalate (B
A mixture of HET) and oligomer (hereinafter referred to as BHET mixture) is produced. 2) (Catalyst addition step) A predetermined amount of a catalyst was added to the above BHET mixture, and the mixture was stirred at 245 ° C for 10 minutes under a nitrogen atmosphere at atmospheric pressure, and then the oligomer was heated for 50 minutes to 275 ° C. The pressure of the reaction system of the mixture is gradually reduced to 0.1 Torr. 3) (Polycondensation step) 275 ° C., 13.3 Pa (0.1 T
The polycondensation reaction is performed at (orr), and the polymerization is performed until IV of polyethylene terephthalate reaches 0.65 dl / g. 4) Let AP (min) be the polymerization time required for the polycondensation step.

These are carried out using a batch type reactor.

The BHET mixture is manufactured by a known method. For example, by charging terephthalic acid and twice its molar amount of ethylene glycol into a batch type autoclave equipped with a stirrer, and carrying out an esterification reaction while distilling water out of the system at 245 ° C. under a pressure of 0.25 MPa. Manufactured.

The "predetermined amount of the catalyst" means the amount of the catalyst which is used in a variable amount according to the activity of the catalyst. The amount of the highly active catalyst is small and the amount of the less active catalyst is large. . The maximum amount of the catalyst used is 0.1 mol% as an aluminum compound based on the number of moles of terephthalic acid. If you add more than this, the remaining amount in the polyester is large,
It is no longer a practical catalyst.

The PET resin chip used for measuring the above-mentioned TS, TOS, and HS is manufactured by quenching from the molten state after the above steps 1) to 3). As the shape of the resin tip used for these measurements, for example, a cylindrical resin tip having a length of about 3 mm and a diameter of about 2 mm is used.

In 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 used as the second compound.
It is a preferred embodiment to coexist as a metal-containing component. 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. . Examples of these alkali metals and alkaline earth metals include Li, Na, K and R.
At least one selected from b, Cs, Be, Mg, Ca, Sr, and Ba is preferable, and the use of an alkali metal or a compound thereof is more preferable. When using an alkali metal or a compound thereof, it is particularly preferable to use Li, Na or K.

Examples of the alkali metal or alkaline earth metal compound include, for example, saturated aliphatic carboxylic acid salts of these metals such as formic acid, acetic acid, propionic acid, butyric acid and oxalic acid, and unsaturated fatty acids such as acrylic acid and methacrylic acid. Group carboxylic acid salts, aromatic carboxylic acid salts such as benzoic acid, halogen-containing carboxylic acid salts such as trichloroacetic acid, lactic acid, citric acid,
Hydroxycarboxylic acid salts such as salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, hydrogen phosphate, hydrogen sulfate, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid,
Inorganic acid salts such as chloric acid and bromic acid, organic sulfonic acid salts such as 1-propanesulfonic acid, 1-pentanesulfonic acid and naphthalenesulfonic acid, organic sulfates such as lauryl sulfuric acid,
Methoxy, ethoxy, n-propoxy, iso-propoxy,
Examples thereof include alkoxides such as n-butoxy and t-butoxy, chelate compounds such as acetylacetonate, oxides and hydroxides.

Of these alkali metals, alkaline earth metals or their compounds, if one having strong alkalinity such as hydroxide is used, these are difficult to dissolve in an organic solvent such as diol such as ethylene glycol or alcohol. Since it tends to occur, 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 side reactions such as hydrolysis during polymerization, and the polymerized polyester tends to be easily colored, and the hydrolysis resistance is also reduced. Tend. Therefore,
Preferable examples of the alkali metal or the compound thereof or the alkaline earth metal or the compound thereof of the present invention include a saturated aliphatic carboxylic acid salt, an unsaturated aliphatic carboxylic acid salt and an aromatic carboxylic acid of an alkali metal or an alkaline earth metal. Acid salt, halogen-containing carboxylate, hydroxycarboxylate, inorganic acid salt, organic sulfate, alkoxide,
Chelate compounds and oxides. Among these, saturated aliphatic carboxylic acid salts of alkali metals or alkaline earth metals are preferable, and acetate salts are particularly preferable, from the viewpoints of ease of handling and availability.

When an alkali metal, an alkaline earth metal or a compound thereof is added, the amount M (mol%) used is
Based on the total number of polycarboxylic acid units constituting the polyester, preferably 1 × 10 ^-6 or more and less than 0.1 mol%, more preferably 5 × 10 ^-6 ~ 0.05 mol%, more preferably It is 1 × 10 ^{−5 to} 0.03 mol%, particularly preferably 1 × 10 ^{−5 to} 0.01 mol%. Since the amount of alkali metal or alkaline earth metal added is small, the reaction rate can be increased without causing problems such as deterioration of thermal stability, generation of foreign matter, and coloring. The amount M of alkali metal, alkaline earth metal and its compound used is
If it is 0.1 mol% or more, thermal stability and hydrolysis resistance may decrease, and the occurrence of foreign matter and increase in coloring may cause problems in product processing. If M is less than 1 × 10 ⁻⁶ , the effect is not clear even if added.

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

It is known that the cobalt compound itself has a certain degree of polymerization activity, but if it is added to the extent that it exerts a sufficient catalytic effect, the thermal stability is lowered. The polyester obtained according to the present invention has good thermal stability, but by adding a cobalt compound in a small amount as described above in an addition amount such that the catalytic effect is not clear, the polyester obtained is colored. It can be erased more effectively. The cobalt compound in the present invention is for the purpose of eliminating coloring, and may be added at any stage of the polymerization or after the completion of the polymerization reaction.

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 according to the present invention can be produced by a method including conventionally known steps except that the polyester polymerization catalyst of the present invention is used as a catalyst. For example, in the case of producing PET, after the esterification of terephthalic acid and ethylene glycol, polycondensation, or after performing the transesterification reaction between an alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol, Any method of polycondensation can be used. Further, the polymerization apparatus is a batch type,
It may be a continuous type.

The catalyst of the present invention has catalytic activity not only in the polymerization reaction but also in the esterification reaction and transesterification reaction. For example, polymerization by transesterification reaction between an alkyl ester of dicarboxylic acid such as dimethyl terephthalate and a glycol such as ethylene glycol is usually performed in the presence of a transesterification catalyst such as a titanium compound or a zinc compound. Alternatively, or together with these catalysts, 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, and polyester can be produced by any method.

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 esterification reaction or transesterification reaction or immediately before the polycondensation reaction or at any stage during the polycondensation 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 slurry or solution of a solvent such as ethylene glycol. Not limited. In addition, a mixture of aluminum metal or its compound and another component, preferably the phosphorus compound of the present invention may be added in advance, or these may be added separately. Further, the aluminum metal or its compound and the other component, preferably the phosphorus compound may be added to the polymerization system at the same addition timing, or 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.

The polymerization catalyst of the present invention is an antimony compound,
Titanium compounds, germanium compounds, tin compounds, and other polymerization catalysts are allowed to coexist within the range of the addition amount such that the addition of these components does not cause a problem in the product such as the characteristics, processability and color tone of the polyester as described above. It is advantageous and preferable to use it when improving the productivity by shortening the polymerization time.

However, as an antimony compound, an antimony atom is added to a polyester obtained by polymerization.
It is preferable to add it in an amount of 50 ppm or less. More preferably, it is added in an amount of 30 ppm or less. When the amount of antimony added is more than 50 ppm, metal antimony is precipitated, and darkening and foreign matter are generated in the polyester, which is not preferable.

The titanium compound is preferably added within the range of 10 ppm or less with respect to the polymer obtained by polymerization. More preferably 5 ppm or less, even more preferably 2 ppm
It is to be added in the following amounts. Addition amount of titanium is 10pp
When it is more than m, the thermal stability of the obtained resin is remarkably reduced.

The germanium compound is preferably added in an amount of 20 ppm or less as germanium atoms in the polyester obtained by polymerization. More preferably 10pp
It is to be added in an amount of m or less. It is not preferable to add germanium in an amount of more than 20 ppm, which is disadvantageous in terms of cost.

When the polyester is polymerized using the polymerization catalyst of the present invention, one or more antimony compounds, titanium compounds, manium compounds and tin compounds can be used.

The antimony compound, titanium compound, germanium compound and tin compound used in the present invention are not particularly limited.

Specifically, as the antimony compound,
Examples thereof include antimony trioxide, antimony pentoxide, antimony acetate, antimony glycoxide, etc. Of these, antimony trioxide is preferable.

As the titanium compound, 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 oxalate titanate, titanium oxide, titanium and Composite oxides 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 orthoesters or Reaction product consisting of condensed orthoester, hydroxycarboxylic acid and phosphorus compound, orthoester of titanium or condensed orthoester and polyvalent having at least two hydroxyl groups And a reaction product of 2-hydroxycarboxylic acid and a base. Among them, titanium-silicon composite oxide, titanium-magnesium composite oxide, titanium orthoester or condensed orthoester, and hydroxycarboxylic acid. A reaction product consisting of a phosphorus compound is preferred.

Examples of the germanium compound include germanium dioxide and germanium tetrachloride. Of these, germanium dioxide is preferable. Both crystalline and amorphous germanium dioxide can be used.

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

The polyester referred to in the present invention is 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.

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 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.

As polyvalent carboxylic acids other than these dicarboxylic acids, 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 the glycol, ethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,
2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,
Aliphatic glycols 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 preferred.

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 alkyl esters, acid chlorides and acid anhydrides thereof.

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 all the acid components. 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 in which the 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, 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.

The polyester of the present invention may contain a known phosphorus compound as a copolymerization component. As the phosphorus compound, a bifunctional phosphorus compound is preferable, for example, (2-carboxyethyl) methylphosphinic acid,
(2-carboxyethyl) phenylphosphinic acid, 9,
Examples thereof include 10-dihydro-10-oxa- (2,3-carboxypropyl) -10-phosphaphenanthrene-10-oxide. By including these phosphorus compounds as a copolymerization component, it is possible to improve the flame retardancy and the like of the obtained polyester.

As a constituent of the polyester of the present invention,
In order to improve the dyeability when polyester is used as the fiber, it is a preferred embodiment to use a polycarboxylic acid having an alkali metal sulfonate as a copolymerization component.

The metal sulfonate group-containing compound used as a copolymerization monomer is not particularly limited, but 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 5-lithium sulfoisophthalic acid, 2-lithium sulfo Examples thereof include terephthalic acid, 5-potassium sulfoisophthalic acid, 2-potassium sulfoterephthalic acid, and lower alkyl ester derivatives thereof. In the present invention, the use of 5-sodium sulfoisophthalic acid or its ester-forming derivative is particularly preferred.

The copolymerization amount of the metal sulfonate group-containing compound is 0.3 to 10.0 with respect to the acidic component constituting the polyester.
Mol% is preferable, and more preferably 0.80 to 5.0 mol%. If the copolymerization amount is too small, the dyeability of the basic dye will be poor, and if it is too large, when it is made into fibers, not only the spinnability will be poor, but also sufficient strength as fibers cannot be obtained due to the thickening phenomenon. In addition, 2.0 mol% metal sulfonate-containing compound
It is also possible to impart atmospheric pressure dyeability to the obtained modified polyester fiber by the above copolymerization. In addition, it is possible to appropriately reduce the amount of the metal sulfonate group-containing compound used by selecting an appropriate dyeing monomer. The easily dyeable monomer is not particularly limited, and examples thereof include long-chain glycol compounds typified by polyethylene glycol and polytetramethylene glycol, and aliphatic dicarboxylic acids typified by adipic acid, sebacic acid, and azelaic acid.

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

The polyester of the present invention may contain organic, inorganic, and organometallic toners, optical brighteners, and the like. By containing one or more of these, the polyester It is possible to suppress coloring such as yellowishness 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 included. As the antioxidant, aromatic amine-based or phenol-based antioxidants can be used, and as the stabilizer, phosphoric acid or phosphate ester-based phosphorus-based, sulfur-based, amine-based, etc. stabilizers can be used. Can be used.

[0092]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The evaluation methods used in each example and comparative example will be described below.

(1) Intrinsic viscosity (IV) Polyester was dissolved using a 6/4 mixed solvent of phenol / 1,1,2,2-tetrachloroethane (weight ratio), and measured at a temperature of 30 ° C. did.

(2) The acid value polyester (0.1 g) was dissolved in 10 ml of benzyl alcohol by heating, and then titrated using a solution of 0.1 N NaOH in methanol / benzyl alcohol = 1/9.

(3) Differential Scanning Calorimetry (DSC) Measurement was carried out using DS Instruments 2920 manufactured by TA Instruments. Put 10.0 mg of polyester in an aluminum pan and heat it to 50 ° C.
The sample was heated to 280 ° C. at a heating rate of / min, and after reaching 280 ° C., it was held for 1 minute and then immediately quenched in liquid nitrogen. After that, the temperature is increased from room temperature to 20 ° C./min at a rate of 300.
The temperature is raised to ℃, the crystallization temperature Tc1 and the melting point T
m was calculated. After the temperature reached 300 ° C., the temperature was maintained for 2 minutes, then the temperature was lowered at 10 ° C./min, and the crystallization temperature Tc2 during cooling was determined. Tc1, Tm, and Tc2 are the temperatures of the maximum parts of the respective peaks.

(4) When the predetermined stirring torque was reached in the hue melt polymerization, nitrogen was introduced into the autoclave to return it to normal pressure and the polycondensation reaction was stopped. Then, the polymer under slight pressure was discharged into cold water in a strand form to be rapidly cooled, and then held in cold water for about 20 seconds and then cut to obtain a cylindrical resin chip 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. For color measurement, a PET resin chip with an IV of about 0.65 dl / g obtained by melt polymerization was used, and a color difference meter (MODEL TC-150 manufactured by Tokyo Denshoku Co., Ltd.) was used.
0MC-88) was used to measure L value, a value, and b value of Hunter.

(5) Thermal stability parameter (TS) The melt-polymerized IV was about 0.65 dl / g (before the melting test;
[IV] _i ) PET resin tip 1g, inner diameter about 14m
m in a glass test tube and dried in vacuum at 130 ° C. for 12 hours, then set in a vacuum line and repeated depressurization and nitrogen filling 5 times or more, and then sealed with 100 mmHg of nitrogen and sealed.
After immersing in a salt bath at 300 ° C. and maintaining the molten state for 2 hours, the sample is taken out, freeze-ground and vacuum-dried.
V (after melting test; IV) _f2 ) was measured and determined using the following calculation formula. The ceremony was previously reported (Kamiyama et al .: Japan Rubber Association Magazine No. 6
3 Vol. 8, No. 497, 1990). TS = 0.245 {[IV] _f2 ^-1.47- [IV] _i
^-1.47 }

(6) Thermal Oxidation Stability Parameter (TOS) Melt-polymerized PET resin chips having an IV of about 0.65 dl / g were freeze-milled into powder of 20 mesh or less, which was vacuum dried at 130 ° C. for 12 hours. Put 300 mg of the product into a glass test tube with an inner diameter of about 8 mm and a length of about 140 mm. 7
After vacuum drying at 0 ° C for 12 hours, attach a drying tube containing silica gel to the upper part of the test tube and dry it in air at 230 ° C.
IV was measured after being immersed in the salt bath of No. 3 and heated for 15 minutes, and was determined using the same calculation formula as the above TS. However, [IV] _i and [IV] _f1 refer to IV (dl / g) before and after the heating test, respectively. Freezer crush is a freezer mill (US Spex model 6750)
Was performed using. After putting about 2g of resin tip and dedicated impactor in the dedicated cell, set the cell in the device, fill the device with liquid nitrogen and hold for about 10 minutes, then R
Grinding was performed for 5 minutes with ATE10 (impactor moves about 20 times per second). TOS = 0.245 {[IV] _f1 ^-1.47- [IV] _i
^-1.47 }

(7) Hydrolysis resistance parameter (HS) The intrinsic viscosity obtained by melt polymerization is about 0.65 dl / g.
The PET resin chips (before the test; [IV] _i ) were freeze-pulverized in the same manner as in 6) above to obtain powder of 20 mesh or less, which was vacuum dried at 130 ° C. for 12 hours. Hydrolysis test is a mini color device (TypeMC12.EL manufactured by Texam Giken Co., Ltd.)
B). 1 g of the above powder was put in a special stainless beaker together with 100 ml of pure water, and a special stirring blade was also inserted to form a closed system and set in a mini color device.
The mixture was heated to 30 ° C. and stirred under pressure for 6 hours. The PET after the test was collected by filtration with a glass filter, vacuum-dried and then IV was measured ([IV] _f2 ) to determine the hydrolysis resistance parameter (HS) by the following formula. HS = 0.245 {[IV] _f2 ^-1.47- [IV] _i
^-1.47 }

(8) Film Formation In each Example and Comparative Example, the PET resin chip before the melting test was vacuum dried at 135 ° C. for 6 hours. Then, it was supplied to an extruder, melt-extruded into a sheet at 280 ° C., and rapidly cooled and solidified on a metal roll kept at a surface temperature of 20 ° C. to obtain a cast film having a thickness of 1400 μm.

Next, this cast film was heated to 100 ° C. by a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction by roll groups having different peripheral speeds to obtain a uniaxially oriented PET film. It was Subsequently, with a tenter, the film was stretched 4.0 times in the width direction at 120 ° C, heated with an infrared heater at 260 ° C for 0.5 seconds with the film width length fixed, and further at 200 ° C for 3 seconds at 3%. Was subjected to relaxation treatment to obtain a biaxially oriented PET film having a thickness of 100 μm.

(9) Preparation of recovered pellets The PET film obtained by the above method was cut into strips, vacuum-dried, then put into an extruder, and molten resin was extruded from a nozzle having a diameter of 5 mm at a temperature setting of 280 ° C. After that, the pellets were collected by cooling with water and cutting.

(10) Film formation by recovered pellets PET resin chips before the film-melting test and the recovered pellets were mixed in a weight ratio of 50:50, and vacuum dried at 135 ° C. for 6 hours. Then, it was supplied to an extruder, melt-extruded into a sheet at 280 ° C., and rapidly cooled and solidified on a metal roll kept at a surface temperature of 20 ° C. to obtain a cast film having a thickness of 1400 μm.

Next, this cast film was heated to 100 ° C. with a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction with roll groups having different peripheral speeds to obtain a uniaxially oriented PET film. It was Then, in the tenter,
Stretched 4.0 times in the width direction at 120 ℃, thickness 100μm
A biaxially oriented PET film of was obtained.

(11) Film heat stability The appearance of the obtained film was visually observed and ranked. ◎: No coloring ○: Slightly colored △: Colored ×: Remarkably colored

(12) Film heat aging resistance The film obtained by the method of (8) above is 10 cm long and 10 cm wide.
The test piece was cut into a 5 cm test piece, and the test piece was treated with a gear type hot air dryer at 200 ° C. for 100 hours, and the film was evaluated by the easiness of breaking when pulled in the length direction. ◯: The strength is sufficiently high and it is difficult to cut. Δ: The strength is slightly reduced and easily broken. X: The strength is reduced and easily cut.

(13) Water resistance of film The film obtained by the method of the above (8) was used in the following manner: length 8 cm, width 4
A test piece of cm was cut out, and the test piece was boiled in boiling water for 5 days. The boiled film was ranked according to the ease of cutting when pulled in the length direction. ◯: The strength is sufficiently high and it is difficult to cut. Δ: The strength is slightly reduced and easily broken. X: The strength is reduced and easily cut.

(14) ¹ H-NMR measurement The compound was dissolved in CDCl ₃ or DMSO-d6, and Vari was added at room temperature.
It was measured using an GEMINI-200.

(15) Melting point measuring compound is placed on a cover glass, and Yanaco MICRO MELTING
POINT APPARATUS was used for measurement at a heating rate of 1 ° C / min.

(16) Elemental analysis Phosphorus was analyzed by molybdenum blue colorimetry after wet decomposition of PET resin chips. For other metals, after incineration / acid dissolution, high frequency plasma emission spectrometry and atomic absorption spectrometry were performed.

(Example 1) (Synthesis example of phosphorus compound) Synthesis of sodium salt of phosphorus compound (phosphorus compound A) represented by the following formula (4)

[0112]

[Chemical 6]

Synthesis of O-Ethyl (1-naphtyl) methylphosphonate Under a nitrogen atmosphere, 8.31 g (50 mmol) of triethyl phosphite and 1-
A mixture of 8.83 g (50 mmol) of chloromethylnaphthalene at 200 ° C.
The mixture was heated at (external temperature) for about 30 minutes until the generation of gas (C ₂ H ₅ Cl) was completed. After cooling to room temperature, the colorless oily liquid NMPA was added.
10.38 g (crude yield 75%) was obtained. ¹ H-NMRCDCl ₃ , δ): 1.151 (6H, t), 3.641 (2H, d), 3.948
(4H, m), 7.381-7.579 (4H, m), 7.749-7.867 (2H, m),
8.088-8.133 (1H, d) Synthesis of Sodium [O-ethyl (1-naphtyl) methylphosphonate] (phosphorus compound A) In a mixed solution of 6.5 g (84 mmol) of 50% sodium hydroxide aqueous solution and 6.1 ml of methanol, -Ethyl (1-naphtyl) methy
6.1 ml of a methanol solution of 5 g (18 mmol) of lphosphonate was added, and the mixture was heated under reflux for 24 hours in a nitrogen atmosphere. After the reaction, while cooling the reaction mixture, concentrated hydrochloric acid 6.59 g (63 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 filtered off, and the isopropanol was distilled off under reduced pressure. The residue was washed with hot n-heptane, recrystallized from isopropanol, dried and dried with Sodium [O-ethyl (1-naphtyl) meth
3.8 g (78%) of ylphosphonate was obtained. Shape: Needle crystal Melting point: 277-281 ° C (decomposition) ¹ H-NMR (DMSO, δ): 0.961 (3H, t, J = 7Hz), 3.223 (2H, d),
3.589 (2H, m), 7.365-7.468 (4H, m, J = 7Hz), 7.651-8.
314 (3H, m)

(Polyester Polymerization Example) A mixture of bis (2-hydroxyethyl) terephthalate and oligomer prepared by a conventional method from high-purity terephthalic acid and ethylene glycol was used as a catalyst, and aluminum acetylacetonate of 2.5 g / l ethylene glycol was used as a catalyst. The solution is 0.01 as aluminum atom with respect to the acid component in polyester.
4 mol% was added, and then 0.01 mol% of the above-mentioned phosphorus compound A was added to the acid component in the polyester.
Stir for 0 minutes. Then, the temperature of the reaction system was gradually decreased while raising the temperature to 275 ° C. over 50 minutes to 0.1 mmHg, and the polycondensation reaction was further performed at the same temperature and the same pressure for 3 hours. The IV of the obtained polymer was 0.54.

Comparative Example 1 A polyester was polymerized in the same manner as in Example 1 except that the above phosphorus compound A was not used. The IV of the obtained polymer was 0.33.

As is clear from the above Examples and Comparative Examples, when the aluminum compound alone is used as a catalyst, the polymerization activity is inferior, but by using the phosphorus compound of the present invention in combination, the polymerization activity is significantly improved. I understand that

[0117]

According to the present invention, there are provided a novel polycondensation catalyst other than an antimony compound, a polyester produced using the same, and a method for producing a polyester. The polyester of the present invention is, for example, a fiber for clothing,
Textiles for interior and bedding such as curtains, carpets, and futons, fibers for industrial materials such as tire cords and ropes, various woven fabrics, various knitted fabrics, short-fiber non-woven fabrics, long-fiber non-woven fabrics, etc. Films, industrial films, optical films, magnetic tape films, photographic films, can laminating films, content film, heat shrink films, gas barrier films, white films, films such as easy-cut films, non-heat-resistant stretch bottles, Various types of hollow molded products such as heat resistant stretch bottles, direct blow bottles, gas barrier bottles, pressure resistant bottles, heat resistant pressure bottles, sheets such as A-PET and C-PET, glass fiber reinforced polyester, engineering plastics such as elastomers, etc. Response to moldings, paints, adhesives, etc. It is possible.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-8-193127 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 63/00-63/91 WPI / L (QUESTEL)

Claims (12)

(57) [Claims] 1. A polyester polymerization catalyst, which comprises at least one selected from aluminum and its compounds as a metal-containing component and at least one metal salt compound of phosphorus. 2. The polyester polymerization catalyst according to claim 1, wherein the phosphorus metal salt compound is one or more compounds selected from the group consisting of metal salts of phosphonic acid compounds. 3. The polyester polymerization catalyst according to claim 1, wherein the metal salt compound of phosphorus is a compound having an aromatic ring structure. 4. The metal portion of the metal salt compound of phosphorus is Li,
Na, K, Be, Mg, Sr, Ba, Mn, Ni, C
4. It is selected from u and Zn.
6. The polyester polymerization catalyst according to any one of 1. 5. A metal salt compound of phosphorus is represented by the following general formula (1):
The polyester polymerization catalyst according to claim 1, which is at least one selected from the compounds represented by: [Chemical 1] (In the formula (1), R ¹ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or a hydrocarbon group having 1 to 50 carbon atoms including an amino group.
R ² represents 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. R ³ is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms,
It represents a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group, an alkoxyl group or carbonyl. l is an integer greater than or equal to 1, 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, a branched structure or an aromatic ring structure. ) 6. The polyester polymerization catalyst according to claim 5, wherein the phosphorus compound represented by the general formula (1) is at least one selected from compounds represented by the following general formula (2). [Chemical 2] (In the formula (2), R ¹ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or a hydrocarbon group having 1 to 50 carbon atoms including an amino group.
R ³ is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, or 1 to 1 carbon atoms containing carbonyl.
It represents 50 hydrocarbon groups. 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 is (l + m)
Represents a valent metal cation. The hydrocarbon group may contain an alicyclic structure, a branched structure or an aromatic ring structure. ) 7. M in the general formula (2) is Li, Na,
K, Be, Mg, Sr, Ba, Mn, Ni, Cu, Zn
The polyester polymerization catalyst according to claim 6, which is selected from the group consisting of: 8. A polyester produced using the polyester polymerization catalyst according to claim 1. 9. A method for producing a polyester, which comprises using the polyester polymerization catalyst according to any one of claims 1 to 7. 10. A polyester polymerization catalyst, comprising at least one selected from the phosphorus compounds represented by the above general formula (1). 11. A polyester containing at least one selected from the phosphorus compounds represented by the general formula (1). 12. M in the general formula (1) is Li, Na,
K, Be, Mg, Sr, Ba, Mn, Ni, Cu, Zn
The polyester according to claim 11, which is selected from the group consisting of: