JP2002240133A - Hollow polyester molding and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an inexpensive hollow polyester molding excellent in safety and transparency which does not use antimony as a main catalyst, and to provide the hollow polyester molding obtained by the method. SOLUTION: In the method, the polyester polymerized by using at least one catalyst selected from the group consisting of aluminum and its compounds is molded.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an inexpensive, transparent polyester hollow molded article comprising a polyester polymerized using at least one selected from the group consisting of aluminum and its compounds as a polyester polymerization catalyst. And a polyester hollow molded article produced by the production method.

[0002]

2. Description of the Related Art Polyethylene terephthalate (hereinafter simply referred to as "PET"), polybutylene terephthalate (hereinafter simply referred to as "PBT"), polyethylene naphthalate (hereinafter simply referred to as "PEN") and the like are represented. Polyester is excellent in mechanical properties and chemical properties. Depending on the properties of each polyester, hollow molded articles such as bottles, films for packaging and magnetic tape, sheets for packaging, electric and It is used in a wide range of fields such as molding materials for electronic parts.

[0003] Among these polyesters, polyethylene terephthalate is particularly preferred because of its excellent transparency, mechanical strength, heat resistance, gas barrier property and the like.
It has been adopted as a material for containers for soft drinks such as juices and mineral water, cosmetics, medicines, detergents and the like, and its use has been remarkable.

[0004] As a method of producing a hollow molded article made of polyester, an injection molding method in which molten polyester is directly injected into a mold to form a molded article as it is, or a molten parison (a preform) is injected by injecting a molten resin into a mold. ) Is formed, and then inserted into a blow mold and air is blown therethrough, or a stretch blow molding method is generally employed. When such a polyester hollow molded article is used for an application requiring heat resistance, it is supplied to a molding machine such as an injection molding machine to form a preform for a hollow molded article as described above. After inserting the reform into a mold having a predetermined shape and performing stretch blow molding, the body of the bottle is heat-treated (heat set) to be molded into a hollow molded container, and if necessary, the plug portion of the bottle is heat-treated (plug). (Partial crystallization).

[0005] In addition, when manufacturing plastic bottles and the like, the ease of molding, high productivity, and relatively low equipment costs for molding machines and dies are required.
The so-called direct blow molding method (extrusion blow method), in which a melt-plasticized resin is extruded through a die orifice to form a cylindrical parison, which is sandwiched by a mold and air is blown into the parison, is currently used. . In the case of direct blow molding, it is necessary to prevent the parison extruded in the molten state from drawing down during blow molding in order to smoothly perform molding, and therefore, a high melt viscosity is required for the resin used. In general, vinyl chloride resins and polyolefins having a high melt viscosity are widely used in this direct blow molding technique.

However, the injection molding method, the injection blow method, or the stretch blow molding method requires a high level of technology in the production and molding of a mold, and is complicated in that it has a small object, a deep object, a large object, a handle, and the like. It has the disadvantage that it is difficult to produce shaped containers. In addition, these molding methods are suitable for containers to be mass-produced due to high equipment costs such as molds and molding equipment, but have a problem that they are not suitable for high-mix, small-quantity production. For these reasons, the extrusion blow molding method (direct blow molding method) of PET is used for molding pharmaceutical containers such as eye drops.

[0007] PET generally used for these applications
Is produced mainly using terephthalic acid and ethylene glycol as raw materials, and using a germanium compound, an antimony compound, a titanium compound and a mixture thereof as a polycondensation catalyst.

Among the above catalysts, the antimony catalyst is a catalyst which is inexpensive and has excellent catalytic activity. When used, metal antimony precipitates during polycondensation, resulting in darkening or foreign matter in the polyester, resulting in a faster crystallization rate and higher transparency of the resulting PET than when using a germanium compound or titanium compound as a catalyst. It is very difficult to obtain a hollow molded article having excellent properties, particularly a hollow molded article having excellent heat resistance and transparency.

Under these circumstances, polyesters containing no antimony or containing no antimony as a main component of the catalyst have been desired.

As a method for solving the above problems, attempts have been made to use antimony trioxide as a catalyst and to suppress the occurrence of darkening or foreign matter in PET. For example, in Japanese Patent No. 2666502, generation of black foreign matter in PET is suppressed by using a compound of antimony trioxide, bismuth, and selenium as a polycondensation catalyst.
JP-A-9-291141 describes that when antimony trioxide containing sodium and iron oxides is used as a polycondensation catalyst, the precipitation of antimony metal is suppressed. However, these polycondensation catalysts cannot ultimately achieve the purpose of reducing the content of antimony in the polyester.

As a method for solving the problems of the antimony catalyst for applications requiring transparency such as PET bottles, for example, JP-A-6-279579 discloses a method.
A method is disclosed in which the transparency is improved by defining the amount ratio of the antimony compound to the phosphorus compound. However, the hollow molded article made of the polyester obtained by this method cannot be said to have sufficient transparency.

Japanese Patent Application Laid-Open No. 10-36495 discloses a continuous process for producing polyester having excellent transparency using antimony trioxide, phosphoric acid and a sulfonic acid compound. However, the polyester obtained by such a method has a problem that heat stability is poor and the acetaldehyde content of the obtained hollow molded article is high.

[0013] A polycondensation catalyst which replaces an antimony-based catalyst such as antimony trioxide is also being studied. Titanium compounds and tin compounds represented by tetraalkoxy titanates have already been proposed. Polyesters are susceptible to thermal degradation during melt molding and have the problem that the polyester is significantly colored.

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

As another attempt to suppress the thermal degradation during melt molding of a polyester polymerized using a titanium compound as a catalyst, for example, Japanese Patent Application Laid-Open No. Hei 10-259296 discloses a method in which a polyester is polymerized using a titanium compound as a catalyst and then phosphorus-based. Methods for adding compounds are disclosed. But,
At present, it is not only technically difficult to effectively mix the additive into the polymer after polymerization, but also to increase the cost, so that it is not practically used.

It is known that aluminum compounds generally have poor catalytic activity. Among the aluminum compounds,
It has been reported that aluminum chelate compounds have higher catalytic activity as polycondensation catalysts than other aluminum compounds, but that they have sufficient catalytic activity compared to the above-mentioned antimony compounds and titanium compounds. However, there has been no known example in which a polyester obtained by polymerization using an aluminum compound as a catalyst is used for a hollow molded article, a film, or the like.

As a catalyst other than an antimony compound, which has excellent catalytic activity and provides a polyester having excellent thermal stability and thermal oxidation stability, a germanium compound has already been put to practical use, but this catalyst is very expensive. And the problem that it is difficult to control the polymerization because the catalyst concentration of the reaction system changes because it is easy to distill out of the reaction system during polymerization. Has a problem.

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

As described above, the inexpensive, transparent and heat-resistant polyester made from a polymerization catalyst containing a metal (component) other than antimony and germanium as a main metal component of the catalyst is used. A hollow molded article is desired.

[0020]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the prior art by providing a polyester hollow molded article which does not use antimony as a main catalyst, is excellent in safety, is inexpensive and has excellent transparency. Provided are a production method and a polyester hollow molded article produced by the production method.

[0021]

In order to achieve the above object, a method for producing a polyester hollow molded article according to the present invention comprises a method for preparing a polyester hollow molded article selected from the group consisting of aluminum and compounds thereof.
It is characterized in that a polymerized polyester is molded by using at least one kind as a catalyst.

The above-mentioned polyester polymerization catalyst does not contain an antimony compound or a germanium compound as a main component of the catalyst and contains aluminum as a main metal component, has excellent catalytic activity, and has a high catalytic activity. The resulting hollow molded article is inexpensive, excellent in transparency, and excellent in safety.

The activity parameter (AP) of at least one catalyst selected from the group consisting of aluminum and its compounds and the heat of polyethylene terephthalate polymerized using at least one catalyst selected from the group consisting of aluminum and its compounds as a catalyst Stability parameter (T
S), thermal oxidation stability parameter (TOS), hydrolysis resistance parameter (HS), color delta b value parameter (Δb), and solution haze value (Haze) are any of the following formulas (1) to (6). It is preferable that one or two or more are satisfied.

(1) TS <0.30 (wherein TS is a melt-polymerized polyethylene terephthalate (PE) having an intrinsic viscosity (IV) of about 0.65 dl / g)
T) 1 g of a resin chip was placed in a glass test tube, vacuum-dried at 130 ° C. for 12 hours, and then dried under a non-circulating nitrogen atmosphere.
The IV after maintaining at 2 ° C. for 2 hours in a molten state is measured and can be determined by the following formula. TS = 0.245 ｛[IV] _f2 ^-1.47 − [IV] _i
^-1.47 ｝ [IV] _i and [IV] _f2 indicate the IV (dl / g) before 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 the pressure is reduced and nitrogen is sealed.
This is a state in which nitrogen is sealed and sealed so that the pressure becomes 100 Torr after the repetition is repeated at least 100 times.

(2) AP (min) <2T (min) (wherein, the activation parameter AP is an intrinsic viscosity (IV) at 275 ° C. and a reduced pressure of 13.3 Pa (0.1 Torr) using a predetermined amount of catalyst. ) Indicates the time (min) required to polymerize 0.65 dl / g of polyethylene terephthalate, and T indicates the AP when antimony trioxide is used as a catalyst, where antimony trioxide is contained in the produced polyethylene terephthalate. 0.05 mol% is added as an antimony atom to the acid component.)

In the measurement of T, antimony trioxide having a purity of 99% or more, for example, commercially available Antimony (III) oxi
de (ALDRICH CHEMICAL, purity 99.999%) is used.

(3) TOS <0.10 (wherein TOS has a melt-polymerized IV of about 0.65 d
1 / g PET resin chip was freeze-pulverized to powder having a size of 20 mesh or less, which was vacuum-dried at 130 ° C. for 12 hours. 0.3 g was placed in a glass test tube and vacuum-dried at 70 ° C. for 12 hours. 230 under dry air
The IV after heating at 15 ° C. for 15 minutes is measured and can be determined using the following formula. TOS = 0.245 ｛[IV] _f1 ^-1.47 − [IV] _i
^-1.47 ｝ [IV] _i and [IV] _f1 indicate the IV (dl / g) before and after the heating test, respectively. )

As a method of heating under air dried 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 frozen and pulverized into powder having a size of 20 mesh or less, and dried in vacuum at 130 ° C. for 12 hours. Intrinsic viscosity ([IV] _f2 ) after stirring at 130 ° C. for 6 hours under pressure and pressure
Is a numerical value calculated by the following equation. HS = 0.245 ｛[IV] _f2 ^-1.47- [IV] _i
^-1.47 ｝)

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

(5) Δb <4.0 (in the above formula, Δb is a polyethylene terephthalate (PET) resin chip having an intrinsic viscosity of about 0.65 dl / g melt-polymerized using a predetermined catalyst, and a colorimeter is used. The value obtained by subtracting the value of b when antimony trioxide is used as a catalyst from the value of b of the hunter measured using antimony trioxide is 0 as an antimony atom with respect to the acid component in the produced polyethylene terephthalate. .05mol%
Added. The purity of antimony trioxide is 99%
The above antimony trioxide, for example, commercially available Antimony
(III) oxide (ALDRICH CHEMICAL, purity 99.99)
9%).

(6) Haze <3.0 (%) (In the above formula, Haze has an intrinsic viscosity of about 0.
65 dl / g polyethylene terephthalate (PET)
Resin chips were p-chlorophenol / 1,1,2,2
Dissolved in a 3/1 mixed solvent of tetrachloroethane (weight ratio) to give a solution of 8 g / 100 ml, and shows the value measured using a haze meter. The haze was measured using a cell having a cell length of 1 cm.
The solution is filled in a cell and measured.

[0034] With this configuration, thermal degradation during melt molding is effectively suppressed without deactivating or removing the catalyst, resulting in excellent thermal stability, excellent thermal oxidation stability, and excellent hydrolysis resistance. A polyester polymerization catalyst which gives a polyester which is excellent in color tone, and which has less defects and excellent transparency, and which has excellent catalytic activity and therefore high productivity of polyester, and a hollow formed of a polyester polymerized using the catalyst. It is preferable because a molded article can be obtained.

The AP is preferably 1.5T or less, more preferably 1.3T or less, more preferably 1.
It is particularly preferable that it is 0T or less.

Further, TS is more preferably 0.25 or less, particularly preferably 0.20 or less. TOS is more preferably 0.09 or less, still more preferably 0.08 or less.
It is as follows. HS is more preferably 0.09 or less, particularly preferably 0.085 or less. Δb
The value is more preferably 3.0 or less, still more preferably 2.5 or less. Haze is more preferably 2.0 or less, further preferably 1.0 or less.

The method of measuring AP is specifically as follows. 1) (BHET production process) Terephthalic acid and a 2-fold molar amount of ethylene glycol were used, and the esterification rate was 95%.
% Bis (2-hydroxyethyl) terephthalate (B
HET) and a mixture of oligomers (hereinafter, referred to as a BHET mixture). 2) (Catalyst addition step) A predetermined amount of a catalyst is added to the above BHET mixture, and the mixture is stirred at 245 ° C. for 10 minutes under a normal pressure under a nitrogen atmosphere, and then heated to 275 ° C. in 50 minutes. Is gradually reduced to 0.1 Torr. 3) (Polycondensation step) 275 ° C, 13.3 Pa (0.1 T
(orr) to carry out a polycondensation reaction and polymerize until the IV of polyethylene terephthalate reaches 0.65 dl / g. 4) The polymerization time required for the polycondensation step is defined as AP (min). These are performed using a batch-type reactor.

The production of the BHET mixture is performed by a known method. For example, terephthalic acid and a 2-fold molar amount of ethylene glycol are charged into a batch type autoclave equipped with a stirrer, and an esterification reaction is performed while distilling water out of the system at 245 ° C. under a pressure of 0.25 MPa. Manufactured. The “predetermined amount of catalyst” means the amount of the catalyst used in a variable amount according to the activity of the catalyst. The amount of the catalyst is small for a highly active catalyst, and is large for a less active catalyst. The amount of the catalyst used is at most 0.1 mol% as an aluminum compound based on the number of moles of terephthalic acid.
If it is added more than this, the residual amount in the polyester is large and it is not a practical catalyst.

The PET resin chip used for measuring the above-mentioned TS, TOS, HS and Haze is as described in 1) above.
After passing through the steps 3) to 3), those produced by rapid cooling from a molten state are used. As the shape of the resin chip used for these measurements, for example, a cylindrical resin chip having a length of about 3 mm and a diameter of about 2 mm is used.

As the above-mentioned resin chip for color measurement, after passing through the above-mentioned steps 1) to 3), a substantially amorphous resin chip produced by rapid cooling from a molten state is used. As a method for obtaining a substantially amorphous resin chip, for example, when taking out the polymer from the reaction system after melt polymerization, quenching with cold water immediately after discharging the polymer from the discharge port of the reaction system, then sufficient cooling It can be obtained by holding in cold water for a time and then cutting it into chips. The resin chip thus obtained is transparent in appearance without whitening due to crystallization. The resin chip thus obtained is air-dried on a filter paper or the like at room temperature for about 24 hours, and then used for color measurement. After the above-mentioned operation, the resin chip remains transparent without any whitening due to crystallization. In addition, no additive affecting the appearance such as titanium dioxide is used for the resin chip for color measurement. As the shape of the resin chip used for color measurement, for example, a cylindrical resin chip having a length of about 3 mm and a diameter of about 2 mm is used.

It is preferable that the above-mentioned catalyst 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, a small amount of at least one selected from alkali metals, alkaline earth metals and compounds thereof is coexisted as the second metal-containing component in addition to aluminum or its compound. The coexistence of such a second metal-containing component in the catalyst system increases the catalytic activity in addition to the effect of suppressing the production of diethylene glycol, and thus provides a catalyst component with a higher reaction rate, which is effective for improving productivity. .

When an alkali metal, an alkaline earth metal or a compound thereof is added, the amount of use M (mol%) is as follows:
It is preferably from 1 × 10 ^{−6 to} less than 0.1 mol%, more preferably from 5 × 10 ^{−6 to} 0.05, based on the number of moles of all the 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%. When the addition amount of the alkali metal and the alkaline earth metal is small, the heat stability is reduced, the hydrolysis resistance is reduced, the generation of foreign substances, and the problems such as coloring do not occur.
This is preferable because the reaction rate can be increased. When the use amount M of the alkali metal, alkaline earth metal and its compound is 0.1 mol% or more, a decrease in thermal stability, a decrease in hydrolysis resistance, an increase in foreign matter generation and an increase in coloring may cause problems in product processing. Occurs. If M is less than 1 × 10 ⁻⁶ mol%, the effect is not clear even if added.

The above-mentioned catalyst is preferably a mixture of an aluminum compound and a phosphorus compound or a phenol compound, particularly a phosphorus compound having a phenol moiety in the same molecule.

The phenolic compound constituting the polycondensation catalyst of the present invention is not particularly limited as long as it is a compound having a phenol structure. For example, 2,6-di-tert-butyl-4-methylphenol, 2 , 6-Di-tert-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-
tert-amyl-4-methylphenol, 2,6-di-tert-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-
n-octylphenol, 2-isopropyl-4-methyl-6-te
rt-butylphenol, 2-tert-butyl-2-ethyl-6-tert
-Octylphenol, 2-isobutyl-4-ethyl-6-tert-
Hexylphenol, 2-cyclohexyl-4-n-butyl-6-
Isopropylphenol, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, triethylene glycol-bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thiodiethylenebis [3-
(3,5-di-tert-butyl-4,4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-tert
-Butyl-4-hydroxy-hydrocinnamide), 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5- Di-tert-
Butyl-4-hydroxybenzyl) isocyanurate, 1,
3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate,
Tris (4-tert-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, tetrakis [methylene (3,5-
Di-tert-butyl-4-hydroxy) hydrocinnamate]
Methane, bis [(3,3-bis (3-tert-butyl-4-hydroxyphenyl) butyric acid) glycol ester, N, N'-bis [3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionyl] hydrazine, 2,2'-oxazamide bis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-
Methyl-6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 1,3,5-trimethyl
-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,9-bis [1,1-dimethyl2- {β- (3-t
ert-butyl-4-hydroxy-5-methylphenyl) propionyloxydiethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2-bis [4- (2- (3 , 5-di-tert-
Butyl-4-hydroxycinnamoyloxy)) ethoxyphenyl] propane, β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid alkyl ester, tetrakis- [methyl-3- (3 ′, 5 '-Di-tert-butyl-4-hydroxyphenyl) propionate] methane, octadecyl-3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-
Butylphenyl) butane, thiodiethylene-bis [3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate], ethylenebis (oxyethylene) bis [3- (5-tert-
Butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol-bis-[-3- (3 ′ -tert-butyl-4-hydroxy-5-methylphenyl)] propionate, 1,1,3-tris [2-methyl-4- [3- (3,
5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -5-tert-butylphenyl] butane. These can be used in combination of two or more at the same time. Of these, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis- [methyl-3- (3 ′, 5 ′) -Di-tert-butyl
4-Hydroxyphenyl) propionate] methane and thiodiethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] are preferred.

The addition of these phenolic compounds during the polymerization of the polyester improves the catalytic activity of the aluminum compound and also improves the thermal stability of the polymerized polyester.

The amount of the phenolic compound of the present invention to be used is 5 × 10 ^{−7 to} 0.01 mol per mol of all the constituent units of the carboxylic acid component such as dicarboxylic acid and polycarboxylic acid of the obtained polyester. Preferably, it is more preferably 1 × 10 ^{−6 to} 0.005 mol.

In the present invention, a phosphorus compound may be used together with the phenolic compound. The phosphorus compound constituting the polycondensation catalyst of the present invention is not particularly limited,
The use of one or more compounds selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds, and phosphine compounds improves the catalytic activity. The effect is large and preferable. Among these, the use of one or two or more phosphonic acid compounds is particularly preferable because the effect of improving the catalytic activity is particularly large.

The phosphonic acid-based compound, phosphinic acid-based compound, phosphine oxide-based compound, phosphonous acid-based compound, phosphinous acid-based compound and phosphine-based compound referred to in the present invention are represented by the following formulas (1) to (6), respectively. Means a compound having a structure represented by

[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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The phosphonic acid compounds of the present invention include, for example, dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate and the like. Can be Examples of the phosphinic acid compound of the present invention include diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate,
Phenylphosphinic acid, methyl phenylphosphinate,
And phenyl phenylphosphinate. As the phosphine oxide compound of the present invention, for example,
Examples include diphenylphosphine oxide, methyldiphenylphosphine oxide, and triphenylphosphine oxide.

Among the phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds and phosphine compounds, the phosphorus compounds of the present invention are represented by the following formulas (7) to (12). It is preferred to use the compounds represented.

[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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

As the phosphorus compound constituting the polycondensation catalyst of the present invention, the compounds represented by the following general formulas (13) to (15) are particularly preferable because the effect of improving the catalytic activity is large.

[0065]

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[0066]

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[0067]

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(Wherein R ¹ , R ⁴ , R ⁵ , and R ⁶ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a halogen group, an alkoxyl group or an amino group, and Represents a hydrocarbon group of 50. R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrogen group may include an alicyclic structure such as cyclohexyl and an aromatic ring structure such as phenyl and naphthyl.)

The phosphorus compounds constituting the polycondensation catalyst of the present invention include, in the above formulas (1) to (3), R ¹ , R ⁴ , R ⁵ ,
Compounds in which R ⁶ is a group having an aromatic ring structure are particularly preferred.

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

The amount of the phosphorus compound of the present invention to be used is based on the number of moles of all the constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the obtained polyester.
5 × 10 ^{−7 to} 0.01 mol is preferable, and 1 × 10 ⁻⁶ is more preferable.
~ 0.005 mol.

The phosphorus compound having a phenol moiety in the same molecule constituting the polycondensation catalyst of the present invention is not particularly limited as long as it is a phosphorus compound having a phenol structure. The use of one or more compounds selected from the group consisting of acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds, and phosphine compounds improves the catalytic activity. Is preferred. Among these, the use of a phosphonic acid-based compound having one or more phenol moieties in the same molecule is particularly preferred because the effect of improving the catalytic activity is particularly large. As the phosphorus compound having a phenol moiety in the same molecule constituting the polycondensation catalyst of the present invention, it is preferable to use a compound represented by the following general formulas (16) to (18) since the catalytic activity is particularly improved. .

[0073]

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[0074]

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[0075]

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(Wherein R ¹ has 1 carbon atom including a phenol moiety)
And represents a hydrocarbon group having 1 to 50 carbon atoms including a substituent such as a hydrocarbon group, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and a phenol moiety. R ⁴ , R
⁵ and R ⁶ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a halogen group, or a hydrocarbon group having 1 to 50 carbon atoms including a substituent such as an alkoxyl group or an amino group. R ² and R ³ are each independently hydrogen and carbon number 1 to
Represents a hydrocarbon group having 1 to 50 carbon atoms including a substituent such as a 50 hydrocarbon group, a hydroxyl group or an alkoxyl group. However, the hydrocarbon group may include a branched structure, an alicyclic structure such as cyclohexyl, or an aromatic ring structure such as phenyl or naphthyl. The terminals of R ² and R ⁴ may be bonded to each other. )

Examples of the phosphorus compound of the present invention having a phenol moiety in the same molecule include p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate, and p-hydroxyphenylphosphonate.
Diphenyl hydroxyphenylphosphonate, bis (p
-Hydroxyphenyl) phosphinic acid, bis (p-hydroxyphenyl) phosphinic acid methyl, bis (p-hydroxyphenyl) phosphinic acid phenyl, p-hydroxyphenylphenylphosphinic acid, p-hydroxyphenylphenylphosphinic acid methyl, 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 (19) to (22)
And the like. Of these,
The compound represented by the following formula (21) and dimethyl p-hydroxyphenylphosphonate are particularly preferred.

[0078]

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[0079]

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[0080]

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[0081]

Embedded image As the compound represented by the above formula (21), SANKO-
220 (manufactured by Sanko Co., Ltd.) is available.

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

The amount of the phosphorus compound having a phenol moiety in the same molecule of the present invention may be 5 × with respect to the number of moles of all the constituent units of the carboxylic acid component such as dicarboxylic acid and polycarboxylic acid of the obtained polyester. It is preferably from 10 ^{-7 to} 0.01 mol, more preferably from 1 × 10 ^{-6 to} 0.005 mol.

In the present invention, it is preferable to use a metal salt compound of phosphorus as the phosphorus compound. The metal salt compound of phosphorus, which is a preferred phosphorus compound constituting the polymerization catalyst of the present invention, 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 compound improves the catalytic activity. Is preferred. Examples of the metal salt of a phosphorus compound include a monometal salt, a dimetal salt, and a trimetal salt.

In 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 preferred.

As the phosphorus metal salt compound constituting the polymerization catalyst of the present invention, it is preferable to use at least one selected from compounds represented by the following general formula (23) because the effect of improving the catalytic activity is large.

[0087]

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(Wherein R ¹ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a hydrocarbon group having 1 to 50 carbon atoms including a halogen group, an alkoxyl group or an amino group. R ² represents Represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group, and R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. Or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl, l is an integer of 1 or more, m is 0 or an integer of 1 or more, l + m is 4 or less, and M is (l + m) Represents a valent metal cation, n represents an integer of 1 or more, and the hydrocarbon group may include an alicyclic structure such as cycloalkylhexyl, a branched structure, or an aromatic ring structure such as phenyl or naphthyl.

As the above R ¹ , for example, phenyl,
Examples include 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like. R above
^{As 2} , for example, hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, phenyl, naphthyl, substituted Phenyl and naphthyl groups,
And a group represented by —CH ₂ CH ₂ OH. R ³
Examples of O ^- include a hydroxide ion, an alcoholate ion, an acetate ion and an acetylacetone ion.

Among the compounds represented by the general formula (23), it is preferable to use at least one selected from the compounds represented by the following general formula (24).

[0091]

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(Wherein, R ¹ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a halogen group, or a hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl group or an amino group. R ³ represents Represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a carbonyl, l is an integer of 1 or more, and m is
Represents an integer of 0 or 1 or more, and l + m is 4 or less. M is
represents a (l + m) -valent metal cation. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. As the above R ¹ , for example, phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl,
2-biphenyl and the like. Examples of R ³ O ⁻ include a hydroxide ion, an alcoholate ion, an acetate ion and an acetylacetone ion. Among the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the effect of improving the catalytic activity is large.

In the above formula (24), M is Li, N
a, K, Be, Mg, Sr, Ba, Mn, Ni, Cu,
It is preferable to use a material selected from Zn because the effect of improving the catalytic activity is large. Of these, Li, Na, and Mg are particularly preferred.

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

The metal salt compound of phosphorus, which is another preferred phosphorus compound constituting the polymerization catalyst of the present invention, is at least one selected from compounds represented by the following general formula (25).

[0096]

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(Wherein, R ¹ and R ² each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. Represents a hydrocarbon group having 1 to 50 carbon atoms including the group.
⁴ is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a carbon atom having 1 to 5 carbon atoms including carbonyl.
Represents a hydrocarbon group of 0. Examples of R ⁴ O ⁻ include a hydroxide ion, an alcoholate ion, an acetate ion and an acetylacetone ion. l is an integer of 1 or more, m is 0 or an integer of 1 or more, and l + m is 4 or less. M represents a (l + m) -valent metal cation. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Among these, it is preferable to use at least one selected from compounds represented by the following general formula (26).

[0099]

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

In the above formula (25) or (26),
M is Li, Na, K, Be, Mg, Sr, Ba, M
It is preferable to use one selected from n, Ni, Cu, and Zn because the effect of improving the catalytic activity is large. Of these, L
i, Na and Mg are particularly preferred.

The specific phosphorus metal salt compounds of the present invention include lithium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-t-t
ethyl ert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], potassium [3,5-di-tert-butyl]
-Butyl-4-hydroxybenzylphosphonate], magnesium bis [3,5-di-tert-butyl-4-]
Ethyl hydroxybenzylphosphonate], magnesium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], beryllium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate methyl], Strontium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], barium bis [3,5-
Phenyl di-tert-butyl-4-hydroxybenzylphosphonate], manganese bis [3,5-di-tert-butyl-4
-Ethyl ethyl hydroxybenzylphosphonate], nickel bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], copper bis [3,5-di-tert-butyl-4]
-Ethyl ethyl hydroxybenzylphosphonate] and zinc bis [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate]. Among them, lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [ Ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate] is particularly preferred.

Another embodiment of the present invention is a polyester polymerization catalyst comprising at least one selected from aluminum salts of phosphorus compounds. An aluminum salt of a phosphorus compound may be used in combination with another aluminum compound, a phosphorus compound, a phenol compound or the like.

The aluminum salt of a phosphorus compound which is a preferable component constituting the polymerization catalyst of the present invention is not particularly limited as long as it is a phosphorus compound having an aluminum portion.
It is preferable to use an aluminum salt of a phosphonic acid compound because the effect of improving the catalytic activity is large. Examples of the aluminum salt of the phosphorus compound include a monoaluminum salt, a dialluminum salt, and a trialuminum salt.

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

As the aluminum salt of the phosphorus compound constituting the polymerization catalyst of the present invention, it is preferable to use at least one selected from the compounds represented by the following general formula (27) because the effect of improving the catalytic activity is large.

[0107]

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(Wherein, 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,
Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl. l represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and l + m is 3. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

As the above R ¹ , for example, phenyl,
Examples include 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like. R above
^{As 2} , for example, hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, phenyl, naphthyl, substituted Phenyl and naphthyl groups,
And a group represented by —CH ₂ CH ₂ OH. Examples of R ³ O ⁻ include a hydroxide ion, an alcoholate ion, an ethylene glycolate ion, an acetate ion and an acetylacetone ion.

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

In another embodiment of the present invention, the following general formula (2)
It is a polyester polymerization catalyst comprising at least one selected from aluminum salts of phosphorus compounds represented by 8). The aluminum salt of the phosphorus compound may be used in combination with another aluminum compound, a phosphorus compound, a phenol compound, or the like.

Another preferred aluminum salt of a phosphorus compound constituting the polymerization catalyst of the present invention is represented by the following general formula (28)
Means at least one selected from the compounds represented by

[0113]

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(Wherein R ¹ and R ² each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. Represents a hydrocarbon group having 1 to 50 carbon atoms including the group.
⁴ is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a carbon atom having 1 to 5 carbon atoms including carbonyl.
Represents a hydrocarbon group of 0. l represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and l + m is 3. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Among them, it is preferable to use at least one selected from compounds represented by the following general formula (29).

[0116]

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(In the formula (29), R ³ is hydrogen, carbon number 1)
Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrocarbon group of 50 to 50, a hydroxyl group or an alkoxyl group. R ⁴ is hydrogen,
It represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group or carbonyl. l represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and l + m is 3. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Examples of R ³ include hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, phenyl, Examples include a naphthyl group, a substituted phenyl group and a naphthyl group, and a group represented by —CH ₂ CH ₂ OH. Examples of R ⁴ O ⁻ include a hydroxide ion, an alcoholate ion, an ethylene glycolate ion, an acetate ion and an acetylacetone ion.

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

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

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

As the phosphorus compound having at least one P-OH bond constituting the polymerization catalyst of the present invention, when at least one selected from compounds represented by the following general formula (30) is used, the effect of improving the catalytic activity is obtained. Is preferred.

[0123]

Embedded image (In the formula (30), .R ² R ¹ is representing hydrogen, a hydrocarbon group having 1 to 50 carbon atoms containing a hydrocarbon group, a hydroxyl group or a halogen group, an alkoxyl group, or an amino group having 1 to 50 carbon atoms, Represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, n represents an integer of 1 or more, and the hydrocarbon group has an alicyclic structure such as cycloalkylhexyl or the like. It may contain a branched structure or an aromatic ring structure such as phenyl or naphthyl.)

As the above R ¹ , for example, phenyl,
Examples include 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like. R above
^{As 2} , for example, hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, phenyl, naphthyl, substituted Phenyl and naphthyl groups,
And a group represented by —CH ₂ CH ₂ OH. Among the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the effect of improving the catalytic activity is large.

The phosphorus compounds having at least one P-OH bond according to 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. Of these, (1
-Naphthyl) ethyl methylphosphonate and ethyl benzylphosphonate are particularly preferred.

The preferred phosphorus compound used in the present invention is a specific phosphorus compound having at least one P-OH bond. The specific phosphorus compound having at least one P-OH bond, which is a preferred phosphorus compound constituting the polymerization catalyst of the present invention, is at least one compound selected from the compounds represented by the following general formula (31). Say

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((In the formula (31), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.
³ represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Among them, it is preferable to use at least one selected from compounds represented by the following general formula (32).

[0129]

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(In the formula (32), R ³ is hydrogen, carbon number 1
Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrocarbon group of 50 to 50, a hydroxyl group or an alkoxyl group. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

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

Specific phosphorus compounds having at least one P-OH bond according to the present invention include ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and 3,5-di-tert-butyl-ethyl. Methyl 4-hydroxybenzylphosphonate, isopropyl 3,5-di-tert-butyl-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. Of these, ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.

A preferred phosphorus compound is represented by the following formula (3)
And the phosphorus compound represented by 3).

Embedded image (In the formula (33), R ¹ represents a hydrocarbon group having ¹ to 49 carbon atoms, and R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a carbon atom containing an alkoxyl group. Number 1
Represents up to 50 hydrocarbon groups. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure. )

More preferably, at least one of R ¹ , R ² and R ^{3 in} the chemical formula (33) is a compound containing an aromatic ring structure.

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

[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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Further, the phosphorus compound used in the present invention having a large molecular weight has a large effect and is preferable since it is difficult to be distilled off during polymerization.

Another phosphorus compound for which it is desirable to use the polycondensation catalyst of the present invention is at least one phosphorus compound selected from the compounds represented by the following formula (40).

[0144]

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(In the above formula (40), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.
R ³ and R ⁴ are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, 1 to 1 carbon atoms including a hydroxyl group or an alkoxyl group.
Represents 50 hydrocarbon groups. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Among the above general formulas (40), it is preferable to use at least one selected from the compounds represented by the following general formula (41) because the effect of improving the catalytic activity is high.

[0147]

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(In the above formula (41), R ³ and R ⁴ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. 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.)

The above R ³ and R ⁴ are, for example, short-chain aliphatic groups such as hydrogen, methyl group and butyl group, long-chain aliphatic groups such as octadecyl, phenyl group, naphthyl group and substituted phenyl group. aromatic groups such as groups or naphthyl group, -CH ₂ CH ₂
And a group represented by OH.

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

Another phosphorus compound for which it is desirable to use the polycondensation catalyst of the present invention is at least one phosphorus compound selected from the compounds represented by the chemical formulas (42) and (43).

[0152]

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[0153]

Embedded image Compounds represented by the above chemical formula (42) include I
rganox1222 (manufactured by Ciba Specialty Chemicals) is commercially available, and as the compound represented by the chemical formula (43), Irganox1425 (manufactured by Ciba Specialty Chemicals) is commercially available and can be used.

Although phosphorus compounds are generally well known as antioxidants, even when these phosphorus compounds are used in combination with a conventional metal-containing polyester polymerization catalyst,
It is not known to greatly promote melt polymerization. In fact, when a polyester compound is melt-polymerized using a typical catalyst for polyester polymerization such as an antimony compound, a titanium compound, a tin compound or a germanium compound as a polymerization catalyst, even if a phosphorus compound is added, a substantially useful level is obtained. No accelerated polymerization is observed.

The amount of the phosphorus compound of the present invention to be used is preferably 0.0001 to 0.1 mol%, more preferably 0.005 to 0.1 mol%, based on the total number of moles of all constituent units of the polycarboxylic acid component of the obtained polyester. More preferably, it is 05 mol%.

When the phosphorus compound of the present invention is used 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. When the amount of the phosphorus compound is less than 0.0001 mol%, the effect of addition may not be exhibited, and when the amount exceeds 0.1 mol%, the catalytic activity as a polyester polymerization catalyst may be reduced. , The trend of decline is
It changes depending on the amount of aluminum used.

According to the present invention, the use of the phosphorus compound of the present invention does not cause problems such as a decrease in thermal stability and thermal oxidative stability and the generation of foreign matter, and the amount of the first metal-containing component as aluminum. A polyester polymerization catalyst having a sufficient catalytic effect can be obtained even in a small amount, and the use of this polyester polymerization catalyst improves the heat stability, heat aging resistance, and generation of foreign matter during melt molding of a polyester hollow molded article. . 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, even when the phosphorus compound of the present invention is used in combination with a conventional antimony compound, a titanium compound, a tin compound, and a metal-containing polyester polymerization catalyst such as a germanium compound in the range of the addition amount of the present invention, the effect of promoting melt polymerization is obtained. It is not allowed.

[0158]

BEST MODE FOR CARRYING OUT THE INVENTION As the aluminum or aluminum compound constituting the polycondensation catalyst used in producing the polyester used in the present invention, known aluminum compounds can be used without limitation in addition to metallic aluminum.

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. Carboxylate such as aluminum lactate, aluminum citrate, aluminum salicylate, inorganic acid salt such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate, aluminum phosphonate, aluminum methoxide, aluminum ethoxy Side, aluminum n-propoxide, aluminum iso-propoxide, aluminum n-butoxide, aluminum t -Aluminum alkoxide such as butoxide, aluminum acetylacetonate,
Examples thereof include aluminum chelate compounds such as aluminum acetylacetate, aluminum ethyl acetoacetate, and aluminum ethyl acetoacetate diiso-propoxide; organic aluminum compounds such as trimethylaluminum and triethylaluminum; partial hydrolysates thereof; and aluminum oxide. Of these, carboxylate, inorganic acid salt and chelate compound are preferred, and among these, aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred.

The amount of the aluminum compound to be used is preferably 0.001 to 0.05 mol% with respect to the total number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid and polycarboxylic acid of the obtained polyester. Preferably it is 0.005 to 0.02 mol%. When the addition amount of the aluminum compound is small, the generation of foreign matter is suppressed,
It is preferable because polyesters having excellent thermal stability and thermal oxidation stability can be produced.

In the present invention, the alkali metal and alkaline earth metal constituting the second metal-containing component which is preferably used in addition to aluminum or its compound include Li, Na, K, Rb, Cs, Be, Mg, Ca,
It is preferably at least one selected from Sr and Ba, and more preferably an alkali metal or a compound thereof. When an alkali metal or a compound thereof is used, it is particularly preferable to use Li, Na, and K. Examples of the alkali metal or alkaline earth metal compound include, for example, saturated aliphatic carboxylate such as formic acid, acetic acid, propionic acid, butyric acid, and oxalic acid, and unsaturated aliphatic carboxylate such as acrylic acid and methacrylic acid. Aromatic carboxylate such as benzoic acid, halogen-containing carboxylate such as trichloroacetic acid, hydroxycarboxylate such as lactic acid, citric acid, salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, phosphorus Inorganic acid salts such as oxyhydrogen, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, and bromic acid; and organic sulfonic acid salts such as 1-propanesulfonic acid, 1-pentanesulfonic acid, and naphthalenesulfonic acid , Organic sulfates such as lauryl sulfate, methoxy, ethoxy, n
-Propoxy, iso-propoxy, n-butoxy, t
alkoxides such as tert-butoxy, chelate compounds with acetylacetonate and the like, hydrides, oxides,
Hydroxide and the like.

When strong alkalis such as hydroxides among these alkali metals, alkaline earth metals or compounds thereof are used, they are less likely to be dissolved in organic solvents such as diols such as ethylene glycol or alcohols. Therefore, an aqueous solution must be added to the polymerization system, which may cause a problem in the polymerization step. Furthermore, when a strong alkali such as a hydroxide is used, the polyester is liable to undergo side reactions such as hydrolysis during polymerization, and the polymerized polyester tends to be colored, and the hydrolysis resistance is also reduced. Tend to. Accordingly, the alkali metal or a compound thereof or an alkaline earth metal or a compound thereof suitable for the present invention is preferably a saturated aliphatic carboxylate, an unsaturated aliphatic carboxylate, or an aromatic salt of an alkali metal or an alkaline earth metal. Group carboxylate, halogen-containing carboxylate, hydroxycarboxylate, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid,
It is an inorganic acid salt selected from chloric acid and bromic acid, an organic sulfonate, an organic sulfate, a chelate compound, and an oxide. Among these, from the viewpoints of ease of handling and availability, it is preferable to use an alkali metal or alkaline earth metal saturated aliphatic carboxylate, particularly an acetate.

It is preferable to further add a cobalt compound to the polyester used in the present invention. In a preferred embodiment, the cobalt compound is added in an amount of less than 10 ppm as a cobalt atom to the polyester. Preferably the amount is less than 5 ppm, more preferably the amount is 3 ppm or less.

It is known that the cobalt compound itself has a certain degree of polymerization activity, but when added to such an extent that a sufficient catalytic effect is exhibited, the thermal stability is reduced. It is preferable to add the cobalt compound in such a small amount as described above in such an amount that the catalytic effect of the addition is not clear, since the coloring obtained can be more effectively improved while improving the thermal stability of the obtained polyester. When the cobalt compound in the present invention is added for the purpose of improving coloring, the timing of addition may be at any stage of polymerization,
Further, it may be at any stage from the end of the polymerization reaction to the time of molding.

The polyester used in the present invention can be produced by a conventionally known production method. That is,
In the case of PET, terephthalic acid and ethylene glycol
Esterification by direct reaction of water and other copolymerization components to remove water and esterification, followed by polycondensation under reduced pressure, or dimethyl terephthalate and ethylene glycol and other After the methyl alcohol is distilled off and the ester exchange is carried out by reacting the copolymer components of the above, the ester is produced by a transesterification method in which polycondensation is carried out under reduced pressure. If necessary, solid-state polymerization may be performed in order to increase the intrinsic viscosity and reduce the acetaldehyde content and the like.
In order to promote crystallization before solid-phase polymerization, the melt-polymerized polyester may be heated and then crystallized after moisture absorption, or steam may be directly blown onto the polyester chip for heat crystallization.

The above-mentioned melt polycondensation reaction may be performed in a batch reactor or a continuous reactor.
In any of these methods, the esterification reaction or transesterification reaction may be performed in one stage, or may be performed in multiple stages. The melt polycondensation reaction may be performed in one stage or may be performed in multiple stages.
The solid-state polymerization reaction can be performed in a batch-type apparatus or a continuous-type apparatus as in the melt polycondensation reaction. The melt polycondensation and the solid phase polymerization may be performed continuously or may be performed separately.

Hereinafter, an example of a preferable production method in a continuous system will be described using polyethylene terephthalate as an example. First, a case where a low polymer is produced by an esterification reaction will be described. A slurry containing ethylene glycol in an amount of 1.02 to 1.5, preferably 1.03 to 1.4 mol per 1 mol of terephthalic acid or its ester derivative is prepared and subjected to an esterification reaction. Feed continuously to the process.

In the esterification reaction, water or alcohol produced by the reaction is purified under a condition in which ethylene glycol is refluxed using a multistage apparatus in which 1 to 3 esterification reactors are connected in series. It is carried out while removing outside the system in a distillation tower. The temperature of the first-stage esterification reaction is 240 to 270.
° C, preferably 245 to 265 ° C, pressure 0.2 to 3k
g / cm ² G, preferably 0.5 to ² kg / cm ² G. The temperature of the final esterification reaction is usually from 250 to 2
90 ° C., preferably 255-275 ° C., and pressure is usually 0-1.5 kg / cm ² G, preferably 0-1.3 kg.
/ Cm ² G. When the reaction is carried out in three or more stages, the reaction conditions for the intermediate stage esterification reaction are those between the above-mentioned first-stage reaction conditions and final-stage reaction conditions. The increase in the conversion of these esterification reactions is preferably distributed smoothly at each stage. Finally, it is desirable that the esterification reaction rate reaches 90% or more, preferably 93% or more. A low-order condensate having a molecular weight of about 500 to 5,000 is obtained by these esterification reactions.

When terephthalic acid is used as a raw material, the above esterification reaction can be carried out without a catalyst by the catalytic action of terephthalic acid as an acid, but may be carried out in the presence of a polycondensation catalyst.

Also, tertiary amines such as triethylamine, tri-n-butylamine and benzyldimethylamine, tetraethylammonium hydroxide,
When a small amount of a quaternary ammonium hydroxide such as n-butylammonium and trimethylbenzylammonium hydroxide and a basic compound such as lithium carbonate, sodium carbonate, potassium carbonate and sodium acetate are added, the reaction of polyethylene terephthalate is reduced. It is preferable because the ratio of the dioxyethylene terephthalate component unit in the chain can be kept at a relatively low level (5 mol% or less based on all diol components).

In the case where a low polymer is produced by a transesterification reaction, 1.1 to 1.6 mol, preferably 1.2 to 1.5 mol of ethylene glycol is added to 1 mol of dimethyl terephthalate. Is prepared and continuously supplied to the transesterification step.

In the transesterification reaction, methanol produced by the reaction is passed through a rectification column under conditions in which ethylene glycol is distilled back using a device in which one or two transesterification reactors are connected in series. Perform while removing outside the system. The temperature of the first-stage transesterification reaction is 180 to 250 ° C, preferably 200 to 240 ° C. The temperature of the final transesterification reaction is usually 230 to 270 ° C., preferably 24 to 270 ° C.
0 to 265 ° C., and as a transesterification catalyst, Zn,
Fatty acid salts such as Cd, Mg, Mn, Co, Ca, and Ba;
Carbonate, Pb, Zn, Sb, Ge oxide or the like is used. By these transesterification reactions, the molecular weight is about 200 to 500.
A low degree of condensate is obtained.

Next, the obtained low-order condensate is supplied to a multi-stage liquid phase condensation polymerization step. The polycondensation reaction conditions are as follows: the reaction temperature of the first stage polycondensation is 250 to 290 ° C, preferably 260 to 280 ° C, and the pressure is 500 to 20 Torr.
r, preferably 200 to 30 Torr, and the temperature of the final polycondensation reaction is 265 to 300 ° C, preferably 275
To 295 ° C., and the pressure is 10 to 0.1 Torr, preferably 5 to 0.5 Torr. When the reaction is carried out in three or more stages, the reaction conditions for the polycondensation reaction in the intermediate stage are those between the above-mentioned first-stage reaction conditions and the last-stage reaction conditions. It is preferred that the degree of increase in the intrinsic viscosity reached in each of these polycondensation reaction steps be distributed smoothly.

Also, low-flavor beverages and mineral waters
When a low acetaldehyde content or a low cyclic trimer content is required as in a heat-resistant hollow molded article for a tar, the melt-polycondensed polyester thus obtained is subjected to solid-state polymerization.

The polyester is subjected to solid-state polymerization by a conventionally known method. First, the polyester to be subjected to solid-state polymerization is treated under an inert gas or under reduced pressure or under an atmosphere of steam or an inert gas containing steam.
It is pre-crystallized by heating at a temperature of ~ 210C for 1-5 hours. Then, under an inert gas atmosphere or under reduced pressure,
The solid state polymerization is performed at a temperature of 230 ° C. for 1 to 30 hours.

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

The polycondensation catalyst used for producing the polyester used in 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 the transesterification reaction and at any stage during the reaction, or immediately before the start of the polycondensation reaction or during the reaction. In particular, it is preferable to add aluminum or its compound immediately before the start of the polycondensation reaction.

The method for adding the polycondensation catalyst used in producing the polyester used in the present invention may be a powdery or neat addition, or a slurry or solution of a solvent such as ethylene glycol. May be added, and there is no particular limitation. Further, aluminum metal or a compound thereof and another component, preferably the phosphorus compound of the present invention, may be added as a premixed mixture or complex, or they may be added separately.
Also, aluminum metal or its compound and other components,
Preferably, the phosphorus compound may be added to the polymerization system at the same time, or each component may be added at a separate time.

The polycondensation catalyst used in the production of the polyester used in the present invention includes other polycondensation catalysts such as an antimony compound, a germanium compound and a titanium compound. Coexistence within the range of an addition amount that does not cause a problem in the product such as properties, processability, and color tone is effective in improving the productivity by shortening the polymerization time and is preferable.

However, the antimony compound can be added so that the residual amount of antimony atoms remaining in the polyester obtained by polymerization is 50 ppm or less. A more preferable residual amount is 30 ppm or less. When the residual amount of antimony is 50 ppm or more, precipitation of metallic antimony occurs, and blackening or foreign matter is generated in polyester, which is not preferable.

The germanium compound can be added so that the amount of germanium atoms remaining in the polyester obtained by polymerization becomes 30 ppm or less.
A more preferred residual amount is 20 ppm or less. It is not preferable to set the remaining amount of germanium to 30 ppm or more, because it is disadvantageous in terms of cost.

Suitable antimony compounds include, as suitable compounds, antimony trioxide, antimony pentoxide, antimony acetate, antimony glycoside, and the like. In particular, antimony trioxide is preferably used. Examples of the germanium compound include germanium dioxide and germanium tetrachloride, with germanium dioxide being particularly preferred.

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

The polyester referred to in the present invention is one or two or more selected from polyhydric carboxylic acids including dicarboxylic acids and one or more selected from ester-forming derivatives thereof and polyhydric alcohols including glycols. A compound consisting of the above, a compound consisting of hydroxycarboxylic acid and an ester-forming derivative thereof, or a compound consisting of 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, 3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic Acid, 1,
Saturated aliphatic dicarboxylic acids exemplified by 2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid and the like, and ester-forming derivatives thereof, Unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid and the like and ester-forming derivatives thereof, orthophthalic acid, isophthalic acid, terephthalic acid, diphenic acid, 1,3-naphthalenedicarboxylic acid, 1,4 -Naphthalenedicarboxylic acid,
1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,
4'-biphenyldicarboxylic acid, 4,4'-biphenylsulfonedicarboxylic acid, 4,4'-biphenyletherdicarboxylic acid, 1,2-bis (phenoxy) ethane-
Aromatic dicarboxylic acids exemplified by p, p'-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid and the like or ester-forming derivatives thereof, 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid,
Metal sulfonate group-containing aromatic dicarboxylic acids exemplified by lithium sulfoisophthalic acid, 2-lithium sulfoterephthalic acid, 5-potassium sulfoisophthalic acid, 2-potassium sulfoterephthalic acid and the like, and lower alkyl ester derivatives thereof and the like. Can be

Of the above dicarboxylic acids, the use of terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid is particularly preferred in terms of the physical properties of the resulting polyester, and other dicarboxylic acids may be used as a component if necessary. I do.

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

As the glycol, ethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 1, 5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2
-Cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol,
1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, polytrimethylene glycol,
Aliphatic glycols exemplified by polytetramethylene glycol, hydroquinone, 4,4'-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis (β-hydroxyethoxyphenyl) ) Sulfone, bis (p-hydroxyphenyl)
Ether, bis (p-hydroxyphenyl) sulfone,
Bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol C, 2,5-naphthalenediol,
Aromatic glycols exemplified by glycols obtained by adding ethylene oxide to these glycols, and the like can be given.

Among the above-mentioned glycols, ethylene glycol, 1,3-propylene glycol, 1,
It is preferable to use 4-butylene glycol and 1,4-cyclohexanedimethanol as main components. Polyhydric alcohols other than these glycols include trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, hexanetriol and the like. Examples of hydroxycarboxylic acids include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, and 4-hydroxycarboxylic acid.
Hydroxycyclohexanecarboxylic acid, or an ester-forming derivative thereof, and the like can be given.

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

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

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

The polyester used in the present invention is preferably a polyester whose main acid component is terephthalic acid or its ester-forming derivative or naphthalenedicarboxylic acid or its ester-forming derivative, and whose main glycol component is an alkylene glycol.

The polyester in which the main acid component is terephthalic acid or an ester-forming derivative thereof is a polyester containing a total of 70 mol% or more of terephthalic acid or its ester-forming derivative with respect to all the acid components. It is preferably a polyester containing more than 80 mol%, more preferably a polyester containing more than 90 mol%. Similarly, the polyester in which the main acid component is naphthalenedicarboxylic acid or an ester-forming derivative thereof is preferably a polyester containing a total of 70 mol% or more of naphthalenedicarboxylic acid or an ester-forming derivative thereof, and more preferably 80% or more. It is a polyester containing at least 90 mol%, more preferably a polyester containing at least 90 mol%.

The polyester in which the main glycol component is an alkylene glycol is preferably a polyester containing 70 mol% or more of alkylene glycol in total with respect to all glycol components, more preferably a polyester containing 80 mol% or more. 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, and 1,5-naphthalenedicarboxylic acid exemplified as the above-mentioned dicarboxylic acids. , 2,6-naphthalenedicarboxylic acid,
2,7-Naphthalenedicarboxylic acid or their ester-forming derivatives are preferred.

Examples of the alkylene glycol used in the present invention include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol and the above-mentioned glycols.
1,3-butylene glycol, 2,3-butylene glycol, 4,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol,
The use of 1,10-decamethylene glycol, 1,12-dodecanediol or the like is preferred. Two or more of these may be used simultaneously. )

A preferred example of the polyester used in the present invention is that the main repeating unit is ethylene terephthalate.
And more preferably a linear polyester containing at least 70 mol% of ethylene terephthalate units, and even more preferably a linear polyester containing at least 80 mol% of ethylene terephthalate units. Particularly preferred is a linear polyester containing at least 90 mol% of ethylene terephthalate units.

Another preferable example of the polyester used in the present invention is that the main repeating unit is ethylene-
It is a polyester composed of 2,6-naphthalate, more preferably a linear polyester containing at least 70 mol% of ethylene-2,6-naphthalate units, still more preferably ethylene-2,6-naphthalate. -8 units
A linear polyester containing 0 mol% or more, and particularly preferred is a linear polyester containing 90 mol% or more of ethylene-2,6-naphthalate units.

Other preferred examples of the polyester used in the present invention include a linear polyester containing at least 70 mol% of propylene terephthalate units, a linear polyester containing at least 70 mol% of propylene naphthalate units, 4-cyclohexane dimethylene terephthalate
Linear units containing at least 70 mol% of butylene naphthalate units, or 70 mol% of butylene terephthalate units.
It is a linear polyester containing the above.

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

The shape of the polyester chip used in the present invention may be any of a cylinder type, a square type, a spherical shape and a flat plate shape, and the average particle size is usually 1.5 to 5 m.
m, preferably in the range of 1.6 to 4.5 mm, more preferably in the range of 1.8 to 4.0 mm. For example, cylinder
In the case of a mold, the length is 1.5-4 mm and the diameter is 1.5-4 m
m is practical. In the case of spherical particles, it is practical that the maximum particle size is 1.1 to 2.0 times the average particle size and the minimum particle size is 0.7 times or more the average particle size.
Further, the weight of the chip is practically in the range of 15 to 30 mg / piece.

The polyester used in the present invention, in particular,
The intrinsic viscosity of a polyester whose main repeating unit is composed of ethylene terephthalate is 0.55 to 1.50 dL / g, preferably 0.58 to 1.30 dL / g, more preferably 0.60 to 1 dL. .
It is in the range of 00 deciliters / gram. If the intrinsic viscosity is less than 0.55 deciliter / gram, the mechanical properties of the obtained molded article and the like are poor. On the other hand, if it exceeds 1.50 deciliter / gram, the resin temperature rises during melting by a molding machine or the like, and thermal decomposition becomes severe, so that free low-molecular-weight compounds that affect fragrance retention increase, Causes problems such as coloring of yellow.

The intrinsic viscosity of the polyester used in the present invention, especially the polyester whose main repeating unit is composed of ethylene-2,6-naphthalate, is 0.40.
~ 1.00 deciliter / gram, preferably 0.42
０．９0.90 deciliter / gram, more preferably 0.45 to 0.80 deciliter / gram. If the intrinsic viscosity is less than 0.40 deciliter / gram, the obtained molded article or the like has poor mechanical properties. Also, 1.
If it exceeds 00 deciliters / gram, the resin temperature rises during melting by a molding machine or the like, and thermal decomposition becomes severe, free low-molecular-weight compounds that affect fragrance retention increase, or the molded product is colored yellow. Problems occur.

Examples of the polyester used in the present invention include other thermoplastic resins such as gas-barrier polyesters, ultraviolet-absorbing polyesters, gas-barrier polyamide resins such as xylylene group-containing polyamides, and polyethylenes which promote crystallinity. An appropriate amount of a polyolefin resin or the like can be blended.

Examples of the hollow polyester molded article of the present invention include injection molded articles such as blood collection tubes and test tubes, stretched blow molded articles such as soft drink bottles and aerosol containers, and extruded pharmaceutical containers such as eye drops. Blow-molded articles. These molded products may be a multilayer laminate containing at least one resin layer containing a gas barrier resin, an oxygen-absorbing resin, or an ultraviolet-absorbing resin.

These polyester hollow molded articles can be produced by a conventionally known molding method. For example, the method for producing a stretched polyester blow-molded article of the present invention will be specifically described.

In order to produce the polyester hollow molded article of the present invention, first, a preform which is a preformed article is produced from the polyester used in the present invention. It can be manufactured by extrusion molding or the like. The formed preform is adjusted to a temperature suitable for stretching in order to be subjected to stretching blow, and then stretch blow-molded to produce a polyester hollow molded article.

In the case of a PET hollow molded article, for example, a preform is once formed by injection molding or extrusion molding, and the biaxially stretched blow molding such as a hot parison method or a cold parison method is performed as it is or after processing a plug portion and a bottom portion. A molding method is applied. The molding temperature in this case, specifically, the temperature of each part of the cylinder and the nozzle of the molding machine is usually from 260 to
The range is 290 ° C. Stretching temperature is usually 70 to 120
C., preferably 80 to 110 ° C., and the stretching ratio may be usually 1.5 to 3.5 times in the longitudinal direction and 2 to 5 times in the circumferential direction. The obtained hollow molded article can be used as it is, but in particular, in the case of a beverage requiring heat filling such as a fruit juice beverage, oolong tea, etc., after heating and crystallizing the plug portion of the preform, as described above. And then heat-set in a blow mold to impart heat resistance. Heat fixation is usually under tension by compressed air, 100-200 ° C,
It is carried out preferably at 120 to 180 ° C. for several seconds to several hours, preferably for several seconds to several minutes.

[0210] In the heat fixing method, a single mold is used to draw a stretch blow.
There are a one-mold type method in which molding and heat setting are performed, and a two-stage blow molding method in which a hollow molded body molded larger than the final shape is heated and shrunk and re-blown.

A method for producing the extruded blow-molded blow-molded article made of polyester of the present invention will be described. Extrusion blow method (direct blow method) is a parison (or preform) molded by an extruder or injection molding machine.
However, the blow molding is completed before the softness and plasticity are lost. As the molding machine, an apparatus conventionally used for blow molding of polystyrene or polyvinyl chloride can be used as it is. In this case, the molding temperature is usually from 260 to 2
A method of forming a cylindrical parison by melt extrusion at 240 to 290 ° C. at 90 ° C., inserting this into a blow mold and blowing air by a conventional method to stretch and expand the parison into a predetermined shape. Can be adopted.

It is possible to simultaneously use a saturated fatty acid monoamide, an unsaturated fatty acid monoamide, a saturated fatty acid bisamide, an unsaturated fatty acid bisamide, and the like with the polyester used in the present invention.

Examples of the saturated fatty acid monoamide include lauric amide, palmitic amide, stearic amide, behenic amide and the like. Examples of unsaturated fatty acid monoamides include oleamide, erucamide, ricinoleamide, and the like. Examples of the saturated fatty acid bisamide include methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bisbehenic acid amide, hexamethylene bisstearic acid amide, hexamethylene bisbehenic acid Amides and the like.

Examples of the unsaturated fatty acid bisamide include ethylene bisoleic acid amide and hexamethylene bisoleic acid amide. Preferred amide compounds are saturated fatty acid bisamide, unsaturated fatty acid bisamide and the like. The compounding amount of such an amide compound is 1
The range is from 0 ppb to 1 × 10 ⁵ ppm.

Metal salt compounds of aliphatic monocarboxylic acids having 8 to 33 carbon atoms, such as naphthenic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid,
Stearic acid, behenic acid, montanic acid, melicic acid,
Lithium salts, potassium salts, magnesium salts, cobalt salts and the like of saturated and unsaturated fatty acids such as oleic acid and linoleic acid can be used together. The compounding amount of these compounds is in the range of 10 ppb to 300 ppm.

The polyester used in the present invention may contain, if necessary, a known ultraviolet absorber, a lubricant added from the outside, a lubricant internally deposited during the reaction, a release agent, a nucleating agent,
Various additives such as a stabilizer, an antioxidant, an additive having an oxygen absorbing ability or an oxygen scavenging ability, an antistatic agent, a dye and a pigment may be blended.

Also, organic, inorganic, and organometallic toners, fluorescent whitening agents, and the like can be blended. By containing one or more of these, yellowing of molded products can be achieved. Can be suppressed to a more excellent level. As the antioxidant, antioxidants such as aromatic amines and phenols can be used,
As the stabilizer, phosphorus-based stabilizers such as phosphoric acid and phosphate esters, sulfur-based stabilizers, and amine-based stabilizers can be used.

These additives can be added at any time during or after the polymerization of the polyester or at the time of molding of the polyester hollow molded article. It differs depending on the required performance of the molded article.

[0219]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The construction and effects of the present invention will be described below based on embodiments, but the present invention is not limited to these embodiments.

[Evaluation Method] 1) Intrinsic Viscosity (IV) Polyester was dissolved in a 6/4 (weight ratio) mixed solvent of phenol / 1,1,2,2-tetrachloroethane, and the solution was heated at 30 ° C. It was measured.

2) Thermal stability parameter (TS) The melt-polymerized IV was about 0.65 dl / g (before the melt test;
[IV] 1 g of PET resin chip of _i ) is about 14 m in inner diameter
m, placed in a glass test tube, vacuum-dried at 130 ° C. for 12 hours, set in a vacuum line, and repeatedly vacuumed and filled with nitrogen five times or more, sealed with 100 mmHg of nitrogen, and sealed.
After being immersed in a salt bath at 300 ° C. and maintained in a molten state for 2 hours, the sample was taken out, freeze-crushed and vacuum-dried.
V (after the melting test; IV] _f2 ) was measured and determined using the following formula. The ceremony is already reported (Kamiyama et al.
3, No. 8, p. 497, 1990). TS = 0.245 ｛[IV] _f2 ^-1.47 − [IV] _i
^-1.47 ｝.

3) Thermal Oxidation Stability Parameter (TOS) A melt-polymerized PET resin chip having an IV of about 0.65 dl / g was freeze-pulverized to a powder of 20 mesh or less, which was vacuum-dried at 130 ° C. for 12 hours. 300 mg was placed in a glass test tube having an inner diameter of about 8 mm and a length of about 140 mm.
After vacuum drying at 0 ° C. for 12 hours, a drying tube containing silica gel was placed on the upper portion of the test tube, and dried under air at 230 ° C.
IV after being immersed in a salt bath and heated for 15 minutes, was determined using the same formula as that for TS described above. Here, [IV] _i and [IV] _f1 indicate the IV (dl / g) before and after the heating test, respectively. For freezing and pulverization, use a freezer mill (Type 6750 manufactured by Spex, USA)
This was performed using After putting about 2 g of resin chip 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
Milling was performed for 5 minutes with ATE10 (impacter moves around 20 times per second). TOS = 0.245 ｛[IV] _f1 ^-1.47 − [IV] _i
^-1.47 ｝.

4) Hydrolysis resistance parameter (HS) The intrinsic viscosity obtained by melt polymerization is about 0.65 dl / g.
(Before the test; [IV] _i ) The PET resin chip was frozen and pulverized in the same manner as in 3) above to obtain a powder having a size of 20 mesh or less, which was vacuum dried at 130 ° C. for 12 hours. The hydrolysis test was performed using a mini color device (TypeMC12.EL manufactured by Texam Giken Co., Ltd.).
B). 1 g of the above-mentioned powder was put into a special stainless beaker together with 100 ml of pure water, a special stirring blade was further put therein, and a closed system was set.
The mixture was stirred for 6 hours while heating and pressurizing to 30 ° C. The PET after the test was collected by filtration with a glass filter, dried under vacuum, and then measured for IV ([IV] _f2 ), and the hydrolysis resistance parameter (HS) was determined by the following equation. HS = 0.245 ｛[IV] _f2 ^-1.47- [IV] _i
^-1.47 ｝

5) Color delta b value parameter (Δ
b) When a predetermined stirring torque was reached in the melt polymerization, nitrogen was introduced into the autoclave to return to normal pressure, and the polycondensation reaction was stopped. Thereafter, the polymer was discharged into cold water in the form of strands under slight pressure and rapidly cooled. After that, the polymer was held in cold water for about 20 seconds and then cut to obtain a cylindrical resin tip having a length of about 3 mm and a diameter of about 2 mm. The resin chip thus obtained was air-dried on a filter paper at room temperature for about 24 hours, and then used for color measurement. The color measurement was performed using a PET resin chip having an IV of about 0.65 dl / g obtained by melt polymerization using a color difference meter (MODEL TC-150 manufactured by Tokyo Denshoku Co., Ltd.).
0MC-88) was used to measure the b value of the Hunter, and b of PET polymerized using 0.05 mol% of antimony trioxide as an antimony atom with respect to the acid component of PET.
It was obtained by subtracting the value.

6) Solution Haze Value (Haze) A melt-polymerized PET resin chip having an IV of about 0.65 dl / g was mixed with a 3/1 mixed solvent of p-chlorophenol / 1,1,2,2-tetrachloroethane (weight Ratio) to give a solution of 8 g / 100 ml, and measured at room temperature using a turbidity meter NDH2000 of Nippon Denshoku Industries Co., Ltd. The measuring method is based on JIS standard JIS-K7105, and the cell length is 1 cm.
The diffuse transmission light (DF) and the total light transmission light (TT) of the solution were measured using the cell No., and the calculation formula Haze (%) = (DF
Haze (%) was determined from (/ TT) × 100.

7) Haze (% haze) A sample was cut out from the body (thickness: about 0.45 mm) of the molded article (thickness: 5 mm) and the hollow molded article of 9), 10) below). Color haze meter, model NDH
Measured at 2000 and ranked as follows: Haze of molded article ○: Haze is 10% or less △: Haze exceeds 10% and less than 15% ×: Haze is 15% or more Haze of hollow molded article ○: Haze is 2% or less △: Haze is 2% Over 5% or less ×: Haze is 5% or more

8) Molding of Stepped Molded Plate The dried polyester was used as a M-150C (D
M) A stepped flat mold (surface temperature of about 2 ° C.) cooled with water of 10 ° C. at a cylinder temperature of 290 ° C. by an injection molding machine.
(2 ° C.). The resulting stepped plate is 2,
A plate having a thickness of about 3 cm × about 5 cm square having a thickness of 3, 4, 5, 6, 7, 8, 9, 10, 11 mm is provided in a stepwise manner, and each piece weighs about 146 g. Plates having a thickness of 5 mm are used for measuring haze (haze%).

9) Molding of Hollow Molded Product The polyester was dried with a drier using dehumidified nitrogen, and was subjected to preform molding at a resin temperature of 290 ° C. and a mold temperature of 20 ° C. using an M-150C (DM) injection molding machine manufactured by each machine. -Molded. This preform was used with LB-01 manufactured by Corpoplast.
E Stretch blow molding machine, blow pressure 20kg / cm
Biaxially stretching blow at ² in 20 ° C. of the mold - molded, 2000
A cc hollow molded body (the body was circular) was obtained.

10) Molding of Heat Resistant Hollow Molded Product The polyester was dried with a dryer using dehumidified nitrogen, and the resin temperature was 290 ° C. and the mold temperature was 20 ° C. using an M-150C (DM) injection molding machine manufactured by each machine. A preform was formed. The plug portion of this preform was heated with a near-infrared heater type home-made plug portion crystallization apparatus to crystallize the plug portion. Next, this preform is used for LB manufactured by Corpoplast.
Approximately 2.3 in the machine direction using a -01E stretch blow molding machine.
Biaxial stretching blow at a magnification of about 3.8 times in the circumferential direction, followed by heat setting in a mold set at about 150 ° C. for about 6.5 seconds, and a hollow molded body having a capacity of 2000 cc (body part) Was round). The stretching temperature was controlled at 100 ° C.

11) Molding of Extruded Blow-Blow Molded Product The polyester was dried with a dryer using dehumidified nitrogen. Using a direct blow molding machine manufactured by Nippon Steel Works "Electric small hollow molding machine JEB-7 / P50 / WS60S", the temperature of each part of the cylinder and the nozzle was set to about 285 ° C, and the capacity was 100
Extrusion blow molding of the hollow molded body of ml was performed.

12) Heat resistance during molding of hollow molded article a) Preparation of pulverized and recovered product from hollow molded article Preform molded in 9), 10) above, or 1
The molded body molded in 1) was pulverized to obtain a pulverized and recovered product from which fine powder was removed. b) Molding of hollow molded article mixed with recovered product The PET resin chip obtained from the polycondensation step and the above-mentioned crushed recovered product were mixed at a weight ratio of 80:20, and were mixed with a dryer using dehumidified nitrogen for about 150. Dry at ℃, each machine M-1
A preform was molded at a resin temperature of 290 ° C. and a mold temperature of 20 ° C. using a 50C (DM) injection molding machine. This preform was pulverized again in the step a), mixed with the PET resin chip obtained from the polycondensation step at a weight ratio of 80:20, and the preform was formed in the same manner. This operation is repeated a total of five times. c) Evaluation of heat resistance Based on the retention of intrinsic viscosity and the degree of visual coloring of the preform obtained in b), the higher the intrinsic viscosity retention and the less the coloring, the better the evaluation. Divided. ：: Intrinsic viscosity retention rate is sufficiently high and coloring is slight. △: Intrinsic viscosity retention rate is slightly low and colored. ×: Intrinsic viscosity retention rate is extremely low and coloring is remarkable.

13) Thermal oxidation resistance 12) Molding was carried out in the same manner as in 12) except that drying in b) was carried out in a dry air atmosphere, and based on the retention of the intrinsic viscosity of the preform and the degree of visual coloring. The higher the intrinsic viscosity retention rate and the less the coloration, the better the evaluation,
The ranking was performed as follows. ：: Intrinsic viscosity retention rate is sufficiently high and coloring is slight. △: Intrinsic viscosity retention rate is slightly low and colored. ×: Intrinsic viscosity retention rate is extremely low and coloring is remarkable.

14) Evaluation of Coloring of Hollow Molded Article The hollow molded articles obtained in 9), 10) and 11) were visually observed. Was ranked. ：: slight coloring △: colored ×: markedly colored

15) Hot water resistance of bottle A test piece having a length of 8 cm and a width of 4 cm was cut out from the body of the hollow molded article obtained in 9), and the test piece was boiled in boiling water for 5 days. The test pieces after boiling were pulled in the length direction by a tensile tester and evaluated by the easiness of cutting. The harder the test pieces, the better, and the following ranking was performed. ：: Strength is sufficiently high and it is difficult to cut △: Strength is slightly reduced and it is slightly cut ×: Strength is reduced and it is easy to cut

16) Foreign matter in the hollow molded article A section is cut from the body of the hollow molded article obtained in 9), 10) and 11), and is enlarged and visually observed with a microscope. It was evaluated and ranked as follows. ○: Almost no foreign matter △: A little foreign matter ×: Very many foreign matters

17) Chip Density The density was measured at 30 ° C. using a density gradient tube of calcium nitrate / water mixed solution.

18) Polyester cyclic trimer content (hereinafter referred to as "CT content") A 300 mg sample was dissolved in 3 ml of a hexafluoroisopropanol / chloroform mixture (volume ratio = 2/3), and chloroform was further dissolved. Add 30 ml to dilute.
To this, 15 ml of methanol was added to precipitate a polymer, followed by filtration. The filtrate was evaporated to dryness, the volume was adjusted to 10 ml with dimethylformamide, and the cyclic trimer was quantified by high performance liquid chromatography.

19) Acetaldehyde content (hereinafter “AA”)
The sample / distilled water = 1 gram / 2 cc was put in a glass ampoule with nitrogen substitution, the upper part was sealed, extracted at 160 ° C for 2 hours, cooled, and the acetaldehyde in the extract was cooled to a high sensitivity gas. The concentration was measured by chromatography and the concentration was expressed in ppm.

Example 1 A mixture of bis (2-hydroxyethyl) terephthalate and an oligomer produced from a high-purity terephthalic acid and ethylene glycol by a conventional method using a stainless steel autoclave equipped with a heating wire equipped with a stirrer was used. A 2.5 g / l ethylene glycol solution of aluminum acetylacetonate as a polycondensation catalyst, 0.015 mol% as an aluminum atom with respect to the acid component in the polyester, and Irganox.
1425 (manufactured by Ciba Specialty Chemicals)
Was added to the acid component in an amount of 0.01 mol% as Irganox 1425, and the mixture was stirred at 245 ° C. for 10 minutes under a nitrogen atmosphere at normal pressure. Next, it took 50 minutes to gradually raise the temperature of the reaction system to 275 ° C. and gradually reduce the pressure of the reaction system to 13.3 Pa (0.1 T).
(orr), a polycondensation reaction was further performed at 275 ° C. and 13.3 Pa. Polymerization time (A) required until the IV of polyethylene terephthalate reached 0.65 dl / g
P) was 86 minutes, and the polycondensation catalyst had a practical polymerization activity.

Further, polyethylene terephthalate having an IV of 0.65 dl / g obtained by the above polycondensation was formed into chips according to a conventional method. A melting test was performed using this PET resin chip to determine a thermal stability parameter (TS). TS was 0.18, and the thermal stability was good.

The chipped PET resin was pulverized according to a conventional method, and a heating test was performed using the powder to determine a thermal oxidation stability parameter (TOS). The TOS is 0.01 or less, and the PE obtained by using the polycondensation catalyst of the present invention.
T was also excellent in thermal oxidation stability. The chipped PET resin is pulverized according to a conventional method, subjected to a hydrolysis test using the powder, and subjected to a hydrolysis resistance parameter (H
S) was determined. HS was 0.05, and PET obtained by using the polycondensation catalyst of the present invention was also excellent in hydrolysis resistance. The color b value was determined using the PET resin chipped. The color b value was 4.4, and the PET resin chip polymerized with antimony trioxide as a catalyst had a b value of 1.1 as described in Comparative Example 1, and thus Δb was 3.3. The chipped P
The solution haze value (Haze) was determined using ET resin. Haze was 0.1%.

The PET obtained by the above melt polycondensation
After heating the resin chip at 160 ° C. to crystallize the surface of the resin chip, the resin chip is dried at about 160 to 170 ° C. under a nitrogen stream in a stationary solid state polymerization tower, and then solid-phase polymerized at 205 ° C.
Was 0.80 dl / g, the AA content was 4.5 ppm, and the density was 1.400 g / cm ³ . Next, a stepped molded plate and a stretched hollow molded body (bottle) were obtained by the methods described in 8) and 9) above. The transparency of the formed plate and the stretched bottle formed by using PET obtained by using the polycondensation catalyst of the present invention was very good without any problem.

Also, the above-mentioned 12), 13), 14), 15) and 16) were obtained using solid-phase polymerized PET resin chips.
Various evaluations were made by the method described in (1). Table 2 shows the evaluation results. The hollow molded article molded using PET obtained by using the polycondensation catalyst of the present invention is excellent in heat resistance, heat oxidation resistance, coloring evaluation, hot water resistance, foreign matter, etc., and is excellent. Was.

Example 2 As a catalyst, a 2.5 g / l solution of aluminum acetylacetonate in ethylene glycol was added in an amount of 0.015 mol% as an aluminum atom with respect to the acid component in the polyester and cobalt acetate (I).
I) 20 g / l ethylene glycol solution of tetrahydrate is 0.005 mol% as a cobalt atom with respect to an acid component.
Except for the addition, the same operation as in Example 1 was performed to obtain PET having an IV of 0.65 dl / g. Table 1 shows the characteristics of AP, TS and the like. Further, the PE obtained by the above melt polycondensation
The T resin chip was subjected to solid-state polymerization under the same conditions as in Example 1, and I
A solid phase polymerized PET having a V of 0.80 dl / g, an AA content of 4.7 ppm, and a density of 1.401 g / cm ³ was obtained.

Then, a stepped plate and a stretched hollow molded body (bottle) were obtained by the methods described in 8) and 9) above. The transparency of the formed plate and the stretched bottle formed by using PET obtained by using the polycondensation catalyst of the present invention was very good without any problem. In addition, various evaluations were performed by the methods 12), 13), 14), 15) and 16) above using a solid-phase polymerized PET resin chip. Table 2 shows the evaluation results.

Example 3 As a catalyst, a 2.5 g / l ethylene glycol solution of aluminum acetylacetonate was used as an aluminum component in an amount of 0.01 mol% as aluminum atoms and 50 g of lithium acetate dihydrate with respect to the acid component in the polyester. The same operation as in Example 1 was carried out except that 1 mol of an ethylene glycol solution was added as a lithium atom to the acid component at 0.1 mol% to obtain PET having an IV of 0.65 dl / g. Table 1 shows the characteristics of AP, TS and the like. Further, the PET resin chip obtained by the above-mentioned melt polycondensation was subjected to solid-state polymerization under the same conditions as in Example 1, and the IV was 0.80 dl.
/ G, AA content 4.5 ppm, density 1.403 g
/ Cm ³ was obtained. Then, 8) above
And Step 9), a stepped plate and a stretched hollow molded body (bottle) were obtained. The transparency of the formed plate and the stretched bottle formed by using PET obtained by using the polycondensation catalyst of the present invention was very good without any problem. In addition, the above 12), 1
Various evaluations were made by the methods 3), 14), 15) and 16). Table 2 shows the evaluation results.

[0247]

[Table 1]

[0248]

[Table 2]

Example 4 A slurry of high-purity terephthalic acid and ethyl glycol was continuously supplied to a first esterification reactor containing a reactant in advance, and the slurry was stirred for about 2 hours.
The reaction was carried out at 50 ° C. and 0.5 kg / cm ² G for an average residence time of about 3 hours. This reaction product was sent to the second esterification reactor, and reacted under agitation at about 260 ° C. and 0.05 kg / cm ² G to a predetermined reactivity. An aluminum glycol solution of aluminum acetylacetonate was added to the acid component in the polyester in an amount of 0.015 as an aluminum atom.
mol%, Irganox 1425 (manufactured by Ciba Specialty Chemicals) in ethylene glycol solution as Irganox 1425 was 0.0
1 mol% separately and continuously fed to this second esterification reactor. This esterification reaction product is continuously fed to the first polycondensation reactor, and is stirred at about 265 ° C. and 25 torr.
r for about 1 hour and then with stirring in a second polycondensation reactor for about 2 hours.
Polycondensation was performed at 65 ° C. and 3 torr for about 1 hour, and further with stirring in a final polycondensation reactor at about 275 ° C. and 0.5 to 1 torr for about 2 hours. The IV of the obtained melt polycondensation PET was 0.65 dl / g.

After the melt polycondensation PET is formed into chips, it is transported to a storage tank, and fines and film-like substances are removed by a vibrating sieving step and an airflow classification step.
Then, it was transported to a continuous solid-state polymerization apparatus. Under nitrogen atmosphere,
Crystallize at about 155 ° C and further under nitrogen atmosphere for about 200
After preheating to ℃, it was sent to a continuous solid-state polymerization reactor and subjected to solid-state polymerization at about 207 ° C under a nitrogen atmosphere. IV is 0.80 dl / g,
AA content of 3.8 ppm, density 1.405 g / cm
PET of ³ was obtained. Then, according to the methods described in 8) and 9) above, a stepped molded plate and a stretched hollow molded body (bottle)
I got PET obtained using the polycondensation catalyst of the present invention
The transparency of the molded plate and the stretched bottle formed by using the above was very good without any problem. In addition, the above 12), 13), 14), 1
Various evaluations were performed by the methods 5) and 16). A hollow molded article molded using PET obtained using the polycondensation catalyst of the present invention has heat resistance, heat oxidation resistance, color evaluation,
There were no problems in hot water resistance, foreign matters, etc., all of which were excellent.

(Example 5) An IV obtained by melt polycondensation under the same conditions as in Example 1 except that the melt polycondensation time was shortened.
A 0.52 dl / g polyethylene terephthalate was formed into chips according to a conventional method. Put this PET resin chip in one
After crystallizing the resin chip surface at 60 ° C., it is dried at about 160 to 170 ° C. under a nitrogen stream in a stationary solid-state polymerization tower, and then dried.
Solid phase polymerization was performed at 5 ° C. to obtain a solid state polymerization PET having an IV of 0.75 dl / g, an AA content of 2.5 ppm, a CT content of 0.35% by weight, and a density of 1.425 g / cm ³ . .

Then, according to the methods described in 8) and 10) above, a step-formed plate and a heat-resistant stretched hollow formed body (bottle)
I got PET obtained using the polycondensation catalyst of the present invention
The transparency of the molded plate and the bottle formed using the above was very good without any problem. Further, the above 12), 13), 14) and 1
Various evaluations were made by the method 6). The hollow molded article molded using PET obtained by using the polycondensation catalyst of the present invention was excellent without any problem in heat resistance, heat oxidation resistance, coloring evaluation, foreign matter, and the like.

Example 6 A melt polycondensation PET resin chip having an IV of 0.65 dl / g obtained in Example 1 was used.
After crystallizing the resin chip surface at 60 ° C., it is dried at about 160 to 170 ° C. in a stationary solid-state polymerization tower under a nitrogen stream, and then dried.
Solid phase polymerization at 0 ° C., IV is 1.20 dl / g, AA content 2.0 ppm, a density of 1.430g / cm ³ PE
T was obtained.

Next, a stepped plate and an extruded blow-hollow molded product were obtained by the methods described in 8) and 11) above. The transparency of the molded plate formed using PET obtained by using the polycondensation catalyst of the present invention was very good, and the transparency of the bottle determined by visual inspection was very good and was not a problem. In addition, various evaluations were performed by the methods 12), 13), 14), and 16) above using a solid-phase polymerized PET resin chip. The hollow molded article molded using PET obtained by using the polycondensation catalyst of the present invention was excellent without any problem in heat resistance, heat oxidation resistance, coloring evaluation, foreign matter, and the like.

(Comparative Example 1) The same operation as in Example 1 was carried out except that antimony trioxide was used as a catalyst so that the added amount was 0.05 mol% as antimony atom with respect to an acid component in PET. And the IV is 0.65 dl / g
Was obtained. Table 1 shows the results of AP and the like. As antimony trioxide, commercially available Antimony (III) oxide (ALDR
ICH CHEMICAL, purity 99.999%) was used.
As antimony trioxide, a solution was used which was dissolved in ethylene glycol by stirring at 150 ° C. for about 1 hour so that the concentration became about 10 g / l. Next, in the same manner as in Example 1, a stepped plate and a stretched hollow molded body (bottle) were obtained by the methods described in 8) and 9) above. The transparency of the resulting shaped plates and bottles was very poor.

[0256]

According to the production method of the present invention, an inexpensive and highly transparent polyester comprising a polyester polymerized using at least one selected from the group consisting of aluminum and its compounds as a polyester polymerization catalyst. A hollow molded body is obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // B29K 67:00 B29K 67:00 B29L 22:00 B29L 22:00 C08L 67:02 C08L 67:02 ( 72) Inventor Shoichi Katamai 1-1-1, Katata, Otsu-shi, Shiga F-term in Toyobo Co., Ltd. Research Laboratory 4F071 AA46 BA01 BB06 BC04 4F208 AA24 AG07 AH55 AR17 LA01 LA02 LB01 LG22 LG28 LJ09 LN01 4J029 AA01 AB04 AB05 AC01 AD10 AE01 BA03 CB06A JC571 JF021 JF031 JF041 JF221 JF291 JF471 JF571

Claims (22)

[Claims] 1. A method for producing a polyester hollow molded article, comprising molding a polymerized polyester using at least one selected from the group consisting of aluminum and its compounds as a catalyst. 2. The thermal stability parameter (T.sub.T) of polyethylene terephthalate polymerized using at least one selected from the group consisting of aluminum and its compounds as a catalyst.
The method for producing a polyester hollow molded article according to claim 1, wherein S) satisfies the following formula (1). (1) TS <0.30 (In the above formula, TS has an intrinsic viscosity (IV) of about 0.65 d.
1 / g of melt polycondensation polyethylene terephthalate (PE
T) 1 g of a resin chip was placed in a glass test tube, and the temperature was 130 ° C.
And dried under vacuum for 12 hours under a non-circulating nitrogen atmosphere.
The intrinsic viscosity IV after maintaining the molten state at 0 ° C. for 2 hours is measured, and can be determined by the following formula. TS = 0.245 ｛[IV] _f2 ^-1.47 − [IV] _i
^-1.47 ｝ [IV] _i and [IV] _f2 indicate the IV (dl / g) before and after the melting test, respectively. ) 3. The polyester according to claim 1, wherein at least one catalyst selected from the group consisting of aluminum and its compound has an activity parameter (AP) satisfying the following formula (2). A method for producing a hollow molded body. (2) AP (min) <2T (min) (in the above formula, the activity parameter AP is such that the intrinsic viscosity (IV) is 275 ° C. and a reduced pressure of 13.3 Pa (0.1 Torr) using a predetermined amount of catalyst. Time required to polymerize 0.65 dl / g of polyethylene terephthalate (min)
Is shown. T indicates AP when antimony trioxide is used as a catalyst. However, antimony trioxide is added in an amount of 0.05 mol% as antimony atoms to the acid component in the produced polyethylene terephthalate. ) 4. The thermal oxidative stability parameter (TOS) of polyethylene terephthalate polymerized using at least one selected from the group consisting of aluminum and its compounds as a catalyst satisfies the following formula (3). The method for producing a polyester hollow molded article according to any one of claims 1 to 3. (3) TOS <0.10 (In the above formula, TOS is obtained by freeze-pulverizing a melt polycondensation PET resin chip having an IV of about 0.65 dl / g to obtain a powder having a mesh size of 20 mesh or less, which is then evacuated at 130 ° C. for 12 hours. After drying, 0.3 g thereof was placed in a glass test tube and dried at 70 ° C. for 12 hours.
After vacuum drying for 2 hours, dry under air dried over silica gel for 2 hours.
The intrinsic viscosity IV after heating at 30 ° C. for 15 minutes was measured,
It is determined using the following formula. TOS = 0.245 ｛[IV] _f1 ^-1.47 − [IV] _i
^-1.47 ｝ [IV] _i and [IV] _f1 indicate the IV (dl / g) before and after the heating test, respectively. ) 5. The hydrolysis resistance parameter (HS) of polyethylene terephthalate polymerized by using at least one selected from the group consisting of aluminum and its compounds as a catalyst, should satisfy the following formula (4). A method for producing a polyester hollow molded article according to any one of claims 1 to 4. (4) HS <0.10 (HS has an IV of about 0.65 dl / g (before the test; [I
V] _i ) The melt polycondensation PET chips were frozen and pulverized to obtain 2)
A powder having a size of 0 mesh or less was dried in a vacuum at 130 ° C. for 12 hours, and 1 g of the powder was put into a beaker together with 100 ml of pure water. The viscosity ([IV] _f2 ) is measured, and is a numerical value calculated by the following equation. HS = 0.245 ｛[IV] _f2 ^-1.47- [IV] _i
^-1.47 ｝) 6. A color delta b value parameter (Δb) of polyethylene terephthalate polymerized by using at least one selected from the group consisting of aluminum and its compound as a catalyst, satisfying the following formula (5). A method for producing a polyester hollow molded article according to any one of claims 1 to 5. (5) Δb <4.0 (in the above formula, Δb was determined using a PET chip having an IV of about 0.65 dl / g melt-polycondensed using a predetermined catalyst,
The value obtained by subtracting the b value when antimony trioxide is used as a catalyst from the b value of a hunter measured using a color difference meter is shown. However, antimony trioxide is added in an amount of 0.05 mol% as antimony atoms to the acid component in the produced polyethylene terephthalate. 7. A solution haze value (Haze) of polyethylene terephthalate polymerized using at least one selected from the group consisting of aluminum and its compounds as a catalyst.
Satisfies the following formula (6): The method for producing a polyester hollow molded article according to any one of claims 1 to 6, wherein (6) Haze <3.0 (%) (In the above formula, Haze has an intrinsic viscosity of about 0.65 dl /
g of melt polycondensation polyethylene terephthalate (PET)
Resin chips were p-chlorophenol / 1,1,2,2
Dissolved in a 3/1 mixed solvent of tetrachloroethane (weight ratio) to give a solution of 8 g / 100 ml, and shows the value measured using a haze meter. ) 8. The method for producing a hollow polyester article according to claim 1, wherein the catalyst does not contain an alkali metal, an alkaline earth metal, or a compound thereof. 9. The catalyst according to claim 1, wherein at least one kind of a second metal-containing component selected from the group consisting of an alkali metal, an alkaline earth metal and a compound thereof is co-present in the catalyst. The method for producing a polyester hollow molded article according to the above. 10. The method according to claim 9, wherein the second metal-containing component is an alkali metal or a compound thereof. 11. The method according to claim 11, wherein the alkali metal is Li, Na, K.
The method for producing a polyester hollow molded article according to claim 10, which is at least one selected from the group consisting of: 12. The addition amount M (mol%) of the second metal-containing component to all carboxylic acid components constituting the polyester is as follows:
The method for producing a polyester hollow molded article according to any one of claims 9 to 11, which satisfies the formula (7). (7) M ≦ 0.05 13. The method for producing a polyester hollow molded article according to claim 1, wherein a cobalt compound is present in the catalyst. 14. The catalyst according to claim 1, wherein at least one selected from phosphorus compounds is present in the catalyst.
14. The method for producing a polyester hollow molded article according to any one of items 13 to 13. 15. The method for producing a polyester hollow molded article according to claim 1, wherein at least one of an antimony compound and a germanium compound coexists in the catalyst. 16. The residual amount of the antimony compound remaining in the polyester is 50 pp as an antimony atom.
The method for producing a polyester hollow molded article according to claim 15, wherein the amount is not more than m. 17. The residual amount of the germanium compound remaining in the polyester is 30 as germanium atoms.
The method for producing a polyester hollow molded article according to claim 15, wherein the amount is not more than ppm. 18. A polyester hollow molded article produced by the production method according to claim 1. 19. A polyester hollow molded article according to claim 18, which is a molded article obtained by stretch blow molding. 20. A polyester hollow molded article according to claim 18, which is a heat-resistant hollow molded article obtained by stretch blow molding and heat treatment. 21. A polyester hollow molded article according to claim 18, which is a molded article obtained by extrusion blow molding. 22. A polyester hollow molded article according to claim 18, which is a molded article obtained by injection molding.