JP5152608B2 - Polyester polymerization catalyst, polyester produced using the same, and method for producing polyester - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyester polymerization catalyst, a polyester produced using the same, and a method for producing the polyester. More specifically, the present invention relates to a novel polyester polymerization catalyst that does not use germanium or an antimony compound as a catalyst main component, and The present invention relates to a polyester produced using the same and a method for producing the polyester.
[0002]
[Prior art]
Polyesters typified by polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), etc. are excellent in mechanical properties and chemical properties. Depending on the properties of each polyester, for example, It is used in a wide range of fields such as textiles for clothing and industrial materials, films and sheets for packaging and magnetic tape, bottles that are hollow molded products, casings for electrical and electronic parts, and other engineering plastic molded products. .
[0003]
For example, in the case of polyethylene terephthalate (PET), a polyester mainly composed of aromatic dicarboxylic acid and alkylene glycol, which is a typical polyester, is obtained by esterification or transesterification of terephthalic acid or dimethyl terephthalate and ethylene glycol. Bis (2-hydroxyethyl) terephthalate is produced and industrially produced by a polycondensation method or the like in which polycondensation is performed using a catalyst at high temperature and under vacuum.
[0004]
Conventionally, antimony trioxide has been widely used as a polyester polymerization catalyst used in such polycondensation of polyester. Antimony trioxide is an inexpensive catalyst with excellent catalytic activity. However, if it is used in an amount of such a main component, that is, a practical polymerization rate, metal antimony is used during polycondensation. As a result of precipitation, blackening and foreign matter are generated in the polyester. Under such circumstances, a polyester that does not contain antimony at all or does not contain antimony as a main catalyst component is desired.
[0005]
The above foreign matter in the polyester causes the following problems.
(1) In the polyester for film, metal antimony deposition becomes a foreign substance in the polyester, which causes not only the contamination of the die during melt extrusion, but also the surface defect of the film. Further, when a raw material such as a hollow molded product is used, it is difficult to obtain a hollow molded product having excellent transparency.
[0006]
(2) The foreign material in the polyester for fibers becomes a foreign material that causes a decrease in strength in the fiber, and causes the base to become dirty during yarn production. In the production of polyester fibers, a polyester polymerization catalyst free from the generation of foreign substances is required mainly from the viewpoint of operability.
[0007]
As a method for solving the above problems, attempts have been made to use antimony trioxide as a catalyst and suppress the occurrence of darkening and foreign matter in PET. For example, in Japanese Patent No. 2666502, generation of black foreign substances in PET is suppressed by using a compound of antimony trioxide, bismuth and selenium as a polycondensation catalyst. Japanese Patent Laid-Open No. 9-291141 states that the use of antimony trioxide containing sodium and iron oxides as a polycondensation catalyst suppresses the precipitation of metal antimony. However, these polycondensation catalysts cannot achieve the purpose of reducing the content of antimony in the polyester after all.
[0008]
As a method for solving the problems of antimony catalysts for applications requiring transparency such as PET bottles, for example, in JP-A-6-279579, it is transparent by defining the use amount ratio of an antimony compound and a phosphorus compound. A method for improving the performance is disclosed. However, it cannot be said that a hollow molded product made of polyester obtained by this method has sufficient transparency.
[0009]
Japanese Patent Application Laid-Open No. 10-36495 discloses a continuous production method of polyester having excellent transparency using antimony trioxide, phosphoric acid and sulfonic acid compounds. However, the polyester obtained by such a method has a problem that the thermal stability is poor and the acetaldehyde content of the obtained hollow molded article is high.
[0010]
Polycondensation catalysts to replace antimony-based catalysts such as antimony trioxide have also been studied, and titanium compounds and tin compounds typified by tetraalkoxy titanates have already been proposed. It has a problem that it is susceptible to thermal degradation during melt molding and that the polyester is remarkably colored.
[0011]
As an attempt to overcome such problems when a titanium compound is used as a polycondensation catalyst, for example, Japanese Patent Application Laid-Open No. 55-116722 proposes a method of using tetraalkoxy titanate simultaneously with a cobalt salt and a calcium salt. ing. JP-A-8-73581 proposes a method using tetraalkoxy titanate as a polycondensation catalyst simultaneously with a cobalt compound and using a fluorescent brightening agent. However, with these techniques, although coloring of PET when tetraalkoxy titanate is used as a polycondensation catalyst is reduced, it has not been achieved to effectively suppress thermal decomposition of PET.
[0012]
As another attempt to suppress thermal degradation during the melt molding of a polyester polymerized using a titanium compound as a catalyst, for example, in JP-A-10-259296, a polyester compound is polymerized using a titanium compound as a catalyst and then a phosphorus compound is added. A method is disclosed. However, it is not only technically difficult to effectively add the additive to the polymer after polymerization, but also the cost is increased and it is not put into practical use.
[0013]
There is also known a technique for forming a polyester polymerization catalyst having sufficient catalytic activity by adding an alkali metal compound to an aluminum compound. When such a known catalyst is used, a polyester having excellent thermal stability can be obtained. However, a known catalyst using an alkali metal compound in combination requires a large amount of addition to obtain a practical catalytic activity. As a result, the amount of foreign matter resulting from the alkali metal compound is increased, and when used for fibers, the spinning property and the physical properties of the yarn are deteriorated. When used for the film, the physical properties of the film are deteriorated, and the hydrolysis resistance is also reduced. The problem also occurs.
[0014]
Germanium compounds have already been put to practical use as catalysts that give polyesters with excellent catalytic activity other than antimony compounds and excellent thermal stability and hydrolysis resistance, but this catalyst is very expensive. There are problems and problems that the catalyst concentration in the reaction system changes due to the tendency of distilling out of the reaction system during polymerization, making it difficult to control the polymerization. is there.
[0015]
Moreover, the method of removing a catalyst from polyester is also mentioned as a method for suppressing thermal degradation during melt molding of polyester. As a method for removing the catalyst from the polyester, for example, JP-A-10-251394 discloses a method of bringing a polyester resin into contact 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 increases costs.
[0016]
As described above, it is a polymerization catalyst that uses a metal component other than antimony and germanium as the main metal component of the catalyst, and has excellent catalytic activity and thermal stability and hydrolysis resistance that hardly cause thermal degradation during melt molding. Polymerization catalysts that provide excellent polyesters are desired.
[0017]
[Problems to be solved by the invention]
The present invention does not contain an antimony compound or a germanium compound as the main component of the catalyst, aluminum is the main metal component, has excellent catalytic activity, and is effective in heat deterioration during melt molding without deactivating or removing the catalyst. A polyester polymerization catalyst that provides a polyester that is suppressed and is excellent in thermal stability and also excellent in hydrolysis resistance is provided. The present invention is also improved in the heat stability and the hydrolysis resistance when melt molding of hollow moldings such as films and bottles, fibers, etc. using the catalyst, and using virgin resin. However, another object of the present invention is to provide a polyester capable of obtaining a product with excellent quality even if the waste generated during molding is reused, and a method for producing a polyester using the polyester polymerization catalyst.
[0018]
[Means for Solving the Problems]
The present invention relates to a polyester polymerization catalyst comprising at least one selected from the group consisting of aluminum and a compound thereof as a first metal-containing component, and hydrolysis resistance of polyethylene terephthalate (PET) polymerized using the catalyst. The characteristic parameter (HS) satisfies the following formula (1).
[0019]
(1) HS <0.10
HS has an intrinsic viscosity obtained by melt polymerization of about 0.65 dl / g (before test: [IV]._i The PET chip of) was frozen and pulverized and dried in a vacuum at 130 ° C. for 12 hours as a powder of 20 mesh or less, and 1 g of the mixture was placed in a beaker with 100 ml of pure water, heated to 130 ° C. in a closed system, and pressurized. Intrinsic viscosity after stirring for 6 hours ([IV]_f2)
HS = 0.245 {[IV]_f2 ^-1.47 -[IV]_i ^-1.47 }
Is a numerical value calculated by.
[0020]
As the beaker used for the measurement of HS, a beaker having no acid or alkali elution is used. Specifically, it is preferable to use a stainless steel beaker or a quartz beaker.
[0021]
By using the catalyst having such a configuration, a polyester polymer that gives a molded article excellent in hydrolysis resistance can be obtained.
[0022]
HS is more preferably 0.09 or less, and particularly preferably 0.085 or less.
[0023]
In the above-described invention, it is further preferable that the thermal stability parameter (TS) of the PET satisfies the following formula (2).
[0024]
(2) TS <0.30
TS is the intrinsic viscosity ([IV]_i ) Was placed in a glass test tube and vacuum-dried at 130 ° C. for 12 hours, and then maintained in a molten state at 300 ° C. for 2 hours in a non-circulating nitrogen atmosphere ([IV ]_f1)
TS = 0.245 {[IV]_f1 ^-1.47 -[IV]_i ^-1.47 }
Is a numerical value calculated by.
[0025]
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 after repeating depressurization and nitrogen filling five or more times, nitrogen is added so that the pressure becomes 100 Torr. It is in a sealed and sealed state.
[0026]
By using the catalyst having such a structure, it is possible to obtain a polyester that provides a molded product having excellent melt heat stability with respect to heat-melting when a molded product such as a film, a bottle, or a fiber is produced, and also having excellent hydrolysis resistance.
[0027]
TS is more preferably 0.25 or less, and particularly preferably 0.20 or less.
[0028]
In the above-mentioned invention, it is preferable that the polymerization activity parameter (AP) satisfies the following formula (3).
[0029]
(3) AP (min) <2T (min)
AP indicates the time (min) required to polymerize polyethylene terephthalate having an intrinsic viscosity of 0.65 dl / g at a reduced pressure of 275 ° C. and 0.1 Torr using a predetermined amount of catalyst, and T is a catalyst of antimony trioxide. As AP when added at 0.05 mol% as an antimony atom with respect to the acid component in the generated polyethylene terephthalate.
[0030]
In the measurement of T, antimony trioxide having a purity of 99% or more, for example, commercially available Antimony (III) oxide (manufactured by ALDRICH CHEMICAL, purity 99.999%) is used.
[0031]
Specifically, the AP measurement method is as follows.
1) (BHET production process) A mixture of bis (2-hydroxyethyl) terephthalate (BHET) and oligomer having an esterification rate of 95% using terephthalic acid and twice its molar amount of ethylene glycol (hereinafter referred to as BHET mixture) ).
[0032]
2) (Catalyst addition step) A predetermined amount of catalyst is added to the above BHET mixture, stirred at 245 ° C. for 10 minutes under a nitrogen atmosphere, and then the oligomer is heated up to 275 ° C. over 50 minutes. The pressure in the reaction system of the mixture is gradually reduced to 0.1 Torr.
[0033]
3) (Polycondensation step) A polycondensation reaction is performed at 275 ° C and 0.1 Torr, and polymerization is performed until the intrinsic viscosity (IV) of polyethylene terephthalate reaches 0.65 dl / g.
[0034]
4) The polymerization time required for the polycondensation step is AP (min).
These are performed using a batch reactor.
[0035]
1) Production of the BHET mixture in (BHET production process) is performed by a known method. For example, terephthalic acid and its 2-fold molar amount of ethylene glycol are charged into a batch-type autoclave equipped with a stirrer and subjected to esterification while distilling water out of the system at 245 ° C. under a pressure of 0.25 MPa. Manufactured by.
[0036]
By setting the activity parameter AP within the above range, the reaction rate is high and the time for producing the polyester by polycondensation is shortened. AP is more preferably 1.5T or less, further preferably 1.3T or less, and particularly preferably 1.0T or less.
[0037]
2) The “predetermined amount of catalyst” in the (catalyst addition step) means the amount of catalyst to be used in a variable amount according to the activity of the catalyst. The amount increases. The amount of the catalyst used is 0.1 mol% at maximum as an aluminum compound with respect to the number of moles of terephthalic acid. If more than this is added, the residual amount in the polyester is large and it is not a practical catalyst.
[0038]
In the present invention, the PET resin chip used for measuring HS and TS is prepared by rapid cooling from the molten state after the steps 1) to 3). As the shape of the resin tip used for these measurements, for example, a cylindrical resin tip having a length of about 3 mm and a diameter of about 2 mm is used.
[0039]
Moreover, it is preferable that the above-mentioned catalyst coexists with a phosphorus compound, and among the phosphorus compounds, it is preferable that at least one selected from the group consisting of phosphonic acid compounds coexists. Among these, it is preferable to use a compound having an aromatic ring structure. In particular, it is preferable to coexist at least one selected from phosphonic acid compounds represented by the following general formulas (Chemical Formula 5) and (Chemical Formula 6).
[0040]
[Chemical formula 5]
Ph-P (= O) (OR¹ ) (OR² )
(In the formula (Chemical Formula 5), R¹ , R² Each independently represents hydrogen, an alkyl group having 1 to 50 carbon atoms, or an aryl group. )
[Chemical 6]
Me-P (= O) (OR^Three ) (OR^Four )
(In the formula (Chemical Formula 6), R^Three , R^Four Each independently represents hydrogen, an alkyl group having 1 to 50 carbon atoms, or an aryl group. )
The compounds represented by the above (Chemical Formula 5) and (Chemical Formula 6) are preferably used when a compound having at least one aryl group is used because the compound is difficult to be distilled out of the system during the polymerization reaction. The phosphorus compound having at least one aryl group is preferably at least one selected from dimethyl phenylphosphonate and diphenyl methylphosphonate, and particularly preferably dimethyl phenylphosphonate.
[0041]
The polyester polymerization catalyst of the present invention contains at least one selected from aluminum and its compounds as a first metal-containing component, and at least one of phosphorus compounds represented by the following general formulas (Chemical Formula 7) and (Chemical Formula 8). It is characterized by coexisting species.
[Chemical 7]
Ph-P (= O) (OR¹ ) (OR² )
(In the formula (Chemical Formula 7), R¹ , R² Each independently represents hydrogen, an alkyl group having 1 to 50 carbon atoms, or an aryl group. )
[Chemical 8]
Me-P (= O) (OR^Three ) (OR^Four )
(In the formula (Chemical Formula 8), R^Three , R^Four Each independently represents hydrogen, an alkyl group having 1 to 50 carbon atoms, or an aryl group. ).
[0042]
In the compounds represented by the above (Chemical Formula 7) and (Chemical Formula 8), when a compound having at least one aryl group is used, it is difficult to distill out of the system during the polymerization reaction. The phosphorus compound having at least one aryl group is particularly preferably at least one selected from dimethyl phenylphosphonate and diphenyl methylphosphonate.
[0043]
Phosphorus compounds are generally well known as antioxidants, but it is not known that melt polymerization is greatly promoted when these phosphorus compounds are used in combination with conventional metal-containing polyester polymerization catalysts. Actually, even when a phosphorus compound is added to melt-polymerize polyester using a polymerization catalyst of an antimony compound, titanium compound, tin compound or germanium compound, which is a typical catalyst for polyester polymerization, to a substantially useful level. It is not observed that polymerization is accelerated.
[0044]
As the usage-amount of the phosphorus compound of this invention, 0.0001-0.1 mol% is preferable with respect to the number-of-moles of all the structural units of the polycarboxylic acid component of polyester obtained, 0.005-0.05 mol% More preferably.
[0045]
By using the phosphorus compound of the present invention in combination, a catalyst exhibiting a sufficient catalytic effect can be obtained even when the amount of addition as aluminum in the polyester polymerization catalyst is small. If the addition amount of the phosphorus compound is less than 0.0001 mol%, the addition effect may not be exhibited. If the addition amount exceeds 0.1 mol%, the catalytic activity as a polyester polymerization catalyst may decrease. The tendency of the change varies depending on the amount of aluminum used.
[0046]
There is a technology that reduces the amount of aluminum compound used and prevents coloration due to a decrease in thermal stability when an aluminum compound is used as a catalyst by adding a cobalt compound, but the cobalt compound has sufficient catalytic activity. When added, the thermal stability is lowered. Therefore, it is difficult to achieve both.
[0047]
Moreover, when a cobalt compound is added to such an extent that it has a sufficient catalytic activity, there also arises a problem that the hydrolysis resistance of the resulting polyester polymer is lowered.
[0048]
According to the present invention, the use of the phosphorus compound of the present invention does not cause problems such as a decrease in hydrolysis resistance, a decrease in thermal stability, and the generation of foreign matter, and the amount of the first metal-containing component added as aluminum is small. A polyester polymerization catalyst having a sufficient catalytic effect can be obtained even in a small amount. By using this polyester polymerization catalyst, hollow molded products such as polyester films and bottles, heat stability during melt molding of fibers and water resistance of melt molded products Is improved. 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 small, which is not practical. Further, even when the phosphorus compound of the present invention is used in combination with a metal-containing polyester polymerization catalyst such as a conventional antimony compound, titanium compound, tin compound or germanium compound within the range of the addition amount of the present invention, the effect of promoting melt polymerization It is not allowed. In addition, even if it uses the phosphorus compound of this invention independently within the range of the addition amount of this invention, catalyst activity is not recognized.
[0049]
It is preferable that the catalyst described above does not contain an alkali metal, an alkaline earth metal, or a compound thereof.
[0050]
On the other hand, in the present invention, it is preferable that at least one selected from a small amount of an alkali metal, an alkaline earth metal, and the compound in addition to aluminum or a compound thereof coexists as the second metal-containing component. The coexistence of such a second metal-containing component in the catalyst system is effective in improving productivity by obtaining a catalyst component having an increased reaction rate in addition to an effect of suppressing the formation of diethylene glycol, and thus a higher reaction rate. .
[0051]
A technique of adding an alkali metal compound or an alkaline earth metal compound to an aluminum compound to obtain a catalyst having sufficient catalytic activity is known. When such a known catalyst is used, a polyester having excellent thermal stability can be obtained. However, a known catalyst used in combination with an alkali metal compound or an alkaline earth metal compound is added in an amount to obtain practical catalytic activity. However, when an alkali metal compound is used, the hydrolysis resistance of the resulting polyester is reduced and the amount of foreign matter resulting from the alkali metal compound is increased. Moreover, when used for a film, the film properties and the like deteriorate. In addition, when an alkaline earth metal compound is used in combination, the thermal stability of the obtained polyester is lowered when it is attempted to obtain practical activity, coloring due to heating is large, the amount of foreign matter generated is increased, and water resistance is increased. Degradability also decreases.
[0052]
When adding an alkali metal, an alkaline earth metal, or a compound thereof, the amount M (mol%) used is 1 × 10 4 with respect to the number of moles of all polycarboxylic acid units constituting the polyester.^-6It is preferably less than 0.1 mol%, more preferably 5 × 10^-6˜0.05 mol%, more preferably 1 × 10^-FiveTo 0.03 mol%, particularly preferably 1 × 10^-Five-0.01 mol%. Since the addition amount of alkali metal and alkaline earth metal is small, it is possible to increase the reaction rate without causing problems such as deterioration of thermal stability, generation of foreign substances, coloring, deterioration of hydrolysis resistance, etc. is there. When the amount M of the alkali metal, alkaline earth metal, or compound thereof is 0.1 mol% or more, the thermal stability decreases, the generation of foreign matter and coloring, and the hydrolysis resistance become problems in product processing. A case occurs. M is 1 × 10^-6If it is less than 1, the effect is not clear even if it is added.
[0053]
DETAILED DESCRIPTION OF THE INVENTION
As the aluminum or aluminum compound constituting the polycondensation catalyst of the present invention, known aluminum compounds can be used without limitation in addition to metallic aluminum.
[0054]
Specific examples of aluminum compounds include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, and aluminum lactate. , Carboxylates such as aluminum citrate, aluminum salicylate, inorganic acid salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate, aluminum phosphonate, aluminum methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum iso-propoxide, aluminum n-butoxide, aluminum t-butoxa Aluminum alkoxides such as aluminum, aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, aluminum ethylacetoacetate diiso-propoxide, and other organic chelate compounds, trimethylaluminum, triethylaluminum and other organoaluminum compounds and their partial hydrolysis Examples include decomposed products and aluminum oxide. Of these, carboxylates, inorganic acid salts and chelate compounds are preferred, and among these, aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred.
[0055]
The amount of the aluminum compound used is preferably 0.001 to 0.05 mol%, more preferably 0, based on the number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the polyester obtained. 0.005 to 0.02 mol%. Thus, the polymerization catalyst of the present invention has a great feature in that it exhibits a sufficient catalytic activity even when the amount of the aluminum component added is small. As a result, hydrolysis resistance is excellent and HS <0.10 is satisfied.
[0056]
In the present invention, the alkali metal or alkaline earth metal constituting the second metal-containing component preferably used in addition to aluminum or a compound thereof includes Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr. , Ba is preferable, and use of an alkali metal or a compound thereof is more preferable. When using an alkali metal or a compound thereof, use of Li, Na, K is particularly preferable. Examples of the alkali metal and alkaline earth metal compounds include saturated aliphatic carboxylates such as formic acid, acetic acid, propionic acid, butyric acid, and succinic acid, and unsaturated aliphatic carboxylates such as acrylic acid and methacrylic acid. , Aromatic carboxylates such as benzoic acid, halogen-containing carboxylates such as trichloroacetic acid, hydroxycarboxylates such as lactic acid, citric acid and salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, phosphorus Inorganic acid salts such as acid hydrogen, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid and bromic acid, and organic sulfonates such as 1-propanesulfonic acid, 1-pentanesulfonic acid and naphthalenesulfonic acid , Organic sulfates such as lauryl sulfate, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert-butyl Alkoxides such as alkoxy, chelate compounds and the like acetylacetonate, hydrides, oxides, and hydroxides and the like.
[0057]
Among these alkali metals, alkaline earth metals or their compounds, when using strongly alkaline substances such as hydroxides, these tend to be difficult to dissolve in diols such as ethylene glycol or organic solvents such as alcohols. However, it must be added to the polymerization system in an aqueous solution, which may cause a problem in the polymerization process. Furthermore, when a strongly alkaline material such as a hydroxide is used, the polyester is liable to undergo side reactions such as hydrolysis during the polymerization, and the polymerized polyester tends to be colored, and the hydrolysis resistance also decreases. Tend to. Accordingly, the alkali metal or their compounds or alkaline earth metals or their compounds suitable for the present invention are preferably saturated aliphatic carboxylates, unsaturated aliphatic carboxylates, aromatics of alkali metals or alkaline earth metals. Aromatic carboxylates, halogen-containing carboxylates, hydroxycarboxylates, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, bromic acid Selected inorganic acid salts, organic sulfonates, organic sulfates, chelate compounds, and oxides. Among these, from the viewpoint of ease of handling, availability, and the like, it is preferable to use an alkali metal or alkaline earth metal saturated aliphatic carboxylate, particularly acetate.
[0058]
In the polyester polymerization catalyst of the present invention, it is further preferable to add a cobalt compound as a cobalt atom in an amount of less than 10 ppm based on the polyester.
[0059]
It is known that the cobalt compound itself has a certain degree of polymerization activity, but if it is added to such an extent that it exhibits a sufficient catalytic effect as described above, the hydrolysis resistance and thermal stability are lowered. Although the polyester obtained according to the present invention has good hydrolysis resistance, the addition of a cobalt compound in such a small amount as described above does not clearly show the catalytic effect of the addition of the resulting polyester. The coloring can be erased more effectively. The cobalt compound in the present invention is for the purpose of eliminating coloration, and may be added at any stage of the polymerization or after the completion of the polymerization reaction.
[0060]
The polyester according to the present invention can be produced by a method having a conventionally known process except that the polyester polymerization catalyst of the present invention is used as a catalyst. For example, in the polymerization method of PET, after esterification of terephthalic acid and ethylene glycol, a polycondensation method, or after transesterification of an alkyl ester of terephthalic acid such as dimethyl terephthalate with ethylene glycol, Any method of polycondensation can be performed. The polymerization apparatus may be a batch type or a continuous type.
[0061]
The catalyst of the present invention has catalytic activity not only for polycondensation but also for esterification and transesterification. For example, polymerization by an ester exchange reaction between an alkyl ester of a dicarboxylic acid such as dimethyl terephthalate and a glycol such as ethylene glycol is usually carried out in the presence of an ester exchange catalyst such as a titanium compound or a zinc compound. Instead, the catalyst of the present invention can be used in combination with these catalysts. Further, the catalyst of the present invention has catalytic activity not only in melt polymerization but also in solid phase polymerization or solution polymerization, and polyester can be produced by any method.
[0062]
The polycondensation catalyst of the present invention can be added to the reaction system at any stage of the polymerization reaction. For example, it can be added to the reaction system before the start of the esterification reaction or transesterification reaction and at any stage during the reaction or immediately before the start of the polycondensation reaction or during the reaction. In particular, aluminum or a compound thereof is preferably added immediately before the start of the polycondensation reaction.
[0063]
The addition method of the polycondensation catalyst of the present invention may be addition in powder form or neat form, and may be addition in a slurry form or a solution form of a solvent such as ethylene glycol, and is not particularly limited. Further, aluminum metal or a compound thereof and other components, preferably the phosphorus compound of the present invention, may be added as a premixed mixture, or these may be added separately. Aluminum metal or a compound thereof and other components, preferably a phosphorus compound, may be added to the polymerization system at the same addition time, and each component may be added at different addition times.
[0064]
The polycondensation catalyst of the present invention is a polycondensation catalyst such as an antimony compound, a germanium compound, or a titanium compound, and the addition of these components does not cause problems in the products such as polyester characteristics, processability, and color tone as described above. Coexistence within the range of the addition amount is effective and preferable in improving productivity by shortening the polymerization time.
[0065]
However, the antimony compound can be added in an amount of 50 ppm or less as an antimony atom to the polyester obtained by polymerization. A more preferable addition amount is 30 ppm or less. When the amount of antimony added is 50 ppm or more, metal antimony is precipitated, and darkening and foreign matter are generated in the polyester.
[0066]
The germanium compound can be added in an amount of 20 ppm or less as germanium atoms to the polyester obtained by polymerization. A more preferable addition amount is 10 ppm or less. If the amount of germanium added is 20 ppm or more, it is not preferable because it is disadvantageous in terms of cost.
[0067]
Examples of the antimony compound that can be added include antimony trioxide, antimony pentoxide, antimony acetate, antimony glycoloxide, and the like, and the use of antimony trioxide is particularly preferable. Examples of the germanium compound include germanium dioxide and germanium tetrachloride, and germanium dioxide is particularly preferable.
[0068]
Other polymerization catalysts such as titanium compounds and tin compounds include tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetracyclohexyl titanate, tetra Examples thereof include phenyl titanate and tetrabenzyl titanate, and tetrabutyl titanate is particularly preferable. In addition, as tin compounds, 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 ethylstannic acid, and the use of monobutylhydroxytin oxide is particularly preferable.
[0069]
The polyester referred to in the present invention is one or two or more types selected from polyvalent carboxylic acids that combine dicarboxylic acids and their ester-forming derivatives and one or two or more types selected from polyhydric alcohols that combine glycols. Or consisting of a hydroxycarboxylic acid and an ester-forming derivative thereof, or consisting of a cyclic ester.
[0070]
Dicarboxylic acids include succinic acid, malonic acid, succinic acid, glutaric acid, adivic acid, vimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 3-cyclobutane Illustrative examples include dicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, and dimer acid. Saturated aliphatic dicarboxylic acids or ester-forming derivatives thereof, unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid and the like, or ester-forming derivatives thereof, orthophthalic acid, isophthalic acid, terephthalic acid, Diphenine 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, Fragrances exemplified by 4,4′-biphenylsulfone dicarboxylic acid, 4,4′-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid, etc. Group dicarboxylic acids or their ester-forming derivatives.
[0071]
Among the dicarboxylic acids described above, the use of terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid is particularly preferred from the viewpoint of the physical properties of the resulting polyester, and other dicarboxylic acids are used as constituents as necessary.
[0072]
As polyvalent carboxylic acids other than these dicarboxylic acids, ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ′, 4′-biphenyltetracarboxylic acid, And ester-forming derivatives thereof.
[0073]
As glycols, 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, polytrimethyl Aliphatic glycols exemplified by tylene glycol and 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 Aromatic glycols exemplified by C, 2,5-naphthalenediol, glycols in which ethylene oxide is added to these glycols, and the like.
[0074]
Among the above glycols, it is particularly preferable to use ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,4-cyclohexanedimethanol as the main component.
[0075]
Examples of polyhydric alcohols other than these glycols include trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, and hexanetriol.
[0076]
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, 4-hydroxycyclohexanecarboxylic acid, or these And ester-forming derivatives thereof.
[0077]
Examples of the cyclic ester include ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycolide, and lactide.
[0078]
Examples of ester-forming derivatives of polyvalent carboxylic acids and hydroxycarboxylic acids include these alkyl esters, acid chlorides, acid anhydrides, and the like.
[0079]
The polyester used in the present invention is preferably a polyester in which the main acid component is terephthalic acid or an ester-forming derivative thereof or naphthalene dicarboxylic acid or an ester-forming derivative thereof, and the main glycol component is alkylene glycol.
[0080]
The polyester in which the main acid component is terephthalic acid or an ester-forming derivative thereof is preferably a polyester containing 70 mol% or more of terephthalic acid or an ester-forming derivative thereof in total with respect to the total acid component. A polyester containing 80 mol% or more is preferable, and a polyester containing 90 mol% or more is more preferable. Similarly, the polyester in which the main acid component is naphthalenedicarboxylic acid or an ester-forming derivative thereof is also preferably a polyester containing 70 mol% or more of naphthalenedicarboxylic acid or an ester-forming derivative thereof, more preferably 80 Polyesters containing at least mol%, more preferably polyesters containing at least 90 mol%.
[0081]
The polyester whose main glycol component is an alkylene glycol is preferably a polyester containing 70 mol% or more of the total amount of alkylene glycol with respect to all glycol components, more preferably a polyester containing 80 mol% or more, More preferably, it is a polyester containing 90 mol% or more. The alkylene glycol here may contain a substituent or an alicyclic structure in the molecular chain.
[0082]
Examples of the naphthalenedicarboxylic acid or ester-forming derivative thereof used in the present invention include 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid exemplified in the above dicarboxylic acids, 2, 6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, or ester-forming derivatives thereof are preferred.
[0083]
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, 1,3-butylene glycol, 2,3 exemplified as the above-mentioned glycol. -Butylene glycol, 4,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1 , 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol and the like are suitable. is there. Two or more of these may be used at the same time.
[0084]
The polyester of the present invention can contain a known phosphorus compound as a copolymerization component. As the phosphorus compound, a bifunctional phosphorus compound is preferable. For example, (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 copolymerization components, it is possible to improve the flame retardancy of the resulting polyester.
[0085]
As a constituent component of the polyester of the present invention, in order to improve dyeability when polyester is used as a fiber, it is a preferable embodiment to use a polycarboxylic acid having an alkali metal sulfonate as a copolymer component.
[0086]
The metal sulfonate group-containing compound used as the copolymerization monomer is not particularly limited, but 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 5-lithium sulfoisophthalic acid, 2-lithium sulfoterephthalic acid, Examples include 5-potassium sulfoisophthalic acid, 2-potassium sulfoterephthalic acid, or lower alkyl ester derivatives thereof. In the present invention, it is particularly preferable to use 5-sodium sulfoisophthalic acid or an ester-forming derivative thereof.
[0087]
The copolymerization amount of the metal sulfonate group-containing compound is preferably 0.3 to 10.0 mol%, more preferably 0.80 to 5.0 mol%, based on the acid component constituting the polyester. If the amount of copolymerization is too small, the dyeability of the basic dye is inferior, and if it is too large, not only the yarn-making property is inferior, but also sufficient strength as a fiber cannot be obtained due to the thickening phenomenon. Moreover, when a metal sulfonate group-containing compound is copolymerized in an amount of 2.0 mol% or more, it is possible to impart atmospheric pressure dyeability to the resulting modified polyester fiber. Moreover, it is possible to reduce the usage-amount of a metal sulfonate group containing compound suitably by selecting a suitable easily dyeable monomer. Although it does not specifically limit as an easily dyeable monomer, The aliphatic dicarboxylic acid represented by the long-chain glycol compound represented by polyethyleneglycol and polytetramethylene glycol, adipic acid, sebacic acid, and azelaic acid is mentioned.
[0088]
Polyesters produced using the polyester polymerization catalyst of the present invention include polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, poly (1,4-cyclohexanedimethylene terephthalate), polyethylene naphthalate, polybutylene naphthalate, polypropylene. Naphthalate and copolymers thereof can be exemplified as preferred polymers, and particularly preferred polymers are polyethylene terephthalate and copolymers thereof.
[0089]
After polymerizing the polyester according to the method of the present invention, the catalyst is removed from the polyester, or the catalyst is deactivated by adding a phosphorus compound or the like, thereby further improving the hydrolysis resistance and thermal stability of the polyester. Can do.
[0090]
The polyester of the present invention can contain organic, inorganic, and organometallic toners, and a fluorescent brightening agent. By containing one or more of these, yellowing of the polyester, etc. Can be suppressed to an even better level. It also contains other optional polymers, antistatic agents, antifoaming agents, dyeability improvers, dyes, pigments, matting agents, fluorescent brighteners, stabilizers, antioxidants, and other additives. Also good. As antioxidants, aromatic amine-based and phenol-based antioxidants can be used, and as stabilizers, phosphoric acid and phosphate ester-based phosphorus-based, sulfur-based, amine-based stabilizers, etc. Can be used.
[0091]
【Example】
Hereinafter, although the structure and effect of this invention are demonstrated based on an Example, this invention is not limited to these Examples from the first.
[0092]
〔Evaluation method〕
1) Intrinsic viscosity (IV)
The polyester was dissolved using a 6/4 (weight ratio) mixed solvent of phenol / 1,1,2,2-tetrachloroethane and measured at a temperature of 30 ° C.
[0093]
2) Thermal stability parameter (TS)
The melt polymerized IV was about 0.65 dl / g (before the melt test: [IV]_i 1 g of PET resin chip of) is put in a glass test tube having an inner diameter of about 14 mm and vacuum-dried at 130 ° C. for 12 hours, and then the glass test tube is connected to a vacuum line, and the pressure reduction and nitrogen filling are repeated 5 times or more to 100 Torr. Thus, nitrogen was sealed and sealed. This test tube was immersed in a 300 ° C. salt bath and maintained in a molten state for 2 hours, and then a sample was taken out, freeze-ground, vacuum dried, and then IV (after the melt test: [IV]_f1) Was measured. This [IV]_f1From the above, TS was determined using the following formula. The formula was quoted from a previous report (Kamiyama et al .: Journal of Japan Rubber Association Vol. 63, No. 8, 497, 1990).
[0094]
TS = 0.245 {[IV]_f1 ^-1.47 -[IV]_i ^-1.47 }
3) Hydrolysis resistance parameter (HS)
Intrinsic viscosity obtained by melt polymerization is about 0.65 dl / g (before test: [IV]_i ) And freeze-pulverize by a conventional method to obtain a powder of 20 mesh or less and dry at 130 ° C. for 12 hours. The hydrolysis test was performed using a mini-color device (TYPE MC12.ELB manufactured by Tecsum Giken Co., Ltd.). 1 g of the above dry powder of PET is put into a special stainless beaker with 100 ml of pure water, and a special stirring blade is added to make a sealed system, which is set in a mini-color device and heated and pressurized at 130 ° C. for 6 hours under stirring. did. The PET after the test was filtered with a glass filter and vacuum-dried, and then IV was measured ([IV]_f2), The hydrolysis resistance parameter (HS) was determined by the following equation.
[0095]
The freeze pulverization was performed using a freezer mill (model 6750 manufactured by Svex Corporation, USA). After putting about 2 g of resin chip and a dedicated impactor in a dedicated cell, the cell is set in the apparatus, filled with liquid nitrogen and held for about 10 minutes, and then RATE10 (the impactor is about 20 per second). Crushed for 5 minutes.
[0096]
HS = 0.245 {[IV]_f2 ^-1.47 -[IV]_i ^-1.47 }
4) Thermal stability of film
(I) Film production
PET resin chips produced by melt polymerization, which were produced in Examples and Comparative Examples described later, were vacuum-dried at 135 ° C. for 6 hours. Then, it was supplied to an extruder, melted and extruded into a sheet form at 280 ° C., and rapidly cooled and solidified on a metal roll maintained at a surface temperature of 20 ° C. to obtain a cast film having a thickness of 1400 μm.
[0097]
Next, this cast film was heated to 100 ° C. with a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction with a roll group having a difference in peripheral speed to obtain a uniaxially oriented PET film. Subsequently, the film was stretched 4.0 times in the width direction at 120 ° C. with a tenter and heated with an infrared heater at 260 ° C. for 0.5 seconds, and further 3% at 200 ° C. for 23 seconds. The biaxially oriented PET film having a thickness of 100 μm was obtained.
[0098]
(Ii) Film formation from recovered pellets
The PET film obtained by the method described in (i) above is cut into strips, vacuum dried, put into an extruder, and the molten resin is extruded from a nozzle having a diameter of 5 mm at a temperature setting of 280 ° C. Collected pellets were obtained by cooling and cutting.
[0099]
The PET resin chip obtained by melt polymerization and the above-described recovered beret were mixed at a weight ratio of 50:50, and vacuum dried at 135 ° C. for 6 hours. Then, it was supplied to an extruder, melted and extruded into a sheet form at 280 ° C., and rapidly cooled and solidified on a metal roll maintained at a surface temperature of 20 ° C. to obtain a cast film having a thickness of 1400 μm.
[0100]
Next, this cast film was heated to 100 ° C. with a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction with a roll group having a difference in peripheral speed to obtain a uniaxially oriented PET film. Subsequently, the film was stretched 4.0 times in the width direction at 120 ° C. with a tenter to obtain a biaxially oriented PET film having a thickness of 100 μm.
[0101]
(Iii) Evaluation of thermal stability of film
The appearance of the obtained film was visually observed, and the less colored the film was evaluated as better depending on the degree of coloring of the film.
[0102]
5) Film water resistance
The film obtained by the method 4) (i) described above was cut into a test piece having a length of 8 cm and a width of 4 cm, and the test piece was boiled in boiling water for 5 days. The film test piece after boiling was pulled in the length direction and evaluated by its ease of cutting.
[0103]
[Polyester synthesis example]
(Example)
For a mixture of bis (2-hydroxyethyl) terephthalate and oligomer produced according to a conventional method from high-purity terephthalic acid and ethylene glycol, a 13 g / l ethylene glycol solution of aluminum chloride as a polycondensation catalyst was used for the acid component in the polyester. An ethylene glycol solution containing 0.015 mol% as aluminum atoms and 10 g / l ethylene glycol solution of dimethyl phenylphosphonate, 0.02 mol% as dimethyl phenylphosphonate based on the acid component, and 50 g / l lithium acetate dihydrate Was added at 0.025 mol% as lithium atoms with respect to the acid component and stirred at 245 ° C. for 10 minutes in a nitrogen atmosphere at normal pressure. Subsequently, the reaction system was gradually heated to 275 ° C. over 50 minutes and the pressure in the reaction system was gradually reduced to 0.1 Torr, and a polycondensation reaction was further performed at 275 ° C. and 0.1 Torr.
[0104]
The polymerization time (AP) required for the polyethylene terephthalate IV to reach 0.65 dl / g was 70 (min), and the polycondensation catalyst had practical polymerization activity.
[0105]
The IV obtained by the above polycondensation ([IV]_i ) Of 0.65 (dl / g) polyethylene terephthalate was made into a chip having a length of about 3 mm and a diameter of about 2 mm according to a conventional method. Using this PET resin chip, a melting test was performed to determine a thermal stability parameter (TS). IV after melting test ([IV]_f1) Was 0.52 and TS was 0.18, and the thermal stability was good.
[0106]
The chip-formed PET resin was pulverized according to a conventional method, a hydrolyzability test was performed using the powder, and a hydrolysis resistance parameter (HS) was also obtained. IV after hydrolysis test ([IV]_f2) Was 0.58 and HS was 0.08, and the PET obtained using the polycondensation catalyst of the present invention was excellent in hydrolysis resistance.
[0107]
Using a PET resin chip obtained by melt polymerization, a film was formed, a recovery pellet was prepared, and a film was formed from the recovery pellet. As a result of evaluating the thermal stability of the film, no coloration was observed in the film and the film was good.
[0108]
As a result of evaluating the water resistance of a film formed by using a virgin PET resin chip obtained by melt polymerization, the film was sufficiently strong and difficult to cut, and was excellent in water resistance.
[0109]
(Comparative Example 1)
As a polycondensation catalyst, an aluminum glycol solution of 13 g / l of aluminum chloride is 0.015 mol% as an aluminum atom with respect to the acid component in the polyester, and an ethylene glycol solution of lithium acetate dihydrate 50 g / l is used as the acid component. Then, the same operation as in Example 1 was performed except that 0.05 mol% was added as a lithium atom.
[0110]
The polymerization time (AP) required for the PET IV to reach 0.65 dl / g was 62 minutes, which was a practical catalytic activity. However, when a hydrolysis test was performed using PET resin powder, the intrinsic viscosity ([IV]) after the hydrolysis test was measured._f2) Was 0.56 and HS was 0.11, and the hydrolysis resistance was not sufficient.
[0111]
Using a PET resin chip obtained by melt polymerization, a film was formed, a recovery pellet was prepared, and a film was formed from the recovery pellet. The water resistance of a film formed using a virgin PET resin chip obtained by melt polymerization was not satisfactory because the strength of the film was lowered and it was easily cut.
[0112]
(Comparative Example 2)
The same operation as in the Example was performed except that 0.015 mol% of an aluminum glycol 13 g / l ethylene glycol solution as a polycondensation catalyst was added as an aluminum atom to the acid component in the polyester. The polymerization reaction was carried out for 180 minutes or more, but the intrinsic viscosity did not reach 0.65 dl / g.
[0113]
(Reference example)
The same operation as in the example was performed except that antimony trioxide was used as a catalyst so that the addition amount was 0.05 mol% as an antimony atom with respect to the acid component in PET. As antimony trioxide, commercially available Antimony (III) oxide (manufactured by ALDRICH CHEMICAL, purity 99.999%) was used. As the antimony trioxide, a solution was used which was dissolved in ethylene glycol by stirring at 150 ° C. for about 1 hour so as to have a concentration of about 10 g / l.
[0114]
AP is 65 (min), [IV]_f1Is 0.50, thermal stability parameter (TS) is 0.22, [IV]_f20.61 and hydrolysis resistance parameter (HS) were 0.05, and these characteristics were excellent.
[0115]
As described above, the hydrolysis resistance parameter (HS) of the PET resin is within the scope of the claims of the present invention, which is excellent in water resistance of the film, excellent in film quality, and in contact with water for a long time. However, there is little decrease in strength. Moreover, what has the thermal stability parameter (TS) of PET resin in the claim of this invention is also excellent in the thermal stability of a film, is excellent in film quality, and reused the waste film. Things are also excellent in quality.
[0116]
On the other hand, when HS is outside the scope of the claims of the present invention, the film has poor water resistance, so the quality of the film is low, and when the film is used for contact with water for a long period of time, the strength is significantly reduced. It happens and there is a problem that the value as a product is scarce. In addition, if TS is outside the scope of the claims of the present invention, the film is poor in thermal stability, so the film quality is low, and a film that reuses scrap film can only be obtained with low quality. Arise.
[0117]
[Industrial application fields]
The polyester polymerization catalyst and the polyester production method of the present invention can be used for production of a polyester polymer. The polyester of the present invention is used in a wide variety of applications, such as fibers for clothing and industrial materials, films and sheets for packaging and magnetic tape, bottles that are hollow molded products, casings for electrical and electronic parts, and other engineering plastic molded products. Can be used in various fields.

Claims (13)

Using the following polyester polymerization catalyst, the total amount of terephthalic acid or its ester-forming derivative or naphthalene dicarboxylic acid or its ester-forming derivative is 70 mol% or more in total with respect to the total acid component, and all of the alkylene glycol. A method for producing a polyester, comprising producing a polyester composed of a glycol component containing 70 mol% or more in total with respect to a glycol component.
(Polyester polymerization catalyst)
Use of the first metal-containing component comprising at least one first metal-containing component selected from the group consisting of an aluminum carboxylate, an inorganic acid salt, and a chelate compound, and a phosphonic acid-based compound having an aromatic ring structure The amount is 0.001 to 0.05 mol% with respect to the number of moles of all constituent units of the carboxylic acid component of the resulting polyester, and the amount of the phosphonic acid compound used is that of the carboxylic acid component of the resulting polyester. Hydrolysis resistance parameter (HS) of polyethylene terephthalate (PET), which is a polyester polymerization catalyst of 0.0001 to 0.1 mol% based on the number of moles of all constituent units, and polymerized using this catalyst Satisfies the following formula (1) and the thermal stability parameter (TS) satisfies the following formula (2).
(1) HS <0.10
(HS is melt-polymerized and PET chip having an intrinsic viscosity of about 0.65 dl / g (before test: [IV] _i ) was freeze-ground and vacuum-dried at 130 ° C. for 12 hours as a powder of 20 mesh or less. Thereafter, 1 g of the mixture was put into a beaker with 100 ml of pure water, and the following formula HS = 0.0 was obtained from the intrinsic viscosity ([IV] _f2 ) after stirring for 6 hours under the condition of heating and pressurizing at 130 ° C. in a closed system. ^{_{245 {[IV] f2 -1.47 -}} [IV] i -1.47}
Is a numerical value calculated by. )
(2) TS <0.30
(TS is 1 g of PET with an intrinsic viscosity ([IV] _i ) of about 0.65 dl / g put in a glass test tube and vacuum dried at 130 ° C. for 12 hours, and then melted at 300 ° C. for 2 hours in a non-circulating nitrogen atmosphere. From the intrinsic viscosity ([IV] _f1 ) after maintaining the following formula, TS = 0.245 {[IV] _f1 ^−1.47 − [IV] _i ^−1.47 }
Is a numerical value calculated by. ) Furthermore, the activity parameter (AP) of superposition | polymerization of the said polyester polymerization catalyst satisfy | fills following formula (3), The manufacturing method of the polyester of Claim 1 characterized by the above-mentioned.
(3) AP (min) <2T (min)
(AP represents the time (min) required to polymerize polyethylene terephthalate having an intrinsic viscosity of 0.65 dl / g at a reduced pressure of 275 ° C. and 0.1 Torr using a predetermined amount of catalyst, and T represents antimony trioxide. (AP when added to 0.05 mol% as an antimony atom with respect to the acid component in the polyethylene terephthalate produced as a catalyst.) The method for producing a polyester according to claim 1 or 2, wherein the phosphonic acid compound is at least one compound represented by the following general formula (Formula 3 ) .
Ph-P (= O) (OR ¹ ) (OR ² )
(In Formula (Chemical Formula 3), R ¹ and R ² each independently represent hydrogen, an alkyl group having 1 to 50 carbon atoms, or an aryl group. )   The method for producing a polyester according to any one of claims 1 to 3, wherein an alkali metal, an alkaline earth metal or a compound thereof is not added to the polyester polymerization catalyst.   4. The polyester polymerization catalyst is allowed to coexist with at least one second metal-containing component selected from the group consisting of alkali metals, alkaline earth metals, or compounds thereof. Polyester production method.   The method for producing a polyester according to claim 5, wherein the second metal-containing component is an alkali metal or a compound thereof.   The method for producing a polyester according to claim 6, wherein the alkali metal is at least one selected from Li, Na, and K. The method for producing a polyester according to any one of claims 5 to 7, wherein an addition amount M (mol%) of the second metal-containing component with respect to the total carboxylic acid component of the polyester satisfies the formula (4).
(4) M ≦ 0.05   The method for producing a polyester according to any one of claims 1 to 8, wherein a cobalt compound is further allowed to coexist in the polyester polymerization catalyst.   The method for producing a polyester according to claim 1, wherein at least one of an antimony compound and a germanium compound is further allowed to coexist in the polyester polymerization catalyst.   The method for producing a polyester according to claim 10, wherein the antimony compound is added in an amount of 50 ppm or less based on the polyester as antimony atoms.   The method for producing a polyester according to claim 10 or 11, wherein the addition amount of the germanium compound is an amount of 20 ppm or less based on the polyester as germanium atoms.   The polyester manufactured by the manufacturing method of the polyester in any one of Claims 1-12.