JP2003171456A - Polyester resin and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester resin obtained by polycondensation in the presence of an antimony compound, having a reduced elution amount of the antimony, and good color, and hardly generating byproducts. <P>SOLUTION: This polyester resin is obtained by carrying out an esterification or ester-interchange reaction of an aromatic dicarboxylic acid or an ester- forming derivative thereof, with a diol component consisting essentially of ethylene glycol, and polycondensing the resultant product at least in the presence of the antimony compound and a phosphorus compound. The amount of the antimony eluted when granules having 24 mg number averaged particle weight are soaked in hot water at 95°C for 60 min is regulated so as to be ≤1 μg per g-polyester resin expressed in terms of antimony atom (Sb). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyester resin which is polycondensed in the presence of an antimony compound, and more specifically, it is used in water or a solvent such as a post-treatment step after polycondensation and a dyeing step after textile processing. The present invention relates to a polyester resin in which the elution amount of antimony during contact with the like is suppressed.

[0002]

2. Description of the Related Art Conventionally, for example, polyester resins such as polyethylene terephthalate resin have excellent mechanical strength, chemical stability, gas barrier properties, hygiene properties, etc., and are relatively inexpensive and lightweight. It is widely used as various packaging materials such as films, or as fibers, and is mainly produced as an antimony compound as a polycondensation catalyst, but the antimony component remaining in the resin is, for example, water such as water after cooling after polycondensation. There is a concern about problems such as elution and causing environmental pollution in the step of contacting with a solvent or the step of contacting with a solvent such as dyeing after fiber processing.

On the other hand, various polyester resins produced by using a titanium compound instead of an antimony compound as a polycondensation catalyst, or by using a titanium compound in combination have been proposed.
There is a problem that by-products such as acetaldehyde and diethylene glycol increase and the melting heat stability decreases.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is a polyester resin polycondensed in the presence of an antimony compound, in which the elution amount of antimony is suppressed, and An object of the present invention is to provide a polyester resin having a good color tone and reduced generation of by-products. A further object of the present invention is to provide a method for producing such polyester resin.

[0005]

The present invention has been made to achieve the above object, that is, the present invention is a dicarboxylic acid component containing an aromatic dicarboxylic acid or an ester-forming derivative thereof as a main component. And a diol component containing ethylene glycol as a main component are subjected to an esterification reaction or a transesterification reaction, and polycondensed in the presence of at least an antimony compound and a phosphorus compound. The gist of the present invention is a polyester resin in which the amount of elution of antimony when immersed in hot water of 95 ° C. for 60 minutes as a granular material having a particle weight of 24 mg is 1 μg or less per 1 g of polyester resin as an antimony atom (Sb).

Another aspect is a method for producing a polyester resin by polycondensing a dicarboxylic acid component containing an aromatic dicarboxylic acid or its ester-forming derivative as a main component and a diol component containing ethylene glycol as a main component. A method for producing a polyester resin, wherein the catalyst is added to the reaction system so that each atom derived from the following polymerization catalyst is contained in the obtained polyester resin in the following concentration range. 0 <T ≦ 50 (weight ppm) 10 ≦ Sb ≦ 250 (weight ppm) 0.1 ≦ P ≦ 20 (weight ppm) 6.0 ≦ Sb / P ≦ 30 (In the above formula, T is a titanium atom in the resin. , At least one selected from hafnium atom and zirconium atom
The total atomic concentration of the seed atoms (ppm), Sb is the antimony atomic concentration (ppm) in the resin, and P is the phosphorus atomic concentration (ppm) in the resin.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester resin of the present invention comprises a dicarboxylic acid component containing an aromatic dicarboxylic acid or an ester-forming derivative thereof as a main component and a diol component containing ethylene glycol as a main component in an esterification reaction or It is produced by polycondensation in the presence of at least an antimony compound and a phosphorus compound through a transesterification reaction.

In the present invention, as the aromatic dicarboxylic acid or its ester-forming derivative, specifically,
For example, terephthalic acid, phthalic acid, isophthalic acid, dibromoisophthalic acid, sodium sulfoisophthalate, phenylenedioxydicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenyl Ketone dicarboxylic acid, 4,
4'-diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and terephthalic acid dimethyl ester,
Examples thereof include alkyl esters of these aromatic dicarboxylic acids having about 1 to 4 carbon atoms such as 2,6-naphthalenedicarboxylic acid dimethyl ester, and halides, among which terephthalic acid, 2,6-naphthalenedicarboxylic acid,
Alternatively, their alkyl esters are preferred, and terephthalic acid is particularly preferred.

Examples of the dicarboxylic acid component other than the aromatic dicarboxylic acid and the ester-forming derivative thereof include alicyclic dicarboxylic acids such as hexahydroterephthalic acid and hexahydroisophthalic acid, and succinic acid and glutaric acid. , Adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecadicarboxylic acid, dodecadicarboxylic acid, and other aliphatic dicarboxylic acids, and the alicyclic dicarboxylic acids and aliphatic dicarboxylic acids having 1 to 1 carbon atoms
Alkyl esters of about 4 and halides are included.

Examples of the diol component other than ethylene glycol include trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, neopentyl glycol, 2-
Aliphatic diols such as ethyl-2-butyl-1,3-propanediol, diethylene glycol, polyethylene glycol, polytetramethylene ether glycol,
1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol,
Alicyclic diols such as 1,4-cyclohexane dimethylol and 2,5-norbornane dimethylol, and xylylene glycol, 4,4′-dihydroxybiphenyl,
2,2-bis (4'-hydroxyphenyl) propane,
Aromatic diols such as 2,2-bis (4′-β-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, and bis (4-β-hydroxyethoxyphenyl) sulfonic acid, and 2,2- Examples thereof include ethylene oxide adducts and propylene oxide adducts of bis (4′-hydroxyphenyl) propane.

Further, for example, hydroxycarboxylic acids and alkoxycarboxylic acids such as glycolic acid, p-hydroxybenzoic acid and p-β-hydroxyethoxybenzoic acid, and stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t- Butylbenzoic acid, benzoylbenzoic acid, and other monofunctional components, tricarballylic acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, and other polyfunctional compounds. One kind or two or more kinds of functional components may be used as a copolymerization component.

The polyester resin of the present invention contains the aromatic dicarboxylic acid or its ester-forming derivative in an amount of 50 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, and particularly preferably 50 mol% or more of the dicarboxylic acid component. 9
A dicarboxylic acid component accounting for 9 mol% or more, and a diol component accounting for 50 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, particularly preferably 97 mol% or more of ethylene glycol with respect to the diol component. ,
It is produced by polycondensation through an esterification reaction or transesterification reaction. In addition, diethylene glycol produced as a by-product in the reaction system may be copolymerized, and the content of diethylene glycol including a component added from outside the system as a copolymerization component is preferably 5 mol% or less. When the content of diethylene glycol is high, the degree of suppression of the elution amount of antimony as a polyester resin tends to decrease, and the melting heat stability as a resin,
The heat resistance and mechanical strength tend to decrease.

In the present invention, the polycondensation is carried out in the presence of at least an antimony compound and a phosphorus compound, and accordingly, the polyester resin of the present invention contains at least an antimony component and a phosphorus component.

Here, as the antimony compound,
Specific examples include antimony trioxide, antimony pentoxide, antimony acetate, methoxyantimony, triphenylantimony, antimony glycolate, and the like, among which antimony trioxide is preferred.

As the phosphorus compound, specifically,
For example, orthophosphoric acid, polyphosphoric acid, and esters thereof, such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (triethylene glycol).
Pentavalent phosphorus compounds such as phosphate, ethyl diethyl phosphonoacetate, methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, monobutyl phosphate, dibutyl phosphate, dioctyl phosphate, triethylene glycol acid phosphate,
Hypophosphorous acid, phosphorous acid, and their esters, such as dimethyl phosphite, diethyl phosphite, trimethyl phosphite, triethyl phosphite, tributyl phosphite, trisdodecyl phosphite, trisnonyl decyl phosphite, diphenyl phosphite. , Triphenyl phosphite, etc., and their metal salts such as lithium, sodium, potassium, etc.,
And trivalent phosphorus compounds, such as pentavalent phosphorus compounds such as orthophosphoric acid esters such as ethyl acid phosphate, hypophosphorous acid, phosphorous acid, and diethyl phosphite.
Trivalent phosphorus compounds such as phosphorous acid esters such as trimethylphosphite and triethylphosphite are preferable, and trivalent phosphorus compounds such as phosphorous acid and phosphorous acid esters are particularly preferable.

In the present invention, the antimony compound,
And the amount of each phosphorus compound used in the polycondensation and the content thereof in the polyester resin, the content of the antimony component in the polyester resin as an antimony atom (Sb) is 10 to 250 ppm by weight. Is more preferable, 30 to 150 ppm by weight is more preferable, and 50 to 110 ppm by weight is particularly preferable.
If the content as an antimony atom is less than the above range, the polycondensability is insufficient and the productivity is lowered, the color tone is also lowered, and the by-products tend to increase, while on the other hand, if the amount exceeds the above range, the amount eluted Tends to be difficult to suppress.

The content of the phosphorus component as the phosphorus atom (P) in the polyester resin is preferably 0.1 to 20 ppm by weight, more preferably 1.0 to 15 ppm by weight, It is particularly preferably 2.0 to 10 ppm by weight. When the content of phosphorus atoms is less than the above range, the color tone tends to deteriorate and by-products tend to increase, while when it exceeds the above range, it tends to be difficult to suppress the elution amount.

The content (weight pp) of the antimony component as the antimony atom (Sb) in the polyester resin.
m) and the content of phosphorus component as phosphorus atom (P) (weight pp
The ratio (Sb / P) with m) is preferably 6.0 to 30, more preferably 8.0 to 20, and 9.0.
It is especially preferable that it is -15. When the ratio of the content as the antimony atom and the content as the phosphorus atom is less than the above range, the polycondensability is insufficient and the productivity is lowered, and
The color tone also decreases and the amount of by-products tends to increase, while
If the amount exceeds the above range, it tends to be difficult to suppress the elution amount.

Further, polycondensation can be carried out by group 1A and group I of the periodic table.
Group IA, zinc, aluminum, gallium, germanium, titanium, zirconium, hafnium, manganese,
It is preferably made in the coexistence of a compound of at least one metal element selected from the group consisting of iron and cobalt, and accordingly, the polyester resin of the present invention has a group 1A group of the periodic table, It is preferable that at least one metal element component selected from the group consisting of Group IIA, zinc, aluminum, gallium, germanium, titanium, zirconium, hafnium, manganese, iron, and cobalt is contained.

In the present invention, the total amount of these metal compounds used at the time of polycondensation and the total amount thereof in the polyester resin are defined as the metal atom (M) of those metal element components in the polyester resin. The total content is preferably 0.1 to 100 ppm by weight.

Examples of the coexisting metal compound include, for example,
Periodic Table Group 1A lithium, sodium, potassium, etc., Group IIA beryllium, magnesium, calcium, strontium, barium, etc., and zinc, aluminum, gallium, germanium, titanium, zirconium, hafnium, manganese, iron, And cobalt oxides, hydroxides, alkoxides, carboxylates, carbonates, oxalates, and halides.

Among these coexisting metal compounds, in the present invention, metal compounds of Group 1A and Group IIA of the Periodic Table, especially magnesium compounds of Group IIA are preferable, and the magnesium compound is preferable. Specifically, for example, magnesium oxide, magnesium hydroxide, magnesium alkoxide, magnesium acetate, magnesium carbonate and the like can be mentioned, of which magnesium acetate is preferable.

The amount of the magnesium compound used in the polycondensation and the content thereof in the polyester resin are such that the content of the magnesium component in the polyester resin as a magnesium atom (Mg) is 0.1 to 30 ppm by weight. Is more preferable, 1.0 to 20 ppm by weight is more preferable, and 3.0 to 15 ppm by weight is particularly preferable. If the content as magnesium atoms is less than the above range, it tends to be difficult to suppress the elution amount. On the other hand, if the content exceeds the above range, the color tone tends to deteriorate and the amount of by-products tends to increase.

When the coexisting metal compound is a magnesium compound, the content (weight pp) as the magnesium atom (Mg) of the magnesium component in the polyester resin.
m) and the content of phosphorus component as phosphorus atom (P) (weight pp
The ratio (Mg / P) with m) is preferably 1.1 to 3.0, more preferably 1.3 to 2.5 ppm by weight, and 1.5 to 2.0. Is particularly preferable. When the ratio of the content of magnesium atoms to the content of phosphorus atoms is less than the above range, it tends to be difficult to suppress the elution amount. On the other hand, when the ratio exceeds the above range, the color tone is lowered and by-products are also generated. It tends to increase.

Among these coexisting metal compounds, titanium compounds are also preferable, and particularly Group 1A and II of the Periodic Table.
A metal compound of Group A, preferably a combination with the magnesium compound of Group IIA is preferable, and specific examples of the titanium compound include tetra-n-propyl titanate and tetra-i-propyl titanate. Tetra-n
-Butyl titanate, tetra-n-butyl titanate tetramer, tetra-t-butyl titanate, tetracyclohexyl titanate, tetraphenyl titanate, tetrabenzyl titanate, titanium acetate, titanium oxalate, titanium acetylacetonate, titanium potassium oxalate, sodium titanium oxalate, Potassium titanate, sodium titanate, titanic acid-aluminum hydroxide mixture, titanium chloride, titanium chloride-aluminum chloride mixture, titanium bromide, titanium fluoride, potassium hexafluorotitanate, cobalt hexafluorotitanate, hexafluoride. Manganese titanate, ammonium hexafluorotitanate, titanium acetylacetonate, and the like, among which tetra-n-propyl titanate, tetra-i-propyl titanate, tetra-n-butyl titanate, and oxalic Titanium, titanium oxalate potassium are preferred.

The amount of the titanium compound used in the polycondensation and the content thereof in the polyester resin are such that the content of the titanium component in the polyester resin as titanium atoms (Ti) is 0.25 to 10 ppm by weight. Is more preferable, 0.75 to 5.0 ppm by weight is more preferable, and 1.5 to 4.0 ppm by weight is particularly preferable. If the content as titanium atoms is less than the above range,
The degree of suppression of the elution amount tends to decrease, while on the other hand, when the amount exceeds the above range, the color tone tends to deteriorate and the amount of by-products tends to increase.

The other coexisting metal compounds are typically, for example, compounds of metals of Group 1A of the periodic table such as lithium acetate, sodium acetate, potassium acetate, calcium oxide, calcium hydroxide, calcium acetate. , Compounds of Group IIA metals such as calcium carbonate, zinc acetate, zinc benzoate, zinc methoxide, zinc acetylacetonate, zinc compounds such as zinc chloride, germanium dioxide, germanium tetroxide, germanium hydroxide,
Germanium compounds such as germanium tetraethoxide, germanium tetrabutoxide, and germanium oxalate;
Manganese oxide, manganese hydroxide, manganese methoxide, manganese acetate, manganese benzoate, manganese acetylacetonate, manganese chloride and other manganese compounds, cobalt formate, cobalt acetate, cobalt stearate, cobalt naphthenate, cobalt benzoate, cobalt acetyl. Examples thereof include cobalt compounds such as acetonate, cobalt carbonate, cobalt oxalate, cobalt chloride and cobalt bromide.

The polyester resin of the present invention undergoes esterification or transesterification reaction between the dicarboxylic acid component containing the aromatic dicarboxylic acid or its ester-forming derivative as the main component and the diol component containing ethylene glycol as the main component. Produced by polycondensation in the presence of at least the antimony compound and the phosphorus compound, preferably in the coexistence of the metal compound, especially the magnesium compound, and / or the titanium compound, but basically, According to a conventional method for producing a polyester resin. That is, a dicarboxylic acid component containing the aromatic dicarboxylic acid or its ester-forming derivative as a main component and a diol component containing ethylene glycol as a main component, together with a copolymerization component used as necessary, in a slurry preparation tank. After being charged and mixed with stirring to form a raw material slurry, under normal pressure to increased pressure in an esterification reaction tank, under heating, an esterification reaction is performed, or after an ester exchange reaction in the presence of an ester exchange catalyst,
The obtained polyester low molecular weight product as an esterification reaction product or a transesterification reaction product is transferred to a polycondensation tank, and melted in the presence of the compound under reduced pressure from atmospheric pressure to gradually reduced pressure, under heating. It is produced by polycondensation.

The production method by which the polyester resin of the present invention in which the elution amount of antimony is in a specific range can be obtained is not particularly limited, but atoms such as antimony and phosphorus are contained in the specific range as described above with respect to the obtained polyester resin, Addition in a specific amount ratio may be mentioned, and the present invention therefore also relates to a method for producing such a polyester resin. That is, as a suitable method for producing the polyester resin of the present invention, a dicarboxylic acid component containing an aromatic dicarboxylic acid or an ester-forming derivative thereof as a main component and a diol component containing ethylene glycol as a main component are combined. A method for producing a polyester resin by condensation, comprising:
A method for producing a polyester resin is characterized in that the catalyst is added to the reaction system so that each atom derived from the polymerization catalyst can be contained in the following concentration range with respect to the polyester resin. 0 <T ≦ 50 ppm 10 ≦ Sb ≦ 250 ppm 0.1 ≦ P ≦ 20 ppm 6.0 ≦ Sb / P ≦ 30 (In the above formula, T is at least one selected from titanium atom, hafnium atom and zirconium atom in the resin. Of the total number of atoms or a plurality of concentrations (ppm), Sb is the concentration of antimony atoms in the resin (ppm), P is the concentration of phosphorus atoms in the resin (ppm)) ppm means weight ppm unless otherwise specified. To do.

Further, the preferred ranges of the dicarboxylic acid component, the diol component, T, Sb, P, etc. in the production method are those described above for the component of the polyester resin of the present invention. Further, in the method for producing a polyester resin of the present invention, preferably, in addition to the above-mentioned polymerization catalyst, the following polymerization catalyst is further added to the obtained polyester resin in a reaction system such that the catalyst is contained in the following concentration range. Added to. 0.1 ≦ M ≦ 200 ppm 1.1 ≦ M / P ≦ 15 (M is at least one selected from the group consisting of a Group IA metal atom, a Group IIA metal atom, a manganese atom, an iron atom, and a cobalt atom in the resin. Total content of seed metal atoms (pp
m)) Preferred ranges of M, P and the like in the production method are those described above for the components of the polyester resin of the present invention.

More preferably, the esterification rate is 90%.
In the following stage, after adding the phosphorus compound to the reaction mixture containing the esterification reaction product and the esterification rate reaches 90% or more, the group IA element compound, the group IIA compound, the manganese compound, the iron compound and the cobalt compound At least one compound selected from the group consisting of metal atoms is added, and then at least one compound selected from the group consisting of titanium compounds, zirconium compounds, and hafnium compounds is added. In the case of the transesterification reaction, it is necessary to use a transesterification catalyst and it is necessary to use a large amount of the transesterification catalyst. Therefore, in the present invention, the transesterification catalyst is preferably produced through the esterification reaction.

Here, in the case of the esterification reaction, the raw material slurry is prepared by a carboxylic acid component having an aromatic dicarboxylic acid as a main component, a diol component having an ethylene glycol as a main component, and a copolymer used as necessary. The components and the like are mixed so that the molar ratio of the diol component to the dicarboxylic acid component is in the range of preferably 1.02 to 2.0, more preferably 1.03 to 1.7. If the molar ratio is less than the above range, the esterification reactivity will decrease, while if it exceeds the above range, the amount of diethylene glycol produced will increase.

The esterification reaction is usually carried out by using a multi-stage reaction apparatus in which a plurality of esterification reaction tanks are connected in series.
While refluxing ethylene glycol and removing water and excess ethylene glycol generated by the reaction to the outside of the system, the esterification rate (of the total carboxyl groups of the raw material dicarboxylic acid component which was reacted with the diol component to be esterified) Ratio) is usually 90% or more, preferably 93% or more. The number average molecular weight of the low molecular weight polyester as the esterification reaction product obtained is 500.
It is preferably 5,000.

As the reaction conditions in the esterification reaction, the reaction temperature in the first stage esterification reaction tank is
Usually 240 to 270 ° C, preferably 245 to 265 ° C,
Relative pressure to atmospheric pressure is usually 5 to 300 kPa
(0.05 to 3 kg / cm ² G), preferably 10 to 2
00 kPa (0.1 to ² kg / cm ² G), the reaction temperature in the final stage is usually 250 to 280 ° C., preferably 255 to 275 ° C., and the relative pressure to atmospheric pressure is usually 0 to 150 kPa (0-1. 5 kg / cm ² G), preferably 0 to 130 kPa (0 to 1.3 kg / cm ² G)
And Incidentally, when the reaction is carried out in a single esterification reaction tank, the reaction conditions in the final stage are adopted.

In the esterification reaction, for example, tertiary amines such as triethylamine, tributylamine and benzyldimethylamine, and quaternary hydroxides such as tetraethylammonium hydroxide, tetrabutylammonium hydroxide and trimethylbenzylammonium hydroxide. By-adding a small amount of a basic compound such as ammonium, lithium carbonate, sodium carbonate, potassium carbonate, sodium acetate or the like, the by-production of diethylene glycol from ethylene glycol can be suppressed.

The melt polycondensation is usually carried out under reduced pressure while distilling the produced ethylene glycol out of the system using a multi-stage reaction apparatus in which a plurality of melt polycondensation tanks are connected in series. As the reaction apparatus, for example, the first stage is a complete mixing type reactor having stirring blades, and the second and third stages are horizontal plug flow type reactors having stirring blades. Is used.

As the reaction conditions in the melt polycondensation, the reaction temperature in the first stage polycondensation tank is usually 250 to 2
90 ° C., preferably 260 to 280 ° C., and the absolute pressure is usually 65 to 1.3 kPa (500 to 10 Torr), preferably 26 to 2 kPa (200 to 15 Torr),
The reaction temperature in the final stage is usually 265 to 300 ° C, preferably 270 to 295 ° C, and the absolute pressure is usually 1.3 to
0.013 kPa (10 to 0.1 Torr), preferably 0.65 to 0.065 kPa (5 to 0.5 Torr)
And As the reaction conditions in the intermediate stage, those intermediate conditions are selected. For example, in a three-stage reaction apparatus, the reaction temperature in the second stage is usually 265 to 295.
C., preferably 270 to 285.degree. C., and the absolute pressure is usually 6.5 to 0.13 kPa (50 to 1 Torr), preferably 4 to 0.26 kPa (30 to 2 Torr).

The addition of the antimony compound, the phosphorus compound, the coexisting metal compound and the like to the reaction system in the polycondensation may be carried out in any of a slurry preparation step of the raw material dicarboxylic acid component and a diol component and an esterification reaction step. Or the initial stage of the melt polycondensation step, but the production of solid foreign matter in the resin is suppressed, and after sufficient polymerization activity is obtained, the elution of antimony in the obtained polyester resin In order to suppress the amount and effectively develop the effect of reducing by-products such as acetaldehyde,
The phosphorus compound is preferably added to the slurry preparation tank or the first stage esterification reaction tank, and particularly preferably added to the slurry preparation tank. Further, the antimony compound and the coexisting metal compound are esterification reaction products having an esterification rate of 90% or more in the esterification reaction step, specifically, for example, the final stage esterification reaction tank in a multi-stage reaction apparatus, Alternatively, it is preferably added to the step of transferring the esterification reaction product to the melt polycondensation step, and the antimony compound and the metal of Group 1A or IIA of the periodic table in the coexisting metal compound are contained. It is particularly preferable that the compound is added before the compounds such as zinc, aluminum, gallium, germanium, titanium, zirconium and hafnium in the coexisting metal compound.

The resin obtained by the melt polycondensation is usually extracted in a strand form from an outlet provided at the bottom of the polycondensation tank and cut with a cutter while cooling with water or after water cooling into pellets or chips. The melt-polycondensed granular material is usually 100 kPa relative to atmospheric pressure in an atmosphere of an inert gas such as nitrogen, carbon dioxide or argon.
(1 kg / cm ² G) or less, preferably 20 kPa
Under a pressure of (0.2 kg / cm ² G) or less, or as an absolute pressure, usually 6.5 to 0.013 kPa (50 to
0.1 Torr), preferably 1.3 to 0.065 kP
a (10-0.5 Torr) under reduced pressure, usually 190-
By heating at a temperature of 230 ° C., preferably 195 to 225 ° C., solid phase polycondensation is performed. By this solid-phase polycondensation, the degree of polymerization can be further increased, and by-products such as acetaldehyde can be reduced.

At that time, prior to the solid-phase polycondensation, heating is usually carried out at 120 to 200 ° C., preferably 130 to 190 ° C. in an inert gas atmosphere, a steam atmosphere or a steam-containing inert gas atmosphere. Therefore, it is preferable to crystallize the surface of the resin granules.

Further, the resin obtained by the melt polycondensation or the solid phase polycondensation as described above is usually treated by immersing it in warm water of 40 ° C. or higher for 10 minutes or more, or steam or steam of 60 ° C. or higher. A treatment such as steam treatment in which the contained gas is contacted for 30 minutes or more is performed, or treatment with an organic solvent, treatment with an acidic aqueous solution of various mineral acids, organic acids, phosphoric acid, etc., Group IA metal, Group IIA The catalyst used for polycondensation can also be deactivated by treatment with an alkaline aqueous solution of a group metal or amine or an organic solvent solution.

The polyester resin of the present invention has a number-average particle weight of 24 mg, and when it is immersed in hot water of 95 ° C. for 60 minutes, the amount of antimony eluted is as antimony atom (Sb) per 1 g of polyester resin. It is 1 μg or less, preferably 0.5 μg or less, more preferably 0.2 μg or less, and 0.1 μg or less.
It is particularly preferably g or less.

The elution amount as antimony atom (Sb) was 95 ° C. after 50 g of polyester resin granules having a number average particle weight of 24 mg were heated at 120 ° C. for 10 hours for crystallization. It was immersed in 150 g of hot water for 60 minutes, and the antimony extracted in the water at that time was measured as the antimony atom concentration C (ppb) by inductively coupled plasma mass spectrometry.
The amount of elution D (μg) as an antimony atom per g is calculated. D (μg) = (C / 10 ⁹ ) × (150/50) × 10
⁶

Further, the polyester resin of the present invention has an intrinsic viscosity ([η]) of melt polycondensation as a value measured at 30 ° C. in a solution of a mixed solvent of phenol / tetrachloroethane (weight ratio 1/1). For resins, usually 0.35 to 0.
75 dl / g, but 0.70 for solid-phase polycondensation resin
Is preferably 0.90 dl / g, and 0.70
It is particularly preferably 0.80 dl / g. As for the color tone, La described in Reference 1 of JIS Z8730 is used.
The color coordinate b of the Hunter color difference formula in the b color system is preferably 3 or less, particularly preferably -5 to 2. Further, the acetaldehyde content is preferably 5 ppm or less, and particularly preferably 3 ppm or less.

In the present invention, the polyester resin includes an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a lubricant, an antiblocking agent, an antifogging agent, a nucleating agent, a plasticizer, a coloring agent, and a filler. Materials and the like may be contained.

The polyester resin of the present invention is molded into a bottle or the like by, for example, forming a preform by injection molding, followed by stretch blow molding, or by blow molding a parison molded by extrusion molding. Further, after being formed into a sheet by extrusion molding, it is formed into a tray or a container by thermoforming, or the sheet is biaxially stretched into a film or the like, or formed into a fibrous shape. Various processed textiles.

[0047]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Example 1 A continuous slurry preparation tank, a two-stage esterification reaction tank connected in series thereto, and a three-stage melt polycondensation tank connected in series to the second-stage esterification reaction tank Using a polymerization apparatus, terephthalic acid and ethylene glycol were continuously supplied at a weight ratio of 865: 485 to a slurry preparation tank, and a 0.3 wt% ethylene glycol solution of ethyl acid phosphate was added to the produced polyester resin. On the other hand, the content as a phosphorus atom (P) is 9.0 weight pp.
A slurry is prepared by continuously adding and stirring the mixture in an amount of m so that the slurry has a relative pressure of 50 kPa (0.5 kg / cm ²⁾ at 260 ° C. under a nitrogen atmosphere.
G), the first stage esterification reaction tank set to an average residence time of 4 hours, then 260 ° C. under a nitrogen atmosphere, a relative pressure of 5 kPa (0.05 kg / cm ² G), an average residence time of 1.5. The esterification reaction was carried out by continuously transferring to the second stage esterification reaction tank set for the time. At that time, the average esterification rate measured by the following method was 85% in the first stage and 9% in the second stage.
It was 5%.

<Average Esterification Rate> Samples were deuterated chloroform / hexafluoroisopropanol (weight ratio 7
/ 3) of a solution dissolved in a mixed solvent of 3% by weight, a nuclear magnetic resonance apparatus ("JNM-EX2" manufactured by JEOL Ltd.).
70 type "), ¹ H-NMR is measured, each peak is assigned, the amount of terminal carboxyl groups (A mol / ton of sample) is calculated from the integrated value of the peak, and the terephthalic acid unit of the terephthalic acid unit is calculated by the following formula. The esterification rate (E%) as a ratio of the esterified ester of all the carboxyl groups was calculated. Esterification rate (E) = [1-A / {(1000000 /
192.2) × 2}] × 100

At this time, a 0.6% by weight solution of magnesium acetate tetrahydrate in ethylene glycol was added as magnesium atoms (Mg) to the produced polyester resin through the upper pipe provided in the second stage. The amount is 15 p
pm and 1.9% by weight of antimony trioxide
The ethylene glycol solution was continuously added to the resulting polyester resin in an amount such that the content of antimony atoms (Sb) was 90 ppm by weight.

Subsequently, when the esterification reaction product obtained above is transferred to the melt polycondensation tank, a 0.2 wt% ethylene glycol solution of tetrabutyl titanate is added to the transfer polyester in the transfer pipe. While continuously adding titanium atoms (Ti) in an amount of 2.0 wt ppm, the temperature is 270 ° C. and the absolute pressure is 2.6 k.
Pa (20 Torr), the first stage melt polycondensation tank set to an average residence time of 1.2 hours, then 278 ° C., an absolute pressure of 0.5 kPa (4 Torr), an average residence time of 1.
Second stage melt polycondensation tank set for 2 hours, then
280 ° C., absolute pressure 0.3 kPa (2 Torr), continuous transfer to the third stage melt polycondensation tank set to an average residence time of 1.2 hours, melt polycondensation, the bottom of the polycondensation tank The strands are extracted from the outlet provided in the machine, cooled with water, and then cut with a cutter to give a number average particle weight of 24 m.
g of a chip-like granular polyester resin was produced. The intrinsic viscosity of the obtained resin was 0.60 dl / g.

Subsequently, the polyester resin chips obtained above were crystallized by continuously supplying them to a stirring crystallization machine maintained at about 160 ° C. under a nitrogen atmosphere so that the residence time was about 60 minutes. After that, the solid phase polycondensation apparatus was continuously supplied to a tower-type solid phase polycondensation apparatus and heated at 205 ° C. in a nitrogen atmosphere for solid phase polycondensation.

Regarding the obtained solid phase polycondensation resin chip,
The elution amount of antimony when immersed in hot water of 95 ° C. for 60 minutes was measured by the following method, and the results are shown in Table 1.

<Elution amount of antimony> Number average particle weight 24 m
50 g of polyester resin granules having a weight of 50 g are heated at 120 ° C. for 10 hours to be crystallized, and then hot water of 95 ° C. 150
It was immersed in g for 60 minutes, and the antimony extracted in the water at that time was measured as an antimony atomic concentration C (ppb) using an inductively coupled plasma mass spectrometer ("HP4500" manufactured by Hewlett-Packard Co.), according to the following formula. ,
The elution amount D (μg) as an antimony atom per 1 g of the polyester resin was calculated. D (μg) = (C / 10 ⁹ ) X (150/50) x 10
⁶

Further, the obtained solid phase polycondensation resin chips have respective phosphorus atoms (P) and magnesium atoms (M) of phosphorus component, magnesium component, antimony component and titanium component.
g), antimony atom (Sb), and titanium atom (T
The content as i) was measured by the method shown below, and the results are shown in Table 1.

<Metal Atom Content> 2.5 g of resin sample
After incineration by hydrogen peroxide in the presence of sulfuric acid by a conventional method and complete decomposition, the volume was adjusted to 50 ml with distilled water.
VON's "JY46P type") was used to quantify by plasma emission spectroscopy.

Further, with respect to the obtained solid phase polycondensation resin chip, the amount of diethylene glycol copolymerized, the intrinsic viscosity, the color coordinate b value as a color tone, and the acetaldehyde content were measured by the following methods, and the results are shown in Table 1. Indicated.

<Diethylene glycol copolymerization amount> A solution prepared by dissolving a resin sample in a mixed solvent of deuterated chloroform / hexafluoroisopropanol (weight ratio 7/3) at a concentration of 3% by weight was analyzed by a nuclear magnetic resonance apparatus (JEOL Ltd.). ¹ H-NMR was measured with "JNM-EX270 Model" manufactured, each peak was assigned, and the mol% of diethylene glycol to all diol components was calculated from the integrated value of the peak.

<Intrinsic Viscosity> Freeze-pulverized resin sample 0.2
5 g of phenol / tetrachloroethane (weight ratio 1 /
After dissolving in the mixed solvent of 1) at a concentration (c) of 1.0 g / dl at 110 ° C. for 30 minutes in the case of a melt polycondensation resin and at 120 ° C. for 30 minutes in the case of a solid polycondensation resin Using an Ubbelohde-type capillary viscous tube, the relative viscosity (η _rel ) with the stock solution was measured at 30 ° C., and this relative viscosity (η
The ratio (η _sp / c) of the specific viscosity (η _sp ) and the concentration (c) obtained from _rel ) -1 was calculated, and the concentration (c) was 0.5 g /
The respective ratios (η _sp / c) were also obtained for dl, 0.2 g / dl and 0.1 g / dl, and the ratio (η _sp ) when the concentration (c) was extrapolated to 0 was calculated from these values. _sp / c) was determined as the intrinsic viscosity [η] (dl / g).

<Color Coordinate b Value> The resin sample has an inner diameter of 36 m.
m and a depth of 15 mm, a cylindrical powder color measuring cell was filled with a shaving, and a color measuring color difference meter (“ND-30 manufactured by Nippon Denshoku Industries Co., Ltd.”) was used.
0A "), the color coordinate b of the Hunter color difference formula in the Lab color system described in Reference 1 of JIS Z8730 is measured by rotating the cell by 90 degrees by a reflection method, and a simple measurement of values It was calculated as an average value.

<Acetaldehyde content> Resin sample 5.
Precisely weigh 0 g, seal it in a micro cylinder with an internal volume of 50 ml together with pure water 10 ml under a nitrogen seal, and perform heat extraction at 160 ° C. for 2 hours. The amount of acetaldehyde in the extract is isobutyl alcohol as an internal standard. It was quantified by gas chromatography (“GC-14A” manufactured by Shimadzu Corporation).

Further, the obtained polyester resin chips were dried in a vacuum dryer at 130 ° C. for 10 hours, and then, using an injection molding machine (“FE-80S” manufactured by Nissei Plastic Industry Co., Ltd.), a cylinder temperature of 280 ° C. Back pressure 5 × 10 ⁵ Pa, injection rate 4
5 cc / sec, holding pressure 30 × 10 ⁵ Pa, mold temperature 20
A preform having a test officer shape having an outer diameter of about 29 mm, a height of about 165 mm, an average wall thickness of about 3.7 mm and a weight of about 60 g was injection-molded at 40 ° C. and a molding cycle of about 40 seconds.
The obtained preform is heated in a near-infrared irradiation furnace equipped with a quartz heater for 70 seconds, left at room temperature for 25 seconds, and then placed in a blow mold set at 160 ° C. Blow pressure 7 × 10 ⁵ while stretching in the transverse direction
Blow molding at Pa for 1 second and further at 30 × 10 ⁵ Pa for 40 seconds, heat setting, and air cooling to obtain an outer diameter of about 95 mm, a height of about 305 mm, and an average wall thickness of about 0.37.
mm, the weight was about 60 g, the internal volume was about 1.5 liters, and the specific surface area was about 0.7 cm ⁻¹ .

With respect to the obtained bottle, the amount of antimony eluted with hot water, the color tone, and the acetaldehyde odor were measured and evaluated by the following methods, and the results are shown in Table 1.

<Elution amount of hot water from bottle> About 1.5 liters of distilled water at 93 ° C. was filled in the bottle and allowed to cool at room temperature, and then an inductively coupled plasma mass spectrometer (“HP4500” manufactured by Hewlett Packard). Was used to measure the concentration (ppb) of antimony atoms in water.

<Color tone of bottle> The color tone of the mouth of the bottle was visually observed and evaluated according to the following criteria. A: Colorless and transparent. ◯: Slightly yellowish, but practically no problem. X: Yellowish, and there is a problem in practical use.

<Acetaldehyde odor of bottle> After the bottle was heated in an oven at 50 ° C. for 1 hour, the odor of acetaldehyde was subjected to a sensory test and evaluated according to the following criteria. A: Very little acetaldehyde odor. ○: There is little acetaldehyde odor. ×: There was an acetaldehyde odor that was nasal.

Examples 2 to 14 Compounds shown in Table 1 as phosphorus compounds (however, in Table 1, "E"
“AP” is ethyl acid phosphate, “H ₃ P
"O ₄ " represents phosphoric acid, and "H ₃ PO ₃ " represents phosphorous acid. ) Is added to the produced polyester resin in an amount such that the content of phosphorus atoms (P) is as shown in Table 1, and the produced polyester resin is added with magnesium atom (Mg) and antimony atom ( A polyester resin was produced in the same manner as in Example 1 except that Sb) and the content of titanium atoms (Ti) were the amounts shown in Table 1, and the obtained polyester resin was used in Example 1. Measurement and evaluation were carried out in the same manner as above, and the results are shown in Table 1.

Comparative Example 1 A solution of phosphoric acid was used as a phosphorus compound, and the solution was added through the upper pipe of the second-stage esterification reaction tank. The magnesium acetate solution was added through the upper pipe of the first-stage esterification reaction tank. That the solution of antimony trioxide and the solution of tetrabutyl titanate were added to the transfer pipe from the esterification reaction tank of the second stage to the melt polycondensation tank of the first stage, and each compound was added. A polyester resin was produced in the same manner as in Example 1 except that each metal atom content was added to the produced polyester resin in the amount shown in Table 1, and the obtained polyester resin was used. Measurement and evaluation were carried out in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 No tetrabutyl titanate was added, and a solution of antimony trioxide and a solution of magnesium acetate tetrahydrate were added to the second stage esterification reaction tank to the first stage melt polycondensation tank. In the same manner as in Example 1 except that each compound was added to the transfer pipe to and the compound was added in an amount such that each metal atom content was the amount shown in Table 1 with respect to the produced polyester resin. A polyester resin was produced by the method described above, and the obtained polyester resin was measured and evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 3 100 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol were used as transesterification catalysts in the amounts of calcium acetate monohydrate and magnesium acetate tetrahydrate in amounts for each metal atom content shown in Table 1. Then, the transesterification reaction is started according to a conventional method, and 2 minutes from the start of the distillation of methanol.
After 0 minutes, antimony trioxide was added in an amount to achieve the metal atom content shown in Table 1, the transesterification reaction was continued, and then trimethyl phosphate was added in an amount to achieve the metal atom content shown in Table 1. , The transesterification reaction was substantially completed. Subsequently, further tetrabutyl titanate was added in Table 1.
After adding in an amount to be the metal atom content shown in, to produce a polyester resin by polycondensation according to a conventional method under high temperature and high vacuum, for the obtained polyester resin,
The measurement and evaluation were performed in the same manner as in Example 1, and the results are shown in Table 1.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

According to the present invention, a polyester resin polycondensed in the presence of an antimony compound, the elution amount of antimony is suppressed, the color tone is good, and the generation of by-products is reduced. Can be provided. Further, according to the method for producing a polyester resin of the present invention, the above polyester resin can be produced with good polymerizability and productivity.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yutaka Yagi             1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Chemical Corporation             Inside the company (72) Inventor Masahiro Nukui             1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Chemical Corporation             Inside the company F-term (reference) 4J029 AA03 AB01 AB04 AD10 AE02                       BA02 BA03 BA04 BA05 BB10A                       BB13A CA02 CA06 CB05A                       CB06A CB07A CB10A CC06A                       CD03 CG06 DB02 HA01 HB01                       JC581 JF011 JF111 JF181                       JF221 JF231 JF321 JF331                       JF341 JF471 JF541 JF561                       JF571 KB25 KC03 KD02                       KD06 KE03 KE05 KE15

Claims (12)

[Claims] 1. A dicarboxylic acid component containing an aromatic dicarboxylic acid or an ester-forming derivative thereof as a main component and a diol component containing ethylene glycol as a main component are subjected to an esterification reaction or a transesterification reaction to obtain at least an antimony compound. Which is a polyester resin produced by polycondensation in the presence of a phosphorus compound and a phosphorus compound, wherein the amount of antimony eluted when immersed in hot water at 95 ° C. for 60 minutes as a granular material having a number average particle weight of 24 mg is A polyester resin having an antimony atom (Sb) of 1 μg or less per 1 g of the polyester resin. 2. The content (weight ppm) of an antimony component as an antimony atom (Sb) in a polyester resin.
Content of phosphorus component as phosphorus atom (P) (ppm by weight)
The polyester resin according to claim 1, having a ratio (Sb / P) of 6.0 to 30. 3. The polyester resin according to claim 1, wherein the content of the phosphorus component as a phosphorus atom (P) in the polyester resin is 0.1 to 20 ppm by weight. 4. The polyester resin according to claim 1, wherein the phosphorus element in the phosphorus component has a valence of three. 5. A periodic table group 1A, group IIA, zinc, aluminum, gallium, germanium, titanium,
Polycondensation in the presence of a compound of at least one metal element selected from the group consisting of zirconium, hafnium, manganese, iron, and cobalt, as a metal atom (M) of those metal element components in the polyester resin 5. The total content is 0.1 to 100 ppm by weight.
The polyester resin according to any one of 1. 6. The coexisting compound is a magnesium compound, and the content of magnesium component as magnesium atom (Mg) in the polyester resin (ppm by weight) and the content of phosphorus component as phosphorus atom (P) (ppm by weight). The ratio (Mg / P) to () is 1.1-3.0, The polyester resin of Claim 5. 7. The polyester according to claim 5, wherein the coexisting compound is a magnesium compound, and the content of the magnesium component in the polyester resin as a magnesium atom (Mg) is 0.1 to 30 ppm by weight. resin. 8. The coexisting compound is a titanium compound, and the content of the titanium component in the polyester resin as a titanium atom (Ti) is 0.25 to 10 ppm by weight. The polyester resin described. 9. The content of an antimony component in a polyester resin as an antimony atom (Sb) is 10 to 25.
The polyester resin according to claim 1, which has an amount of 0 ppm by weight. 10. A method for producing a polyester resin by polycondensing a dicarboxylic acid component containing an aromatic dicarboxylic acid or an ester-forming derivative thereof as a main component and a diol component containing ethylene glycol as a main component, A method for producing a polyester resin, comprising adding a catalyst to a reaction system so that each atom derived from the following polymerization catalyst is contained in the obtained polyester resin in the following concentration range. 0 <T ≦ 50 (weight ppm) 10 ≦ Sb ≦ 250 (weight ppm) 0.1 ≦ P ≦ 20 (weight ppm) 6.0 ≦ Sb / P ≦ 30 (In the above formula, T is a titanium atom in the resin. , At least one selected from hafnium atom and zirconium atom
Total concentration of seed atoms (ppm), Sb is antimony atom concentration in resin (ppm), P is phosphorus atom concentration in resin (ppm)) 11. The catalyst according to claim 10, wherein the catalyst is added to the reaction system so that each atom derived from the following polymerization catalyst is contained in the obtained polyester resin in the following concentration range. Method for producing polyester resin. 0.1 ≦ M ≦ 200 (ppm by weight) 1.1 ≦ M / P ≦ 15 (M is at least 1 selected from the group IA metal atom, the group IIA metal atom, the manganese atom, the iron atom and the cobalt atom in the resin. Total content of seed metal atoms (ppm) 12. The esterification reaction between the dicarboxylic acid component and the diol component, and at the stage where the esterification rate is less than 90%, a phosphorus compound is added to the reaction mixture containing the esterification reaction product to obtain the esterification rate. Has reached over 90%,
A compound of at least one metal atom selected from the group consisting of Group IA element compounds, Group IIA compounds, manganese compounds, iron compounds and cobalt compounds is added, and thereafter,
The method for producing a polyester resin according to claim 10, wherein at least one compound selected from the group consisting of titanium compounds, zirconium compounds and hafnium compounds is added.