JP2013136730A - Polyester resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst solution for manufacturing a polyester resin that can obtain a polyester resin producing a less amount of foreign matter, and a polyester resin using the same, and to provide a method for manufacturing a polyester resin.SOLUTION: The polyester resin includes a pyrrole ring or pyridine ring structure, and contains, in 100 g polyester resin, 6.0 x 10mole or more and less than 3.0 x 10mole of a compound (A) containing one or more atoms retaining an unshared electron pair other than nitrogen.

Description

  The present invention relates to a catalyst solution for producing a polyester resin, a polyester resin using the same, and a method for producing a polyester resin.

  Polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) have excellent mechanical properties, heat resistance, moldability, recyclability, and excellent chemical resistance. For this reason, polyester resins are widely used for molded articles, films, fibers and the like. Among them, PBT is widely used as a material for industrial molded products such as connectors, relays and switches for automobiles and electrical / electronic devices.

  In general, the polyester resin used for such applications is produced by a direct polymerization method or a transesterification method. In the direct polymerization method, a polyester resin is produced by the following treatment. That is, first, an oligomer that is a precursor of a polyester resin is formed by a direct esterification reaction between a dicarboxylic acid and a diol. Next, the oligomer is polycondensed under normal pressure or reduced pressure to produce a polyester resin. In the transesterification method, a polyester resin is produced by the following treatment. That is, first, an ester as a precursor of a polyester resin is formed by transesterification of an ester-forming derivative of a dicarboxylic acid and a diol. Then, the oligomer is polycondensed under normal pressure or reduced pressure to produce a polyester resin.

  Conventionally, antimony compounds, germanium compounds, and titanium compounds have been industrially used as catalysts for polyester resin production. Titanium compounds are more active than antimony compounds and germanium compounds. However, the titanium compound has a problem that the polyester resin obtained is yellowed because its activity is too high. In addition, an organic titanium compound typified by a titanate ester has an essential problem that it is easily hydrolyzed by water and easily deactivated while having excellent catalytic activity. Further, when titanic acid ester is used as a catalyst, foreign matters are formed due to the catalyst residue hydrolyzed with water, and the following problems appear. That is, in a polymer in a molten state, transparency is deteriorated. Moreover, in a polymer in a solution state, the solution haze deteriorates. When such a problem is remarkable, the strength of the molded product or fiber is reduced. For this reason, improvement of the manufacturing method of a polyester resin is desired.

  Various methods have been proposed so far for producing a polyester resin using a titanium compound as a catalyst. For example, Patent Document 1 proposes a catalyst solution for polyester production comprising a titanium-containing solution containing water and / or a base compound. Patent Document 2 proposes a polyester polycondensation catalyst using a titanium compound and N-methylimidazole as a base. However, the polyester obtained by using these techniques contains a large amount of foreign matter, and further improvement has been demanded.

  Patent Document 3 discloses a catalyst for producing a polyester resin to which tetra-n-butyl titanate and 2-pyridinemethanol (2-hydroxymethylpyridine) having a molar ratio of 1.2 to 4.0 moles of a titanium compound are added. Has been proposed. By using the polyester resin production catalyst obtained by this proposal, a polymer with few foreign matters can be obtained. However, the polymer obtained by this technique has a problem in color tone. For this reason, the further improvement was calculated | required.

  Patent Document 4 proposes a polyester resin production catalyst having a moisture content of 250 ppm or less in a catalyst solution in which tetra-n-butyl titanate is dissolved in 1,4-butanediol. However, the polyester resin production catalyst obtained by this proposal lacks long-term storage stability. For this reason, the catalyst for polyester resin manufacture excellent in storage stability was calculated | required.

  Patent Document 5 proposes a polyester resin production catalyst having excellent storage stability, in which water is added to a mixed solution of tetrabutyl titanate and 1,4-butanediol. However, the amount of foreign matter in the resulting polyester resin has increased, and further reduction of the foreign matter content has been demanded.

WO2004 / 111105 (Claims, Examples) JP 2010-126614 A (Claims, Examples) JP 2002-284869 A (Claims, Examples) JP 2009-235288 A (Claims, Examples) JP 58-206625 A (Claims, Examples)

  An object of the present invention is to provide a polyester resin production catalyst solution that is excellent in color tone and has little foreign matter and has excellent long-term storage stability, a polyester resin using the same, and a method for producing the polyester resin There is to do.

As a result of diligent studies to solve the above-mentioned problems, a catalyst solution for producing a polyester resin capable of obtaining a polyester resin having excellent color tone and less foreign matter, a polyester resin using the same, and a method for producing the polyester resin have been found. Reached. That is, the present invention provides a compound (A) having a pyrrole ring or pyridine ring structure and containing one or more atoms having an unshared electron pair in addition to nitrogen in 6.0 × 10 ^{−7 in} 100 g of a polyester resin. It is a polyester resin containing at least 3 mol and less than 3.0 × 10 ⁻⁴ mol.

  ADVANTAGE OF THE INVENTION According to this invention, the catalyst solution for polyester resin manufacture which is excellent in long-term storage stability can be obtained, and the polyester resin which is excellent in color tone and there are few foreign materials can be obtained using this catalyst solution for polyester resin manufacture.

  Next, the form for implementing this invention is demonstrated in detail.

The polyester resin as an embodiment of the present invention is generally obtained by an esterification reaction or transesterification reaction between a dicarboxylic acid component and a diol component, followed by a polycondensation reaction, and a structure derived from the dicarboxylic acid component and a diol. It has a structure derived from components. Further, when a catalyst is used in the esterification reaction, transesterification reaction and / or polycondensation reaction, foreign matter may be generated due to the catalyst. The polyester resin of the present invention has a compound (A) having a pyrrole ring or pyridine ring structure and containing one or more atoms having an unshared electron pair in addition to nitrogen in 6.0 × 10 ^{− in} 100 g of the polyester resin. It is characterized by containing ⁷ mol or more and less than 3.0 × 10 ⁻⁴ mol. By containing the compound (A), the catalyst is stabilized, foreign matter generated due to the catalyst can be reduced, and foreign matter of the polyester resin can be greatly reduced. Here, the “foreign matter” refers to an insolubilized substance generated in the polyester resin due to the catalyst. By containing the compound (A) in the polyester resin, such insolubilized materials can be reduced.

  The compound (A) has a pyrrole ring or pyridine ring structure. A pyridine ring is preferable in that the amount of foreign matter in the polyester resin can be further reduced.

  In the embodiment of the present invention, the compound (A) preferably contains one or more atoms having an unshared electron pair other than nitrogen in that the amount of foreign matter in the polyester resin can be further reduced. Specific examples of the atom having an unshared electron pair include a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom. You may contain 2 or more types of atoms which hold | maintain these unshared electron pairs. Among these, as the atom having an unshared electron pair, a nitrogen atom or an oxygen atom is more preferable in that a polyester resin having excellent color tone and excellent mechanical properties can be obtained, and the obtained polyester resin is preferable. Oxygen atoms are particularly preferable in that the foreign matter can be further reduced. However, the compound (A) is realized in an aspect in which an oxygen atom is not included in an atom having an unshared electron pair, for example, in an aspect in which only a phosphorus atom or a sulfur atom is included as an atom having an unshared electron pair. You can also

In an embodiment of the present invention, as a specific example of the compound (A), at least one hydrogen atom of a pyrrole ring or a pyridine ring is represented by the formula: —R ¹ OH (wherein R ¹ is the number of carbon atoms) 1-3 represents an aliphatic hydrocarbon group of 1 to 3). In the above formula, the oxygen atom in the hydroxy group is an atom having an unshared electron pair. Examples of the compound having such a structure include 1-hydroxymethyl pyrrole, 1-hydroxyethyl pyrrole, 1-hydroxypropyl pyrrole, 2-hydroxymethyl pyrrole, 2-hydroxyethyl pyrrole, 2-hydroxypropyl pyrrole, 3-hydroxymethyl pyrrole, 3-hydroxyethylpyrrole, 3-hydroxypropylpyrrole, 1-hydroxymethylpyridine, 1-hydroxyethylpyridine, 1-hydroxypropylpyridine, 2-hydroxymethylpyridine, 2-hydroxyethylpyridine, 2-hydroxypropylpyridine, 3- Hydroxymethylpyridine, 3-hydroxyethylpyridine, 3-hydroxypropylpyridine, 4-hydroxymethylpyridine, 4-hydroxyethylpyridine, 4-hydroxypropyl Pyridine, and the like. The polyester resin may contain two or more of these compounds. From the viewpoint of excellent mechanical properties of the polyester resin, 1-hydroxymethylpyrrole, 1-hydroxyethylpyrrole, 1-hydroxypropylpyrrole, 2-hydroxymethylpyridine, 2-hydroxyethylpyridine, and 2-hydroxypropylpyridine are preferable. 1-hydroxypropylpyrrole and 2-hydroxymethylpyridine are particularly preferred, and 2-hydroxymethylpyridine is most preferred in that foreign matters of the polyester resin can be further reduced.

In an embodiment of the present invention, the content of the compound (A) is in the range of 6.0 × 10 ⁻⁷ mol or more and less than 3.0 × 10 ⁻⁴ mol in 100 g of the obtained polyester resin. When the content of the compound (A) is less than 6.0 × 10 ⁻⁷ mol, the amount of foreign matter contained in the polyester resin increases. The content of the compound (A) in the polyester resin is preferably 1.5 × 10 ⁻⁵ mol or more, and more preferably 3.0 × 10 ⁻⁵ mol or more. On the other hand, when the content of the compound (A) is 3.0 × 10 ⁻⁴ mol or more, the amount of foreign matter contained in the polyester resin increases and the color tone deteriorates. The content of the compound (A) in the polyester resin is preferably 1.5 × 10 ⁻⁴ mol or less, and more preferably 9.0 × 10 ⁻⁵ mol or less. The amount of the compound (A) in 100 g of the polyester resin can be determined by elemental analysis, ¹ H-NMR, ¹³ C-NMR measurement or the like. In the embodiment of the present invention, the amount of the compound (A) in 100 g of the polyester resin is a value measured by an elemental analysis method.

In the production of the polyester resin, since the reaction time can be shortened, the titanium compound (B) is preferably used as a catalyst. However, the polyester resin may be produced without using the titanium compound (B). In addition, the content of the titanium compound (B) in 100 g of the polyester resin obtained according to the embodiment of the present invention can shorten the reaction time of the esterification reaction or the transesterification reaction or the polycondensation reaction, and can be produced efficiently. In this respect, 6.0 × 10 ⁻⁵ mol or more is preferable, and 1.2 × 10 ⁻⁴ mol or more is more preferable. Furthermore, in order to suppress the generation amount of byproduct tetrahydrofuran (THF) and efficiently obtain a polyester resin, the content of the titanium compound (B) in 100 g of the polyester resin obtained according to the embodiment of the present invention is 2. 0 × 10 ⁻⁴ mol or more is more preferable. On the other hand, since the amount of foreign matter contained in the polyester resin can be further reduced, the content of the titanium compound (B) in 100 g of the polyester resin obtained by the embodiment of the present invention is 1.8 × 10 ⁻³ mol or less. Preferably, 1.2 × 10 ⁻³ mol or less is more preferable. The amount of the titanium compound (B) in 100 g of the polyester resin can be determined by elemental analysis, ¹ H-NMR, ¹³ C-NMR measurement or the like. In the embodiment of the present invention, the amount of the titanium compound (B) in 100 g of the polyester resin is a value measured by an elemental analysis method.

  In the embodiment of the present invention, the content of the compound (A) and the titanium compound (B) contained in the polyester resin may be a content loss due to volatilization or the like in the esterification reaction or transesterification reaction and the polycondensation reaction. Since there is no, it matches the amount of charge. Therefore, for example, in the manufacturing method of the polyester resin mentioned later, content of each compound can be adjusted to a desired range by adjusting the addition amount of each compound.

  In the polyester resin of the embodiment of the present invention, the molar ratio (A / B) of the content of the compound (A) to the content of the titanium compound (B) from the viewpoint that the amount of foreign matter contained in the polyester resin can be further reduced. ) Is preferably 0.01 or more, more preferably 0.1 or more. On the other hand, the molar ratio (A / B) of the content of the compound (A) to the content of the titanium compound (B) is less than 1.0 from the viewpoint that the amount of foreign matter contained in the polyester resin can be further reduced. Is preferably 0.75 or less, more preferably 0.5 or less, and particularly preferably 0.3 or less.

In an embodiment of the present invention, the titanium compound (B) has the formula: (R ² O) _n Ti (OR ³ ) _4-n (wherein R ² and R ³ may be the same or different, Represents an aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 10 carbon atoms, and n represents a range of 0 to 4 (including a decimal number)) or a condensate thereof. It is preferable that the polyester resin is excellent in mechanical properties. However, the titanium compound (B) can have other configurations. Specific examples of the titanate represented by the above formula include tetra-methoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetraisopropoxy titanium, tetraisobutoxy titanium, tetra-tert-butoxy. Examples thereof include titanium, cyclohexyl ester of titanic acid, phenyl ester of titanic acid, benzyl ester of titanic acid, tolyl ester of titanic acid, and mixed esters thereof. In addition, a polyester resin may contain 2 or more types of these titanium compounds (B), such as a titanate ester. Among these, tetra-n-propoxy titanium, tetra-n-butoxy titanium, and tetraisopropoxy titanium are preferable from the viewpoint that the polyester resin is excellent in mechanical properties. Furthermore, tetra-n-butoxytitanium is preferably used in that foreign substances of the obtained polyester resin can be further reduced.

  The amount of foreign matter in the polyester resin according to the embodiment of the present invention was such that 5.4 g of the polyester resin was dissolved in 40 mL of a 6: 4 (weight ratio) mixture of phenol and tetrachloroethane, and a cell having an optical path length of 10 mm was used. By measuring, it can evaluate by a solution haze value. The smaller the solution haze value, the smaller the amount of foreign matter in the polyester resin. With respect to the polyester resin of the embodiment, the solution haze value is preferably less than 0.2%, more preferably less than 0.17%, further preferably less than 0.15%, particularly preferably less than 0.1%, and 0%. Most preferably, no foreign matter is detected. In addition, solution haze measurement shall be performed using Nippon Denshoku "turbidity meter 300A".

  Next, the manufacturing method of the polyester resin of embodiment of this invention is demonstrated.

  The method for producing a polyester resin according to an embodiment of the present invention includes an esterification reaction between a dicarboxylic acid component (D-1) composed of a dicarboxylic acid and a diol component (E), or a dicarboxylic acid component composed of an ester-forming derivative of a dicarboxylic acid ( D-2) is a method for producing a polyester resin by a transesterification reaction between the diol component (E) and a subsequent polycondensation reaction, and as a reaction catalyst for the esterification reaction or the transesterification reaction and the polycondensation reaction, This is a method for producing a polyester resin, in which a catalyst solution for producing a polyester resin, which is a mixed solution of the compound (A), titanium compound (B) and organic solvent (C), is added to the reaction system. In addition, in embodiment of this invention, in order to provide high heat stability to a polyester resin, you may make the compound (F) which has a 3 or more functional group react further.

  In the embodiment of the present invention, the dicarboxylic acid component constituting the dicarboxylic acid unit of the polyester resin includes a dicarboxylic acid component (D-1) composed of an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid and a mixture thereof, and a dicarboxylic acid unit. The dicarboxylic acid component (D-2) which consists of ester formation derivatives is mentioned. Any of these may be derived from fossil resources or biomass resources.

  Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4 4,4'-diphenyl ether dicarboxylic acid and 5-sodium sulfoisophthalic acid. Examples of the ester-forming derivative of the aromatic dicarboxylic acid include lower alkyl esters of the aromatic dicarboxylic acid. More specifically, methyl ester, ethyl ester, propyl ester, butyl ester and the like can be mentioned. Two or more of these may be used.

  Examples of the aliphatic dicarboxylic acid include aliphatic dicarboxylic acids such as oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, 1,3-cyclohexanedicarboxylic acid, and 1,4. -Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Examples of the ester-forming derivative of the aliphatic dicarboxylic acid include lower alkyl esters of the aliphatic dicarboxylic acid. More specifically, methyl ester, ethyl ester, propyl ester, butyl ester and the like can be mentioned. Two or more of these may be used as the dicarboxylic acid component constituting the dicarboxylic acid unit of the polyester resin of the present embodiment.

  Among these, it is preferable to use an aromatic dicarboxylic acid in that a polyester resin excellent in heat resistance and chemical resistance is obtained, and the polyester resin can be produced efficiently. As the aromatic dicarboxylic acid, terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid are preferable, and terephthalic acid is particularly preferably used.

  When the dicarboxylic acid component is terephthalic acid, a polyester resin having excellent heat resistance, mechanical properties and chemical resistance can be obtained, and terephthalic acid in all dicarboxylic acid components can be efficiently produced. It is preferably 50 mol% or more, more preferably 90 mol% or more, and most preferably 100 mol%. It is also a preferred embodiment that isophthalic acid and 2,6-naphthalenedicarboxylic acid are used in combination as aromatic dicarboxylic acid components other than terephthalic acid.

  Examples of the diol component (E) in the embodiment of the present invention include aromatic diols, aliphatic diols, alicyclic diols, heterocyclic diols, and mixtures thereof. Any of these may be derived from fossil resources or biomass resources.

  Examples of the aromatic diol include polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (2.3) -2,2-bis (4 -Hydroxyphenyl) propane, polyoxyethylene- (2.8) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene- (3.0) -2,2-bis (4-hydroxyphenyl) Bisphenol A derivatives added with ethylene oxide such as propane, and polyoxypropylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.3) -2,2- Bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.8) -2,2-bis (4-hydroxyphenyl) propane And polyoxypropylene - (3.0) -2,2-bis (4-hydroxyphenyl) bisphenol A derivative obtained by adding propylene oxide such as propane. Two or more of these aromatic diols may be used as the diol component (E) in the present embodiment.

  Examples of the aliphatic diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, Examples include 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Two or more of these aliphatic diols may be used as the diol component (E) in the present embodiment.

  Examples of the alicyclic diol include cyclopentanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and the like. Two or more of these alicyclic diols may be used as the diol component (E) in the present embodiment.

  Examples of the heterocyclic diol include isosorbide, isomannide and isoidet. Two or more of these heterocyclic diols may be used as the diol component (E) in the present embodiment.

  Among these, as the diol component (E), it is preferable to use an aliphatic diol because a polyester resin excellent in heat resistance is obtained and the polyester resin can be efficiently produced. As the aliphatic diol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol are preferable, and particularly polyester having excellent crystallization characteristics, moldability, heat resistance, and chemical resistance. 1,4-butanediol is preferably used in that a resin is obtained and a polyester resin can be produced efficiently.

  When the diol component (E) is 1,4-butanediol, a polyester resin having excellent crystallization characteristics, moldability, heat resistance and mechanical properties can be obtained, and the polyester resin can be efficiently produced. In the total aliphatic diol, 1,4-butanediol is preferably 50 mol% or more, more preferably 90 mol% or more, and most preferably 100 mol%. It is also a preferred embodiment that ethylene glycol, 1,3-propanediol and 1,4-cyclohexanedimethanol are used in combination as diol components other than 1,4-butanediol.

  Examples of the combination of the dicarboxylic acid component (D-1) and the diol component (E) in the polyester resin according to the embodiment of the present invention include terephthalic acid and ethylene glycol, terephthalic acid and 1,3-propanediol, terephthalic acid and 1,4. -Butanediol, terephthalic acid and 1,4-cyclohexanediol. Instead of the dicarboxylic acid component (D-1), a dicarboxylic acid component (D-2) comprising an ester-forming derivative of dicarboxylic acid may be used. Examples of the dicarboxylic acid component (D-2) include lower alkyl esters such as methyl ester, ethyl ester, propyl ester, and butyl ester of terephthalic acid. Two or more of these may be used as the dicarboxylic acid component in the polyester resin of the embodiment of the present invention. Among these, it is preferable to use an aromatic dicarboxylic acid as the dicarboxylic acid component (D-1) in that a polyester resin excellent in heat resistance and chemical resistance is obtained and the polyester resin can be efficiently produced. It is more preferable to use terephthalic acid and ethylene glycol, or terephthalic acid and 1,4-butanediol in that a polyester resin having excellent heat resistance, mechanical properties, and chemical resistance can be obtained. That is, it is more preferable to select polyethylene terephthalate (PET) as the polyester resin, or polybutylene terephthalate (PBT) as the polyester resin. A polyester resin excellent in crystallization characteristics, moldability, heat resistance and chemical resistance can be obtained, and the polyester resin can be efficiently produced. The esterification reaction and polycondensation reaction start of the catalyst solution for polyester production according to the embodiment of the present invention It is possible to use terephthalic acid and 1,4-butanediol, that is, to select polybutylene terephthalate (PBT) as the polyester resin in that the effect of improving the amount of foreign matter is increased by adding it to the reaction system before. Most preferred.

  In the production of the polyester resin according to the embodiment of the present invention, as the dicarboxylic acid component (D-1), terephthalic acid may be the main component, and isophthalic acid or 2,6-naphthalenedicarboxylic acid may be used in combination. In the production of the polyester resin of the embodiment of the present invention, as the diol component (E), ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, and polytetra Copolyesters using two or more diol components selected from methylene glycol may be used. As a more preferred embodiment of the copolyester, a polyester resin excellent in heat resistance, mechanical properties and chemical resistance is obtained, and 50 mol of terephthalic acid is contained in all dicarboxylic acid components in that the polyester resin can be produced efficiently. % Or more, preferably 90 mol% or more, and most preferably 100 mol%. In addition, a polyester resin having excellent crystallization characteristics, moldability, heat resistance, and mechanical properties can be obtained, and the polyester resin according to the embodiment of the present invention has 1, It is preferable that 4-butanediol is a main component. In particular, in all diol components, 1,4-butanediol is preferably 50 mol% or more, more preferably 90 mol% or more, and most preferably 100 mol%.

  The functional group possessed by the compound (F) having three or more functional groups includes a hydroxyl group, an aldehyde group, a carboxylic acid group, a sulfo group, an amino group, a glycidyl group, an isocyanate group, a carbodiimide group, an oxazoline group, an oxazine group, and an ester. Group, amide group, silanol group, silyl ether group and the like. From the viewpoint of excellent thermal properties, a hydroxyl group or a carboxylic acid group is preferred. Examples of the compound (F) include polyhydric alcohols such as glycerin, diglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, (poly) oxyethylene glycerin, (poly) oxypropylene glycerin, ( Polyhydric alcohols containing alkylene oxide units such as poly) oxyethylenetrimethylolpropane, (poly) oxypropylenetrimethylolpropane, (poly) oxyethylenepentaerythritol, (poly) oxypropylenepentaerythritol, propane-1,2, 3-tricarboxylic acid, trimellitic acid, trimesic acid and polycarboxylic acids such as anhydride thereof, trimellitic acid containing (poly) ethylene oxide units, and (poly) propylene oxide units Polycarboxylic acids and their anhydrides containing alkylene oxide units, such as trimellitic acid, and the like.

  In the method for producing a polyester resin according to an embodiment of the present invention, when a direct polymerization method is used, a polyester resin is produced by performing a direct esterification reaction between a dicarboxylic acid and a diol to obtain an oligomer, and then performing a polycondensation reaction. To do. When the transesterification method is used, a polyester resin is produced by performing an ester exchange reaction between an ester-forming derivative of a dicarboxylic acid and a diol to obtain an oligomer, and then performing a polycondensation reaction.

  In the esterification reaction or transesterification reaction, the usual esterification reaction or transesterification reaction conditions used in the production of a polyester resin in a batch method or a continuous method can be applied as they are.

  In the embodiment of the present invention, the esterification reaction or transesterification reaction is usually performed under a pressure of 101 kPa or less. From the viewpoint that the polyester resin can be produced efficiently, it is preferable to carry out under a slightly reduced pressure of 95 kPa or less.

  The reaction temperature of the esterification reaction or transesterification reaction is preferably 140 ° C. or higher, more preferably 150 ° C. or higher, and particularly preferably 160 ° C. or higher. Further, the reaction temperature of the esterification reaction or transesterification reaction is preferably 290 ° C. or lower, more preferably 280 ° C. or lower, and particularly preferably 240 ° C. or lower.

  In addition, the reaction rate of the oligomer after the esterification reaction or the transesterification reaction is preferably 97% or more.

  In an embodiment of the present invention, the molar ratio ((E) / (D-1)) of the diol component (E) and the dicarboxylic acid component (D-1) or the ester-forming derivative of the diol component (E) and the dicarboxylic acid The molar ratio ((E) / (D-2)) of the dicarboxylic acid component (D-2) consisting of is preferably in the range of 1.1 to 6.0. More preferably, the molar ratio ((E) /) is more preferable in that the amount of THF generated as a by-product due to cyclization of 1,4-butanediol during the esterification reaction or transesterification reaction can be suppressed and efficient production can be achieved. (D-1)) or molar ratio ((E) / (D-2)) is in the range of 1.1 to 3.0, more preferably in the range of 1.1 to 2.0. From the viewpoint of shortening the polycondensation reaction time, the molar ratio ((E) / (D-1)) or the molar ratio ((E) / (D-2)) is particularly 1.1 to 1. Is preferably in the range of .8.

  In the esterification reaction or transesterification reaction in the embodiment of the present invention, an additional addition of the diol component (E) may be performed from the viewpoint that the reaction proceeds efficiently. The additional addition of the diol component (E) may be performed after completion of the esterification reaction or transesterification reaction and before the start of the polycondensation reaction, but from the viewpoint of shortening the polymerization time, the esterification reaction or transesterification reaction starts. Thereafter, it is more preferable to carry out at any stage until the start of the polycondensation reaction. The additional addition of the diol component (E) may be performed a plurality of times, but from the viewpoint of operability, it is performed once at any stage from the start of the esterification reaction or transesterification reaction to the start of the polycondensation reaction. It is preferable.

  In the method for producing a polyester resin according to an embodiment of the present invention, the compound (F) having three or more functional groups may be any stage from the start of the esterification reaction or the start of the transesterification reaction to just before the end of the polycondensation reaction. May be added. The compound (F) can be added once or a plurality of times. The above compound (F) is added once at any stage from the esterification reaction or the ester exchange reaction to the start of the polycondensation reaction in that a polyester resin having high heat stability can be obtained. Is preferred. In terms of workability, at the start of the esterification reaction or transesterification reaction, a dicarboxylic acid component (D-2) comprising a dicarboxylic acid component (D-1) or an ester-forming derivative of dicarboxylic acid, and a diol component (E It is the most preferred embodiment that the above compound (F) is added to a mixture of the compound (A).

  In the method for producing a polyester resin according to an embodiment of the present invention, “the start of esterification reaction or the start of transesterification” is a stage where a reaction component such as a dicarboxylic acid component or a diol component is mixed to prepare a reaction, , And used to mean the beginning of the reaction before the esterification reaction or the transesterification reaction.

  In the esterification reaction or transesterification reaction, it is preferable to add a catalyst in order to advance the reaction effectively. It is more preferable to add the below-described catalyst solution for producing a polyester resin of the present invention before the start of the esterification reaction or transesterification reaction.

In the esterification reaction or transesterification reaction, the amount of the compound (A) added when the polyester-producing catalyst solution containing the compound (A) is used is 3.0 × with respect to 100 g of the obtained polyester resin. A range of 10 ⁻⁷ mol or more and less than 1.5 × 10 ⁻⁴ mol is desirable. When the amount of the compound (A) added is less than 3.0 × 10 ⁻⁷ mol, the amount of foreign matter contained in the polyester resin tends to increase. The addition amount of the compound (A) is preferably 7.5 × 10 ⁻⁶ mol or more, and more preferably 1.5 × 10 ⁻⁵ mol or more. On the other hand, when the content of the compound (A) is 1.5 × 10 ⁻⁴ mol or more, the amount of foreign matter contained in the polyester resin increases and the color tone tends to deteriorate. The addition amount of the compound (A) is more preferably 7.5 × 10 ⁻⁵ mol or less, and most preferably 4.5 × 10 ⁻⁵ mol or less. In addition, the quantity of the polyester resin obtained refers to the production amount of the polyester resin calculated | required on the assumption that a yield is 100% with respect to the preparation amount. The same applies to the following description.

In the esterification reaction or transesterification reaction, the amount of titanium compound (B) added is preferably 3 × 10 ⁻⁵ mol or more, more preferably 6 × 10 ⁵ mol, relative to 100 g of the obtained polyester resin. ^-5 moles or more. Moreover, it is preferable that the addition amount of a titanium compound (B) is 9 * 10 <^-4> mol or less with respect to 100 g of obtained polyester resins, More preferably, it is 6 * 10 <^-4> mol. The amount of titanium compound (B) added is, for example, preferably in the range of 3 × 10 ⁻⁵ mol to 9 × 10 ⁻⁴ mol, more preferably 6 × 10 ⁻⁵ mol to 6 g, with respect to 100 g of the obtained polyester resin. It is preferable to add a catalyst solution for producing a polyester resin, which will be described later, so as to be in the range of × 10 ⁻⁴ mol. By setting the addition amount of the titanium compound (B) in such a range, the amount of the titanium compound (B) contained in the obtained polyester resin can be easily adjusted to the aforementioned range, and the foreign matter content of the polyester resin can be adjusted. It can be further reduced.

  The oligomer obtained from the esterification reaction or transesterification reaction is then subjected to a polycondensation reaction. In the reaction, the polycondensation conditions used for the production of ordinary polyester resins in batch or continuous processes can be applied as they are. For example, it is a preferable embodiment to carry out the reaction under the reduced pressure of 230 to 260 ° C., preferably 240 to 255 ° C. and the pressure of 667 Pa or less, preferably 133 Pa or less.

  In the polycondensation reaction after the esterification reaction or after the transesterification reaction in the method for producing a polyester resin according to an embodiment of the present invention, a catalyst solution for producing a polyester resin, which will be described later, is used to effectively advance the polycondensation reaction. The polycondensation reaction is preferably added before the polycondensation reaction. However, the polyester resin production catalyst solution for effectively advancing the polycondensation reaction can be added during the polycondensation reaction before or before the polycondensation reaction.

In the polymerization reaction, the addition amount of the compound (A) when using the catalyst solution for polyester production containing the compound (A) is 3.0 × 10 ⁻⁷ mol or more with respect to 100 g of the obtained polyester resin. A range of less than 1.5 × 10 ⁻⁴ mol is desirable. When the amount of the compound (A) added is less than 3.0 × 10 ⁻⁷ mol, the amount of foreign matter contained in the polyester resin tends to increase. The addition amount of the compound (A) is preferably 7.5 × 10 ⁻⁶ mol or more, and more preferably 1.5 × 10 ⁻⁵ mol or more. On the other hand, when the addition amount of the compound (A) is 1.5 × 10 ⁻⁴ mol or more, the amount of foreign matter contained in the polyester resin increases and the color tone tends to deteriorate. The addition amount of the compound (A) is more preferably 7.5 × 10 ⁻⁵ mol or less, and most preferably 4.5 × 10 ⁻⁵ mol or less.

In addition, in the polycondensation reaction, the addition amount of the titanium compound (B) is preferably 3 × 10 ⁻⁵ mol or more, more preferably 6 × 10 ⁻⁵ mol or more with respect to 100 g of the obtained polyester resin. It is. Moreover, it is preferable that the addition amount of a titanium compound (B) is 9 * 10 <^-4> mol or less with respect to 100 g of obtained polyester resins, More preferably, it is 6 * 10 <^-4> mol. The amount of titanium compound (B) added is, for example, preferably in the range of 3 × 10 ⁻⁵ mol to 9 × 10 ⁻⁴ mol, more preferably 6 × 10 ⁻⁵ mol to 6 g, with respect to 100 g of the obtained polyester resin. It is preferable to add a catalyst solution for producing a polyester resin, which will be described later, so as to be in the range of × 10 ⁻⁴ mol. By setting the addition amount of the titanium compound (B) in such a range, the amount of the titanium compound (B) contained in the obtained polyester resin can be easily adjusted to the above range, and the foreign matter content of the polyester resin can be further increased. Can be reduced.

  In the esterification reaction or transesterification reaction and the polycondensation reaction in the method for producing a polyester resin according to the embodiment of the present invention, the polyester resin production is carried out in order to effectively advance the esterification reaction or transesterification reaction and polycondensation reaction. The catalyst solution for use is preferably added to the reaction system before the start of the esterification reaction, transesterification reaction or polycondensation reaction. The catalyst may be added only to any one of the esterification reaction, transesterification reaction or before the start of the polycondensation reaction. However, in order to advance the reaction effectively, the esterification reaction or transesterification reaction and the polycondensation reaction are performed. It is preferred to carry out the catalyst addition both before the start. As the polyester resin production catalyst solution, it is preferable to use a polyester resin production catalyst solution obtained by a production method described later, from the viewpoint that the amount of foreign matter contained in the obtained polyester resin can be further reduced.

  In the method for producing a polyester resin according to an embodiment of the present invention, as a preferable aspect, within a range not impairing the object of the present invention, usual additives such as an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant (hin Dirtphenol antioxidants, amine antioxidants, sulfur antioxidants, etc.), copper damage inhibitors, lubricants, mold release agents, coloring agents including dyes and pigments, or one or more esters It can be added at any stage before the start of the polymerization reaction or transesterification reaction and before the end of the polycondensation reaction. In particular, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, phosphoric acid triamide, monoammonium phosphate, trimethyl phosphate, dimethyl phosphate, diphenyl phosphate, triphenyl phosphate, diphenyl phosphite, phosphorous acid When a phosphorus compound selected from triphenyl acid and dimethylphenyl phosphonate is added, the color tone of the produced polyester resin can be further improved.

  In the embodiment of the present invention, the catalyst solution for producing a polyester resin preferably contains the compound (A), the titanium compound (B) and the organic solvent (C). In addition, the specific example of a compound (A) and a titanium compound (B) is as having illustrated as each component of a polyester resin.

  In an embodiment of the present invention, by containing the compound (A) in a polyester resin production catalyst solution, the amount of foreign matter contained in the polyester resin obtained using the catalyst solution can be reduced, and the polyester resin production catalyst. There is an effect that the long-term storage stability of the solution is excellent. The content of the compound (A) in the catalyst solution for producing a polyester resin is preferably 15% by weight or less, more preferably 8% by weight or less, more preferably 3% by weight in that the long-term storage stability can be further improved. % Or less is more preferable, and 1% by weight or less is particularly preferable. On the other hand, the content of the compound (A) in the polyester resin production catalyst solution is preferably 0.001% by weight or more, in that the amount of foreign matter contained in the obtained polyester resin can be further reduced. % Or more is more preferable, and 0.004% by weight or more is still more preferable.

  From the point that the amount of foreign matter contained in the polyester resin can be further reduced, the content of the titanium compound (B) in the catalyst solution for polyester resin production is the content of the compound (A) relative to the content of the titanium compound (B). The molar ratio (A / B) is preferably set to be 0.01 or more, and more preferably set to be 0.1 or more. On the other hand, the molar ratio (A / B) of the content of the compound (A) to the content of the titanium compound (B) is preferably less than 1.0, more preferably 0.75 or less, The following is more preferable, and 0.3 or less is particularly preferable.

  Moreover, 50 weight% or less is preferable and content of the titanium compound (B) in a catalyst solution is excellent in the long-term storage stability of the catalyst solution for polyester resin manufacture. 30 wt% or less is more preferable, and 20 wt% or less is still more preferable. Furthermore, the content of the titanium compound (B) in the catalyst solution is preferably 10% by weight or less, more preferably 1.0% by weight or less, in that the foreign matter of the polyester resin can be further reduced. 5% by weight or less is particularly preferable. The lower limit of the content of the titanium compound (B) in the catalyst solution is preferably 0.005% by weight or more, preferably 0.01% by weight or more from the viewpoint that a catalyst solution for producing a polyester resin having high polymerizability can be produced. Further preferred. Furthermore, the content of the titanium compound (B) in the catalyst solution in that the amount of by-product tetrahydrofuran (THF) generated by cyclization of 1,4-butanediol during the esterification reaction or transesterification reaction can be suppressed. The lower limit of is particularly preferably 0.03% by weight or more. In the present invention, “excellent in long-term storage stability” means that no precipitate is generated in the catalyst solution even when the colorless and transparent catalyst solution is stored for one month or longer.

In the embodiment of the present invention, the catalyst solution for producing a polyester resin contains an organic solvent (C), thereby suppressing deactivation due to hydrolysis of the titanium compound (B) and having excellent catalytic activity. The organic solvent (C) used in this embodiment has the formula: R ⁴ (OH) _m (wherein R ⁴ is an aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 10 carbon atoms. Or it represents a heterocyclic ring, and m represents 1 or 2.) is preferable from the viewpoint that the long-term storage stability of the catalyst solution for polyester resin production is excellent. However, the organic solvent (C) can have other configurations.

  Specific examples of the alcohol represented by the above formula include (i) methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n- Aliphatic alcohols such as decanol, (ii) ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, Aliphatic diols such as 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, diethylene glycol, (iii) cyclopentanol, cyclohexanol, cyclohexanemethanol, etc. An alicyclic alcohol, (iv) Cyclopentanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, alicyclic diols such as 1,4-cyclohexanedimethanol, (v) isosorbide, isomannide, isoidet, etc. Heterocyclic diols, (vi) aromatic alcohols such as benzyl alcohol and methylbenzyl alcohol, (vii) 1,4-benzenedimethanol, 1,4-benzenediethanol, 1,4-bis (2-hydroxyethoxy) benzene And aromatic diols. The catalyst solution for polyester resin production may contain two or more of these as the organic solvent (C). Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexane, which are raw materials for polyester resins, can be used to produce a catalyst solution for producing a polyester resin having high polymerizability. It is preferable to use one or more of dimethanol. Furthermore, it is particularly preferable to use 1,4-butanediol from the viewpoint that foreign matters of the polyester resin can be further reduced. The alcohol represented by the above formula may be one derived from a fossil resource or one derived from a biomass resource.

  In the embodiment of the present invention, the combination of the titanium compound (B) and the organic solvent (C) used in the catalyst solution for producing the polyester resin includes tetra-n-propoxy titanium, ethylene glycol, and tetra-n-butoxy titanium. Ethylene glycol, tetraisopropoxy titanium and ethylene glycol, tetra-n-propoxy titanium and 1,3-propanediol, tetra-n-butoxy titanium and 1,3-propanediol, tetraisopropoxy titanium and 1,3-propanediol Tetra-n-propoxytitanium and 1,4-butanediol, tetra-n-butoxytitanium and 1,4-butanediol, tetraisopropoxytitanium and 1,4-butanediol, tetra-n-propoxytitanium and 1, 4-cyclohexanedimethanol, tetra- - butoxy and 1,4-cyclohexanedimethanol, combinations selected from titanium tetraisopropoxide and 1,4-cyclohexanedimethanol are preferred. Tetra-n-propoxytitanium and 1,4-butanediol, tetra-n-butoxytitanium and 1,4-butanediol, tetraisopropoxytitanium, in that a catalyst solution for producing a polyester resin having high polymerizability can be produced. More preferably, a combination selected from 1,4-butanediol is used. Furthermore, it is most preferable to use a combination of tetra-n-butoxytitanium and 1,4-butanediol in that a polyester resin with reduced foreign matters can be obtained.

  As a method for producing a catalyst solution for producing a polyester resin in an embodiment of the present invention, the compound (A) and the organic solvent (C) are mixed, and the water content in the mixed solution is adjusted to 0.05% by weight or less. It is preferable to mix the aforementioned amount of the titanium compound (B). By mixing the titanium compound (B) after adjusting the water content to 0.05% by weight or less, the amount of foreign matter contained in the resulting polyester resin can be further reduced. The water content in the mixed liquid of the compound (A) and the organic solvent (C) is preferably 0.03% by weight or less in that a polyester resin with a reduced foreign matter content can be obtained. Examples of the method for adjusting the amount of water include a method in which the mixed solution is heated and stirred at 150 ° C. under a nitrogen stream. The “moisture content” in the present invention is determined under the conditions described later using a Karl Fischer coulometric titration trace moisture measurement device (“Mitsubishi Chemical's“ trace moisture measurement device CA-100 ”)”.

  Furthermore, after adjusting the liquid mixture temperature of the said compound (A) and organic solvent (C) to 100 degrees C or less, it is preferable to mix a titanium compound (B). By adjusting the mixed solution temperature to 100 ° C. or lower and mixing the titanium compound (B), the amount of foreign matter contained in the obtained polyester resin can be further reduced. The temperature of the mixed solution is preferably 80 ° C. or less, and particularly preferably 60 ° C. or less in that a polyester resin with a reduced foreign matter content can be obtained. The lower limit of the mixed solution temperature is preferably 30 ° C. or higher in view of the operability of the organic solvent (C). Examples of the method for adjusting the temperature of the mixed solution include a method of allowing the mixed solution to cool at room temperature. Either the temperature adjustment and the water content adjustment described above may be performed first or simultaneously, but it is preferable to adjust the temperature after adjusting the water content. For example, it can be adjusted to a desired temperature by allowing the mixed liquid after adjusting the moisture content to cool at room temperature.

  The mixing method and conditions for the compound (A) and the organic solvent (C) are not particularly limited as long as the water content of the mixed solution is within the above range, and known mixing methods and conditions can be used. Further, the mixing method and conditions of the titanium compound (B) are not particularly limited as long as the water content and temperature of the mixed solution composed of the compound (A) and the organic solvent (C) are within the above ranges, and are not particularly limited. Methods and conditions can be used.

  The catalyst solution for polyester production according to the embodiment of the present invention may contain a compound other than the compound (A) and the titanium compound (B). Examples of compounds other than the compound (A) and the titanium compound (B) contained in the catalyst solution for polyester production include metal elements of Group 2A of the periodic table, aluminum, manganese, iron, cobalt, zinc, gallium, and germanium. Examples thereof include a compound containing one or more selected metal elements or a phosphorus compound. Two or more of these compounds may be used. Content with respect to the titanium compound (B) of these compounds is not specifically limited. However, since the reaction time of the esterification reaction or the reaction time of the transesterification reaction and the reaction time of the polycondensation reaction can be shortened, and a polyester resin with few foreign matters can be obtained, the catalyst solution for polyester production is prepared from the periodic table. It is preferable not to contain a compound containing one or more metal elements selected from Group 2A metal elements, aluminum, manganese, iron, cobalt, zinc, gallium, and germanium, and / or not to contain a phosphorus compound. In particular, it is more preferable that the catalyst solution for polyester production does not contain a phosphorus compound in that the reaction time of the esterification reaction or the reaction time of the transesterification reaction and the reaction time of the polycondensation reaction can be shortened.

  The polyester resin according to the embodiment of the present invention has excellent mechanical properties, hydrolysis resistance, crystallization properties, and heat resistance of the polyester resin, and has less foreign matter and excellent color tone. It can be suitably used as a molding material for parts. The polyester resin of the present invention can be widely used for films, sheets, fibers, blow bottles, and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. The measurement method and determination method used in the examples and comparative examples of the present invention are as follows. These measurement methods are also used when determining the extension of the present invention.

(1) Moisture measurement Mitsubishi Chemical's “Aquamicron” (registered trademark) CXU is used as the catholyte and “Aquamicron” is used as the anolyte. Using “AX”, the water content of the mixture of the compound (A) and the organic solvent (C), which is heated and stirred at 150 ° C. under a nitrogen stream and adjusted in the water content by Karl Fischer coulometric titration method. Went.

(2) Long-term storage stability evaluation The produced catalyst solution was put into a container dried for 3 hours with a dryer set at 50 ° C., sealed in a nitrogen atmosphere, and stored at room temperature for 3 months. The catalyst solution was visually observed every week for 4 weeks from the preparation of the catalyst solution and every month thereafter.

(3) Measurement of amount of by-product THF The distillate generated during the esterification reaction is sampled, and the amount of by-product THF contained in the distillate is measured using the Shimadzu “GC-17A” gas chromatograph as an internal standard substance. And measured. It shows that it can manufacture efficiently, so that the amount of byproduct THF is small.

(4) Molecular weight measurement Using WATERS, WATERS410 as a detector, MODEL510 high performance liquid chromatography as a pump, Shodex GPC HFIP-806M and Shodex GPC HFIP-LG connected in series as a column The weight average molecular weight of the polyester resin in terms of standard polymethyl methacrylate was measured by gel permeation chromatography (GPC). Measurement conditions were a flow rate of 1.0 mL / min, hexafluoroisopropanol was used as a solvent, and 0.1 mL of a solution having a sample concentration of 1 mg / mL was injected.

(5) Solution haze measurement A polyester resin was dissolved in a 6: 4 (weight ratio) mixed solution of phenol and tetrachloroethane to prepare a solution having a polyester resin concentration of 5.4 g / 40 mL. Using Nippon Denshoku "turbidity meter 300A", the solution haze measurement of the polyester resin was performed at a temperature of 25 ° C using an optical cell having a cell length of 10 mm. It shows that there are few foreign materials, so that the value of solution haze is small.

(6) Color tone measurement Using Nippon Denshoku "spectral color difference meter SE-2000", the color tone of the film produced in thickness 0.7mm was measured, and b value was measured. It shows that yellow value is so strong that b value is large, and blueness is so strong that it is small. The smaller the b value (when the b value has a negative value, the larger the absolute value of the b value), the better the color tone.

(7) Measurement of amount of compound (A) and titanium compound (B) contained in polyester resin 3 mL of sulfuric acid was added to 1.5 g of the polyester resin, and then 15 mL of nitric acid was gradually added. After confirming that the polyester resin was decomposed, add 3 mL of a 1: 5 (volume ratio) mixed solution of perchloric acid and nitric acid, and add 3 mL of hydrofluoric acid if insoluble, and completely decompose the polyester resin. I let you. Dissolved by heating with dilute nitric acid and dissolved, and using an ICP emission spectroscopic analyzer “SPS4000” manufactured by SII Nanotechnology, the amount of nitrogen atoms of compound (A) in 100 g of polyester resin and the amount of compound (B) were analyzed by elemental analysis. The amount of metal atoms was determined, and the molar amounts of compound (A) and compound (B) were calculated.

[Example 1]
Compound (A) is 2-hydroxymethylpyridine (HMP) (Tokyo Kasei), organic solvent (C) is 1,4-butanediol (BDO) (Tokyo Kasei), and organic solvent (C): 100 g of compound ( A): 0.4 g (3.3 × 10 ⁻³ mol) was added, and the mixture was heated and stirred at 150 ° C. under a nitrogen stream to prepare a mixed solution. The water content of the mixed solution was measured and found to be 0.05% by weight.

Next, the mixed solution was cooled and the temperature of the mixed solution was adjusted to 100 ° C., and then tetra-n-butoxy titanate (TBT) (Tokyo Kasei) as a titanium compound (B): 11.2 g (3.3 × 10 ⁻²⁾ The catalyst solution for producing a polyester resin was obtained. In this catalyst solution for polyester resin production, the molar ratio (A / B) of the content of the compound (A) to the titanium compound (B) is 0.10, and the content of the titanium compound (B) is the catalyst. 10.0% by weight in solution.

The molar ratio ((E) / (D-1)) of the diol component (E) to the dicarboxylic acid component (D-1) in the esterification reaction is 1.7, and terephthalic acid as the dicarboxylic acid component (D-1): 250 g, BDO: 230 g as the diol component (E), and 7.5 × 10 ⁻⁵ mol as the esterification reaction catalyst with respect to 100 g of the polyester resin produced by the TBT addition amount (0.025 to 100 parts by weight of the polyester resin) The catalyst solution for producing a polyester resin: 0.8 mL was charged into a reactor equipped with a rectifying column so that the esterification reaction was started at 160 ° C. under a reduced pressure of 90 kPa. Thereafter, the temperature was gradually raised, and an esterification reaction was finally carried out at a temperature of 225 ° C. The completion of the esterification reaction was confirmed by the state of the distillate and the reaction time of the esterification reaction was 210 minutes. As a polycondensation reaction catalyst, the resulting reaction product is 7.5 × 10 ⁻⁵ mol (0.025 parts by weight with respect to 100 parts by weight of the polyester resin) with respect to 100 g of the polyester resin produced. Polyester resin production catalyst solution: 0.25 mL was added thereto, and a polycondensation reaction was carried out under conditions of a temperature of 245 ° C. and a pressure of 100 Pa. The completion of the polycondensation reaction was confirmed by the viscosity of the reaction product, and the reaction time of the polycondensation reaction for obtaining the polyester resin was set to 165 minutes to obtain a polyester resin.

[Example 2]
Using the catalyst solution for producing the polyester resin used in Example 1, 1.5 × 10 ⁻⁴ mol (0.05 parts by weight with respect to 100 parts by weight of the polyester resin) with respect to 100 g of the polyester resin in which the TBT addition amount is generated. Example 1 except that the amount of the polyester resin production catalyst solution used as the esterification reaction catalyst was changed to 1.6 mL, and the reaction time of the esterification reaction was 180 minutes. The esterification reaction was carried out in the same manner as above. Further, the polyester used as a polycondensation reaction catalyst so that the amount of TBT added is 1.5 × 10 ⁻⁴ mol (0.05 parts by weight with respect to 100 parts by weight of the polyester resin) with respect to 100 g of the produced polyester resin. A polyester resin was obtained by performing a polycondensation reaction in the same manner as in Example 1 except that the amount of the catalyst solution for resin production was changed to 0.5 mL and that the reaction time of the polycondensation reaction was 150 minutes. It was.

[Example 3]
In the preparation of the polyester resin production catalyst solution of Example 2, the amount of the compound (A) in the catalyst solution was changed to 0.04 g (3.3 × 10 ⁻⁴ mol), and the polyester resin production prepared A catalyst solution for polyester resin production was prepared in the same manner as in Example 2 except that the molar ratio (A / B) of the content of the compound (A) to the titanium compound (B) in the catalyst solution was 0.01. . A polyester resin was obtained by performing an esterification reaction and a polycondensation reaction in the same manner as in Example 2 except that the above-mentioned catalyst solution for polyester resin production was used instead of the catalyst solution for polyester resin production used in Example 2. .

[Example 4]
In the preparation of the catalyst solution for producing the polyester resin of Example 2, the amount of the compound (A) added in the catalyst solution was changed to 1.8 g (1.7 × 10 ⁻² mol), and the addition of the titanium compound (B) The molar ratio (A / B) of the content of the compound (A) to the titanium compound (B) in the catalyst solution for polyester resin production prepared by changing the amount to 11.3 g (3.3 × 10 ⁻² mol) ) Was changed to 0.50, and a catalyst solution for polyester resin production was prepared in the same manner as in Example 2. A polyester resin was obtained by performing an esterification reaction and a polycondensation reaction in the same manner as in Example 2 except that the above-mentioned catalyst solution for polyester resin production was used instead of the catalyst solution for polyester resin production used in Example 2. .

[Example 5]
In the preparation of the catalyst solution for producing the polyester resin of Example 2, the addition amount of the compound (A) in the catalyst solution was changed to 2.7 g (2.5 × 10 ⁻² mol), and the addition of the titanium compound (B) The molar ratio (A / B) of the content of the compound (A) to the titanium compound (B) in the catalyst solution for polyester resin production prepared by changing the amount to 11.4 g (3.3 × 10 ⁻² mol) ) Was adjusted to 0.75, and a catalyst solution for polyester resin production was prepared in the same manner as in Example 2. A polyester resin was obtained by performing an esterification reaction and a polycondensation reaction in the same manner as in Example 2 except that the above-mentioned catalyst solution for polyester resin production was used instead of the catalyst solution for polyester resin production used in Example 2. .

[Example 6]
Polyester resin production prepared by changing the amount of compound (A) added to the catalyst solution to 0.9 g (8.2 × 10 ⁻³ mol) in the preparation of the catalyst solution for producing the polyester resin of Example 2. The catalyst solution for polyester resin production was prepared in the same manner as in Example 2 except that the molar ratio (A / B) of the content of the compound (A) to the titanium compound (B) in the catalyst solution was 0.25. It was. A polyester resin was obtained by performing an esterification reaction and a polycondensation reaction in the same manner as in Example 2 except that the above-mentioned catalyst solution for polyester resin production was used instead of the catalyst solution for polyester resin production used in Example 2. .

[Example 7]
In the preparation of the catalyst solution for producing the polyester resin of Example 6, the amount of the titanium compound (B) in the catalyst solution was changed to 25.5 g (7.5 × 10 ⁻² mol), and the polyester resin produced The amount of compound (A) added was 2.0 g so that the molar ratio (A / B) of the content of compound (A) to titanium compound (B) in the catalyst solution was 0.25 as in Example 6. The content of the titanium compound (B) in the prepared catalyst solution for polyester resin production was changed to 20.0% by weight in the catalyst solution by changing to (1.9 × 10 ⁻² mol). In other respects, a catalyst solution for polyester resin production was prepared in the same manner as in Example 6. The polyester resin production catalyst solution was used instead of the polyester resin production catalyst solution used in Example 6, and the catalyst solution addition amount in the esterification reaction was 0.8 mL, and the catalyst solution addition amount in the polycondensation reaction A polyester resin was obtained by carrying out an esterification reaction and a polycondensation reaction in the same manner as in Example 6 except that was changed to 0.25 mL.

[Example 8]
In the preparation of the catalyst solution for producing the polyester resin of Example 7, the mixture was heated and stirred at 150 ° C. under a nitrogen stream, and the water content in the mixed solution of the compound (A) and the organic solvent (C) was 0.03% by weight. A catalyst solution for producing a polyester resin was prepared in the same manner as in Example 7 except that the titanium compound (B) was mixed after the adjustment. A polyester resin was obtained by carrying out an esterification reaction and a polycondensation reaction in the same manner as in Example 7 except that the catalyst solution for polyester resin production was used instead of the catalyst solution for polyester resin production used in Example 7. .

[Example 9]
In the preparation of the catalyst solution for producing the polyester resin of Example 8, after adjusting the water content, the mixture was cooled and the mixed solution temperature of the compound (A) and the organic solvent (C) was adjusted to 80 ° C., and then the titanium compound (B) was mixed. A catalyst solution for producing a polyester resin was prepared in the same manner as in Example 8 except that. A polyester resin was obtained by carrying out an esterification reaction and a polycondensation reaction in the same manner as in Example 8 except that the catalyst solution for polyester resin production was used instead of the catalyst solution for polyester resin production used in Example 8. .

[Example 10]
In the preparation of the polyester resin production catalyst solution of Example 8, after adjusting the water content, cooling, adjusting the mixed solution temperature of the compound (A) and the organic solvent (C) to 60 ° C., and then mixing the titanium compound (B) A catalyst solution for producing a polyester resin was prepared in the same manner as in Example 8 except that. A polyester resin was obtained by carrying out an esterification reaction and a polycondensation reaction in the same manner as in Example 8 except that the catalyst solution for polyester resin production was used instead of the catalyst solution for polyester resin production used in Example 8. .

[Example 11]
In the preparation of the catalyst solution for producing the polyester resin of Example 10, the molar ratio ((E) / (D-1)) of the diol component (E) to the dicarboxylic acid component (D-1) in the esterification reaction was 2.0. And the amount of BDO was changed to 270 g, and the reaction time of the esterification reaction was 190 minutes and the reaction time of the polycondensation reaction was 160 minutes, as in Example 10. An esterification reaction and a polycondensation reaction were performed to obtain a polyester resin.

[Example 12]
In the preparation of the catalyst solution for producing the polyester resin of Example 6, the mixture was heated and stirred at 150 ° C. under a nitrogen stream, and the water content in the mixed solution of the compound (A) and the organic solvent (C) was 0.03% by weight. A catalyst solution for producing a polyester resin was prepared in the same manner as in Example 6 except that the titanium compound (B) was mixed after the temperature of the mixture was adjusted to 60 ° C. by cooling and the titanium compound (B) was mixed. A polyester resin was obtained by carrying out an esterification reaction and a polycondensation reaction in the same manner as in Example 6 except that the catalyst solution for polyester resin production was used instead of the catalyst solution for polyester resin production used in Example 6. .

[Example 13]
In the implementation of the esterification reaction and the polycondensation reaction in Example 12, the amount of the catalyst solution added in the esterification reaction was 1.3 mL (corresponding to 1.2 × 10 ⁻⁴ mol of TBT added to 100 g of polyester resin). And the amount of the catalyst solution added in the polycondensation reaction was changed to 0.4 mL (the amount of TBT added was equivalent to 1.2 × 10 ⁻⁴ mol per 100 g of the polyester resin). As in Example 12, an esterification reaction and a polycondensation reaction were performed to obtain a polyester resin.

[Example 14]
In the preparation of the catalyst solution for producing the polyester resin of Example 12, the amount of the titanium compound (B) in the catalyst solution was changed to 3.0 g (8.9 × 10 ⁻³ mol), and the polyester resin produced The amount of the compound (A) added was 0.24 g so that the molar ratio (A / B) of the content of the compound (A) to the titanium compound (B) in the catalyst solution was 0.25 as in Example 12. (2.2 × 10 ⁻³ mol), the addition amount of the organic solvent (C) is changed to 300 g, and the content of the titanium compound (B) in the prepared catalyst solution for polyester resin production is set to 1 0.0% by weight. In other respects, a catalyst solution for polyester resin production was prepared in the same manner as in Example 12. The amount of BDO used as the diol component (E) used in the esterification reaction was changed to 225 g, the catalyst solution for polyester resin production was used in place of the catalyst solution for polyester resin production used in Example 12, And the esterification reaction and the polycondensation reaction were carried out in the same manner as in Example 12 except that the addition amount of the catalyst solution in the esterification reaction was changed to 16 mL and the addition amount of the catalyst solution in the polycondensation reaction was changed to 4.9 mL. A polyester resin was obtained.

[Example 15]
In the preparation of the catalyst solution for producing the polyester resin of Example 14, the addition amount of the compound (A) in the catalyst solution was changed to 0.05 g (0.4 × 10 ⁻³ mol), and the addition of the titanium compound (B) The amount was changed to 0.6 g (1.8 × 10 ⁻³ mol), and the content of the titanium compound (B) in the prepared polyester resin production catalyst solution was changed to 0.2% by weight in the catalyst solution. did. In other respects, a catalyst solution for polyester resin production was prepared in the same manner as in Example 14. The amount of BDO used as the diol component (E) used in the esterification reaction was changed to 160 g, the catalyst solution for polyester resin production was used instead of the catalyst solution for polyester resin production used in Example 14, In addition, the esterification reaction and the polycondensation reaction were performed in the same manner as in Example 14 except that the addition amount of the catalyst solution in the esterification reaction was changed to 81 mL, and the addition amount of the catalyst solution in the polycondensation reaction was changed to 25 mL. Got.

[Example 16]
In the preparation of the polyester resin production catalyst solution of Example 6, compound of the catalyst solution (A) was a 1-hydroxypropyl pyrrole (HPT) (Tokyo Kasei), the addition amount of 1.0g (8.2 × 10 ^{- A} catalyst solution for producing a polyester resin was prepared in the same manner as in Example 6 except that it was changed to ³ mol).

  The esterification reaction and polycondensation reaction were carried out in the same manner as in Example 6 except that the above was used instead of the catalyst solution for production of the polyester resin used in Example 6 and that the polycondensation reaction was 155 minutes. And a polyester resin was obtained.

[Example 17]
About 100 kg of bis (hydroxyethyl) terephthalate was charged in advance, and the esterification reaction tank maintained at a temperature of 250 ° C. and a pressure of 1.2 × 10 ⁵ Pa was charged with terephthalic acid (Mitsui Chemicals) as the dicarboxylic acid component (D-1). 82.5 kg, 35.4 kg of ethylene glycol (EG) (Nippon Shokubai) slurry as diol component (E) was sequentially fed over 4 hours, and the esterification reaction was carried out for an additional hour after the supply was completed. For 5 hours. 101.5 kg of the obtained esterification reaction product was transferred to a polycondensation tank.

As a polycondensation reaction catalyst for the obtained esterification reaction product, 1.0 × 10 ⁻⁵ mol (based on 100 parts by weight of the polyester resin) with respect to 100 g of the polymer obtained with respect to 100 g of the polyester resin with the added amount of TBT The catalyst solution for polyester resin production used in Example 6: 71.1 mL was added so as to be 0.0035 parts by weight). After 5 minutes, the reaction system was decompressed to initiate the reaction. The reactor was gradually heated from 250 ° C. to 290 ° C., and the pressure was reduced to 40 Pa. The final temperature and the time to reach the final pressure were both 60 minutes, and the polycondensation reaction was performed for 160 minutes to obtain a polyester resin.

[Comparative Example 1]
In preparing the polyester resin production catalyst solution of Example 2, a polyester resin production catalyst solution was produced in the same manner as in Example 2 except that the compound (A) was not added. A polyester resin was obtained by performing an esterification reaction and a polycondensation reaction in the same manner as in Example 2 except that the above-mentioned catalyst solution for polyester resin production was used instead of the catalyst solution for polyester resin production used in Example 2. .

[Comparative Example 2]
In preparing the catalyst solution for producing a polyester resin of Example 2, a catalyst solution for producing a polyester resin was prepared in the same manner as in Example 2 except that the addition of the compound (A) was not performed and the water content was not adjusted. A polyester resin was obtained by performing an esterification reaction and a polycondensation reaction in the same manner as in Example 2 except that the above-mentioned catalyst solution for polyester resin production was used instead of the catalyst solution for polyester resin production used in Example 2. . In addition, the moisture content of the organic solvent (C) which did not implement moisture content was 0.10 weight%.

[Comparative Example 3]
In the preparation of the catalyst solution for producing the polyester resin of Example 2, the amount of the compound (A) added in the catalyst solution was changed to 3.7 g (3.4 × 10 ⁻² mol), and the amount of the compound (A) relative to the titanium compound (B) was changed. A catalyst solution for polyester resin production was prepared in the same manner as in Example 2 except that the molar ratio (A / B) of the content of the compound (A) was changed to 1.0. A polyester resin was obtained by performing an esterification reaction and a polycondensation reaction in the same manner as in Example 2 except that the above-mentioned catalyst solution for polyester resin production was used instead of the catalyst solution for polyester resin production used in Example 2. .

[Comparative Example 4]
Comparative Example 3 except that the titanium compound (B) was mixed without adjusting the water content of the mixed liquid of the compound (A) and the organic solvent (C) in the preparation of the catalyst solution for producing the polyester resin of Comparative Example 3. In the same manner as in 3, a catalyst solution for producing a polyester resin was prepared. A polyester resin was obtained by carrying out an esterification reaction and a polycondensation reaction in the same manner as in Comparative Example 3 except that the catalyst solution for polyester resin production was used instead of the catalyst solution for polyester resin production used in Comparative Example 3. . In addition, the water content of the mixed liquid of the compound (A) and the organic solvent (C) for which the water content was not adjusted was 0.10% by weight.

[Comparative Example 5]
In the preparation of the catalyst solution for producing the polyester resin of Comparative Example 4, the titanium compound (B) was changed to tetra-n-propoxide titanium (TPT), and the catalyst solution for producing the polyester resin was prepared in the same manner as in Comparative Example 4. The compound in the catalyst solution so that the content of the titanium compound (B) is 10.0 and the molar ratio (A / B) of the content of the compound (A) to the titanium compound (B) is 1.0. The addition amount of (A) was changed to 4.4 g (4.1 × 10 ⁻² mol), and the addition amount of the titanium compound (B) was changed to 11 g (4.1 × 10 ⁻² mol). In other respects, a catalyst solution for polyester resin production was prepared in the same manner as in Comparative Example 4. The above polyester resin production catalyst solution was used instead of the polyester resin production catalyst solution used in Comparative Example 4, and the reaction time of the esterification reaction was 185 minutes, and the reaction time of the polycondensation reaction was 165 minutes. Except for the above, an esterification reaction and a polycondensation reaction were carried out in the same manner as in Comparative Example 4 to obtain a polyester resin.

[Comparative Example 6]
In the preparation of the catalyst solution for producing the polyester resin of Comparative Example 4, the amount of the compound (A) in the catalyst solution was changed to 4.5 g (4.1 × 10 ⁻² mol), and the compound relative to the titanium compound (B) The molar ratio (A / B) of the content of (A) was changed to 1.2, and after adjusting the mixed solution temperature of the compound (A) and the organic solvent (C) to 150 ° C., the titanium compound (B) was mixed. did. In other respects, a catalyst solution for polyester resin production was prepared in the same manner as in Comparative Example 4. A polyester resin was obtained by carrying out an esterification reaction and a polycondensation reaction in the same manner as in Comparative Example 4 except that the above-mentioned catalyst solution for polyester resin production was used instead of the catalyst solution for polyester resin production used in Comparative Example 4. .

[Comparative Example 7]
With respect to the catalyst solution for polyester resin production used in Comparative Example 2, pure water was added to the mixed solution of the compound (B) and the organic solvent (C), and the water content in the mixed solution was set to 2.0% by weight. A catalyst solution for polyester resin production was prepared in the same manner as in Comparative Example 2 except that the change was made. A polyester resin was obtained by carrying out an esterification reaction and a polycondensation reaction in the same manner as in Comparative Example 2 except that the catalyst solution for polyester resin production was used instead of the catalyst solution for polyester resin production used in Comparative Example 2. .

[Comparative Example 8]
In the preparation of the catalyst solution for producing the polyester resin of Comparative Example 4, the addition amount of the compound (A) in the catalyst solution was changed to 16 g (1.5 × 10 ⁻¹ mol), and the addition amount of the titanium compound (B) was changed. change to 13g (3.8 × 10 ^-2 mol), as a result, the molar ratio of the content of the compound to titanium compound (B) (a) (a / B) is 4.0, and the addition, the compound (a ) And an organic solvent (C) in a mixed solution, the water content in the mixed solution is adjusted to 4.0% by weight, the mixed solution temperature is adjusted to 180 ° C., and then the titanium compound (B). Was added. In other respects, a catalyst solution for polyester resin production was prepared in the same manner as in Comparative Example 4. The same as Comparative Example 4 except that the catalyst solution for polyester resin production was used in place of the catalyst solution for polyester resin production used in Comparative Example 4 and that the reaction time of the esterification reaction was 190 minutes. An esterification reaction and a polycondensation reaction were performed to obtain a polyester resin.

[Comparative Example 9]
In the preparation of the polyester resin production catalyst solution of Comparative Example 8, the preparation of the polyester resin production catalyst solution was conducted in the same manner as in Comparative Example 8, except that the organic solvent (C) in the catalyst solution was changed to ethylene glycol (EG). went. The above polyester resin production catalyst solution was used in place of the polyester resin production catalyst solution used in Comparative Example 8, and the reaction time of the esterification reaction was 200 minutes, and the reaction time of the polycondensation reaction was 160 minutes. In the same manner as in Comparative Example 8, an esterification reaction and a polycondensation reaction were performed to obtain a polyester resin.

[Comparative Example 10]
In the preparation of the catalyst solution for producing the polyester resin of Example 16, the compound (A) in the catalyst solution was changed to pyridine (Py) (Tokyo Kasei), and the amount added was 0.7 g (8.2 × 10 ^−3). The catalyst solution for polyester resin production was prepared in the same manner as in Example 16 except that it was changed to (mol).

  A polyester resin was obtained by conducting an esterification reaction and a polycondensation reaction in the same manner as in Example 16 except that the above-mentioned catalyst solution for polyester resin production was used instead of the catalyst solution for polyester resin production used in Example 16. .

[Comparative Example 11]
In the preparation of the catalyst solution for producing the polyester resin of Example 16, the compound (A) in the catalyst solution was changed to pyrrole (Tp) (Tokyo Kasei), and the addition amount was 0.6 g (8.2 × 10 ^−3). The catalyst solution for polyester resin production was prepared in the same manner as in Example 16 except that it was changed to (mol).

  A polyester resin was obtained by conducting an esterification reaction and a polycondensation reaction in the same manner as in Example 16 except that the above-mentioned catalyst solution for polyester resin production was used instead of the catalyst solution for polyester resin production used in Example 16. .

[Comparative Example 12]
In the preparation of the polyester resin production catalyst solution of Comparative Example 4, the compound (A) in the catalyst solution was changed to thiophene (Tip) (Tokyo Kasei), and the amount added was 0.7 g (8.2 × 10 ^−3). The catalyst solution for polyester resin production was prepared in the same manner as in Comparative Example 4 except that it was changed to (mol).

  The above polyester resin production catalyst solution was used instead of the polyester resin production catalyst solution used in Comparative Example 4, and the reaction time of the esterification reaction was 190 minutes, and the reaction time of the polycondensation reaction was 155 minutes. Except for the above, an esterification reaction and a polycondensation reaction were carried out in the same manner as in Comparative Example 4 to obtain a polyester resin.

[Comparative Example 13]
In the preparation of the catalyst solution for producing the polyester resin of Comparative Example 4, the compound (A) in the catalyst solution was changed to morpholine (Mp) (Tokyo Kasei), and the amount added was 0.7 g (8.2 × 10 ^−3). The catalyst solution for polyester resin production was prepared in the same manner as in Comparative Example 4 except that it was changed to (mol).

  The above polyester resin production catalyst solution was used instead of the polyester resin production catalyst solution used in Comparative Example 4, and the reaction time of the esterification reaction was 190 minutes, and the reaction time of the polycondensation reaction was 155 minutes. Except for the above, an esterification reaction and a polycondensation reaction were carried out in the same manner as in Comparative Example 4 to obtain a polyester resin.

[Comparative Example 14]
In preparing the polyester resin production catalyst solution of Comparative Example 4, the compound (A) in the catalyst solution was changed to N-methylimidazole (NMI) (Tokyo Kasei), and the amount added was 0.7 g (8.2 ×). A catalyst solution for preparing a polyester resin was prepared in the same manner as in Comparative Example 4 except that it was changed to 10 ⁻³ mol).

  The above polyester resin production catalyst solution was used instead of the polyester resin production catalyst solution used in Comparative Example 4, and the reaction time of the esterification reaction was 190 minutes, and the reaction time of the polycondensation reaction was 155 minutes. Except for the above, an esterification reaction and a polycondensation reaction were carried out in the same manner as in Comparative Example 4 to obtain a polyester resin.

  Tables 1 and 2 collectively show the results of the examples and comparative examples.

From the results of the above Examples and Comparative Examples, in the present invention, the content of the compound (A) is in the range of 6.0 × 10 ⁻⁷ mol or more and less than 3.0 × 10 ⁻⁴ mol in 100 g of the polyester resin. It can be seen that a certain polyester resin has a small solution haze and a small amount of foreign matter, a small color tone b value, and a small yellowness. That is, 6.0 × 10 ⁻⁷ mol or more of a compound (A) having a pyrrole ring or pyridine ring structure and containing at least one atom having an unshared electron pair other than nitrogen in 100 g of a polyester resin. By containing less than 0 × 10 ⁻⁴ mol, it was possible to obtain a polyester resin with less foreign matter and excellent color tone.

From the results of the above Examples 1 to 16 and Example 17, in the present invention, the content of the compound (B) is 6.0 × 10 ⁻⁵ mol or more and 1.8 × 10 ⁻³ mol in 100 g of the polyester resin. It can be seen that the polyester resin in a range of less than that has a small solution haze and a small amount of foreign matter, a small color tone b value, and a small yellowness. That is, by containing the titanium compound (B) in an amount of 6.0 × 10 ⁻⁵ mol or more and less than 1.8 × 10 ⁻³ mol in 100 g of the polyester resin, a polyester resin having few foreign matters and excellent color tone can be obtained. I was able to.

From the results of Examples 1 and 2, the esterification reaction time and the polycondensation reaction time can be shortened when the amount of the titanium compound contained in 100 g of the polyester resin is 2.0 × 10 ⁻⁴ mol or more. It can be seen that the amount of by-product THF can be reduced and the polyester resin can be produced efficiently.

  From the results of Examples 2 to 6 and Comparative Examples 1 to 3, the molar ratio (A / B) of the compound (A) to the titanium compound (B) can be further reduced from the foreign matter of the polyester resin. The molar ratio is preferably not less than 1.0 mol times, more preferably not less than 0.01 mol times and not more than 0.75 mol times, further preferably not less than 0.1 mol times and not more than 0.75 mol times, and more than 0.1 mol times 0.5 mole times or less is particularly preferable, and 0.1 mole times or more and 0.25 mole times or less is most preferable.

  From the results of Examples 7 to 8 and Comparative Example 7, the amount of water in the mixture of the compound (A) and the organic solvent (C) before mixing the titanium compound (B) in the catalyst solution for polyester resin production was From the point that the foreign substance of a polyester resin can be reduced more, it turns out that 0.05 weight% or less is preferable and 0.03 weight% or less is especially preferable.

  From the results of Examples 8 to 10 and Comparative Example 6, the mixed solution temperature of the compound (A) and the organic solvent (C) before mixing the titanium compound (B) in the polyester resin production catalyst solution was It can be seen that 100 ° C. or lower is preferable, 80 ° C. or lower is more preferable, and 60 ° C. or lower is particularly preferable because foreign matters can be further reduced.

  From the results of Examples 10 to 11, the molar ratio of the diol component (E) to the dicarboxylic acid (D-1) is 1.1 to 1.8 in that the esterification reaction time and the polycondensation reaction time can be shortened. It can be seen that it is preferable to be within the range.

  From the results of Examples 7, 12, 14, and 15, the content of the titanium compound (B) in the catalyst solution for producing the polyester resin is preferably 10% by weight or less from the viewpoint that foreign matters of the polyester resin can be further reduced. It is understood that 1.0% by weight or less is more preferable, and 0.5% by weight or less is particularly preferable.

  From the results of Examples 6 and 16 and Comparative Examples 10 to 14, the compound (A) contains one or more oxygen atoms, which are atoms having an unshared electron pair, from the viewpoint that foreign matters of the polyester resin can be further reduced. It can be seen that HMP is preferred.

  From the results of Examples 6 and 17, it can be seen that it is preferable to select polybutylene terephthalate as the polyester resin from the viewpoint that foreign matters of the polyester resin can be further reduced and the color tone is excellent.

  From the results of Examples 1 to 17 and Comparative Examples 1 and 2, it can be seen that long-term storage stability is excellent by adding the compound (A) to the catalyst solution for polyester resin production.

Claims (7)

A compound (A) having a pyrrole ring or pyridine ring structure and containing at least one atom having an unshared electron pair other than nitrogen is added in an amount of 6.0 × 10 ⁻⁷ mol to 3.0 × in 100 g of a polyester resin. A polyester resin containing less than 10 ⁻⁴ mol. The polyester resin according to claim 1, further comprising:
The titanium compound (B) is contained in a polyester resin 100 g in an amount of 6.0 × 10 ⁻⁵ mol to 1.8 × 10 ⁻³ mol,
The polyester resin whose molar ratio (A / B) of content of the said compound (A) with respect to content of a titanium compound (B) is 0.01 or more and less than 1.0. The polyester resin according to claim 1 or 2,
The polyester resin in which the compound (A) contains one or more oxygen atoms. A method for producing a polyester resin according to claim 2 or 3,
Esterification reaction of dicarboxylic acid component (D-1) composed of dicarboxylic acid and diol component (E), or ester of dicarboxylic acid component (D-2) composed of ester-forming derivative of dicarboxylic acid and diol component (E) A method for producing a polyester resin by an exchange reaction and a subsequent polycondensation reaction,
As a reaction catalyst for the esterification reaction or transesterification reaction and polycondensation reaction, the compound (A) and the organic solvent (C) are mixed, and the water content in the mixed solution is adjusted to 0.05% by weight or less. A method for producing a polyester resin, wherein a catalyst for producing a polyester resin obtained by mixing a titanium compound (B) is added to a reaction system. It is a manufacturing method of the polyester resin of Claim 4, Comprising:
The polyester resin production catalyst is obtained by adjusting the mixed liquid temperature of the compound (A) and the organic solvent (C) to 100 ° C. or less and then mixing the titanium compound (B). Production method.   Catalyst solution for producing a polyester resin containing a compound (A) having one or more atoms having a pyrrole ring or pyridine ring structure and having an unshared electron pair other than nitrogen, a titanium compound (B), and an organic solvent (C) The compound (A) and the organic solvent (C) are mixed, the water content in the mixed solution is adjusted to 0.05% by weight or less, and then the compound (A) relative to the titanium compound (B) is prepared. ) Content ratio (A / B) is 0.01 to less than 1.0, and a method for producing a polyester resin production catalyst solution is added. It is a manufacturing method of the catalyst solution for polyester resin manufacture of Claim 6, Comprising:
The manufacturing method of the catalyst solution for polyester resin manufacture which adjusts the liquid mixture temperature of the said compound (A) and organic solvent (C) to 100 degrees C or less, and then adds a titanium compound (B).