JP2006028482A - Polyester resin and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester resin containing 1,4-cyclohexanedicarboxylic acid (1,4-CHDA) as main dicarboxylic acid units, having a high melting point and excellent in heat resistance, by preventing trans-1,4-CHDA from being isomerized in esterification and polycondensation reaction, and to provide a method for producing the same. <P>SOLUTION: This polyester resin is obtained by preparing an oligomer by the esterification reaction of a dicarboxylic acid component which contains the 1,4-CHDA as a main component with a diol component, and then polycondensing the oligomer in the presence of a polycondensation catalyst, wherein the polyester resin satisfies inequality: 0 ≤ ä(T0-Tp)/T0}×100 ≤ 12 (T0 is a mol% of trans forms in the raw material 1,4-CHDA; and Tp is a mol% of trans forms in 1,4-CHDA units of the obtained polyester resin). The method for producing the polyester resin is characterized by conducting the polycondensation reaction by using the polycondensation catalyst, after the esterification reaction is conducted by using a basic compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polyester resin and a method for producing the same. More specifically, the present invention relates to a polyester resin excellent in heat resistance and hydrolysis resistance, and a method for producing the same.

  Among polyester resins, polyester resins containing 1,4-cyclohexanedicarboxylic acid (hereinafter sometimes abbreviated as 1,4-CHDA) units as main dicarboxylic acid units are transparent, hydrolysis resistant (hydrolysis). The properties are difficult to do) and the weather resistance is excellent, so the applications are expanding. A polyester resin containing a 1,4-CHDA unit as a main dicarboxylic acid unit is obtained through an esterification reaction or an ester exchange reaction between 1,4-CHDA or an ester-forming derivative of 1,4-CHDA and a diol component. The resulting esterification reaction product (oligomer) is obtained by polycondensation in the presence of a polycondensation catalyst. There are (1) a direct esterification method using a dicarboxylic acid component and a diol component as raw materials, and (2) a transesterification method of an ester-forming derivative component of a dicarboxylic acid and a diol component. According to the transesterification method of (2), the resulting polyester resin has the disadvantages of poor hydrolysis resistance, and the cost of 1,4-CHDA ester-forming derivatives is higher than 1,4-CHDA. is there.

  On the other hand, 1,4-CHDA usually has a trans isomer and a cis isomer, and the trans isomer is isomerized to a cis isomer during the esterification reaction and the polycondensation reaction. When the mol% of the cis form in the 1,4-CHDA unit contained in the polyester resin increases, there is a problem that a polyester resin having a high melting point cannot be obtained and the heat resistance is poor. Japanese Patent Laid-Open No. 2000-290356 discloses a technique for producing an alicyclic polyester using 1,4-CHDA containing 100 mol% of a trans isomer as a raw material. However, the relationship between the ratio of the cis isomer contained in the 1,4-CHDA unit of the obtained polyester resin and the heat resistance, the trans isomer isomerization to the cis isomer during the polycondensation reaction, There is no suggestion of how to prevent it.

In addition, U.S. Pat. No. 2,901,466 discloses that 1,4-dimethylcyclohexanedicarboxylate with 100% trans isomer and 1,4-cyclohexanedimethanol with 100% trans isomer (hereinafter, cyclohexanedimethanol is referred to as “CHDM”). Examples of the production of alicyclic polyesters are described. However, in order to prepare such 100% trans CHDA and CHDM, a very complicated and difficult purification operation is usually required. In addition, no suggestion has been made regarding the prevention of isomerization of the trans isomer.
US Patent Publication No. 2003-232958 proposes a technique for producing an alicyclic polyester using 1,4-CHDA as a raw material. However, there is a suggestion about the relationship between the proportion of cis-isomer contained in 1,4-CHDA and the physical properties of the polyester resin, the trans-isomerization of the trans-isomer into the cis-isomer during the polycondensation reaction, and a method for preventing this isomerization It has not been.
Further, in US Pat. No. 6,084,055, 1,4-dimethylcyclohexanedicarboxylate and 1,4-cyclohexanedimethanol (hereinafter sometimes abbreviated as 1,4-CHDM) were used as raw materials. Production examples of alicyclic polyesters are described. However, there is no suggestion that the trans isomer isomerizes to the cis isomer during the polycondensation reaction.

In view of the above circumstances, the present inventors have conducted extensive studies with the aim of providing a polyester resin and a method for producing the same that have eliminated all the disadvantages existing in the technical field to which the present invention belongs. Is completed. That is, the object of the present invention is as follows.
1. Provided is a polyester resin excellent in heat resistance, in which isomerization of trans-1,4-CHDA in esterification and polycondensation reactions is suppressed, and a 1,4-CHDA unit having a high melting point is a main carboxylic acid unit.
2. Provided is a method for producing a polyester resin in which isomerization of a raw material 1,4-CHDA trans to a cis isomer is suppressed in a polycondensation reaction process.

The present inventor has studied to solve the above problems and has reached the present invention. That is, the gist of the present invention is as follows.
1. In esterification and polycondensation reaction of dicarboxylic acid and diol mainly composed of 1,4-cyclohexanedicarboxylic acid, after performing esterification reaction using basic compound, polycondensation reaction using polycondensation catalyst A process for producing a polyester resin, characterized in that
2. Polyester resin obtained by preparing an oligomer by an esterification reaction of a dicarboxylic acid component mainly composed of 1,4-cyclohexanedicarboxylic acid and a diol component, and polycondensing the oligomer in the presence of a polycondensation catalyst. Where T0 is the mol% of the trans isomer in the raw material 1,4-cyclohexanedicarboxylic acid, and Tp is the mol% of the trans isomer in the 1,4-cyclohexanedicarboxylic acid unit in the resulting polyester resin. And Tp satisfy the following formula (I): 0 ≦ {(T0−Tp) / T0} × 100 ≦ 12.
3. A method comprising a step of preparing an oligomer by an esterification reaction of a dicarboxylic acid component containing 1,4-cyclohexanedicarboxylic acid as a main component and a diol component, and a step of polycondensing the oligomer in the presence of a polycondensation catalyst. In the production of the polyester resin, T0 is the mol% of the trans isomer in the raw material 1,4-cyclohexanedicarboxylic acid, and Tp is the mol% of the trans isomer in the 1,4-cyclohexanedicarboxylic acid unit in the resulting polyester resin. When T60 is the mol% of the trans isomer in the 1,4-cyclohexanedicarboxylic acid unit in the oligomer at an esterification rate of 60%, T0, T60 and Tp are represented by the following formula (II): 0 ≦ {( T0−T60) / T0} × 100 ≦ 5, and T0 and Tp of the obtained polyester resin are the following formulas (I) Chi, 0 ≦ {(T0-Tp) / T0} × 100 ≦ 12, the manufacturing method of the polyester resin and satisfies the.

The present invention has the following advantageous effects, and its industrial utility value is extremely great.
1. According to the present invention, there is provided a polyester resin having a 1,4-CHDA unit as a main dicarboxylic acid unit and having a high melting point and excellent heat resistance.
2. According to the present invention, in the polycondensation reaction process, isomerization of trans 1,4-CHDA to cis 1,4-CHDA is suppressed, and a polyester resin having a high content of trans 1,4-CHDA units is obtained. Can do.
3. Since the method for producing a polyester resin of the present invention is based on a direct esterification method of 1,4-CHDA, it is industrially advantageous compared to a transesterification method using an ester-forming derivative.

The description of the constituent requirements described below is a representative example of the embodiment of the present invention, and is not limited to these contents.
The polyester resin according to the present invention prepares an oligomer by an esterification reaction between a dicarboxylic acid component mainly composed of 1,4-cyclohexanedicarboxylic acid (1,4-CHDA) and a diol component, and polycondensates the oligomer. It is a polyester resin obtained by polycondensation in the presence of a catalyst. Here, “main component” means that the main component of the dicarboxylic acid component is 1,4-CHDA. Specifically, it means that the proportion of 1,4-CHDA in the total carboxylic acid component is 80 mol% or more, and the remainder is a dicarboxylic acid other than 1,4-CHDA. If the proportion of 1,4-CHDA in the total dicarboxylic acid component is less than 80 mol%, the resulting polyester resin may not have sufficient heat resistance, which is not preferable. The proportion of 1,4-CHDA in the total dicarboxylic acid component is preferably 90 mol% or more, and more preferably 95 mol% or more. 1,4-CHDA usually has an isomer of a trans isomer and a cis isomer, and the ratio of the trans isomer / cis isomer is selected so as to increase the ratio of the trans isomer. The preferred trans isomer / cis isomer molar ratio is 80/20 or more, more preferably 85/15 or more, and particularly preferably 90/10 or more.

  The dicarboxylic acid component used for the production of the polyester resin according to the present invention is mainly composed of the above-described 1,4-CHDA, but as described above, a dicarboxylic acid component other than 1,4-CHDA is used as a copolymer component. can do. Examples of the corresponding copolymer component include terephthalic acid, phthalic acid, isophthalic acid, 1,4-phenylenedioxydicarboxylic acid, 1,3-phenylenedioxydiacetic acid, 4,4′-diphenyldicarboxylic acid, 4, Aromatic dicarboxylic such as 4'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl ketone dicarboxylic acid, 4,4'-diphenoxyethane dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 2,6-naphthalenedicarboxylic acid Acids, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, hexahydroisophthalic acid, and succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecadicarboxylic acid, dodecadicarboxylic acid And aliphatic dicarboxylic acids such as These copolymerization components may be one kind or a mixture of two or more kinds. Of these, terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid are preferably used. Examples of the ester-forming derivative of dicarboxylic acid include aliphatic alcohol diesters having 1 to 4 carbon atoms of the above-mentioned dicarboxylic acid, and among them, dimethyl ester is preferably used.

In the production method of the present invention, the diol used for the esterification reaction preferably contains 1,4-CHDM. The 1,4-CHDM in the diol is preferably 60 mol% or more, and if it is less than 60 mol%, the polymerizability tends to be inferior.
In addition, 1,4-CHDM is usually a mixture of trans and cis isomers in terms of availability, but depending on the application, the trans / cis ratio is usually 100/0 to 100% depending on the required heat resistance and the like. It is preferably selected from 60/40. If the trans / cis ratio is lower than 60/40, the heat resistance of the resulting polyester resin tends to be inferior.

  The diol component used for the production of the polyester resin according to the present invention is not particularly limited as long as it can be directly esterified with the dicarboxylic acid component, but 1,4-cyclohexanedimethanol (1,4-CHDM) is used. The inclusion is preferred. The ratio of 1,4-CHDM is preferably 30 mol% or more with respect to the total diol component. If the ratio of 1,4-CHDM is less than 30 mol%, the strength of the resulting polyester resin is lowered, which is not preferable. The ratio of 1,4-CHDM is more preferably 50 mol% or more, and particularly preferably 70 mol% or more. In addition, 1,4-CHDM has an isomer and is usually a mixture of a trans isomer and a cis isomer. If the ratio of isomers is by weight, the ratio of trans isomer / cis isomer is 60/40 to 100/0, and the ratio of trans isomer is less than 60%, esterification reactivity tends to decrease, which is not preferable. .

  The diol component used for the production of the polyester resin contains 1,4-CHDM as described above, but a diol component other than 1,4-CHDM can be used as a copolymerization component. Examples of copolymer components that can be used include ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, neopentyl glycol, diethylene glycol, polyethylene glycol, and polytetramethylene ether. Aliphatic diols such as glycol, alicyclic diols such as 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, and xylylene glycol, 4,4′-dihydroxybiphenyl, 2 , 2-bis (4′-hydroxyphenyl) propane, 2,2-bis (4′-β-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfo , And aromatic diols such as bis (4-beta-hydroxyethoxyphenyl) sulfonic acid. These copolymer components may be one kind or a mixture of two or more kinds.

When the polyester resin is produced, in addition to the dicarboxylic acid component and the diol component, other copolymer components can be used as long as the purpose and effect of the present invention are not impaired. Other copolymer components include, for example, hydroxycarboxylic acids such as glycolic acid, p-hydroxybenzoic acid, p-β-hydroxyethoxybenzoic acid, alkoxycarboxylic acids, stearyl alcohol, benzyl alcohol, stearic acid, behenic acid, Monofunctional components such as benzoic acid, t-butylbenzoic acid, benzoylbenzoic acid, tricarballylic acid, trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetetracarboxylic acid, gallic acid, trimethylolethane, trimethylolpropane, glycerol , Trifunctional or higher polyfunctional components such as pentaerythritol and sugar ester.
The polyester resin according to the present invention can be produced according to the following steps. That is, a dicarboxylic acid component having 1,4-CHDA as a main component and a diol component, and if necessary, another copolymer component in the absence or presence of a polycondensation catalyst, continuously or batchwise. An esterification reaction is performed to prepare an oligomer. In this esterification reaction, the above raw material components are charged into an esterification reaction tank equipped with a stirrer and a reflux condenser, and if necessary, a catalyst, a basic compound, and other additives are added, and the mixture is stirred in an inert gas atmosphere. However, the reaction is carried out while distilling off the water produced by the reaction. After completion of the esterification reaction, the reaction mixture is transferred to the same reaction tank as the esterification reaction tank, or the reaction mixture is transferred from the esterification reaction tank to the polycondensation reaction tank. Active compounds and other additives, and under continuous inert gas atmosphere, stirring, adjusting temperature and pressure, and performing polycondensation reaction continuously or batchwise

  Examples of the polycondensation catalyst used include metal compounds containing at least one metal element. The polycondensation catalyst can also be used in the esterification reaction. Examples of the metal element include titanium, germanium, antimony, aluminum, nickel, zinc, tin, cobalt, rhodium, iridium, zirconium, hafnium, lithium, calcium, and magnesium. More preferable metals are titanium, germanium, antimony, aluminum, tin, etc. Among them, a titanium compound is particularly preferable because it exhibits high activity in both the esterification reaction and the polycondensation reaction.

  Specific examples of titanium compounds suitable as polycondensation catalysts include, for example, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetracyclohexyl titanate, tetra Ferrite titanate, tetrabenzyl titanate, lithium oxalate titanate, potassium oxalate titanate, ammonium oxalate titanate, titanium oxide, titanium orthoester or condensed orthoester, reaction consisting of titanium orthoester or condensed orthoester and hydroxycarboxylic acid Products, reaction products comprising titanium orthoesters or condensed orthoesters, hydroxycarboxylic acids and phosphorus compounds, titanium orthoesters or condensed orthoesters and at least Polyhydric alcohols having two hydroxyl groups, 2-hydroxycarboxylic acid, or a reaction product comprising a base and the like.

  Examples of the antimony compound include antimony trioxide, antimony pentoxide, antimony acetate, and antimony glycoloxide. Examples of germanium compounds include germanium dioxide, germanium tetroxide, germanium hydroxide, germanium oxalate, germanium tetraethoxide, germanium tetra-n-butoxide, and the like.

Examples of the aluminum compound include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, aluminum lactate, and aluminum tartrate. , Carboxylates such as aluminum citrate, aluminum salicylate, inorganic acid salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate, aluminum phosphonate, aluminum methoxide, aluminum ethoxide, aluminum -N-propoxide, aluminum isopropoxide, aluminum-n-butoxide, aluminum Aluminum alkoxide such as tert-butoxide, aluminum acetylacetonate, aluminum acetyl acetate, aluminum ethyl acetoacetate, aluminum chelate compound such as aluminum ethyl acetoacetate diisopropoxide, organoaluminum compound such as trimethylaluminum and triethylaluminum, or these A partial hydrolyzate, aluminum oxide, etc. are mentioned.
Of these aluminium compounds, carboxylates, inorganic acid salts or chelate compounds are preferred, and among these, basic aluminum acetate, aluminum lactate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride or aluminum acetylacetonate are particularly preferred. preferable. The basic aluminum acetate may be stabilized with an additive such as boric acid.

  These catalysts may be used alone or in combination. The amount of the catalyst used in these esterification reaction and polycondensation reaction is preferably from 5 ppm to 1000 ppm, particularly preferably from 10 ppm to 500 ppm, in terms of metal atom, with respect to the polyester usually produced in a system that is used alone or in combination. The amount is as follows.

In the method for producing a polyester resin according to the present invention, during the esterification reaction, preferably, when a basic compound is added to the esterification reaction mixture, the trans isomer of 1,4-CHDA is isomerized to a cis isomer. There is an effect of suppressing, which is preferable. In the present invention, the “reaction mixture” includes not only a mixture in the middle of the reaction but also a mixture of raw material materials before the start of the reaction. Examples of the basic compound include a compound containing an alkali metal, a compound containing an alkaline earth metal, an organic amine, an organic ammonium compound, and the like. Examples of the alkali metal in the compound containing the alkali metal include lithium, sodium, potassium, rubidium, cesium and the like. Examples of the alkaline earth metal in the compound containing the alkaline earth metal include beryllium, magnesium, calcium, strontium, barium and the like.
Examples of the compound containing these metals include salts of saturated aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid and succinic acid, salts of unsaturated aliphatic carboxylic acids such as acrylic acid and methacrylic acid, Salts of aromatic carboxylic acids such as benzoic acid, salts of hydroxycarboxylic acids such as lactic acid, citric acid and salicylic acid, salts of inorganic acids such as carbonic acid, phosphonic acid and hydrogen carbonate, methoxy, ethoxy, n-propoxy, iso-propoxy Alkoxides such as n-butoxy and tert-butoxy, chelate compounds such as acetylacetonate, oxides and hydroxides. In addition, since a strong basic hydroxide or the like may undergo a hydrolysis reaction during the polycondensation reaction, a salt with a weak acid is preferably used. Among these, alkali metal carboxylates and alkaline earth metal carboxylates are preferably used. In particular, acetates of these metals and hydrates thereof are preferably used.

  Examples of the organic amine compound include triethylamine, ammonia, morpholine, piperidine and the like. Examples of the organic ammonium compound include ammonium, trimethylammonium, tetramethylammonium and the like. Among these, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraalkylammonium hydroxide compounds, tetramethylammonium acetate, tetraethylammonium acetate, tetrapropylammonium acetate, etc. Preferred are chlorides such as tetraalkylammonium acetate compounds, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, and quaternary ammonium salts such as halogenated tetraalkylammonium compounds. In particular, a tetraalkylammonium hydroxide compound that is difficult to decompose during the esterification reaction and the condensation polymerization reaction and is volatile and does not remain in the polyester resin after the condensation polymerization reaction is preferable. These basic compounds may be used alone or in combination of two or more.

Ratio of acid-base equivalent of basic compound used in the present invention to molar equivalent of polycondensation catalyst used (* alkali metal, alkaline earth metal: alkali metal, alkaline earth metal mol / valence / polymerization catalyst metal mol , Organic amine, organic ammonium salt: organic amine, organic ammonium salt mol / polymerization catalyst metal mol) is preferably 0.1 or more and 10 or less. Further, when the basic compound is an alkali metal or alkaline earth metal carboxylate, the molar ratio is preferably 0.1 or more and 1 or less, more preferably 0.2 or more and 0.8 or less. Is more preferable.
When the basic compound is an organic amine compound or an organic ammonium compound, the molar ratio is preferably 1 or more and 10 or less, more preferably 2 or more and 8 or less. When the molar ratio is less than 1, the effect of suppressing isomerization from trans-1,4-CHDA to cis-1,4-CHDA tends to decrease. On the other hand, when the molar ratio exceeds 10, the polymerization activity tends to decrease, and the thermal stability of the resulting polyester resin tends to deteriorate.

Further, in the method for producing a polyester resin according to the present invention, in addition to the basic compound described above, a phosphorus compound is added to the reaction mixture for the purpose of improving the catalytic activity and controlling the molecular weight, and for the purpose of improving the thermal stability. Antioxidants can also be added. These compounds may be one kind or a mixture of two or more kinds. The amount of the additive is not particularly limited, but is usually selected in the range of 100 to 5000 ppm with respect to the produced polyester resin.
The phosphorus compound that can be used is not particularly limited, but phosphoric acid or phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, phenyl phosphate, and triphenyl phosphate, phosphorous acid, trimethyl phosphate, triphenyl phosphate, or the like. Phosphites such as phyto, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) phosphite, dimethyl methylphosphonate, diphenyl methylphosphonate, phenyl Phosphonic acid compounds such as dimethyl phosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate, diphenylphosphinic acid, methyl diphenylphosphinate, diphenylphosphinic acid Phosphinic compounds such as phenyl, phenylphosphinic acid, methyl phenylphosphinate, phenylphenylphosphinate, phosphine oxide compounds such as diphenylphosphine oxide, methyldiphenylphosphine oxide, triphenylphosphine oxide, triphenylphosphopropionate Phosphonous acid compounds, phosphinic acid compounds, phosphine compounds, phosphonium betaine compounds, and the like.

As the antioxidant, for example, a phenolic compound is preferable. The phenolic compound is not particularly limited as long as it is a compound having a phenolic hydroxyl group. Specifically, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, pentaerythritol tetrakis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, octadecyl-3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide]], benzenepropanoic acid, 3,5 -Bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 alkyl ester, 2,4-dimethyl-6- (1-methylpen Decyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa Tert-butyl a, a ′, a ″-(mesitylene-2,4,6-tolyl) tri-p-cresol, calcium diethylbis [[[3,5-bis (1,1-dimethylethyl) -4 -Hydroxyphenyl] methyl] phosphonate], 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate ], Hexamethylenebis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris (3,5-tert-butyl- -Hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6 -Xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, 2 ', 3-bis [[3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide, etc. Is mentioned.
These additives may be used alone or in combination. The amount of the additive to be used is not particularly limited, but is about 100 to 5000 ppm with respect to the polyester resin that is usually produced.

<Other additives>
In the method for producing a polyester resin of the present invention, various additives can be blended as necessary within a range that does not impair the object effects of the present invention. Examples of such additives include inorganic fillers such as glass beads, glass powder, glass balloons, mica, talc, and calcium carbonate, antioxidants, heat stabilizers, ultraviolet absorbers, neutralizers, lubricants, and compatibilizers. Agents, antifogging agents, antiblocking agents, plasticizers such as paraffin oil, fluororesin powders, slip agents, dispersants, colorants, antibacterial agents, fluorescent whitening agents, and the like.

<Manufacturing>
In the method for producing a polyester resin of the present invention, a dicarboxylic acid component mainly composed of 1,4-CHDA and a diol component are subjected to an esterification reaction using a basic compound in the absence of a catalyst or in the presence of a catalyst, This is carried out by polycondensation reaction using a polycondensation catalyst. In addition, in the esterification reaction, when the dicarboxylic acid and the diol are charged, about 5 to 60% by weight of water may be added to the diol in order to reduce the slurry viscosity and facilitate the charging.

  The amount of the polycondensation catalyst used is usually 5 ppm or more and 1000 ppm or less, preferably 10 ppm or more and 500 ppm or less in terms of metal atom with respect to the polyester to be produced. The addition timing of these catalysts is not particularly limited, and may be added from the beginning of the esterification reaction or may be added during the polycondensation reaction. Further, a part may be added during the esterification reaction and the remaining part may be added during the polycondensation reaction.

The basic compound used in the production method of the present invention may be used as it is, or may be used as an aqueous solution or a solution. The basic compound is preferably added before the start of the esterification reaction. The basic compound may be used alone or in combination, but it is more preferable to suppress isomerization by using an organic amine or organic ammonium compound in combination with an alkali metal salt or an alkaline earth metal salt.
The esterification reaction of dicarboxylic acid and diol is usually carried out by adding the dicarboxylic acid, diol and basic compound to an esterification reaction tank equipped with a stirrer and a distillation pipe, and adding a reaction catalyst if necessary and stirring in an inert atmosphere. The water generated by the reaction is distilled off. The usage ratio of the diol component and the dicarboxylic acid component is usually 1 to 2 mol of the diol component with respect to 1 mol of the dicarboxylic acid component. When a polyester resin is produced using a diol component containing 80 mol% or more of 1,4-CHDM as a diol component which is a preferred embodiment of the present invention, the molar ratio of the diol component to 1 mol of the dicarboxylic acid component is 1. To 1.2 are preferable, 1 to 1.1 are more preferable, and 1 to 1.05 are particularly preferable.

In the esterification reaction, the reaction pressure is usually 10 to 200 kPa in absolute pressure, the reaction temperature is usually 150 to 230 ° C., preferably 180 to 220 ° C., and the reaction time is 10 minutes to 10 hours, preferably 30 It is performed for 5 minutes or more. A reaction product as a polyester precursor is obtained by this esterification reaction.
The polycondensation reaction is usually performed at an esterification reaction completion temperature of 280 ° C. or lower, preferably 260 ° C. or lower, and usually for 10 minutes to 10 hours, preferably 30 minutes to 5 hours. If the temperature is too high, the polycondensation reaction tends not to proceed because thermal decomposition occurs during the polymerization reaction. The internal pressure of the tank is a pressure that finally becomes 1 kPa or less in absolute pressure from normal pressure, and is preferably 0.5 kPa or less.

  After completion of the reaction, the obtained polyester is usually drawn out in a strand form from the bottom of the tank and cut while cooling with water to obtain pellets. The reaction may be performed by a batch method or a continuous method.

  The esterification reaction time depends on the reaction temperature, the presence or absence of a catalyst, the type of catalyst, the amount of catalyst, the type of other compounds, and the amount of addition (use), but is usually in the range of 10 minutes to 10 hours, Preferably, it is selected in the range of 30 minutes to 5 hours. For the purpose of reducing the viscosity of the reaction mixture, about 5 to 60 parts by weight of water can be added to the diol component. The catalyst that can be used in the esterification reaction may be the same as the polycondensation catalyst, and the addition to the reaction mixture is (1) a part before the esterification reaction and / or during the esterification reaction, and the rest to the polycondensation step. Either a method of adding during transition and / or during the polycondensation reaction, or (2) a method of adding all during transition to the polycondensation step and / or during the polycondensation reaction may be used.

According to the study by the present inventors, when the initial temperature of the esterification reaction is set to a high temperature, the esterification reaction rate increases, but the 1,4-CHDA trans isomer is easily isomerized to a cis isomer, which is not preferable. I understood. Further, it was found that the esterification reaction temperature after the esterification rate exceeding 60% is preferably 220 ° C. or less because the 1,4-CHDA trans isomer is difficult to isomerize to the cis isomer. The esterification reaction is performed while the temperature is gradually raised at an absolute pressure of 10 to 200 kPa and a temperature of 220 ° C. or lower, and the steps until the esterification rate reaches 60% are performed in a temperature range up to 185 ° C. It is preferable to do this.
In the process of raising the temperature, it is difficult to clearly determine the temperature at which the esterification reaction starts. For example, when the esterification reaction is performed at normal pressure, water produced as a by-product with the reaction at the time when the temperature exceeds 100 ° C. Since distillation starts, it is assumed that the reaction starts at around 100 ° C.

  In the polycondensation reaction, after the esterification rate exceeds 60% in the esterification reaction, a polycondensation catalyst, a basic compound as necessary, and other compounds described above are partially added to the reaction tank in the esterification reaction step. Is added to the reaction mixture, and the remainder is added to the polycondensation reaction mixture all at once or dividedly when not added in the esterification reaction step. The polycondensation reaction is preferably carried out in a temperature range of 180 ° C. to 250 ° C. under reduced pressure. The polycondensation reaction time is selected in the range of 10 minutes to 10 hours, preferably in the range of 30 minutes to 5 hours, although it depends on the temperature, the type of catalyst, the amount of catalyst, the type of other compounds, and the amount added. It is observed that if the polycondensation reaction temperature is too high, it is difficult for the polycondensation reaction to proceed, probably because thermal decomposition occurs during the reaction. The pressure in the reaction vessel when carrying out the polycondensation reaction is reduced from normal pressure to the final absolute pressure of usually 1 kPa or less, preferably 0.5 kPa or less. After completion of the polycondensation reaction, the reaction product is extracted in the form of a strand from the bottom of the polycondensation reaction tank, and the strand is cooled with water and cut to obtain polyester resin pellets.

  According to the studies by the present inventors, in order to effectively achieve the object of the present invention, the mol% of the trans isomer in 1,4-CHDA as a raw material is T0 (%), and 1,1 in the resulting polyester resin. T0, where Tp (%) is the mol% of the trans isomer in the 4-CHDA unit and T60 is the mol% of the trans isomer in the 1,4-cyclohexanedicarboxylic acid unit in the oligomer at an esterification rate of 60%, T60 and Tp satisfy the following formula (II): 0 ≦ {(T0−T60) / T0} × 100 ≦ 5, and in the 1,4-cyclohexanedicarboxylic acid unit of the obtained polyester resin It was found that the mol% of the trans isomer needs to satisfy the following formula (I): 0 ≦ {(T0−Tp) / T0} × 100 ≦ 12.

  In the esterification reaction, T0 and the value of T60 at an esterification rate of 60% do not satisfy the following formula (II): 0 ≦ {(T0−T60) / T0} × 100 ≦ 5 (exceeding the upper limit) ), The melting point of the finally obtained polyester resin tends to be low, which is not preferable. The value calculated by the above formula at an esterification rate of 60% is more preferably 4 or less, and particularly preferably 2 or less. Further, T0 and the mol% Tp of the trans isomer in the 1,4-cyclohexanedicarboxylic acid unit in the polyester resin have the following formula (I): 0 ≦ {(T0−Tp) / T0} × 100 ≦ 12, When not satisfying (over the upper limit), the melting point of the finally obtained polyester resin tends to be low, which is not preferable.

  The mol% T0 of the trans isomer in the raw material 1,4-CHDA can be measured by a liquid chromatography method. In addition, the esterification rate of the oligomer is determined by first quantifying the amount of free carboxylic acid end groups (AV) of the oligomer according to a conventional method, and then quantifying the total amount of carboxylic acid-derived groups (SV) of the oligomer according to the conventional method. , Esterification rate (%) = {(SV−AV) / SV} × 100. Furthermore, T60 at an esterification rate of 60% can also be measured by liquid chromatography. The mol% (Tp) of the trans isomer unit in the 1,4-cyclohexanedicarboxylic acid unit in the polyester resin can be quantified by nuclear magnetic resonance spectroscopy.

  The intrinsic viscosity of the polyester resin according to the present invention is preferably in the range of 0.6 to 1.5 dl / g. If the intrinsic viscosity is less than 0.6 dl / g, the mechanical strength of the polyester resin may be insufficient, and if it exceeds 1.5 dl / g, the fluidity may be reduced and the moldability may be poor. Neither is preferred. A more preferable range of the intrinsic viscosity is 0.7 to 1.4 dl / g.

  The polyester resin according to the present invention itself or mixed with other thermoplastic resins and further blended with various resin additives other than the above-mentioned compounds within a range not impairing the object and effect of the present invention. Can do. For example, resin additives include glass beads, glass powder, glass balloons, mica, talc, calcium carbonate and other inorganic fillers, antioxidants, heat stabilizers, UV absorbers, neutralizers, lubricants, compatibilizers, Examples include antifogging agents, antiblocking agents, plasticizers, fluororesin powders, slip agents, dispersants, colorants, antibacterial agents, fluorescent whitening agents, and rust inhibitors.

Examples of other thermoplastic resins that can be mixed with the polyester resin according to the present invention include polyethylene resins such as polyethylene terephthalate and polybutylene terephthalate, polyester resins, polyamide resins, polycarbonates, ABS resins, polymethyl methacrylates, polyamides having a different composition from the above polyester resins. Based elastomer, polyester based elastomer and the like. The polyester resin according to the present invention and a resin composition obtained by mixing other thermoplastic resin with the polyester resin can produce various products by an extrusion molding method, an injection molding method, an extrusion blow molding method, and a calendar molding method. .
The obtained pellet-like polyester resin can be further subjected to solid phase polymerization as necessary to have a higher intrinsic viscosity.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by a following example, unless the summary is exceeded.
In addition, the measuring method of the various physical properties in a following example and a comparative example is shown below.
(Quantification of trans form in monomer CHDA)
Dissolve 1.2 ml of 4N sodium hydroxide in 0.2 ml of CHDA in a 50 ml volumetric flask. Furthermore, after adding 40 ml of pure water and adjusting the pH to 5 with 200 μl of phosphoric acid, pure water is added to make 50 ml. This was measured by liquid chromatography under the following conditions.

Device: Shimadzu Corporation LC-10AD
Column: J'sphere ODS-H80 4.6 mm x 250
Temperature: 500 ° C
Mobile phase: AcN / H ₂ O / H ₃ PO ₄ = 200/800/4
Flow rate: 0.6ml / min
Detector: UV (210 nm)
Injection volume: 20 μl
The ratio of trans body and cis body was calculated | required from the area of each peak.

(Quantification of dicarboxylic acid unit and diol unit in polymer, and determination of trans form and cis form of CHDA and CHDM)
D-chloroform is used as a solvent, the polyester resin is dissolved, 1H-NMR (GSX-400 manufactured by JEOL Ltd.) is used to quantify the dicarboxylic acid unit and diol unit in the polymer, and further, the CHDA component and the CHDM component are trans. Body and cis bodies were quantified.

(Measurement of melting point of polymer)
The melting point of the polymer was measured using DSC220 (differential scanning calorimeter) manufactured by Seiko in accordance with JIS K7121. About 10 mg of the polymer was put in an aluminum pan made by the same company, sealed, heated from room temperature to 300 ° C. at a temperature rising rate of 20 ° C./min, held at 300 ° C. for 3 minutes, and then cooled to room temperature at 20 ° C./min. After further holding for 3 minutes, the temperature was raised from room temperature to 300 ° C. at 20 ° C./min. The melting point Tm of the polymer was the value at the second temperature increase. The Tm value was the temperature at the maximum part of the peak.

(Intrinsic viscosity)
Using 0.5 g of a polyester resin sample, a solution having a concentration (c) of 1.0 g / dl was prepared using a mixed solution of phenol / tetrachloroethane (weight ratio 1/1) as a solvent. When the sample was a melt polycondensation resin, it was dissolved by heating to 110 ° C. and holding for 30 minutes. This solution was measured at 30 ° C. using a Ubbelohde viscometer to measure the relative viscosity (ηrel) with respect to the solvent only (c = 0), and 1 was subtracted from the relative viscosity (ηrel) to obtain a specific viscosity (ηsp). The ratio (ηsp / sc) to the concentration (c) was determined. Similarly, the concentration (c) is 0.5 g / dl, 0.2 g / dl, and 0.1 g / dl, and the respective ratios (ηsp / c) are obtained. From these values, the concentration (c) is set to 0. The ratio (ηsp / c) when extrapolated was determined as intrinsic viscosity [η] (dl / g).

Example 1-1
In a reactor equipped with a stirrer, a distilling tube and a decompressor, 92.12 g of 1,4-CHDA (trans / cis = 98/2) and 79.07 g of 1,4-CHDM (CHDM / CHDA charged molar ratio was 102 0.5 / 100), and 0.54 g (0.31 mmol) of tetraethylammonium hydride 10 wt% aqueous solution, heated to 150 ° C. in an oil bath under nitrogen flow, heated to 200 ° C. over 1 hour, The esterification reaction was carried out by maintaining at 200 ° C. for 1 hour. Thereafter, 0.88 g (0.155 mmol) of a tetra n-butyl titanate 6 wt% -n-butanol solution was added to the reactor, and the temperature inside the reactor was gradually increased from 200 ° C. to 250 ° C. over 45 minutes. The polycondensation reaction was carried out under reduced pressure. The reactor internal pressure was kept at 0.1 kPa in absolute pressure, the temperature was kept at 250 ° C., and after the reaction for 2.5 hours, the obtained polyester resin was extracted into strands into water and pelletized. Table 1-1 shows the intrinsic viscosity, melting point, and trans / cis ratio of 1,4-CHDA component of the obtained polyester resin.

Example 1-2
A polycondensation reaction was carried out under the same conditions as in Example 1-1 except that the 10 wt% aqueous solution of tetraethylammonium hydride was changed to 64 mg (0.078 mmol) of 10 wt% aqueous solution of sodium acetate. Table 1-1 shows the intrinsic viscosity, melting point, and trans / cis ratio of 1,4-CHDA component of the obtained polyester resin.

Example 1-3
A polycondensation reaction was performed under the same conditions as in Example 1-1 except that the 10 wt% aqueous solution of tetraethylammonium hydride was changed to 77 mg (0.078 mmol) of 10 wt% potassium acetate. Table 1-1 shows the intrinsic viscosity, melting point, and trans / cis ratio of 1,4-CHDA component of the obtained polyester resin.

Example 1-4
A polycondensation reaction was carried out under the same conditions as in Example 1-1 except that the 10 wt% aqueous solution of tetraethylammonium hydride was changed to 170 mg (0.078 mmol) of 10 wt% magnesium acetate. Table 1-1 shows the intrinsic viscosity, melting point, and trans / cis ratio of 1,4-CHDA component of the obtained polyester resin.

Example 1-5
Example 1-1, except that during the polycondensation reaction, 64 mg (0.078 mmol) of a 10 wt% sodium acetate aqueous solution was added to the reactor along with 0.88 g (0.155 mmol) of a 6 wt% n-butanol solution of tetra n-butyl titanate. The polycondensation reaction was carried out under the same conditions as above. Table 1-1 shows the intrinsic viscosity, melting point, and trans / cis ratio of 1,4-CHDA component of the obtained polyester resin.

Comparative Example 1-1
A polycondensation reaction was performed under the same conditions as in Example 1-1 except that a 10 wt% aqueous solution of tetraethylammonium hydride was not used. Table 1-1 shows the intrinsic viscosity, melting point, and trans / cis ratio of 1,4-CHDA component of the obtained polyester resin.

  According to the production method of the present invention, the polyester resins obtained in Examples 1-1 to 1-5 using a basic compound in the esterification reaction have a high melting point of 225 ° C. or higher, The trans / cis ratio of 4-CHDA units also had a high trans ratio of 90/10 or higher. On the other hand, in Comparative Example 1-1 in which a basic compound was not used for the esterification reaction and the polycondensation reaction, only a polyester resin having a low melting point and a reduced trans / cis ratio was obtained.

  In the following examples and comparative examples, the mol% of the trans isomer in the raw material 1,4-cyclohexanedicarboxylic acid (1,4-CHDA) is T0 (%), and 1,4 in the resulting polyester resin. -Mol% of trans (t) isomer unit in cyclohexanedicarboxylic acid unit is Tp (%), isomerization rate at 60% esterification rate is T60 (%), esterification rate of oligomer, melting point of polyester resin Etc. are measured by the method described below.

(1) Quantification of trans isomer (t) (T0) (unit: mol%) in 1,4-CHDA: 0.2 g of 1,4-CHDA was weighed into a volumetric flask having a volume of 50 ml. Dissolved in 1.2 ml of sodium hydroxide, 40 ml of pure water was added thereto, pH was adjusted to 5 with 200 μl of phosphoric acid, and then pure water was added to make 50 ml. This sample was measured by liquid chromatography (manufactured by Shimadzu Corporation, model: LC-10AD). The apparatus was operated according to a conventional method, and the ratio of trans isomer (t) and cis isomer (c) was calculated from the peak areas of the respective components. The measurement conditions were as follows.
Column: J'sphere ODS-H80 4.6 mm x 250.
Temperature: 50 ° C., mobile phase: acetonitrile / water / phosphoric acid.
Flow rate: 0.6 ml / min, calibrator: UV (210 nm), injection volume: 20 μl.

(2) Measurement of oligomerization rate (unit:%) of oligomer: First, the amount of free carboxylic acid end groups (AV) of the oligomer was quantified according to the method described in (2-1) below, The total amount of carboxylic acid-derived groups (SV) was quantified according to the method described in the following (2-2), and the following formula, ie, esterification rate (%) = {(SV-AV) / SV} × 100 Can be calculated.

(2-1) Quantification of free carboxylic acid end group amount (AV): Collect 10 mg of oligomer in a test tube, add 25 ml of benzyl alcohol, and stir the contents with a magnetic stirrer, temperature to 195 plus / minus 3 ° C. Immerse in a controlled oil bath and dissolve the oligomer in benzyl alcohol. The resulting dissolved solution was allowed to cool to room temperature, and 2 ml of ethyl alcohol was gently added. The obtained solution was titrated with a 0.01N sodium hydroxide / benzyl alcohol solution using an automatic titration apparatus (manufactured by Toa DKK, model: AUT-501) using a composite pH electrode. The 0.01N sodium hydroxide / benzyl alcohol solution was prepared and standardized according to JIS K8006, and the factor was calculated. The titration amount was determined from the inflection point of the obtained titration curve, and AV was calculated based on the following formula, that is, AV = {(A−B) × 0.01N × F} / W. In this formula, AV is the amount of free carboxylic acid end groups (meq / g) of the oligomer, A is the measurement titration (ml), B is the blank titration (ml), and F is the 0.01N sodium hydroxide / benzyl alcohol solution Titer, W is oligomer weight (g).

(2-2) Quantification of total carboxylic acid-derived group amount (SV) of oligomer: 0.3 g of oligomer of sample crushed in a mortar and precisely weighed into an Erlenmeyer flask with a capacity of 50 ml. 20 ml of a potassium / ethanol solution was added with a whole pipette, followed by 10 ml of pure water, and a reflux condenser was set. The sample was hydrolyzed by heating and refluxing for 2 hours with occasional stirring on a hot plate whose surface temperature was adjusted to 200 ° C. The obtained sample solution was transparent. After allowing to cool, titration with 0.5N aqueous hydrochloric acid was performed using phenolphthalein as an indicator. A 0.5N potassium hydroxide / ethanol solution and a 0.5N hydrochloric acid aqueous solution were prepared and standardized according to JIS K8006. The indicator of phenolphthalein is 1 g dissolved in 90 ml of ethanol and pure water is added to make 100 ml. SV was calculated based on the following formula, that is, SV = {(Vb−Vs) × f × (1/2)} / W. In this formula, SV is the total amount of oligomer-derived carboxylic acid (meq / g), Vs is the sample titration (ml), Vb is the blank titration, f is the factor of 0.5N aqueous hydrochloric acid, and W is the oligomer. Weight (g).

(3) Determination of 1,4-CHDA trans isomer (t) unit (unit: mol%) in reaction product and oligomer: 0.1 g of reaction product or oligomer was collected in an Erlenmeyer flask having a volume of 50 ml. 10 ml of 0.5 mol / l ethanolic potassium hydroxide is added, and the Erlenmeyer flask is immersed in an oil bath at a temperature of 80 to 90 ° C. and shaken to dissolve the reaction product or oligomer. The obtained solution is transferred to a volumetric flask having a volume of 50 ml, and after adding pure water and phosphoric acid to adjust the pH to 6, pure water is added to make 50 ml. This sample was measured by liquid chromatography (manufactured by Shimadzu Corporation, model: LC-10AD). The measurement conditions were the same as in (1) above.

(4) Quantification of 1,4-CHDA trans form (t) and cis form (c) in polyester resin: Deuterated chloroform is used as solvent, polyester resin is dissolved in this, and nuclear magnetic resonance spectrometer (JEOL) The trans isomer (t) and cis isomer (c) in the polyester resin were quantified according to a conventional method using a model manufactured by the company, model: GSX-400).
(5) Intrinsic viscosity: phenol and tetrachloroethane were mixed in a 1: 1 ratio by weight, and a solution of 1.0 g / dl of a sample polyester resin was prepared in this mixed solvent, and an Ubbelohde type at a temperature of 30 ° C. It is a value measured by a viscometer.
(6) Melting point (Tm) (unit: ° C.): Measured according to JIS K7121.

Example 2-1
A stainless steel reactor equipped with a stirrer, reflux condenser, heating device, pressure gauge, thermometer, and decompression device and having a capacity of 200 milliliters, 1,4-CHDA (trans isomer / cis isomer molar ratio = 98/2) 92.12 g, 1,4-CHDM (trans isomer / cis isomer molar ratio = 70/30) 79.07 g (the molar ratio of 1,4-CHDA to 1,4-CHDM is 1 / 1.025), Then, 0.88 g of a 6 wt% butanol solution of tetra-n-butyl titanate (catalyst) was charged, and the inside of the reactor was replaced with nitrogen gas. While sealing the inside of the reactor with nitrogen gas, raise the internal temperature from room temperature to 150 ° C in an oil bath, raise the temperature from 150 ° C to 180 ° C in 30 minutes, and hold at 180 ° C for 2 hours Then, esterification reaction was performed.

  The reaction solution was collected from the reactor when the internal temperature reached 180 ° C. and every 15 minutes thereafter, and the trans form (t) of the esterification rate, 1,4-CHDA unit in the oligomer was collected. The molar ratio of the / cis isomer (c) was measured, and a relationship curve between the esterification rate and the trans cis / cis isomer molar ratio was drawn. From this relationship curve, the molar ratio of trans isomer / cis isomer at an esterification rate of 60% is read, and isomerization is performed from this molar ratio and the molar ratio of trans isomer / cis isomer at an esterification rate of 0% (98/2). The rate was calculated. The esterification rate after carrying out the esterification reaction at a temperature of 180 ° C. for 2 hours was 60%. Subsequently, the polycondensation reaction was performed while the internal temperature was raised from 180 ° C. to 250 ° C. over 2 hours and the internal pressure of the reactor was reduced. The pressure inside the reactor was maintained at an absolute pressure of 0.1 kPa and a reaction temperature of 250 ° C. for 2 hours to complete the polycondensation reaction. After completion of the polycondensation reaction, the obtained resin was drawn out into water as a strand and cut into pellets.

  1,4-CHDA ratio of trans to cis isomer, temperature and time conditions during esterification reaction, reaction temperature at esterification rate 60%, esterification rate, 1 in oligomer at esterification rate 60% , Ratio of trans-cis and cis-isomer of 4-CHDA unit, value of formula (I) (T60), esterification rate of oligomer at the end of esterification reaction, temperature / time condition for polycondensation reaction, polyester resin The ratio between the trans isomer and the cis isomer of the 1,4-CHDA unit, the value of the formula (II) (Tp), the intrinsic viscosity, the melting point (Tm) and the like were measured by the above methods and described in Table 2-1. did.

Example 2-2
In the same reactor used in Example 2-1, raw materials 1,4-CHDA, 1,4-CHDM and catalyst were charged in the same amount as in the same example, and the inside of the reactor was replaced with nitrogen gas. While sealing the inside of the reactor with nitrogen gas, the internal temperature was raised from normal temperature to 150 ° C. in an oil bath, and the temperature was raised from 150 ° C. to 180 ° C. in 30 minutes. After maintaining at 180 ° C. for 2 hours, the temperature was further increased from 180 ° C. to 215 ° C. over 1 hour to carry out an esterification reaction to obtain an oligomer. The esterification rate at this time was 85%. Subsequently, the polycondensation reaction was carried out while increasing the internal temperature from 215 ° C. to 250 ° C. over 30 minutes and reducing the internal pressure of the reactor. The pressure inside the reactor was maintained at an absolute pressure of 0.1 kPa and a reaction temperature of 250 ° C. for 2 hours to complete the polycondensation reaction. After completion of the polycondensation reaction, the obtained resin was drawn out into water as a strand and cut into pellets. About an oligomer, a polyester resin, etc., it measured similarly to in Example 2-1, and the result was described in Table 2-1.

Example 2-3
In the same reactor used in Example 2-1, raw materials 1,4-CHDA, 1,4-CHDM and catalyst were charged in the same amount as in the same example, and the inside of the reactor was replaced with nitrogen gas. While sealing the inside of the reactor with nitrogen gas, the internal temperature was raised from normal temperature to 150 ° C. in an oil bath, and the temperature was raised from 150 ° C. to 200 ° C. in 30 minutes. The esterification reaction was carried out by maintaining at 200 ° C. for 1 hour to obtain an oligomer. The esterification rate at this time was 80%. Subsequently, a polycondensation reaction was performed while increasing the internal temperature from 200 ° C. to 250 ° C. over 45 minutes and reducing the internal pressure of the reactor. The pressure inside the reactor was maintained at an absolute pressure of 0.1 kPa and a reaction temperature of 250 ° C. for 2 hours to complete the polycondensation reaction. After completion of the polycondensation reaction, the obtained resin was drawn out into water as a strand and cut into pellets. About an oligomer, a polyester resin, etc., it measured similarly to in Example 2-1, and the result was described in Table 2-1.

Example 2-4
In the example described in Example 2-1, the esterification reaction and polycondensation were carried out in the same procedure as in Example 2 except that 0.54 g of 10% tetraethylammonium aqueous solution was charged into the reactor at the stage of the esterification reaction. Reaction was performed. After completion of the polycondensation reaction, the obtained resin was drawn out into water as a strand and cut into pellets. About an oligomer, a polyester resin, etc., it measured similarly to in Example 2-1, and the result was described in Table 2-1.

Comparative Example 2-1
In the same reactor used in Example 2-1, raw materials 1,4-CHDA, 1,4-CHDM and catalyst were charged in the same amount as in the same example, and the inside of the reactor was replaced with nitrogen gas. While sealing the inside of the reactor with nitrogen gas, the internal temperature was raised from normal temperature to 150 ° C. in an oil bath, and the temperature was raised from 150 ° C. to 220 ° C. in 30 minutes. The esterification reaction was carried out by maintaining at 220 ° C. for 1 hour to obtain an oligomer. Subsequently, the polycondensation reaction was performed while the internal temperature was raised from 220 ° C. to 250 ° C. over 30 minutes and the internal pressure of the reactor was reduced. The pressure inside the reactor was maintained at an absolute pressure of 0.1 kPa and a reaction temperature of 250 ° C. for 2 hours to complete the polycondensation reaction. After completion of the polycondensation reaction, the obtained resin was drawn out into water as a strand and cut into pellets. About an oligomer, a polyester resin, etc., it measured similarly to in Example 2-1, and the result was described in Table 2-1.

Comparative Example 2-2
In the same reactor used in Example 2-1, raw materials 1,4-CHDA, 1,4-CHDM and catalyst were charged in the same amount as in the same example, and the inside of the reactor was replaced with nitrogen gas. While sealing the inside of the reactor with nitrogen gas, the internal temperature was raised from normal temperature to 150 ° C. in an oil bath, and the temperature was raised from 150 ° C. to 200 ° C. in 30 minutes. The esterification reaction was carried out by holding at 200 ° C. for 4 hours to obtain an oligomer. Subsequently, a polycondensation reaction was performed while increasing the internal temperature from 200 ° C. to 270 ° C. over 30 minutes and reducing the internal pressure of the reactor. The polycondensation reaction was completed by maintaining the pressure in the reactor at an absolute pressure of 0.1 kPa and the reaction temperature at 270 ° C. for 2 hours. After completion of the polycondensation reaction, the obtained resin was drawn out into water as a strand and cut into pellets. About an oligomer, a polyester resin, etc., it measured similarly to in Example 2-1, and the result was described in Table 2-1.

From Table 2-1, the following becomes clear.
1. The polyester resin of Example 2-1 to Example 2-5 of the present invention has a value (isomerization rate) calculated by the above formula (I) of 12 or less and satisfies the requirement of claim 1. The melting point is 220 ° C. or higher, and the heat resistance is excellent.
2. In the polyester resins of Example 2-1 to Example 2-4 of the present invention, the value (isomerization rate of the oligomer) calculated by the formula (II) satisfies the requirement of claim 3 and the melting point is 220. Excellent heat resistance at over ℃.
3. When a basic compound is added to the reaction system in the polyesterification reaction step, the value calculated by the above formula (II) (the isomerization rate of the oligomer) is 0.51, and the value calculated by the above formula (I) The (isomerization rate) is as low as 3.06, and the melting point of the polyester resin is particularly high at 231 ° C. (see Example 2-4).
4). On the other hand, the polyester resin of Comparative Example 1 and Comparative Example 2 has a value (isomerization rate of the oligomer) calculated by the formula (II) of 5 or more and a value calculated by the formula (I) (isomerization rate). ) Exceeds 12, the melting point is low.

  The polyester resin according to the present invention can be used as a raw material resin for producing various products requiring heat resistance by an extrusion molding method, an injection molding method, an extrusion blow molding method, or a calendar molding method. Products include hollow molded products, tubular bodies, plate-like bodies, sheets, films, monofilaments, cable ties, containers for food, pharmaceuticals, cosmetics, etc., automobile parts, OA equipment parts, home appliance parts, etc. Is mentioned. In particular, it is suitable as a raw material for manufacturing automobile parts that are frequently contacted with moisture at high temperatures.

Claims (13)

It is a polyester resin obtained by preparing an oligomer by an esterification reaction of a dicarboxylic acid component mainly composed of 1,4-cyclohexanedicarboxylic acid and a diol component, and polycondensing the oligomer in the presence of a polycondensation catalyst. When the molar percentage of the trans isomer in the 1,4-cyclohexanedicarboxylic acid contained in the raw material is T0, and the molar percentage of the trans isomer in the 1,4-cyclohexanedicarboxylic acid unit contained in the resulting polyester resin is Tp. , T0 and Tp satisfy the following formula (I):
0 ≦ {(T0−Tp) / T0} × 100 ≦ 12 (I) Formula   The polyester resin according to claim 1, wherein the mol% (Tp) of the trans isomer in the 1,4-cyclohexanedicarboxylic acid unit contained in the polyester resin is 80 mol% or more. Polyester by a method comprising a step of preparing an oligomer by an esterification reaction of a dicarboxylic acid component mainly composed of 1,4-cyclohexanedicarboxylic acid and a diol component, and a step of polycondensing the oligomer in the presence of a polycondensation catalyst. In producing the resin, the mol% of the trans isomer in 1,4-cyclohexanedicarboxylic acid contained in the raw material is T0, and the mol% of the trans isomer in the 1,4-cyclohexanedicarboxylic acid unit contained in the obtained polyester resin is calculated. T0, T0, T60 and Tp satisfy the following formula (II) when the molar percentage of the trans isomer in the 1,4-cyclohexanedicarboxylic acid unit at an esterification rate of 60% is T60, and is obtained: A method for producing a polyester resin, wherein T0 and Tp of the polyester resin satisfy the following formula (I):
0 ≦ {(T0−Tp) / T0} × 100 ≦ 12 (I) Formula 0 ≦ {(T0−T60) / T0} × 100 ≦ 5 (II) Formula   Polyester by a method comprising a step of preparing an oligomer by an esterification reaction of a dicarboxylic acid component mainly composed of 1,4-cyclohexanedicarboxylic acid and a diol component, and a step of polycondensing the oligomer in the presence of a polycondensation catalyst. In producing the resin, the esterification reaction is performed while gradually raising the temperature at a temperature of 220 ° C. or lower, and the step until the esterification rate reaches 60% is performed in a temperature range of 185 ° C. or lower. A method for producing a polyester resin.   The method for producing a polyester resin according to claim 3, wherein the esterification reaction is performed while gradually raising the temperature at a temperature of 220 ° C or lower, and the step until the esterification rate reaches 60% is performed in a temperature range of 185 ° C or lower. .   In the method for producing a polyester resin in which an esterification reaction and a polycondensation reaction between a dicarboxylic acid component mainly composed of 1,4-cyclohexanedicarboxylic acid and a diol component are performed, an esterification reaction is performed using a basic compound. A method for producing a polyester resin, comprising performing a polycondensation reaction using a polycondensation catalyst.   The method for producing a polyester resin according to any one of claims 3 to 5, wherein a basic compound is used when the esterification reaction is performed.   The polyester resin according to claim 6 or 7, wherein the basic compound is at least one compound selected from the group consisting of an alkali metal carboxylate, an alkaline earth metal carboxylate, an organic amine, and an organic ammonium compound. Production method.   The method for producing a polyester resin according to any one of claims 6 to 8, wherein the ratio of the acid-base equivalent of the basic compound to the molar equivalent of the polycondensation catalyst is 0.1 or more and 10 or less.   The method for producing a polyester resin according to any one of claims 3 to 9, wherein the polycondensation reaction is performed in a temperature range of 180 ° C to 250 ° C under reduced pressure.   A metal in which the polycondensation catalyst contains at least one metal element selected from the group consisting of titanium, germanium, antimony, aluminum, nickel, zinc, tin, cobalt, rhodium, iridium, zirconium, hafnium, lithium, calcium, and magnesium The manufacturing method of the polyester resin of any one of Claims 3 thru | or 10 which is a compound.   The method for producing a polyester resin according to any one of claims 3 to 11, wherein the diol component is a diol containing 1,4-cyclohexanedimethanol.   13. The production of a polyester resin according to claim 3, wherein the trans-1,4-cyclohexanedicarboxylic acid unit in the 1,4-cyclohexanedicarboxylic acid unit contained in the polyester resin is 80 mol% or more. Method.