JP2020050765A - Method for producing polyester - Google Patents

Abstract

To provide a method for producing polyester capable of obtaining polyester having the same glass transition point as that of polyethylene terephthalate substantially not containing a copolymer, and excellent in heat resistance and transparency.SOLUTION: The method for producing a polyester including a dicarboxylic acid constituent containing dimethyl 1,4-cyclohexanedicarboxylate having a trans isomer content of 10-40% and an acid value of 0.02-1.00 mgKOH/g by 25-40 mol% to the polyester to be obtained, and a diol constituent containing spiroglycol by 15-25 mol% to the polyester to be obtained comprises: subjecting total carboxylic constituents and total diol constituents to ester exchange reaction after adding manganese acetate as an ester exchange reaction catalyst by 100-200 ppm (weight ratio) in terms of the manganese element to the polyester to be obtained, and an alkali metal compound by 15-45 ppm (weight ratio) in terms of the metal element to the polyester to be obtained; further adding a phosphorous compound by 75-150 ppm (weight ratio) in terms of the phosphorous element to the polyester to be obtained, and a titanium compound by 20-40 ppm (weight ratio) in terms of the titanium element to the polyester to be obtained; and subjecting X to polycondensation reaction by reducing a pressure from a normal pressure to 133 Pa while raising a temperature.SELECTED DRAWING: None

Description

  The present invention is a method for producing dimethyl 1,4-cyclohexanedicarboxylate and spiroglycol-containing polyester. More specifically, by using a specific dimethyl 1,4-cyclohexanedicarboxylate, a polyester having a glass transition temperature equivalent to that of polyethylene terephthalate containing substantially no copolymer and having excellent heat resistance and transparency And a method for producing a polyester.

  Polyester containing dimethyl 1,4-cyclohexanedicarboxylate has optical properties different from polyethylene terephthalate substantially free of copolymer, and polyethylene terephthalate substantially free of copolymer and polyester. Films obtained by lamination are used for various optics, for example, prism sheets for liquid crystal display members, light diffusion sheets, reflectors, base films for touch panels, etc., antireflection base films, explosion proof base films for displays, PDP filters. Since it is used for various applications such as a film for use and a laminated polyester film having excellent light reflectivity can be obtained, it is also suitably used as a metallic glossy film and a heat ray reflective film.

  However, since the polyester containing dimethyl 1,4-cyclohexanedicarboxylate becomes amorphous and has a low glass transition temperature, the polyester having a glass transition temperature of polyethylene terephthalate containing substantially no copolymer is produced. Since the unevenness in lamination or the like due to the difference between the two causes the film formation stability to deteriorate, it is used in combination with an alicyclic diol such as spiroglycol in order to increase the glass transition temperature of the polyester.

  However, there is a problem that spiroglycol is easily decomposed when exposed to high temperature, moisture or acid, and the heat resistance of the obtained polyester is reduced, and foreign matter is easily generated.

  As a method for suppressing foreign substances due to decomposition of spiroglycol, for example, Patent Document 1 includes a method of containing a large amount of a phosphorus compound.

  However, the above-described method has a problem in that a large amount of phosphorus compound reacts with a metal compound in the polyester to form coarse particles, thereby impairing the transparency of the polyester.

JP 2008-297336 A

  An object of the present invention is to solve the above-mentioned conventional objects, to obtain a polyester having a glass transition temperature equivalent to that of polyethylene terephthalate substantially free of a copolymer, and having excellent heat resistance and transparency. To provide a method for producing polyester.

  The above object of the present invention can be achieved by the following configurations. That is, the trans-isomer content is 10 to 40% and the acid value is 0.02 to 1.00 mgKOH / g. A method for producing a polyester comprising a dicarboxylic acid component and a diol component containing 15 to 25 mol% based on the polyester from which spiroglycol is obtained, wherein all dicarboxylic acid components and all diol components are converted to manganese acetate as a transesterification catalyst. The polyester obtained is added with 100 to 200 ppm (weight ratio) in terms of manganese element, and the alkali metal compound is added with 15 to 45 ppm (weight ratio) in terms of metal element with respect to the obtained polyester. Phosphorus element conversion for polyester from which phosphorus compounds can be obtained 75 to 150 ppm (weight ratio) and 20 to 40 ppm (weight ratio) in terms of titanium element with respect to the polyester from which the titanium compound is obtained are added, and the pressure is reduced from normal pressure to 133 Pa or less while raising the temperature, and the polycondensation reaction is performed. A method for producing a polyester.

  According to the present invention, by using a specific dimethyl 1,4-cyclohexanedicarboxylate, it has a glass transition temperature equivalent to that of polyethylene terephthalate containing substantially no copolymer, and has excellent heat resistance and transparency. Polyester can be obtained.

  The polyester of the present invention is a polyester comprising a dicarboxylic acid component containing dimethyl 1,4-cyclohexanedicarboxylate and a diol component containing spiroglycol. Here, spiroglycol refers to 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane.

  The dimethyl 1,4-cyclohexanedicarboxylate used in the present invention needs to have a trans-form content of 10 to 40%. The preferred content is 15 to 35%, more preferably 20 to 30%. Dimethyl 1,4-cyclohexanedicarboxylate has a cis-isomer and a trans-isomer as stereoisomers. When the trans-isomer content is less than 10%, the glass transition temperature substantially does not include a copolymer. When it is higher than polyethylene terephthalate and exceeds 40%, the glass transition temperature is lower than that of polyethylene terephthalate substantially not containing a copolymer, and the heat resistance of polyester is further reduced, so that foreign matter is easily generated.

  The dimethyl 1,4-cyclohexanedicarboxylate used in the present invention needs to have an acid value of 0.02 to 1.00 mgKOH / g. A preferred range is 0.10 to 0.75 mg KOH / g, more preferably 0.20 to 0.50 mg KOH / g. The acid value is an index of the content of an acid component which is a by-product during the production of dimethyl 1,4-cyclohexanedicarboxylate. A slight amount of the acid component acts on the polyester to affect the glass transition temperature and heat resistance of the polyester. It is thought that it is exerting. When it is less than 0.02 mgKOH / g, the glass transition temperature is lower than that of polyethylene terephthalate containing substantially no copolymer, and the heat resistance of the polyester is further reduced, so that foreign matter is easily generated. If it exceeds 1.00 mgKOH / g, the glass transition temperature will be higher than that of polyethylene terephthalate containing substantially no copolymer.

  The content of dimethyl 1,4-cyclohexanedicarboxylate in the present invention needs to be 25 to 40 mol% based on the obtained polyester. The preferred range is 27-35 mol%, more preferably 28-30 mol%. If it is less than 25 mol%, the glass transition temperature is higher than that of polyethylene terephthalate substantially free of copolymer, and if it is more than 40 mol%, the glass transition temperature is higher than that of polyethylene terephthalate substantially free of copolymer. Lower.

  The dicarboxylic acid component other than dimethyl 1,4-cyclohexanedicarboxylate in the present invention includes adipic acid, terephthalic acid, isophthalic acid, sebacic acid, phthalic acid, naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, and a metal sulfonate group. And an ester-forming derivative of a dicarboxylic acid such as isophthalic acid. The two or more of these may be used as a mixture. Note that the isophthalic acid component containing a metal sulfonate group refers to an alkali metal salt, an alkaline earth metal salt, a phosphonium salt, or a derivative thereof of sulfoisophthalic acid, and specifically, 5-sodium sulfoisophthalic acid. , 5-Lithium sulfoisophthalic acid, 5- (tetraalkyl) phosphonium sulfoisophthalic acid, and derivatives thereof such as dimethyl 5-sodium sulfoisophthalate, dimethyl 5-lithium sulfoisophthalate, and 5- (tetraalkyl) phosphonium sulfoisophthalic acid Dimethyl is exemplified.

  The content of spiroglycol in the present invention needs to be 15 to 25 mol% based on the obtained polyester. A preferred range is 17 to 23 mol%, more preferably 19 to 22 mol%. If it is less than 15 mol%, the glass transition temperature is lower than that of polyethylene terephthalate containing substantially no copolymer, and if it exceeds 25 mol%, the glass transition temperature is lower than that of polyethylene terephthalate containing substantially no copolymer. , And the heat resistance of the polyester is lowered, so that foreign matter is easily generated.

  The diol component other than spiro glycol in the present invention includes ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol, Examples include trimethylolpropane, diethylene glycol, neopentyl glycol, and methylpentanediol, and two or more of these may be used in combination. In addition, oxycarboxylic acids such as p- (β-oxyethoxy) benzoic acid and ester-forming derivatives thereof and the like can be mentioned.

  In the production method of the present invention, it is necessary to perform a transesterification reaction after adding manganese acetate and an alkali metal compound using all dicarboxylic acid components and all diol components as a transesterification catalyst. Performing the transesterification reaction in the presence of manganese acetate and an alkali metal compound makes it possible to suppress the decomposition of spiroglycol.

  The added amount of manganese acetate in the present invention needs to be 100 to 200 ppm in terms of manganese element with respect to the obtained polyester. A preferred range is 115-175 ppm, more preferably 125-150 ppm. If it is less than 100 ppm, the transesterification reaction will be poor and the reaction will not be completed. If it exceeds 200 ppm, manganese acetate will form coarse particles and impair the transparency of the polyester.

  The added amount of the alkali metal compound in the present invention needs to be 15 to 45 ppm in terms of an alkali metal element with respect to the obtained polyester. A preferred range is 20-40 ppm, more preferably 25-35 ppm. If the amount is less than 15 ppm, the effect of suppressing the decomposition of spiroglycol cannot be obtained, causing a sharp increase in viscosity during the polycondensation reaction, and the heat resistance of the obtained polyester decreases. If it exceeds 45 ppm, the polycondensation reaction time is delayed and the reaction cannot be completed.

  In the production method of the present invention, the alkali metal compound is not particularly limited, but it is preferable to add at least one selected from sodium hydroxide, potassium hydroxide, and lithium hydroxide.

  In the production method of the present invention, in the transesterification reaction, from the viewpoint of making the glass transition temperature equivalent to that of polyethylene terephthalate substantially containing no copolymer and from the viewpoint of reactivity, the raw material is heated to reach 210 ° C. Thereafter, the reaction is preferably completed at a temperature of 210 to 225 ° C. for 75 to 150 minutes. The reaction time at the specified temperature is more preferably 90 to 125 minutes, further preferably 100 to 110 minutes. By setting the reaction time within the specified range, the reaction rate of spiroglycol during the transesterification reaction is increased, and by suppressing the decomposition, the glass transition temperature and the same as those of polyethylene terephthalate substantially containing no copolymer are obtained. Good polycondensation reactivity can be obtained.

  In the production method of the present invention, after the transesterification reaction is completed, it is necessary to add a phosphorus compound and a titanium compound to the obtained low polymer, and reduce the pressure from normal pressure to 133 Pa or less while performing temperature increase to perform the polycondensation reaction. . From the viewpoint of reactivity and transparency of the polyester, it is preferable to add the titanium compound 15 to 60 minutes after the addition of the phosphorus compound.

  In the production method of the present invention, it is necessary to add 75 to 150 ppm in terms of phosphorus atom to the polyester from which the phosphorus compound is obtained. A preferred addition amount is 85 to 140 ppm, and more preferably 95 to 130 ppm. If it is less than 75 ppm, the heat resistance of the obtained polyester will be reduced. If it exceeds 150 ppm, coarse particles are generated by the phosphorus compound, and the transparency of the polyester is deteriorated.

  The phosphorus compound used in the present invention is at least one selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, and methyl ester or ethyl ester, phenyl ester, and further half ester thereof, particularly triethyl phosphonate. Noacetate, trimethyl phosphate, dimethyl phenylphosphonate are preferred.

  In the production method of the present invention, the added amount of the titanium compound needs to be 20 to 40 ppm in terms of titanium atoms with respect to the obtained polyester. A preferred addition amount is 25 to 35 ppm, more preferably 28 to 32 ppm. If it is less than 20 ppm, the polycondensation reaction is delayed, and the reaction cannot be completed. If it exceeds 40 ppm, the polyester is decomposed by an excessive polycondensation catalyst, and the heat resistance decreases.

  As the titanium catalyst used in the present invention, a titanium compound whose substituent is at least one of an alkoxy group, a phenoxy group, an acylate group, an amino group and a hydroxyl group is preferably used. Specific alkoxy groups include tetraethoxide, tetrapropoxide, tetraisopropoxide, tetrabutoxide, titanium tetraalkoxides such as tetra-2-ethylhexoxide, 6-diketone functional groups such as acetylacetone, lactic acid, Examples thereof include hydroxy polycarboxylic acid functional groups such as malic acid, tartaric acid, salicylic acid, and citric acid, and keto ester functional groups such as methyl acetoacetate and ethyl acetoacetate, and aliphatic alkoxy groups are particularly preferable. Further, examples of the phenoxy group include phenoxy and cresylate. In addition, the acylate group includes tetraacylate groups such as lactate and stearate, phthalic acid, trimellitic acid, trimesic acid, hemi-mellitic acid, pyromellitic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid. , Polybasic carboxylic acid functional groups such as sebacic acid, maleic acid, fumaric acid, cyclohexanedicarboxylic acid or anhydride thereof, ethylenediaminetetraacetic acid, nitrilotripropionic acid, carboximinodiacetic acid, carboxymethyliminodipropionic acid, diethylenetriamine Nitrogen-containing polycarboxylic acid functional groups such as minopentaacetic acid, triethylenetetraminohexacetic acid, iminodiacetic acid, iminodipropionic acid, hydroxyethyliminodiacetic acid, hydroxyethyliminodipropionic acid, and methoxyethyliminodiacetic acid. , Especially aliphatic acylate Group is preferred. The amino group includes aniline, phenylamine, diphenylamine and the like. Further, diisopropoxybisacetylacetone, triethanolaminate isopropoxide, etc. containing two kinds of these substituents may be mentioned.

  In the production method of the present invention, when the low polymer is subjected to the polycondensation reaction, after the low polymer reaches 270 ° C, the reaction is carried out at 270 to 290 ° C and at a pressure of 6000 Pa or lower for 120 to 250 minutes. Preferably, it is terminated. The reaction time is more preferably 170 to 240 minutes, even more preferably 220 to 230 minutes. By keeping the reaction time within a predetermined range, the balance between the polycondensation reaction and decomposition of the spiroglycol component in the polyester is maintained, the glass transition temperature is substantially the same as that of polyethylene terephthalate containing substantially no copolymer, and the heat resistance is excellent. And good polycondensation reactivity can be obtained.

  Next, each method for producing the polyester of the present invention will be described in detail.

  In the method for producing a polyester of the present invention, for example, dimethyl terephthalate, dimethyl cyclohexanedicarboxylate, ethylene glycol, and spiroglycol are charged into a reactor as raw materials so as to have a predetermined polymer composition. In this case, if ethylene glycol is added in an amount of 1.7 to 2.3 mole times based on all dicarboxylic acid components, the reactivity becomes good. After melting these at about 140 to 150 ° C., an alkali compound such as manganese acetate and potassium hydroxide is added as a transesterification catalyst.

  At 140 to 150 ° C., these monomer components become a homogeneous molten liquid. Next, methanol is distilled while elevating the temperature in the reaction vessel to the range of 210 ° C. to 225 ° C., and after reaching 210 ° C., transesterification is performed for 75 to 150 minutes while maintaining the temperature at 210 to 225 ° C. . After the transesterification reaction is completed in this way, ethylene glycol is distilled out of the resulting low polymer.

  After distilling ethylene glycol out of the system, a phosphorus compound such as triethylphosphonoacetate is added while maintaining the temperature of the low polymer at 225 to 250 ° C.

  After 15 to 60 minutes from the end of the addition of the phosphorus compound, then, after adding a titanium catalyst such as tetra-n-butoxytitanium as a polycondensation catalyst, the internal pressure of the apparatus is increased while slowly raising the internal temperature of the apparatus to 270 to 290 ° C. The pressure is reduced from normal pressure to 133 Pa or less. As the polycondensation reaction proceeds, the viscosity of the reaction product increases. The temperature is maintained at 270 to 290 ° C., and after reaching 270 ° C. and within a range of 120 to 250 minutes after the pressure reaches 6000 Pa or less, the reaction is terminated at a predetermined stirring torque, and the polyester is discharged from the reactor. To the water tank in the form of a strand. The discharged polyester is quenched in a water tank and made into chips by a cutter.

  The polyester can be obtained in this manner, but the above is merely an example, and the monomers, catalysts, and polymerization conditions are not limited thereto.

  The polyester thus obtained has a glass transition temperature equivalent to that of polyethylene terephthalate substantially free of a copolymer, and a film can be stably formed by alternately laminating. In addition, the film obtained by laminating with polyethylene terephthalate containing substantially no copolymer is excellent in transparency and light reflectivity, coarse particles and foreign substances are suppressed, and as a metallic glossy film or heat ray reflective film It is suitable.

Hereinafter, the present invention will be described more specifically with reference to examples.
In addition, the measuring method of the physical property and the evaluation method of the effect were performed according to the following methods.

(1) Trans-form of dimethyl 1,4-cyclohexanedicarboxylate A sample was diluted 5- to 6-fold with methanol, and 0.4 μl of the diluted solution was measured by liquid chromatography under the following conditions.
Apparatus: LC-10ADvp made by Shimadzu
Column: Capillary column DB-17 manufactured by Agilent Technologies (length 30 m, inner diameter 0.32 mm, membrane pressure 0.25 μm)
Temperature rising conditions: Initial temperature 110 ° C., initial temperature holding time 25 minutes, temperature rising rate 6 ° C./min, final temperature 200 ° C., analysis time: 40 minutes (2) Acid value of dimethyl 1,4-cyclohexanedicarboxylate 20 g sample Weighed accurately in an Erlenmeyer flask, add 100 ml of neutralized methanol and several drops of phenolphthalein solution, shake until the sample is completely dissolved, titrate with 0.1 mol / L potassium hydroxide-ethanol solution, The end point is the time when the light red color of for 30 seconds has continued, and is calculated by the following formula.
A = B × f × 5.611 / S
A: Acid value (mgKOH / g)
B: 0.1 mol / L potassium hydroxide-ethanol solution (ml) used for titration
f: Concentration of 0.1 ml / L potassium hydroxide-ethanol solution (mol / L)
S: Mass of sample (g)
(3) Intrinsic Viscosity of Polyester 0.1 g of polyester chips were dissolved in 10 ml of orthochlorophenol (hereinafter referred to as OCP) by heating at 100 ° C. for 30 minutes, and then measured at 25 ° C. using an Ubbelohde viscometer.

(4) Glass Transition Temperature of Polyester 10 g of a polyester chip was weighed, sealed using an aluminum pan and a pan cover, and measured with a differential scanning calorimeter (TA Instruments Q100). In the measurement, the temperature was increased from 20 ° C. to 285 ° C. at a rate of 16 ° C./min in a nitrogen atmosphere, rapidly cooled using liquid nitrogen, and again increased from a temperature of 20 ° C. to 285 ° C. in a nitrogen atmosphere at a rate of 16 ° C./min. To raise the temperature. The glass transition temperature was measured during the second heating process.

(5) Gelation rate of polyester A polyester chip was pulverized with a freeze pulverizer (manufactured by Splex CertiPerp), and 0.5 g was weighed in a stainless beaker. After vacuum drying at 50 ° C. for 2 hours using a vacuum drier, a sample-containing container was sufficiently purged by passing a mixed gas having an oxygen concentration of 1% with air and nitrogen through a pipe. And subjected to a heat treatment under a mixed gas flow of 1% oxygen (flow rate 0.5 L / min) for 2.5 hours. This was dissolved in 20 ml of OCP at 160 ° C. for 1 hour and regulated. This solution was filtered using a glass filter (3GP40, manufactured by Shibata Chemical Co., Ltd.), and the glass filter was washed with dichloromethane. The glass filter was dried at 130 ° C. for 2 hours, and the weight of the OCP insoluble matter (gel) remaining on the filter was calculated from the weight increase of the glass filter before and after filtration, and the weight fraction of the OCP insoluble matter relative to the polyester weight was determined. And the gelation rate (%).

(6) Polyester solution haze 2 g of a polyester chip was dissolved in OCP, and the solution was subjected to integrating sphere photometry using a quartz cell having an optical path length of 20 mm and a haze meter (HGM-2DP type, manufactured by Suga Test Instruments Co., Ltd.). The haze value was measured.

Example 1
55.5 parts by weight of dimethyl terephthalate, 24.5 parts by weight of dimethyl 1,4-cyclohexanedicarboxylate, 59.8 parts by weight of ethylene glycol, 24.9 parts by weight of spiro glycol, and manganese acetate manganese tetrahydrate An amount of 140 ppm as an element and an amount of 30 ppm of potassium hydroxide as a potassium element were respectively weighed and charged into a reactor, and the contents were dissolved at 140 ° C. and stirred.

  The temperature of the reaction contents was slowly raised to 220 ° C. with stirring, and methanol was distilled out to a predetermined amount while maintaining the temperature at 210 to 225 ° C. The transesterification reaction time after reaching 210 ° C. was 105 minutes. After the transesterification was completed, ethylene glycol was distilled out of the system at 220 ° C. for 45 minutes.

  After the distillation of ethylene glycol out of the system was completed, when the low polymer was heated to a temperature of 235 ° C., triethylphosphonoacetate was added in an amount of 120 ppm as a phosphorus atom, followed by stirring for 30 minutes. Thereafter, tetra-n-butoxytitanium was added in an amount of 30 ppm as titanium atoms.

  Then, the pressure was reduced and the temperature was raised while stirring the low polymer, and the polycondensation reaction was performed while distilling ethylene glycol. The pressure was reduced from normal pressure to 133 Pa or less over 90 minutes, and the temperature was raised from 235 ° C to 285 ° C over 90 minutes.

  The polycondensation reaction was completed by setting the stirring torque of the reactor so that the intrinsic viscosity of the polyester became 0.73. The polycondensation reaction time after the low polymer reaches 270 ° C. and the pressure in the reactor becomes 6000 Pa or less is 225 minutes, and the polycondensation reaction time after starting the depressurization and heating is 285 minutes, which is good. Met.

  Next, the inside of the reactor was returned to normal pressure with nitrogen gas, and a valve at the lower part of the polycondensation reaction apparatus was opened to discharge strand-like polyester into a water tank. The strand cooled in the water tank was cut with a cutter to obtain chips. Tables 1 and 2 show the polyester production conditions and the properties of the obtained polyester. The polyester had a glass transition temperature of 76 ° C., a gelation ratio of 9.9%, and a haze of 0.5%.

Examples 2 to 7
A polyester was polymerized in the same manner as in Example 1 except that the content of the trans form of dimethyl 1,4-cyclohexanedicarboxylate was changed. The conditions and results are shown in Tables 1 and 2. In Examples 2 to 4, an increase in the glass transition temperature was observed due to the decrease in the trans form, but at a level that did not cause any problem, and the gelation rate and haze were good. In Examples 5 to 7, a decrease in the glass transition temperature and an increase in the gelation rate due to an increase in the trans form were observed, but the level was not a problem and the haze was good.

Examples 8 to 13
A polyester was polymerized in the same manner as in Example 1 except that the acid value of dimethyl 1,4-cyclohexanedicarboxylate was changed. The conditions and results are shown in Tables 1 and 2. In Examples 8 to 10, an increase in the glass transition temperature and an increase in the gelation rate due to a decrease in the acid value were observed, but the level was not a problem and the haze was good. In Examples 11 to 13, a decrease in the glass transition temperature was observed due to an increase in the acid value, but at a level that did not cause any problem, and the gelation rate and haze were good.

Examples 14 and 15
A polyester was polymerized in the same manner as in Example 1 except that the content of dimethyl 1,4-cyclohexanedicarboxylate was changed. The conditions and results are shown in Tables 1 and 2. In Example 14, although the glass transition temperature was increased due to the small content of dimethyl 1,4-cyclohexanedicarboxylate, the glass transition temperature was at a satisfactory level, and the gelation rate and haze were good. In Example 15, although the glass transition temperature was lowered due to the large content of dimethyl 1,4-cyclohexanedicarboxylate, the glass transition temperature was at a satisfactory level, and the gelation rate and haze were good.

Examples 16 and 17
A polyester was polymerized in the same manner as in Example 1 except that the content of spiroglycol was changed. The conditions and results are shown in Tables 1 and 2. In Example 16, although the glass transition temperature was lowered due to the small content of spiroglycol, it was at a level without any problem, and the gelation rate and haze were good. In Example 17, although the spiroglycol content was high, the glass transition temperature and the gelation rate were increased, but the levels were not problematic, and the glass transition temperature and haze were good.

Examples 18 to 21
A polyester was polymerized in the same manner as in Example 1 except that the amount of manganese acetate added was changed. The conditions and results are shown in Tables 1 and 2. In Examples 18 and 19, the glass transition temperature, the gelation rate, and the haze were good. In Examples 20 and 21, coarse particles in the polyester were increased due to the large amount of manganese acetate, and haze was increased. However, these levels were no problem, and the glass transition temperature and the gelation ratio were good. Was.

Examples 22 to 25
A polyester was polymerized in the same manner as in Example 1 except that the amount of potassium hydroxide was changed. The conditions and results are shown in Tables 1 and 2. In Examples 22 and 23, the heat resistance was lowered due to the small amount of the alkali metal compound, and the gelation rate was increased. However, the levels were not problematic, and the glass transition temperature and haze were good. In Examples 24 and 25, although the reactivity was lowered due to the large amount of the alkali metal compound and the polycondensation reaction time was delayed, the glass transition temperature, the gelation rate and the haze were good.

Examples 26 to 29
A polyester was polymerized in the same manner as in Example 1 except that the amount of triethylphosphonoacetate was changed. The conditions and results are shown in Tables 1 and 2. In Examples 26 and 27, the heat resistance was lowered due to the small amount of the phosphorus compound, and the gelation rate was increased. However, the levels were not problematic, and the glass transition temperature and haze were good. In Examples 28 and 29, coarse particles in the polyester increased due to the large amount of the phosphorus compound, and haze was increased. However, these levels were not problematic, and the glass transition temperature and the gelation ratio were good. Was.

Examples 30 and 31
A polyester was polymerized in the same manner as in Example 1 except that the amount of tetra-n-butoxytitanium was changed. The conditions and results are shown in Tables 1 and 2. In Example 30, although the polycondensation reaction was delayed due to the small amount of the titanium compound, the polycondensation reaction was at a satisfactory level, and the glass transition temperature, the gelation ratio, and the haze were good. In Example 31, an increase in the gelation rate was observed due to the large amount of the titanium compound, but the level was not a problem, and the glass transition temperature and the haze were good.

Examples 32-37
After reaching 210 ° C., a polyester was polymerized in the same manner as in Example 1 except that the transesterification reaction time at 210 to 225 ° C. was changed. The conditions and results are shown in Tables 1 and 2. In Examples 32 to 34, although the glass transition temperature was lowered due to the short transesterification reaction time in the specified range, the level was not a problem, and the gelation rate and haze were good. In Examples 35 to 37, an increase in the glass transition temperature was observed due to a long transesterification reaction time in the specified range, but the level was not a problem, and the gelation rate and haze were good.

Examples 38 to 42
After reaching 270 ° C., the polyester was polymerized in the same manner as in Example 1 except that the polycondensation reaction time at 270 to 290 ° C. and a pressure of 6000 Pa or less was changed. The conditions and results are shown in Tables 1 and 2. In Examples 38 to 40, the glass transition temperature was lowered due to the short polycondensation reaction time in the specified range, but the level was not a problem, and the gelation rate and haze were good. In Examples 41 and 42, the polycondensation reaction time in the specified range was long, so that the glass transition temperature was increased. However, the level was not a problem, and the gelation rate and haze were good.

Comparative Examples 1 and 2
A polyester was polymerized in the same manner as in Example 1 except that the content of the trans form of dimethyl 1,4-cyclohexanedicarboxylate was changed. The conditions and results are shown in Tables 3 and 4. In Comparative Example 1, the glass transition temperature of the obtained polyester was higher than that of polyethylene terephthalate containing substantially no copolymer because the amount of the trans form was below the specified range. In Comparative Example 2, since the amount of the trans form exceeded the specified range, the glass transition temperature of the obtained polyester was lower than that of polyethylene terephthalate containing substantially no copolymer, and the gelation rate further increased. .

Comparative Examples 3 and 4
A polyester was polymerized in the same manner as in Example 1 except that the acid value of dimethyl 1,4-cyclohexanedicarboxylate was changed. The conditions and results are shown in Tables 3 and 4. In Comparative Example 3, since the acid value was below the specified range, the glass transition temperature was lower than that of polyethylene terephthalate containing substantially no copolymer, and the gelation rate further increased. In Comparative Example 4, since the acid value exceeded the specified range, the glass transition temperature was higher than that of polyethylene terephthalate containing substantially no copolymer.

Comparative Examples 5 and 6
A polyester was polymerized in the same manner as in Example 1 except that the content of dimethyl 1,4-cyclohexanedicarboxylate was changed. The conditions and results are shown in Tables 3 and 4. In Comparative Example 5, since the content of dimethyl 1,4-cyclohexanedicarboxylate was below the specified range, the glass transition temperature was higher than that of polyethylene terephthalate containing substantially no copolymer. In Comparative Example 6, since the content of dimethyl 1,4-cyclohexanedicarboxylate exceeded the specified range, the glass transition temperature was lower than that of polyethylene terephthalate containing substantially no copolymer.

Comparative Examples 7 and 8
A polyester was polymerized in the same manner as in Example 1 except that the content of spiroglycol was changed. The conditions and results are shown in Tables 3 and 4. In Comparative Example 7, since the content of spiroglycol was below the specified range, the glass transition temperature was lower than that of polyethylene terephthalate containing substantially no copolymer. In Comparative Example 8, since the content of spiroglycol exceeded the specified range, the glass transition temperature was higher than that of polyethylene terephthalate containing substantially no copolymer, and the gelation rate further increased.

Comparative Examples 9 and 10
A polyester was polymerized in the same manner as in Example 1 except that the amount of manganese acetate added was changed. The conditions and results are shown in Tables 3 and 4. In Comparative Example 9, since the addition amount of the manganese element was less than the specified range, the activity of the catalyst was insufficient, the transesterification reaction was not completed, and the target polyester could not be obtained. In Comparative Example 10, since the amount of manganese acetate exceeded the specified range, coarse particles in the polyester increased and haze increased.

Comparative Examples 11 and 12
A polyester was polymerized in the same manner as in Example 1 except that the amount of potassium hydroxide was changed. The conditions and results are shown in Tables 3 and 4. In Comparative Example 11, since the addition amount of the alkali metal compound was less than the specified range, decomposition of spiroglycol during the polycondensation reaction, a sudden increase in torque due to crosslinking occurred, and the polycondensation time became extremely short. The heat resistance of the obtained polyester decreased, and the gelation rate increased. In Comparative Example 12, since the added amount of the alkali metal compound exceeded the specified range, the reactivity was reduced, the polycondensation reaction was not completed, and the target polyester could not be obtained.

Comparative Examples 13 and 14
A polyester was polymerized in the same manner as in Example 1 except that the amount of triethylphosphonoacetate was changed. The conditions and results are shown in Tables 3 and 4. In Comparative Example 13, since the amount of the phosphorus compound added was below the specified range, the heat resistance was reduced and the gelation rate was increased. In Comparative Example 14, since the amount of the phosphorus compound exceeded the specified range, coarse particles in the polyester increased and haze increased.

Comparative Examples 15 and 16
A polyester was polymerized in the same manner as in Example 1 except that the amount of tetra-n-butoxytitanium was changed. The conditions and results are shown in Tables 3 and 4. In Comparative Example 15, since the amount of the titanium compound added was below the specified range, the activity of the catalyst was insufficient and the polycondensation reaction was not completed, and the desired polyester could not be obtained. In Comparative Example 16, since the amount of the titanium compound added was below the specified range, the gelation rate increased due to the accelerated decomposition by the titanium compound.

Claims (3)

  Dicarboxylic acid containing 25 to 40 mol% based on the polyester from which dimethyl 1,4-cyclohexanedicarboxylate having a trans-form content of 10 to 40% and an acid value of 0.02 to 1.00 mgKOH / g is obtained. A process for producing a polyester comprising a diol component and 15 to 25 mol% of a polyester from which spiroglycol can be obtained, wherein manganese acetate is obtained by transesterifying all dicarboxylic acid components and all diol components. 100 to 200 ppm (weight ratio) in terms of manganese element relative to the polyester to be obtained, and 15 to 45 ppm (weight ratio) in terms of metal element relative to the polyester from which the alkali metal compound can be obtained, followed by a transesterification reaction and further a phosphorus compound 75 to 1 in terms of phosphorus element based on the resulting polyester 0 ppm (weight ratio) and 20 to 40 ppm (weight ratio) in terms of titanium element are added to the polyester from which the titanium compound can be obtained, and the pressure is reduced from normal pressure to 133 Pa or less while the temperature is raised, and the polycondensation reaction is performed. A method for producing a polyester, characterized in that:   2. The method according to claim 1, wherein when performing the transesterification reaction of the raw material, the temperature of the raw material is raised, and after the temperature reaches 210 ° C., the reaction is completed at a temperature of 210 to 225 ° C. for 75 to 150 minutes to terminate the reaction. Polyester manufacturing method.   When the low polymer obtained by the transesterification reaction is subjected to the polycondensation reaction, after the low polymer reaches 270 ° C., the reaction is completed at a pressure of 270 to 290 and a pressure of 6000 Pa or less for 120 to 250 minutes to complete the reaction. The method for producing a polyester according to claim 1, wherein the polyester is produced.