JP2011068880A - Molded article made of copolymerized polyester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molded article made of a copolymerized polyester with a high commodity value in which contamination of a molding dice and generation of deposition of foreign matter are less when it is continuously molded. <P>SOLUTION: The molded article made of the copolymerized polyester includes terephthalic acid as a main dicarboxylic acid component and includes ethylene glycol and neopentyl glycol as main glycol components. The copolymerized polyester in which the content of the neopentyl glycol relative to the amount of entire glycol component is more than 25 mol% and not more than 80 mol% is molded. The content of an isolated cyclic dimer comprising terephthalic acid and neopentyl glycol is 17,000 ppm or lower. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a molded body made of a copolymerized polyester, which is excellent in transparency and color tone, and is less likely to cause dirt on a molding die and adhesion of foreign matter.

  Polyester, especially polyethylene terephthalate (PET) produced from terephthalic acid (hereinafter sometimes abbreviated as TPA) and ethylene glycol (hereinafter sometimes abbreviated as EG), has chemical and physical properties. Therefore, it is widely used for applications such as containers, films, sheets, and fibers.

  In recent years, polyesters obtained by copolymerizing neopentyl glycol (hereinafter sometimes abbreviated as NPG) at the time of manufacturing such polyethylene terephthalate (PET) have become transparent and impact resistant. It has been attracting attention because of its excellent properties, moldability, heat resistance, and the like, and has been used as a raw material polymer for various applications, in particular, molded articles such as films, sheets, injection molded articles, and deformed shaped articles.

  On the other hand, vinyl chloride resin is used for outdoor-use molded products for building materials because of processability, environmental stability, price competitiveness, etc., but carcinogenesis due to elution of monomers and plasticizers from these molded products. Due to concerns about the properties and endocrine disrupting action and the problem of toxic gas generation during incineration, there is an increasing demand for alternatives to polyester resins containing polyesters copolymerized with NPG.

  In order to improve transparency, chemical resistance, moldability, etc., a technology relating to a copolymerized polyester in which a neopentyl glycol copolymerization amount is specified within a specific range and a molded product from the copolymerized polyester has been proposed (for example, (See Patent Documents 1 and 2). Moreover, the technique regarding the copolymerization polyester resin which improved the extrusion moldability by copolymerizing a branched structure introduction | transduction agent and increasing a melt viscosity is proposed (for example, refer patent document 3).

  However, when molding a molded product continuously by these technologies, foreign matter adheres to the vicinity of the die of the extrusion molding machine, which causes problems such as adhesion to the surface of the molded product and deterioration of the commercial value. There is a need for a solution.

JP-A-8-337659 JP 2000-109546 A JP 2004-27176 A

  The present invention was devised in view of the problems of the prior art, and provides a molded article made of a copolymer polyester having a high commercial value with little occurrence of dirt on a molding die and adhesion of foreign matter when continuously molded. For the purpose.

As a result of intensive studies to achieve the above object, the present inventor has completed the present invention. That is, the present invention has the constitutions (1) to (7).
(1) Copolymer having terephthalic acid as the main dicarboxylic acid component and ethylene glycol and neopentyl glycol as the main glycol components, and the content of neopentyl glycol with respect to all glycol components is more than 25 mol% and not more than 80 mol% A copolymerized polyester molded body formed by molding polyester, wherein the content of a free cyclic dimer composed of terephthalic acid and neopentyl glycol is 17000 ppm or less.
(2) The copolyester molded article according to (1), wherein the content of the cyclic trimer composed of terephthalic acid and ethylene glycol is 5500 ppm or less.
(3) The copolymer polyester molded article according to (1) or (2), wherein the content of free monohydroxyneopentyl terephthalate comprising terephthalic acid and neopentyl glycol is 50 ppm or less.
(4) The copolymer polyester molded article according to any one of (1) to (3), wherein the content of diethylene glycol relative to the total glycol component is 1.0 to 5.0 mol%.
(5) The copolyester molded article according to any one of (1) to (4), wherein the color b value is −5.0 to 5.0.
(6) The copolymer polyester molded article according to any one of (1) to (5), wherein a haze value at a thickness of 5 mm is 15% or less.
(7) The copolymer polyester molded body according to any one of (1) to (6), wherein the copolymer polyester molded body is a film or a sheet.

  The copolyester molded product of the present invention has a characteristic that the molding die is not easily contaminated or adhered to foreign matter when continuously molded, and is suitably used as a molded product having no foreign matter on the surface. be able to. Furthermore, when used in a container or the like, the odor does not transfer to the contents, and therefore, it can be suitably used for a container for containing contents that require fragrance retention.

Hereinafter, the copolyester molded article of the present invention will be specifically described below.
The copolyester molded product of the present invention has terephthalic acid as the main dicarboxylic acid component, ethylene glycol and neopentyl glycol as the main glycol components, and the content of neopentyl glycol with respect to the total glycol components is more than 25 mol% and It is a molded article formed by molding a copolymerized polyester of 80 mol% or less. The molded article of the present invention is characterized in that the content of a free cyclic dimer (hereinafter sometimes referred to as CD) composed of terephthalic acid and neopentyl glycol is 17000 ppm or less.

  The content of neopentyl glycol with respect to the total glycol component is preferably 28 to 75 mol%, more preferably 28 to 70 mol%, and most preferably 30 to 60 mol%. If the content of neopentyl glycol is less than the above range, it becomes crystalline and the transparency of the molded article becomes worse. In particular, in the case of a thick molded article, sufficient transparency cannot be achieved and the commercial value is lost. If the above range is exceeded, the free cyclic dimer consisting of terephthalic acid and neopentyl glycol will increase, and during continuous molding, the area near the resin outlet of the extrusion die and the mold of the injection molding machine will be very dirty. The adhering foreign matter adheres to the surface of the molded body and the commercial value decreases.

  The term “amorphous” as used herein means that a sample left in a Yamato DP63 dryer at 120 ° C. for 120 minutes is subjected to 20 ° C./min from −100 ° C. to 300 ° C. using a differential scanning calorimeter (DSC). No melting peak is shown in either of the two temperature raising processes in which the temperature is raised, then lowered to −100 ° C. at 50 ° C./min, and subsequently raised from −100 ° C. to 300 ° C. at 20 ° C./min. Refers to things. Since the copolymer polyester according to the present invention is amorphous, it can have transparency that can be suitably used even if it is a thick molded article. In other words, being “amorphous” under the present measurement conditions means that sufficient transparency can be maintained when molded into a thick molded body.

  The content of the free cyclic dimer (CD) composed of terephthalic acid and neopentyl glycol is preferably 12000 ppm or less, more preferably 9000 ppm or less, and most preferably 8000 ppm or less. If the content of the free cyclic dimer exceeds the above range, the dirt near the resin outlet of the die of the extrusion molding machine becomes severe during continuous molding, and the adhered foreign matter adheres to the surface of the molded body and the surface condition becomes worse. The value of merchandise decreases due to transparency. Further, at the time of continuous injection molding, the injection mold outlet is clogged and a normal molded product cannot be obtained. Moreover, the lower limit of this content is 1000 ppm from the economical efficiency at the time of production. The free cyclic dimer consisting of terephthalic acid and neopentyl glycol is a value quantified by the measurement method of the examples described later.

  The content of the cyclic trimer (CT) composed of terephthalic acid and ethylene glycol in the copolymer polyester molded body of the present invention is preferably 5500 ppm or less, more preferably 4500 ppm or less, still more preferably 3500 ppm or less, most preferably. Is 2500 ppm or less. If the content of the cyclic trimer exceeds the above range, the contamination near the resin outlet of the die of the extrusion molding machine as described above and the clogging of the injection mold die will become more severe, and the continuous production time at the time of molding Can become shorter and the economic efficiency can be hindered. Moreover, the lower limit of this content is 100 ppm from the economical efficiency at the time of production.

  The content of free monohydroxyneopentyl terephthalate (hereinafter sometimes referred to as MHNT) composed of terephthalic acid and neopentyl glycol in the copolymer polyester molded body of the present invention is preferably 50 ppm or less, more preferably 48 ppm. Hereinafter, it is more preferably 45 ppm or less. Inclusion of free MHNT is within the above range, thereby improving the fragrance retention. Therefore, it is suitably used for a container for containing contents that require aroma retention. Moreover, the lower limit of this content is 10 ppm from the economical efficiency at the time of production.

  The main dicarboxylic acid component of the copolyester according to the present invention is terephthalic acid, and the ratio of the terephthalic acid component to the total dicarboxylic acid component is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol%. Above, most preferably 100 mol%.

  Other dicarboxylic acid components that can be used with terephthalic acid include (1) aromatic dicarboxylic acids such as isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, and the like. Acids and functional derivatives thereof, (2) aliphatic dicarboxylic acids such as adipic acid, sebacic acid, succinic acid, glutaric acid, dimer acid, dodecanedicarboxylic acid, azelaic acid and functional derivatives thereof, (3) hexahydroterephthalic acid And alicyclic dicarboxylic acids such as hexahydroisophthalic acid and cyclohexanedicarboxylic acid, and functional derivatives thereof.

  In the copolymerized polyester according to the present invention, the entire glycol component is preferably composed of ethylene glycol and neopentyl glycol. However, the copolymerized polyester may have other properties as long as the various characteristics targeted by the present invention are not impaired. Other glycol components other than ethylene glycol and neopentyl glycol may be used to impart function or improve properties. The total amount of ethylene glycol and neopentyl glycol with respect to all glycol components is preferably 70 mol% or more, more preferably 85 mol% or more, particularly preferably 95 mol% or more, and most preferably 100 mol%.

  Other glycol components include (1) aliphatic glycols such as trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, (2) 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethyl Examples include alicyclic glycols such as methanol, and (3) aromatic glycols such as p-xylylene glycol and m-xylylene glycol. Of these, 1,4-cyclohexanedimethanol is preferred. In addition, these glycol components may be used alone or in combination of two or more at an arbitrary ratio.

  The copolymerized polyester according to the present invention is copolymerized with a polyfunctional compound having three or more carboxyl groups, hydroxyl groups or ester-forming groups thereof (for example, trimellitic acid, pyromellitic acid, glycerin, trimethylolpropane, etc.). It is preferable to contain 0.001 to 5 mol% of the acid component and / or glycol component of the polyester in order to enhance the profile extrusion moldability.

  The copolyester according to the present invention can be produced by any of a production method by direct esterification reaction and polycondensation reaction, or a production method by transesterification reaction and polycondensation reaction. The reaction may be performed in a batch reactor or a continuous reactor, but is preferably performed in a continuous reactor in terms of economy and quality stability.

  In a continuous reaction apparatus (continuous polycondensation method), the esterification reaction, the transesterification reaction and the melt polycondensation reaction may each be performed in one stage, but are preferably performed in a plurality of stages. When the esterification reaction or transesterification reaction is performed in a plurality of stages, the number of reaction cans is preferably 2 to 3 cans. Further, when the melt polycondensation is performed in a plurality of stages, the number of reaction cans is preferably 3 to 7 cans.

  When the copolyester according to the present invention is produced by the continuous polycondensation method, it is 1.02 to 1.5 mol, preferably 1.03 to 1.4 mol, relative to 1 mol of all dicarboxylic acids or ester derivatives thereof. A slurry containing all the glycol is prepared and fed continuously to the esterification reaction step containing the oligomer. The esterification reaction temperature is usually 240 to 270 ° C, preferably 250 to 265 ° C. Moreover, the pressure in a reaction can is 0.2 MPa or less normally, Preferably it is 0.01-0.05 MPa. Moreover, the temperature of a polycondensation reaction is 265-285 degreeC normally, Preferably it is 270-280 degreeC, and the pressure in a reaction container is 1.5 hPa or less normally, Preferably it is 0.5 hPa or less. The reaction time of the esterification reaction is preferably 5 hours or less, particularly preferably 2 to 3.5 hours. The reaction time for the polycondensation reaction is preferably 3 hours or less, particularly preferably 1 to 2 hours.

  When the copolyester according to the present invention is produced by a batch polycondensation method, the esterification reaction temperature is usually 220 to 250 ° C, preferably 230 to 245 ° C. Moreover, the pressure in a reaction can is 0.2-0.4MPa normally, Preferably it is 0.25-0.30MPa. Further, the polycondensation reaction may be performed in one stage or may be performed in a plurality of stages. When it is carried out in one stage, the pressure is gradually reduced and the temperature is raised, the final temperature is 260 to 280 ° C., preferably 265 to 275 ° C., and the final pressure is usually 3 hPa or less, preferably 0.5 hPa. The following. The reaction time of the esterification reaction is preferably 4 hours or less, particularly preferably 2 to 3 hours. The reaction time for the polycondensation reaction is preferably 5 hours or less, particularly preferably 1 to 3 hours.

  Next, in the case of producing a low polycondensate by continuous transesterification, 1.1 to 1.6 mol, preferably 1.2 to 1.5 mol of glycol is contained per 1 mol of dimethyl terephthalate. A solution is prepared and continuously fed to the transesterification step. The transesterification reaction temperature is usually 200 to 270 ° C, preferably 230 to 265 ° C. In the case of the transesterification method, it is necessary to use a transesterification catalyst in addition to the polycondensation catalyst. The obtained low polycondensate is reacted in the same manner as the above-mentioned continuous polycondensation.

  When a low polycondensate is produced by batch transesterification, it is 2.3 to 2.0 mol, preferably 2.2 to 2.0 mol, based on 1 mol of dimethyl terephthalate in the batch reactor. The glycol and dimethyl terephthalate are added and the reaction is carried out in the presence of a transesterification catalyst. The resulting low polycondensate is polycondensed in the same manner as in the above esterification reaction.

  As the polycondensation catalyst, at least one of an antimony compound, a germanium compound, a titanium compound, and an aluminum compound can be used. Examples of the antimony compound include antimony trioxide, antimony pentoxide, antimony acetate, and antimony glycoloxide. Among these, antimony trioxide, antimony acetate, and antimony glycoloxide are preferable, and antimony trioxide is particularly preferable. These antimony compounds are preferably contained in an amount of 50 to 400 ppm, more preferably 100 to 350 ppm, and particularly preferably 150 to 300 ppm with respect to the copolymerized polyester.

  Examples of the germanium compound include crystalline germanium dioxide, amorphous germanium dioxide, germanium tetroxide, germanium hydroxide, germanium oxalate, germanium chloride, germanium tetraethoxide, germanium tetra-n-butoxide, and phosphorous acid. Examples include compounds such as germanium. Among these, crystalline germanium dioxide and amorphous germanium dioxide are more preferable, and amorphous germanium dioxide is particularly preferable. These germanium compounds are preferably contained in an amount of 10 to 100 ppm, more preferably 30 to 70 ppm, and particularly preferably 30 to 50 ppm with respect to the resulting copolyester.

  Examples of the titanium compound include tetraalkyl titanates such as tetraethyl titanate, tetraisopropyl titanate, tetra-n-propyl titanate, and tetra-n-butyl titanate, and partial hydrolysates thereof, titanium acetate, titanyl oxalate, and oxalic acid. Titanylammonium, sodium titanyl oxalate, potassium titanyl oxalate, titanyl calcium oxalate, titanyl oxalate compounds such as titanyl strontium oxalate, titanium trimellitic acid, titanium sulfate, titanium chloride, titanium halide hydrolyzate, titanium oxalate, titanium fluoride , Potassium hexafluorotitanate, ammonium hexafluorotitanate, cobalt hexafluorotitanate, manganese hexafluorotitanate, titanium acetylacetonate, hydroxy polyvalent carboxylic acid or nitrogen-containing polyvalent potassium Titanium complex thereof with carbon acid, a complex oxide comprising titanium and silicon or zirconium, a reaction product of titanium alkoxide and the phosphorus compound. Among these, titanium tetraisopropoxide, titanium tetrabutoxide, and potassium titanyl oxalate are preferable, and titanium tetrabutoxide is particularly preferable. These titanium compounds are preferably contained in an amount of 1 to 50 ppm, more preferably 2 to 20 ppm, and particularly preferably 3 to 10 ppm with respect to the resulting copolymerized polyester.

  Examples of the aluminum compound include carboxylates such as aluminum formate, aluminum acetate, aluminum propionate and aluminum oxalate, oxides, inorganic acid salts such as aluminum hydroxide, aluminum chloride, aluminum hydroxide chloride and aluminum carbonate, aluminum Aluminum alkoxide such as methoxide and aluminum ethoxide, aluminum acetylacetate, aluminum chelate compound with aluminum acetylacetate, etc., organoaluminum compounds such as trimethylaluminum and triethylaluminum, and partial hydrolysis thereof Thing etc. are mentioned. Among these, aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, and aluminum acetylacetonate are particularly preferable. These aluminum compounds are preferably contained in an amount of 10 to 100 ppm, more preferably 15 to 50 ppm, and particularly preferably 15 to 40 ppm with respect to the produced polyester.

  In the production of the copolyester according to the present invention, an alkali metal compound or an alkaline earth metal compound may be used in combination. Examples of the alkali metal compound or alkaline earth metal compound include carboxylates such as acetates of these elements, alkoxides, and the like, which are added to the reaction system as powders, aqueous solutions, ethylene glycol solutions, or the like.

  In the case of the direct esterification method, the polycondensation catalyst can be added at any time before the start of the esterification reaction or after the completion of the pressure esterification reaction and before the start of the initial polycondensation reaction. However, when an antimony compound or a titanium compound is used as a polycondensation catalyst, it is preferably added before the esterification reaction. Further, other polycondensation catalyst, heat stabilizer and additives are preferably added after the esterification reaction.

  In the case of the transesterification method, the polycondensation catalyst can be added at an arbitrary time from the start of the transesterification reaction to the start of the initial polycondensation reaction. However, since the titanium compound has not only a function as a polycondensation catalyst but also a function as a transesterification catalyst, it is preferably added before the start of the transesterification reaction. Moreover, it is preferable to add other polycondensation catalysts, heat stabilizers, and additives after the end of the transesterification reaction. As the transesterification catalyst, titanium compounds such as manganese acetate, magnesium acetate and titanium tetrabutoxide are suitable. The transesterification catalyst needs to be added before the start of the transesterification reaction.

  Moreover, a phosphorus compound can be used as a stabilizer. Examples of the phosphorus compound include phosphoric acid, phosphorous acid, phosphonic acid, and derivatives thereof. Preferred examples include phosphoric acid, trimethyl phosphate, tributyl phosphate, triphenyl phosphate, monomethyl phosphate, dimethyl phosphate, monobutyl phosphate, dibutyl phosphate, phosphorous acid, trimethyl phosphite, phosphorus phosphite Examples include tributyl acid, methylphosphonic acid, dimethyl methylphosphonate, dimethyl ethylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, and diphenyl phosphonate. Among these, trimethyl phosphate and phosphoric acid are particularly preferable. These phosphorus compounds are preferably contained in an amount of 1 to 100 ppm, more preferably 3 to 70 ppm, and particularly preferably 5 to 50 ppm with respect to the resulting copolyester.

  A cobalt compound can be blended for improving the color tone of the copolyester. By adding this cobalt compound, the color b value can be particularly reduced. The cobalt compound is preferably contained as a cobalt atom in an amount of 0.5 to 30 ppm, more preferably 1 to 20 ppm, and particularly preferably 1 to 15 ppm with respect to the copolyester. If the content of cobalt atoms exceeds the above range, the copolymerized polyester may become dark or bluish due to the reduction of cobalt metal, the color L value may be less than 50, or the color b value may be less than −5. And the product value is reduced. Examples of the cobalt compound include cobalt acetate, cobalt chloride, cobalt benzoate, and cobalt chromate. Of these, cobalt acetate is preferred.

  The copolyester obtained by the above-mentioned continuous polycondensation method or batch polycondensation method is usually extracted in a strand form from the outlet provided in the bottom of the reaction can, and after water cooling, it is cut into chips or sheets. The

  The copolyester molded product of the present invention has a CD content of 17000 ppm or less, but in order to satisfy the CD content in the molded product, the CD content in the copolyester before molding is It is necessary to be 15000 ppm or less. The copolymer polyester having a CD content of 15000 ppm or less has, for example, a carboxyl end group concentration of the copolymer polyester oligomer at the end of the esterification reaction of 100 to 650 eq / ton and a hydroxyl end group concentration of 3000 to 8000 eq / ton. And then obtained by a polycondensation method. The carboxyl end group concentration of the copolyester oligomer at the end of the esterification reaction is preferably 150 to 630 eq / ton, more preferably 180 to 600 eq / ton. The hydroxyl terminal group concentration of the copolyester oligomer at the end of the esterification reaction is preferably 3300-7500 eq / ton, more preferably 3500-7500 eq / ton. As a method of adjusting the carboxyl end group concentration of the copolymerized polyester oligomer at the end of the esterification reaction to 100 to 650 eq / ton and the hydroxyl end group concentration of 3000 to 8000 eq / ton, an esterification reaction step or a transesterification reaction is performed. An amount of 10 to 40 mol%, preferably 15 to 35%, more preferably 25 to 30% of ethylene glycol used in the process is added to the low polymerization degree reaction product after completion of the esterification reaction or after completion of the transesterification reaction. It can be obtained by a method of adding and stirring for 10 minutes or more. Since the carboxyl end group concentration of the copolymerized polyester oligomer at the end of the esterification reaction is 100 to 650 eq / ton and the hydroxyl end group concentration is 3000 to 8000 eq / ton, it has already been generated during the polycondensation reaction. It is considered that the amount of CD was decreased by opening the CD. More preferably, the copolymer polyester obtained by such a method can be obtained by a method of heat-treating with an infrared irradiation device. It is considered that the amount of CD is reduced by adding and stirring ethylene glycol to open the already formed CD during the polycondensation reaction.

For example, the treatment with an infrared radiation device can be performed using a horizontal crystallization apparatus in which the infrared radiation apparatus is installed. Copolymer polyester chips are supplied to the crystallization apparatus, and the chips are transferred under stirring or rotation. However, it is possible to perform the heat treatment at a chip temperature in the range of 150 to 250 ° C. At this time, it is also possible to flow the heated inert gas in the counterflow direction. This device is preferably a continuous device in which polyester chips are supplied from one side and discharged from the other. In the treatment using the infrared radiation device, the copolyester chip absorbs infrared rays and causes molecular motion, so that frictional heat is generated and the inner and outer layers of the chip are heated almost uniformly. It is thought that it is decreased by the heat treatment. Therefore, as long as such a mechanism can be achieved, it can be achieved by other methods such as far infrared rays, near infrared rays, ultraviolet ray irradiation devices or electron beam irradiation devices, and a combination thereof can also be used.
However, the amount of CD tends to depend on the content of neopentyl glycol relative to the total glycol component, and if the content of neopentyl glycol is more than 80 mol%, the CD amount is 15000 ppm even if the above method is used. It is difficult to make it below. Although depending on the reactor used, if the content of neopentyl glycol is about 40 mol% or less, the amount of CD can be reduced to 15000 ppm or less only by the method of adding and stirring ethylene glycol. .

In order to obtain the copolymer polyester molded body of the present invention, the content of the free cyclic dimer composed of terephthalic acid and neopentyl glycol of the copolymer polyester to be used must be 15000 ppm or less, preferably 12000 ppm or less. It is. The copolyester is dried, the molding temperature of the polyester resin is made as low as possible, the temperature of the polymer at the time of melting is 200 to 300 ° C., preferably 220 to 295 ° C., and the residence time in the molten state at the time of molding is about It is necessary to reduce the thermal history received by the copolyester as much as possible, for example, within 1 minute, preferably within 50 seconds.
The molded body made of the copolymerized polyester according to the present invention is obtained by generally used extrusion blow molding, drawing molding, injection molding, stretch blow molding, etc. using the above-mentioned copolymerized polyester and setting the moisture content to 100 ppm or less by drying or the like. I can do it.

Further, the copolymer polyester molded body of the present invention preferably has a CT content of 5500 ppm or less, but in order to satisfy the CT content in the molded body, The CT content needs to be 5000 ppm or less. A copolymer polyester having a CT content of 5000 ppm or less is a method of adjusting the carboxyl end group concentration and the hydroxyl end group concentration of the copolymer polyester oligomer at the end of the esterification reaction and heat-treating with the infrared irradiation device, or An equivalent method is required. The effect of the oligomer end group concentration and the effect of infrared irradiation are considered to be the same as the mechanism of CD reduction.
Furthermore, the copolymer polyester molded body of the present invention preferably has a MHNT content of 50 ppm or less, but in order to satisfy the MHNT content in the molded body, The MHET content must be 40 ppm or less. A copolymer polyester having an MHNT of 50 ppm or less is a method of adjusting the carboxyl end group concentration and hydroxyl end group concentration of the copolymer polyester oligomer at the end of the esterification reaction and heat-treating with the infrared irradiation apparatus, or an equivalent thereof. A method is needed. At this time, an amount of 25 to 30% of ethylene glycol used in the esterification reaction step or transesterification reaction step is additionally added to the low polymerization degree reaction product after completion of the esterification reaction or after completion of the ester exchange reaction. It is necessary to keep the hydroxyl end group concentration of the oligomer high by stirring for more than a minute. The effect of the oligomer end group concentration and the effect of infrared irradiation are considered to be the same as the mechanism of CD reduction. If it is this aspect, even if content of neopentyl glycol is about 70 mol%, it can be satisfied as a molded article made of a copolyester for packaging materials such as containers for containing contents that require fragrance retention. .

  The copolymer polyester obtained as described above has a terminal carboxyl group concentration of 40 equivalents or less per ton of polymer. The terminal carboxyl group concentration is preferably 30 equivalent / ton or less, and more preferably 20 equivalent / ton or less. When the terminal carboxyl group concentration is within the above range, it is possible to contribute to suppressing coloring after molding of the copolyester.

  The number average molecular weight of the copolyester according to the present invention is preferably 15000 to 40000, more preferably 18000 to 35000, and still more preferably 20000 to 35000. When the number average molecular weight is less than the above range, the strength and elongation of the molded product are insufficient due to insufficient resin cohesive strength, and may become brittle and cannot be used. On the other hand, if the above range is exceeded, the melt viscosity is excessively increased, so that the optimum temperature for various molding processes is also increased, and the content of the cyclic dimer and the cyclic trimer is increased. This is a problem because the transparency of the molded article deteriorates.

  The diethylene glycol component copolymerized with the copolymerized polyester according to the present invention is one in which diethylene glycol produced as a reaction by-product is incorporated into the polymer main chain, and the amount of copolymerized diethylene glycol is the total glycol component content. It is 1.0-5.0 mol%, Preferably it is 1.5-4.0 mol%. When the amount of diethylene glycol is less than the above range, the crystallization speed of the copolyester is increased, affecting the transparency.When the amount exceeds the above range, the thermal stability and the thermal oxidation stability are deteriorated. The contamination at the melt outlet becomes severe and becomes a problem.

  Further, tertiary amines such as triethylamine, tri-n-butylamine, benzyldimethylamine, quaternary ammonium hydroxides such as tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, trimethylbenzylammonium hydroxide, and lithium carbonate When a small amount of a basic compound such as sodium carbonate, potassium carbonate or sodium acetate is added, the proportion of dioxyethylene terephthalate component units in the main chain of polyethylene terephthalate is relatively low (3% relative to all diol components). Mol% or less).

  The glass transition temperature of the copolyester according to the present invention is 55 ° C. or higher and lower than 120 ° C., preferably 60 ° C. or higher and lower than 115 ° C., and most preferably 65 ° C. or higher and lower than 110 ° C. Here, the glass transition temperature refers to a value measured by raising the temperature at 20 ° C./min using a differential scanning calorimeter (DSC). If the glass transition temperature is less than the above range, the profile extrudate may be thermally deformed when it is used outdoors in summer, or during product transport or storage in a sealed state in summer. Problems often occur.

  The upper limit of the color b value of the copolyester molded product of the present invention is preferably 5.0, more preferably 4.0, still more preferably 3.0, and particularly preferably 2.5. When the color b value exceeds the upper limit value, the yellowness of the copolyester molded product becomes strong, which is not preferable in terms of color tone. On the other hand, when the value of the color b value is larger than -5.0, the blueness of the copolyester molded product becomes conspicuous and may not be used depending on the application.

  When the copolymerized polyester according to the present invention is molded into a stepped molded plate, the haze value at a 5 mm thickness portion of the stepped molded plate when molded at a mold temperature of 10 ° C. is preferably 15% or less, More preferably, it is 13% or less, and particularly preferably 10% or less. When the haze value exceeds the above value, the transparency of the molded product is deteriorated and may not be used in applications where the requirement for transparency is severe.

  Other components can be appropriately added to the copolyester according to the present invention depending on the application. For example, impact resistance improvers, fillers, UV absorbers, surface treatment agents, lubricants, light stabilizers, pigments, antistatic agents, antibacterial agents, crosslinking agents, sulfur-based antioxidants, flame retardants, plasticizers, processing Auxiliaries, foaming agents and the like can be added. The copolyester according to the present invention can be applied to various molded products by extrusion blow molding, drawing molding, injection molding, profile extrusion molding, calendering molding, etc. that have been conventionally used in PET and polyvinyl chloride. It is suitably molded.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. The properties of the copolyester were measured according to the following method.

1) Number average molecular weight Measured by Waters gel permeation chromatography using tetrahydrofuran as solvent and polystyrene as assay standard. A measurement value in terms of polystyrene was obtained using chloroform as an eluent.

2) Diethylene glycol content of copolymerized polyester (hereinafter referred to as [DEG content])
Decomposition with methanol, the amount of DEG was quantified by gas chromatography, and expressed as a ratio (mol%) to the total glycol components.

3) Content of free cyclic dimer composed of terephthalic acid and neopentyl glycol of copolymerized polyester (molded product) (hereinafter referred to as “CD content”)
About 100 mg of the sample was precisely weighed and dissolved in 3 ml of HFIP / chloroform = 2/3 (v / v). 20 ml of chloroform was added and reprecipitation was carried out with 10 ml of methanol. After filtration, it was concentrated to dryness and redissolved with 10 ml of DMF. The centrifugally filtered solution was subjected to HPLC. Note that the copolymer polyester was a chip, and the stepped molded plate obtained in 7) below was used as a sample.
Apparatus: L-7000 (manufactured by Hitachi, Ltd.)
Column: μ-Bondsphere C18 5μ 100Å 3.9 mm × 15 cm (manufactured by waters)
Calibration curve: A cyclic dimer composed of terephthalic acid and neopentyl glycol isolated separately was used.

4) Content of cyclic trimer of terephthalic acid and ethylene glycol in copolymer polyester (molded product) (CT content)
300 mg of the sample is dissolved in 3 ml of a hexafluoroisopropanol / chloroform mixed solution (volume ratio = 2/3), and further diluted with 30 cc of chloroform. The polymer is precipitated by adding 15 cc of methanol to this, and then filtered. The filtrate was evaporated to dryness, adjusted to a constant volume with 10 cc of dimethylformamide, and the cyclic trimer was quantified by high performance liquid chromatography. Note that the copolymer polyester was a chip, and the stepped molded plate obtained in 7) below was used as a sample.

5) Composition ratio of copolymer polyester About 5 mg of copolymer polyester sample is dissolved in 0.7 ml of a mixed solution of deuterated chloroform and trifluoroacetic acid (volume ratio 9/1) and ¹ H-NMR (manufactured by varian, UNITY 50) is used. And asked.

6) Color tone (color b)
After the copolymer polyester pellets were vacuum-dried at 50 ° C. for 72 hours, after confirming that the moisture content was 250 ppm or less, the pellets were supplied to a hopper of an injection molding machine adjusted to a cylinder temperature of 230-270-270 ° C. Using a mold whose surface temperature is adjusted to 20 ° C, a flat plate of 100 x 100 x 4 mm with a film gate with a thickness of 1 mm and a land length of 1 mm under conditions of an injection time of 15 seconds and a cooling time of 30 seconds Was molded as an evaluation sample. The flat plate having a thickness of 4 mm was measured for the central portion of the flat plate using a color difference meter (TC1500MC-88 manufactured by Tokyo Denshoku Industries Co., Ltd.) and a C light source.

7) Haze value Using an injection molding machine (M-150C-DM, manufactured by Meiki Seisakusho), the copolymerized polyester is melted at 280 ° C, and a stepped molded plate having a mold temperature of 10 ° C and a thickness of 2 to 11 mm. Then, the haze value (%) of a 5 mm thick part was measured with a haze meter (manufactured by Nippon Denshoku Co., Ltd., Model NDH2000).

8) Molding test The dried copolymer polyester sample was put into an extruder equipped with a sheet die, and a sheet having a thickness of about 0.5 mm was continuously molded for 2 days. According to the following criteria, the state of dirt adhesion at the die outlet and the state of the sheet surface were evaluated with the naked eye.
(Evaluation criteria)
◎: Dirt exit dirt is hardly adhered and sheet surface condition is good. ○: Dice exit dirt is slightly adhered, but sheet surface condition is good. ×: Dust exit dirt adheres very severely, and there are many deposits on the sheet surface

9) DSC measurement of copolyester A sample left for 120 minutes at 120 ° C in a Yamato DP63 dryer was raised from -100 ° C to 300 ° C at 20 ° C / min using a differential scanning calorimeter (DSC). Check whether it shows a melting peak in the two temperature rising processes where the temperature is lowered to 50 ° C./min to −100 ° C. and then raised from −100 ° C. to 300 ° C. at 20 ° C./min. In each of the two temperature rising processes, a sample that does not show a melting peak is indicated by “◯”, and a sample that indicates a melting peak is indicated by “X”.
10) Sensory test The copolyester sample was dried with a vacuum dryer, and a preform was molded with a M-150C-DM injection molding machine manufactured by Meiki Seisakusho. 10 g of the mouth of this preform was cut out, extracted with 200 cc of distilled water at 80 ° C. for 1 hour, cooled to room temperature, allowed to stand at room temperature for 1 month, and tested for flavor and odor after opening. Distilled water was used as a blank for comparison. The sensory test was carried out by 10 panelists according to the following criteria.
(Evaluation criteria)
○: Feeling no taste or odor, or slightly feeling the difference from the blank △: Feeling the difference from the blank ×: Clearly feel the difference from the blank

11) Oligomer carboxyl end group concentration The oligomer was pulverized by a handy mill (pulverizer) without exhibiting drying. A sample of 1.00 g was precisely weighed and 20 ml of pyridine was added. Several grains of zeolite were added and dissolved by boiling for 15 minutes. Immediately after boiling and refluxing, 10 ml of pure water was added and allowed to cool to room temperature. Titration with N / 10-NaOH was performed using phenolphthalein as an indicator. The same operation was performed on a blank without a sample. When the oligomer did not dissolve in pyridine, the reaction was carried out in benzyl alcohol. AVo (eq / ton) is calculated according to the following equation.
AVo = (A−B) × 0.1 × f × 1000 / W
(A = drop constant (ml), B = blank drop constant (ml), f = factor N / 10-NaOH, W = weight of sample (g))
12) Oligomer hydroxyl end group concentration The oligomer was pulverized with a handy mill (pulverizer) without drying. 0.5 g of the sample was precisely weighed and added to a mixed solution of 1.02 g of acetic anhydride and 10 ml of pyridine, and reacted at 95 ° C. for 1.5 hours. Distilled water (10 ml) was added to the reaction product and allowed to cool at room temperature. Subsequently, it was titrated with an N / 10 sodium hydroxide solution (solution: water / methanol = 5/95 (volume ratio)) using phenolphthalein as an indicator. In addition, the oligomer hydroxyl value was calculated | required from following Formula.
OHV (eq / ton) = ((BA) × f) / (Wg × 10 ³ ) × 10 ⁶
(A = drop constant (ml), B = blank drop constant (ml), f = factor N / 10-NaOH, W = weight of sample (g))

Example 1
In a first esterification reaction vessel in which a reactant remains in advance, 100 parts by mass of high-purity terephthalic acid (TPA) as a dicarboxylic acid component, 53 parts by mass of ethylene glycol (EG) as a glycol component, and neopentyl glycol (NPG) ) And 31 parts by mass of slurry, and a slurry prepared by adjusting the molar ratio of all glycol components to dicarboxylic acid components (G / A) to 2.2 was continuously supplied. Furthermore, the ethylene glycol solution of antimony trioxide was continuously supplied to the first esterification reactor so that the antimony trioxide was 200 ppm with respect to the produced copolymerized polyester. Subsequently, the esterification reaction was performed under stirring under the conditions of a can internal pressure of 0.05 MPa and a temperature of 250 ° C. so that the average residence time was 3 hours. This reaction product was transferred to a second esterification reaction can, and an esterification reaction was carried out under stirring at a pressure in the can of 0.05 MPa and an average residence time of 1 hour under the condition of 260 ° C. Subsequently, this esterification reaction product was transferred to a third esterification reaction can, and an esterification reaction was performed under stirring at a pressure in the can of 0.05 MPa and 260 ° C.

  An amount corresponding to 20% of the amount of EG added before the esterification reaction is added to the resulting oligomer and allowed to react for about 15 minutes or more, and then the phosphorus content is 50 ppm, cobalt based on the resulting copolymerized polyester. The EG solution of trimethyl phosphate and the EG solution of cobalt acetate tetrahydrate were continuously supplied to the third esterification reactor through separate supply ports so that the content was 5 ppm.

  The esterification reaction product was continuously supplied to the first polycondensation reaction vessel, and stirred for 1 hour at 265 ° C. and 35 hPa. Further, the polycondensation reaction was carried out at 280 ° C. and 0.5 to 1.5 hPa for 1 hour with stirring in the final polycondensation reaction vessel. After the polycondensation reaction, it was passed through a polymer filter, and the molten copolymerized polyester was extracted in the form of a strand from the die nozzle, cooled with water in a cooling bath, and then cut into chips. The number average molecular weight was 31,000. This copolymerized polyester was put into an infrared radiation device and heat-treated.

  The evaluation results are shown in Table 1. The copolymer polyester obtained in this example was evaluated by sheet molding by the method of 8), but the moldability was good.

(Example 2)
As a catalyst, an esterification reactor having a volume of 10 L having a stirrer and a distillation condenser was charged with 2414 parts by mass of terephthalic acid (TPA), 1497 parts by mass of ethylene glycol (EG), and 515 parts by mass of neopentyl glycol (NPG). An ethylene glycol solution of antimony trioxide was added so as to contain 180 ppm of antimony metal with respect to the resulting copolymerized polyester.

  Thereafter, the temperature in the reaction system was gradually raised until it finally reached 240 ° C., and the esterification reaction was performed at a pressure of 0.25 MPa for 180 minutes. After confirming that distillate water from the reaction system stops, the inside of the reaction system is returned to normal pressure, and an amount corresponding to 10% of the amount of EG added before transesterification is added to the produced oligomer. For about 15 minutes, and then form an ethylene glycol solution of trimethyl phosphate in the resulting copolyester such that cobalt metal is contained at 5 ppm relative to the copolyester. The residual phosphorus atom was added so as to contain 50 ppm.

  The obtained oligomer was transferred to a polycondensation reaction tank, and the pressure was reduced while gradually raising the temperature so that the final temperature was 280 ° C. and the pressure was 0.2 hPa. The reaction was continued until the torque value of the stirring blade corresponding to the intrinsic viscosity reached a desired value, and the polycondensation reaction was completed. The obtained melt-copolymerized polyester resin was extracted in the form of a strand from the outlet at the bottom of the polycondensation tank, cooled in a water tank, and then cut into chips. The number average molecular weight was 30,000. Heat treatment was performed in the same manner as in Example 1.

  The results are shown in Table 1. The copolymer polyester obtained in this example was evaluated by sheet molding by the method of 8), but the moldability was good.

(Examples 3 to 5)
A copolyester was obtained by reacting in the same manner as in Example 1 except that the amounts of EG and NPG were changed. Further, heat treatment was performed in the same manner as in Example 1. The evaluation results are shown in Table 1. The copolymer polyester obtained in this example was evaluated by sheet molding by the method of 8), but the moldability was good.

(Example 6)
A copolyester was obtained by reacting in the same manner as in Example 1 except that the contents of EG and NPG were adjusted to those of Example 3 and heat treatment with an infrared radiation device after polymerization was not performed. The evaluation results are shown in Table 1. The copolymer polyester obtained in this example was evaluated by sheet molding by the method of 8), but the moldability was slightly inferior to that of Example 3.

(Example 7)
The contents of EG and NPG were adjusted to those in Example 5, and the reaction was carried out in the same manner as in Example 1 except that the amount of EG was added to 25% of the amount added before the esterification reaction. Thus, a copolyester was obtained. The evaluation results are shown in Table 1. The copolyester obtained in this example was subjected to a sensory test evaluation by the method of 9), which was superior to Example 5.

(Comparative Example 1)
A copolyester was obtained by reacting in the same manner as in Example 1 except that the amounts of EG and NPG were changed. Further, heat treatment was performed in the same manner as in Example 1. The evaluation results are shown in Table 1. The copolymerized polyester obtained in this comparative example was not amorphous, and thus did not have transparency enough to be suitably used as a thick molded article.

(Comparative Example 2)
A copolyester was obtained by reacting in the same manner as in Example 1 except that the amounts of EG and NPG were changed. Further, heat treatment was performed in the same manner as in Example 1. The evaluation results are shown in Table 1. The copolymer polyester obtained in this comparative example was evaluated by sheet molding by the method of 8), but there was a problem in moldability.

(Comparative Example 3)
A copolyester was obtained by reacting in the same manner as in Example 1 except that no EG was added after the transesterification reaction and no heat treatment was performed by the infrared radiation device after polymerization. The evaluation results are shown in Table 1. The copolymer polyester obtained in this comparative example was evaluated by sheet molding by the method of 8), but there was a problem in moldability.

  The copolymerized polyester of the present invention is excellent in transparency, color tone and moldability, and is less likely to cause dirt on the molding die and foreign matter adhesion to the molded body. It is possible to contribute to the industry.

Claims (7)

  Molding a copolyester with terephthalic acid as the main dicarboxylic acid component, ethylene glycol and neopentyl glycol as the main glycol components, and a neopentyl glycol content of more than 25 mol% and less than 80 mol% of all glycol components A copolymerized polyester molded body, wherein the content of a free cyclic dimer composed of terephthalic acid and neopentyl glycol is 17000 ppm or less.   The copolymer polyester molded article according to claim 1, wherein the content of the cyclic trimer composed of terephthalic acid and ethylene glycol is 5500 ppm or less.   The copolymerized polyester molded article according to claim 1 or 2, wherein the content of free monohydroxyneopentyl terephthalate composed of terephthalic acid and neopentyl glycol is 50 ppm or less.   The copolymerized polyester molded article according to any one of claims 1 to 3, wherein the content of diethylene glycol with respect to all glycol components is 1.0 to 5.0 mol%.   5. The copolyester molded article according to any one of claims 1 to 4, wherein the color b value is -5.0 to 5.0.   The molded body made of a copolyester according to any one of claims 1 to 5, wherein a haze value at a thickness of 5 mm is 15% or less.   The copolyester molded product is a film or a sheet, The copolyester molded product according to any one of claims 1 to 6.