(19)
(11)EP 3 369 776 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
29.04.2020 Bulletin 2020/18

(21)Application number: 16859615.3

(22)Date of filing:  17.10.2016
(51)International Patent Classification (IPC): 
C08L 67/02(2006.01)
C08J 5/18(2006.01)
C08G 63/83(2006.01)
C08G 63/87(2006.01)
C08G 63/183(2006.01)
C08K 3/08(2006.01)
C08G 63/86(2006.01)
(86)International application number:
PCT/JP2016/080660
(87)International publication number:
WO 2017/073385 (04.05.2017 Gazette  2017/18)

(54)

POLYETHYLENE TEREPHTHALATE RESIN COMPOSITION AND FILM FORMED FROM SAME

POLYETHYLENTEREPHTHALATHARZZUSAMMENSETZUNG UND DARAUS HERGESTELLTER FILM

COMPOSITION DE RÉSINE DE TÉRÉPHTALATE DE POLYÉTHYLÈNE ET FILM FORMÉ À PARTIR DE CELLE-CI


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 29.10.2015 JP 2015213051
26.11.2015 JP 2015230429

(43)Date of publication of application:
05.09.2018 Bulletin 2018/36

(73)Proprietor: Toray Industries, Inc.
Tokyo 103-8666 (JP)

(72)Inventors:
  • FUJIWARA, Susumu
    Mishima-shi Shizuoka 411-8652 (JP)
  • SAI, Hiromitsu
    Mishima-shi Shizuoka 411-8652 (JP)
  • YOSHIMURA, Hitoshi
    Mishima-shi Shizuoka 411-8652 (JP)
  • KAMIGAITO, Yoshiki
    Mishima-shi Shizuoka 411-8652 (JP)

(74)Representative: Mewburn Ellis LLP 
Aurora Building Counterslip
Bristol BS1 6BX
Bristol BS1 6BX (GB)


(56)References cited: : 
EP-A1- 2 698 401
WO-A1-2008/029842
JP-A- H1 121 337
JP-A- 2014 118 574
EP-A1- 2 899 229
WO-A1-2010/103945
JP-A- S61 174 223
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    TECHNICAL FIELD



    [0001] The present invention relates to polyethylene terephthalate resin compositions and films formed from the same.

    BACKGROUND ART



    [0002] Polyethylene terephthalate resin compositions have excellent mechanical characteristics, heat characteristics, chemical resistance, electrical characteristics, and formability, are widely used for various applications, and are demanded in increasing quantity.
    Along with the expansion of the applications and demand, however, the characteristics and productivity that the polyesters need are more and more stringent in each application field.

    [0003] Whenever processed into a form, a polyethylene terephthalate resin composition is melted and extruded at a temperature of 250°C to 300°C, which is equal to or greater than the melting point of the polyester, but this temperature condition will also cause the polyester to undergo thermal decomposition and then oxidative decomposition if contaminated with oxygen. There is a problem in that this results in generating gelatinous foreign matter and causing defects on the surface of the film.

    [0004] Patent Document 1 describes polyethylene terephthalate resin compositions in which a ratio of the amount of alkaline earth metal and alkali metal to the amount of a phosphorus compound, M/P, is within a specific range. Patent Documents 2 and 3 describe polyesters and polyester films for which manganese acetate is used.

    [0005] A polyethylene terephthalate resin composition described in Patent Document 1 is regulated at a high M/P to thereby have a gelation ratio reduced when left to stand under the conditions of a 20% oxygen concentration and 300°C for 5 hours, but a high M/P will accelerate thermal decomposition and fails to afford sufficient heat resistance to the composition. In addition, magnesium acetate is used therefore and thus the gelation ratio is no more reduced in a further long time.

    [0006] Patent Document 2 describes Examples in which manganese acetate is used, and a sufficient gelation suppression effect is not obtained because the M/P is high.

    [0007] Patent Document 3 also describes Examples in which manganese acetate is used, but a large amount of antimony is used therefore, which poses a concern about solution haze and defects caused by antimony. In addition, the gelation ratio is not expected to be improved sufficiently.
    Patent Document 4 discloses a polyethylene terephthalate composition which contains an alkali metal phosphate compound in an amount greater than or equal to 1.0 mol/ton and less than or equal to 3.0 mol/ ton in terms of an alkali metal element, and contains a phosphorus element in an amount greater than or equal to 1.5 mol/ton and less than or equal to 5.0 mol/ton, wherein a white extraneous matter containing a phosphorus element and an alkali metal element and being greater than or equal to 50 µm is in an amount less than or equal to 1 ppm in volume fraction, an inherent viscosity is greater than or equal to 0.65 dl/g and less than 0.90 dl/g, a content of a cyclic trimer is less than or equal to 0.6 wt%, an amount of carboxylic acid terminal groups is less than or equal to 15 eq/ton, and an increase in the amount of the carboxylic acid terminal groups (ΔCOOH) when a moist heat treatment (in a 155°C and 100% RH atmosphere, for 4 hours) is performed is less than or equal to 30 eq/ton. In the production method for the polyethylene terephthalate composition an addition is performed such that a molar ratio (M/P) between a sum (M) of a total molar amount of a manganese element, a calcium element and a magnesium element added as promoters in the polycondensation reaction and 0.5 molar time a molar amount of the alkali metal element and the molar amount (P) of the phosphorus element is 1.00 to 1.20.

    CITATION LIST


    Patent Documents



    [0008] 

    Patent Document 1: JP 2003-96280 A

    Patent Document 2: JP 11-21337 A

    Patent Document 3: JP 2014-22027 A

    Patent Document 4: EP 2899229 A1


    SUMMARY OF INVENTION


    Technical Problem



    [0009] An object of the present invention is to solve the above-mentioned conventional problems, thereby providing a polyethylene terephthalate resin composition which generates less gelled matter in a melt-extruding process, which causes a smaller change in color tone and a smaller amount of oligomer generation during heating, and which has excellent transparency (solution haze) and film formability.

    Solution to Problem



    [0010] In other words, the present invention has the following characteristics in order to solve the above-mentioned problems.
    1. (1) A polyethylene terephthalate resin composition which has a manganese element content of 30 to 60 ppm, a potassium element content of 2 to 10 ppm, and an antimony element content of 70 to 150 ppm with respect to the total weight of elements of the polyethylene terephthalate resin composition, in which a molar ratio of metal elements to phosphorus element, (M/P = (M1 + M2 / 2) / P), satisfies the below-mentioned formula, and in which the composition has a gelation ratio of 5% by weight or less.

      (In the formula, M1 represents the content (mol/t) of a bivalent metal element selected from the group consisting of Mg, Mn, and Ca;

      M2 represents the content (mol/t) of a monovalent metal element selected from the group consisting of Li, Na, and K; and

      P represents the content (mol/t) of phosphorus element.)

    2. (2) The polyethylene terephthalate resin composition according to (1), in which the total content of metal elements: Mg, Ca, and Li is less than 0.1 ppm.
    3. (3) The polyethylene terephthalate resin composition according to (1) or (2), in which the composition generates linear oligomer in an amount of 210 µg/g or less when melted at 290°C for 20 minutes.
    4. (4) The polyethylene terephthalate resin composition according to any of (1) to (3), in which the composition comprises internal particles whose largest particle diameter is 0.3 µm or less, and has 1.0% or less solution haze.
    5. (5) The polyethylene terephthalate resin composition according to any of (1) to (4), in which the content of phosphorus element is 15 ppm to 45 ppm.
    6. (6) The polyethylene terephthalate resin composition according to any of (1) to (5), having a COOH terminal group content of 25 to 40 eq/t, in which the COOH terminal group amount increased between before and after heat-moisture treatment is 80 eq/t or less.
    7. (7) The polyethylene terephthalate resin composition according to (1), having an intrinsic viscosity of 0.60 to 0.70, a COOH terminal group content of 5 to 20 eq/t, and 0.40% by weight or less of cyclic trimeric oligomer.
    8. (8) A polyester film formed from the polyethylene terephthalate resin composition according to any of (1) to (7).

    Effects of Invention



    [0011] The polyethylene terephthalate resin composition according to the present invention generates less foreign matter into which the polyethylene terephthalate resin composition has gelled in a melt-extruding process, causes a smaller change in color tone and a smaller amount of oligomer generation during heating, and has good transparency (solution haze) and good film formability (electrostatic casting properties).
    In addition, the composition generates a smaller amount of oligomer when melted, and thus can provide a film having less process contamination and less film defects in film formability.

    DESCRIPTION OF EMBODIMENTS



    [0012] Below, the present invention will be described in detail.
    Examples of components of the polyethylene terephthalate resin composition in the present invention include: a terephthalic acid or naphthalenedicarboxylic acid component as a dicarboxylic acid component; and an alkylene glycol component such as ethylene glycol or propylene glycol as a diol component.
    Further, in the polyethylene terephthalate resin composition according to the present invention, up to 20 mol% of the carboxylic acid components can contain, as a copolymerization component, one or more dicarboxylic acids other than a terephthalic acid component and a naphthalenedicarboxylic acid component, and similarly up to 20 mol% of the glycol components can contain, as a copolymerization component, one or more glycol components other than an ethylene glycol component or an alkylene glycol component. Further, the composition may contain a trifunctional or multifunctional compound as a copolymerization component, to the extent that the composition does not lose thermoplasticity.

    [0013] The polyester according to the present invention needs to contain 70 to 150 ppm antimony element. It is preferably 90 to 130 ppm, more preferably 100 to 120 ppm. If the content is more than 150 ppm, antimony metal is deposited, thereby increasing solution haze in the polyethylene terephthalate resin composition, which will cause the film to lose transparency. On the other hand, a content of less than 70 ppm increases a color tone b value and increases a gelation ratio.

    [0014] The polyethylene terephthalate resin composition according to the present invention needs to contain 30 to 60 ppm manganese element. It is preferably 35 to 50 ppm, more preferably 40 to 50 ppm. A content of more than 60 ppm increases a color tone b value, increases a gelation ratio, and increases the amount of linear oligomer generated in heat-melting. On the other hand, a content of less than 30 ppm results in degrading film formability in the view point of electrostatic casting.

    [0015] The polyethylene terephthalate resin composition according to the present invention needs to contain 2 to 10 ppm potassium element. Potassium element has a large electropositivity and thus lowers the melt specific resistance of the polyethylene terephthalate resin composition, thereby enhancing electrostatic charging properties in film-forming and also affording good transparency (solution haze) to the obtained polymer. It is preferably 3 to 7 ppm, more preferably 4 to 6 ppm. A content of more than 10 ppm results in increasing a haze and increasing a gelation ratio. On the other hand, a content of less than 2 ppm results in degrading film formability in the view point of electrostatic casting.

    [0016] The polyethylene terephthalate resin composition according to the present invention needs to satisfy the following formula.

    More preferably, (M1 + M2 / 2) / P is 0.7 or more but 1.2 or less, further preferably 0.8 or more but 1.1 or less. If (M1 + M2 / 2) / P is less than 0.6 ppm, the film formability are degraded in the view point of electrostatic casting, and more than 1.3 increases a gelation ratio and increases a color tone b value.

    [0017] The polyethylene terephthalate resin composition according to the present invention contains Mg, Ca, and Li in an amount of preferably less than 0.1 ppm for the purposes of suppressing a gelation ratio and reducing a color tone b value. A content of less than 0.1 ppm enables the maintenance of a low gelation ratio and further can reduce the deterioration of color tone and the generation of linear oligomer in heat-melting.

    [0018] The gelation ratio is 5% by weight or less, preferably 3% by weight or less. The gelation ratio of more than 5% by weight causes defects on the film, posing a problem. In addition, the gel clogs filters in a film-forming process and increases filtration pressure, thereby posing a problem by increasing the frequency of exchange and cleaning of filters and leading to production capacity reduction and cost increase.

    [0019] Examples of oligomers in the present invention include, but are not particularly limited to: linear oligomers such as terephthalic acid, mono-2-hydroxyethyl terephthalate, and bis-2-hydroxyethyl terephthalate; and cyclic trimeric oligomers.

    [0020] The amount of linear oligomer generated when the polyethylene terephthalate resin composition according to the present invention is heated at 290°C for 20 minutes is preferably 210 µg/g or less, more preferably 205 µg/g or less, further preferably 200µg/g or less. By controlling the generated amount of linear oligomer to 210 µg/g or less, process contamination during heat-processing in a film-forming process can be prevented and, in particular, film defects during film-forming can be suppressed.

    [0021] The polyethylene terephthalate resin composition according to the present invention contains cyclic trimeric oligomer in an amount of preferably 0.50 wt% or less, more preferably 0.40 wt% or less, further preferably 0.35 wt% or less. A low content of cyclic trimeric oligomer makes it difficult for the cyclic trimeric oligomer to be deposited on the film surface during film-forming or in a film-processing process. The content of cyclic trimeric oligomer is not limited to a particular lower limit, but is preferably 0.10 wt% or more in that a higher content prolongs the time required for solid phase polymerization which reduces cyclic trimeric oligomer, thereby causing a large increase in intrinsic viscosity and a tendency to increase load in melt-extruding.

    [0022] In the present invention, the largest particle diameter of internal particles is preferably 0.3 µm or less, more preferably 0.25 µm or less, further preferably 0.22 µm or less. By containing internal particles whose largest particle diameter is 0.3 µm or less, the polyester resin can maintain transparency (solution haze).

    [0023] The polyethylene terephthalate resin composition according to the present invention has a solution haze of preferably 1.0 % or less, more preferably 0.9 wt% or less, further preferably 0.8 wt% or less. A solution haze of 1.0% or less enables the resin to maintain transparency, which makes the composition preferred as a film for process applications, particularly a film for mold release applications.

    [0024] In the present invention, the content of phosphorus element is preferably 15 to 45 ppm, more preferably 20 to 40 ppm, further preferably 25 to 35 ppm. Containing a phosphorus compound in this range can afford a polyethylene terephthalate resin composition having low solution haze and low melt specific resistance.

    [0025] The polyethylene terephthalate resin composition according to the present invention preferably has a carboxyl (COOH) terminal group content of 25 to 40 eq/t, more preferably 28 to 37 eq/t, further preferably 30 to 35 eq/t. The COOH terminal group content in the above-mentioned ranges can suppress decomposition reaction and suppress blemishes and the like in film-forming processing. In addition, to obtain good hydrolysis resistance, a lower COOH terminal group content is more advantageous, and it is preferably 5 to 20 eq/t, more preferably 5 to 15 eq/t, further preferably 5 to 10 eq/t. In this case, the lower limit of the COOH terminal group content is, the better the hydrolysis resistance is, and the lower limit is considered to be about 5eq/ton in conventional polycondensation reactions and solid phase polymerization reactions. To achieve a COOH terminal group content of 0 eq/ton, an excessive amount of a terminal blocking agent is required.

    [0026] An increase in the amount of COOH terminal groups (ΔCOOH) which is caused when the polyethylene terephthalate resin composition according to the present invention is treated under water vapor at 155°C for 4 hours is preferably 80 eq/t or less, more preferably 75 eq/t or less, further preferably 70 eq/t or less. An increase within this range can suppress decomposition reaction during melting and prevent the generated oligomer from causing process contamination and film defects.

    [0027] Below, methods of producing the polyethylene terephthalate resin composition according to the present invention will be described in detail.
    As methods of producing polyester compositions, those of a batch type and a continuous type are well-known, and continuous polymerization, which involves less heat history, is preferable in order to achieve a lower gelation ratio.
    Further, as reaction processes in production methods of a batch type and a continuous type, there are a esterification method using terephthalic acid as a raw material and a DMT method using dimethyl terephthalate as a raw material, and the esterification method is preferable in the view point of cost and reaction efficiency.

    [0028] In producing the polyethylene terephthalate resin composition according to the present invention in continuous polymerization facilities, the number of reaction vessels is not limited to a particular one, but, for example, in the case of production with a esterification method, one or more vessels for esterification reaction and two or more vessels for polycondensation reaction are preferably used in the view point of reaction efficiency, and two vessels as esterification vessels and three vessels for polycondensation reaction are further preferably used.

    [0029] Examples of antimony compounds used as polymerization catalysts include antimony trioxide, antimony pentoxide, antimony acetate, antimony salts of aliphatic carboxylic acids, and the like, and among these, antimony trioxide is preferably used in the view point of polycondensation reactivity, the color tone of the obtained polymer, and inexpensive availability.

    [0030]  Examples of methods of adding antimony include using it in powder form, in ethylene glycol slurry, in ethylene glycol solution, and the like, and it is preferably added in ethylene glycol solution because of the capability to prevent antimony from aggregating and thereby being coarsened and to afford good transparency (solution haze) as a result.
    Examples of phosphorus compounds used in the present invention include phosphoric acid, phosphorous acid, phosphonic acid, ester compounds thereof, and the like, and phosphoric acid is preferably used because of the capability to reduce gelation ratio.
    Methods of adding a phosphorus compound is not limited to a particular one. The compound can be added with various methods using an aqueous solution, an ethylene glycol solution, and the like.

    [0031] In producing the polyethylene terephthalate resin composition in the present invention, a potassium compound is preferably added at two or more positions in a reaction process, considering the transparency of the composition. The position of addition is not limited to a particular one, but, for example, when the number of esterification reaction vessels is two and that of polycondensation reaction vessels is three in a esterification method, the potassium compound is preferably added to the two esterification reaction vessels. Adding the potassium compound to two esterification reaction vessels can suppress a rapid decrease in temperature in the system, and the addition can be carried out without reducing the dispersibility of the potassium compound, whereby the largest particle size of the internal particles produced during polycondensation can be made smaller to thus enable the reduction of solution haze.

    [0032] Examples of potassium compounds include potassium hydroxide, potassium acetate, and the like, and potassium hydroxide is preferable in the view point of color tone and solution haze.

    [0033] Examples of manganese compounds added in the present invention include manganese acetate, manganese oxide, and the like, and manganese acetate is preferably used in the view point of color tone, solution haze, and suppression of gelation ratio.

    [0034] Examples of forms of addition of a manganese compound include using it in powder form, adding it in ethylene glycol slurry or ethylene glycol solution, adding it in an aqueous solution, and the like, and adding it in a solution mixture of water and ethylene glycol is preferable in the view point of color tone, solution haze, and reaction efficiency. Specifically, the manganese compound is preferably added in a solution having a water concentration of 10% or less and an ethylene glycol concentration of 90% or more in the view point of color tone.

    [0035] The polyethylene terephthalate resin composition according to the present invention has manganese element and antimony element at a ratio (Mn/Sb) that preferably satisfies the following formula.

    (wherein Mn represents a manganese element content, Sb represents an antimony element content, and Mn and Sb each indicate the total number of moles per 106 g of the polyethylene terephthalate resin composition.)
    With regard to the intrinsic viscosity of the polyethylene terephthalate resin composition, the endpoint of melt polymerization can be determined on the basis of the stirring torque of the polymer, and a torque for determining the endpoint can be set on a melt polymerization device so that the composition can obtain an intrinsic viscosity of interest.
    Then, using a method in which the obtained melt polyethylene terephthalate resin composition is discharged in strand form through a die, cooled, and pelletized with a cutter, a liquid phase polyethylene terephthalate resin composition can be produced.

    [0036] In addition, the obtained liquid phase polyethylene terephthalate resin composition is preferably subjected to solid phase polymerization so as to have a further lower amount of cyclic trimeric oligomer and a further lower amount of COOH terminal groups. Examples of solid phase polymerization methods include the below-mentioned.

    [0037] It is preferable that the polyethylene terephthalate resin composition obtained through liquid phase polymerization be preliminarily crystallized before being subjected to solid phase polymerization. For the preliminary crystallization of the polyethylene terephthalate resin composition, a method in which a mechanical impact is made on the composition to thereby subject it to shearing treatment, a method in which the composition is heated under a hot air stream, and the like can be adopted.

    [0038] The preliminarily crystallized polyethylene terephthalate resin composition is subsequently subjected to solid phase polymerization. The polyethylene terephthalate resin composition is fed into a solid phase polymerization device, through which an inert gas flow is passed, and the composition is subjected to solid phase polymerization at a predetermined temperature. The polyethylene terephthalate resin composition of which the solid phase polymerization has completed is cooled and then taken out of the device.

    [0039]  The intrinsic viscosity of the polyethylene terephthalate resin composition to be subjected to solid phase polymerization is preferably in a range of 0.40 to 0.52, more preferably in a range of 0.45 to 0.50. An intrinsic viscosity of 0.40 or more is preferable because it reduces the amount of cyclic trimeric oligomer at a predetermined temperature or in a predetermined time, thereby enhancing productivity. An intrinsic viscosity of 0.52 or less is preferable because it facilitates crystallization in a short time and reduces the amount of cyclic trimeric oligomer before the intrinsic viscosity of the polyethylene terephthalate resin composition is raised, and the intrinsic viscosity of 0.52 or less is preferable also because it causes less heat history and thus suppresses the coloring of the polyethylene terephthalate resin composition.

    [0040] Examples of inert gases include: rare gases such as helium, neon, argon, and the like; nitrogen gas; carbon dioxide gas; and the like. Among these, nitrogen is preferable because it is readily available. In addition, the dew point of an inert gas is preferably -5°C or higher. An inert gas having a dew point of -5°C or more is preferable because it can suppress the reduction of carboxyl terminal groups of the polyethylene terephthalate resin composition in solid phase polymerization. The dew point of an inert gas is not limited to a particular upper limit, and is preferably 20°C or less in order to facilitate solid phase polymerization smoothly.

    [0041] Temperatures at which solid phase polymerization is carried out are preferably in a range of 200 to 220°C, more preferably in a range of 210 to 215°C. A temperature of 200°C or more is preferable because it facilitates a decrease in the amount of cyclic trimeric oligomer smoothly. A temperature of 220°C or less is preferable in order to suppress the coloring that is caused to the polyethylene terephthalate resin composition through heat deterioration.

    [0042] A solid phase polymerization device used in the present invention is not limited to a particular model, but, for example, a stationary type dryer, a fluid type dryer, a dryer having a stirring blade, a continuous type tower dryer, and the like can be used, and a continuous type tower dryer is preferable in the view point of productivity.

    [0043] The polyethylene terephthalate resin composition according to the present invention can be formed into a polyester film in the following manner.
    For example, the polyethylene terephthalate resin composition is dried in vacuo, supplied into an extruder, dissolved at 260 to 300°C, extruded in sheet form through a T-die, wound with an electrostatic casting method on a mirror casting drum whose surface temperature is 10 to 60°C, and solidified by cooling, to produce an unstretched polyester film.

    [0044] The unstretched film is stretched 2.5- to 5-fold in the longitudinal direction between rolls heated to 70 to 120°C. At least one side of this film may be coated with a coating solution and the like by carrying out corona discharge treatment. Subsequently, the film is stretched 2.5- to 5-fold in the transverse direction in a hot air zone continuously heated to 70 to 150°C, then introduced into a heat treatment zone where temperature is kept at 200 to 240°C, heat-treated for 5 to 40 seconds, and passed through a cool zone which is kept at 100 to 200°C, to complete crystalline orientation. In addition, the film may be relaxed by 3 to 12% in the transverse direction or the longitudinal direction, if necessary, during the above-mentioned heat treatment.
    The polyethylene terephthalate resin composition obtained in the present invention is preferred as a film for industrial material applications, especially for mold release applications, because the composition has excellent transparency, heat resistance, and wet heat resistance and forms a smaller amount of gel that originates film defects, while being capable of reducing the amount of linear oligomer generated during melt-processing. An example of composition considered to be the gel mentioned could be PET molecules which are cross-linked.

    EXAMPLES



    [0045] Below, the present invention will be specifically described with reference to Examples. Here, the measurement methods in Examples are as below-mentioned.

    (1) Gelation Ratio



    [0046] The polyethylene terephthalate resin composition was pulverized using a cryogenic mill (made by Sprex CertiPerp, Inc.), and weighed out at 0.5 g into a stainless steel beaker. The resulting sample was dried in vacuo at 50°C for 2 hours using a vacuum dryer; air and nitrogen were made into a gas mixture having an oxygen concentration of 1%; the container containing the sample was sufficiently purged with the gas mixture having an oxygen concentration of 1% passed through piping; and the container was then immersed in an oil bath at 300°C and heated under a stream of 1% concentration oxygen/nitrogen (at a flow rate of 0.5 L/minute) for 6 hours. This sample was dissolved in 20 ml of orthochlorophenol (hereinafter referred to as OCP) at 160°C for one hour and left to stand. This solution was filtered using a glass filter (3GP40, made by Sibata Scientific Technology Ltd.), and the glass filter was cleaned with dichloromethane. The glass filter was dried at 130°C for two hours, and the weight of the OCP-insoluble matter (gel) remaining on the filter was calculated from the increase in the weight of the filter between before and after filtration, whereby the weight percentage of the OCP-insoluble matter with respect to the polyester weight (0.5 g) was determined and regarded as a gelation ratio (% by weight). With the obtained polyester, a gelation ratio of 5.0% by weight or less was rated good and 3.0% by weight or less best. More than 5.0% by weight was rated unacceptable in terms of film defects and film-forming process productivity.

    (2) COOH Terminal Group Content



    [0047] The esterified product and polyethylene terephthalate resin composition obtained through liquid phase polymerization were measured using the Maulice method described in the following document: M. J. Maulice, F. Huizinga "Anal. Chim. Acta" Vol. 22, p-363 (1960). In other words, 2 g of the esterified reactant or the polyethylene terephthalate resin composition was dissolved in 50 ml of o-cresol/chloroform (at a weight ratio of 7/3), the resultant solution was titrated with an N/20-sodium hydroxide methanol solution, and the COOH terminal group content was measured and expressed in terms of eq/ton of polyester. In addition, 2 g of the polyethylene terephthalate resin composition obtained through solid phase polymerization was dissolved in o-cresol, the resultant solution was titrated with an N/20-sodium hydroxide methanol solution, and the COOH terminal group content was measured and expressed in terms of eq/ton of polyester. A potentiometric titration method was used to draw a titration curve, and the inflection point thereof was used as an endpoint to determine a COOH terminal group content.

    (3) Solution Haze of Polyethylene Terephthalate Resin Composition



    [0048] The polyethylene terephthalate resin composition in an amount of 0.5 g was dissolved in 20 ml of a solvent mixture of phenol/ethane tetrachloride (at a ratio by weight of 6/4) with stirring at 100°C for 60 minutes, and cooled to room temperature; and then the solution was poured into a 20 mm glass cell, and measured using a haze computer (HGM-2DP) made by Suga Test Instruments Co., Ltd.

    (4) Largest Particle Diameter of Internal Particles



    [0049] The largest particle diameter of particles was measured using a particle diameter analyzer (LA-950, made by Horiba, Ltd.). The diameters of the internal particles as equivalent circular diameters and their frequencies (%) were measured in a range of 0.01 µm to 3000 µm, and the largest particle size value in the particle diameter distribution was taken.

    (5) Measurement of COOH Terminal Groups before and after Heat-Moisture Treatment (hereinafter may be referred to as ΔCOOH)



    [0050] Chips of the polyethylene terephthalate resin composition were treated in water vapor at 155°C for 4 hours.
    The measurement device was PRESSURE COOKER 306SIII (made by Hirayama Manufacturing Corp.).
    The increase amount of COOH terminal groups was measured in accordance with (2). The increase amount of COOH terminal groups (ΔCOOH) was evaluated with the samples before and after treatment. A ΔCOOH of 90 eq/t or less, which is considered applicable to photovoltaic cell applications, was rated acceptable.

    (6) Alkali Metal Content in Polyethylene Terephthalate Resin Composition



    [0051] The contents of Li and K were quantified with atomic absorption spectrophotometry (a Zeeman splitted spectrum type atomic absorption spectrophotometer 180-80 made by Hitachi Ltd.; flame: acetylene-air).

    (7) Phosphorus Element Content and Bivalent Metal Element Content in Polyethylene Terephthalate Resin Composition



    [0052] A fluorescent X-ray type analyzer (model number: 3270) made by Rigaku Corporation was used to measure the contents of P, Mn, Mg, Ca, and Sb with sample pellets of the polyethylene terephthalate resin composition which were molded into a cylindrical form using a melt-press machine.

    (8) Amount of Linear Oligomer Generated after Melting at 290°C for 20 Minutes (hereinafter may simply be referred to as Linear Oligomer Generation Amount)



    [0053] The polyethylene terephthalate resin composition in an amount of 0.1 g was freeze-pulverized, dried in vacuo at 160°C for 6 hours, and then encapsulated in ampoules under a N2 atmosphere. The ampoules were then heated at 290°C for 20 minutes; LC20A (made by Shimadzu Corporation) was used to measure the amounts of terephthalic acid, mono-2-hydroxyethyl terephthalate, and bis-2-hydroxyethyl terephthalate as linear oligomers; and the total amount thereof was regarded as a linear oligomer generation amount.

    (9) Intrinsic Viscosity



    [0054] The polyethylene terephthalate resin composition obtained through liquid phase polymerization was measured for solution viscosity at 25°C, using 0.1 g of the composition which was dissolved in 10 ml of o-chlorophenol at 100°C in 30 minutes. In addition, the polyethylene terephthalate resin composition obtained through solid phase polymerization was measured for solution viscosity at 25°C, using 0.1 g of the composition which was dissolved in 10 ml of o-chlorophenol at 160°C in 15 minutes.

    (10) Esterification Reaction Ratio of Esterified Reactant



    [0055] The total COOH terminal group amount A and the unreacted COOH terminal group amount B in the oligomer of the polyethylene terephthalate resin composition were determined using the below-mentioned method, and an esterification reaction ratio was calculated using the following formula.

    The total COOH terminal group amount A was measured using an automatic titrator (COM-550, made by Hiranuma Sangyo Co., Ltd.) and a 0.5 N hydrochloric acid solution to titrate the solution obtained by hydrolysing the oligomer of the polyethylene terephthalate resin composition with a potassium hydroxide aqueous solution. In addition, the unreacted COOH terminal group amount B was measured using an automatic titrator (COM-550, made by Hiranuma Sangyo Co., Ltd.) and a methanol solution of 0.1 N potassium hydroxide to titrate the polyester oligomer dissolved in N,N-dimethyl formamide.

    (11) Melt Specific Resistance



    [0056] Two copper plates were used to sandwich a spacer made of Teflon (registered trademark) therebetween to form electrodes composed of 22 cm2 copper plates spaced 9 mm therebetween. These electrodes were immersed in the polyethylene terephthalate resin composition melted at 290°C, and a resistance was calculated from the amount of current generated when a voltage of 5,000V was applied across the electrodes.

    (12) Color Tone b Value (b Value)



    [0057] The resin pellets of the polyethylene terephthalate resin composition were filled into a cylindrical powder measurement cell, and a color difference meter (SM Color Meter SM-T, made by Suga Test Instruments Co., Ltd.) was used to measure a color tone b value with a reflection method.

    (13) Cyclic Trimeric Oligomer Content



    [0058] The sample pellets or film of the polyethylene terephthalate resin composition was dissolved in o-chlorophenol, to which an internal standard was added. Further, methanol was added to the resulting mixture to deposit a polymer; the supernatant was taken from the resulting solution by means of centrifugation; and the cyclic trimeric oligomer was quantitated using a liquid chromatograph (made by Shimadzu Corporation; SYSTEM CONTROLLER Model Number: SCL-10A VP, LIQUID CHROMATOGRAPH Model Number: LC-10AD VP, UV-VIS DETECTOR Model Number: SPD-10A VP, COLUMN OVEN Model Number: CTO-10A VPLC-2010A).

    (14) Regeneration Rate of Cyclic Trimeric Oligomer



    [0059] The sample pellets of the polyethylene terephthalate resin composition were dried in vacuo at 175°C for 7.5 hours, melted by means of heating under a nitrogen atmosphere at 300°C for 30 minutes, then cooled to normal temperature, and solidified, to take a sample. The cyclic trimeric oligomer content (A) in the sample which had yet to be melted by means of heating and the cyclic trimeric oligomer content (B) in the sample which had been melted by means of heating were quantified, and the regeneration rate (C) of the cyclic trimeric oligomer was calculated from the following formula.


    (15) Film Defects during Long-Term Extrusion (also referred to as Film Defects)



    [0060] The polyethylene terephthalate chips were dried at 160°C for 5 hours, supplied into an extruder equipped with a T-die, and extruded in the shape of a casting drum through the die at 300°C with the casting drum being rotated, to obtain an unstretched film continuously. The surface of the film was observed for one hour after 10 hours elapsed and until 11 hours elapsed; and it was rated unacceptable if any stripe-like defect, none of which was observed before the 10 hours period elapsed, was newly observed on the surface in this one hour period, and it was rated acceptable if no such defect was observed.

    (16) Electrostatic Casting Properties



    [0061] A direct current voltage of 6 kV was applied across an electrode disposed above the melt-extruded film and a cooling roll; the casting rate was gradually increased; a casting rate (m/min) was determined when any irregularity was generated by voltage application; and the casting rate was evaluated in accordance with the following criteria. Grade 2 or higher is rated acceptable. Grade 1 is given for 50 m/min or more, Grade 2 for 40 m/min or more but 50 m/min or less, Grade 3 for 30 m/min or more but 40 m/min or less, and Grade 4 for less than 30 m/min.

    (17) Depositing Characteristic of Cyclic Trimeric Oligomer



    [0062] Films, 5 cm × 5 cm, were cut out and heated in a hot air dryer at 150°C for 60 minutes; the film surfaces were observed using a scanning electron microscope at 1,000×; and the number of deposits of cyclic trimeric oligomer was counted on the shot image of the surface of an arbitrarily selected film. The depositing characteristic of the cyclic trimeric oligomer was rated Good (A) for less than 5 pieces, Acceptable (B) for 5 pieces or more but less than 10 pieces, and Unacceptable (C) for 10 pieces or more, on which criteria judgements were made.

    (Example 1)



    [0063] A continuous polymerization device was used, which had a total of 5 vessels: an esterification reaction vessel composed of a first esterification reaction vessel and a second esterification reaction vessel; accompanied by a first polycondensation reaction vessel, a second polycondensation reaction vessel, and a third polycondensation reaction vessel. Reaction was carried out in the first esterification reaction vessel at a reaction temperature of 240 to 255°C to reach an esterification reaction rate of 90 to 95%, and in the second esterification vessel at a reaction temperature of 255°C to reach an esterification reaction rate of 97%; polycondensation reaction was carried out in the first polycondensation reaction vessel at a temperature of 260°C, in the second polycondensation reaction vessel at a temperature of 275°C, and in the third esterification reaction vessel at a temperature of 280°C respectively; and the reactions were allowed to progress so as to achieve an intrinsic viscosity of interest. The details will be described below.

    [0064] In the first esterification reaction vessel, slurry of terephthalic acid and ethylene glycol (at an ethylene glycol/terephthalic acid molar ratio of 1.05 to 1.30) was continuously added at a constant flow rate of 8.0 to 8.7 t/hr, and the esterification reaction was carried out at 245 to 255°C with water being distilled out until an esterification reaction rate of 90 to 95% was achieved. A potassium hydroxide solution (0.216% by weight) prepared with water and ethylene glycol mixed thereinto was split and continuously added into the first esterification reaction vessel and the second esterification reaction vessel in such a manner as to have a concentration of 0.0005% by weight (equivalent to 0.09 mol/t) with respect to the polyester resin.
    In addition, a phosphoric acid aqueous solution was continuously added to the second esterification reaction vessel in such a manner as to have a concentration of 0.014% by weight (equivalent to 1.428 mol/t) with respect to the polyethylene terephthalate resin composition.
    In the second esterification reaction vessel, the esterification reaction was carried out at 255°C with water being distilled out until an esterification reaction rate of 97% was achieved, whereby the esterification reaction was completed.

    [0065] With regard to polycondensation reaction, the polycondensation reaction was carried out in the first polycondensation reaction vessel at a temperature of 260°C and at a degree of vacuum of 10kPa; antimony trioxide was added in such a manner as to have a concentration of 0.0127% by weight (equivalent to 0.422 mol/t) with respect to the polyester resin; and manganese acetate was added in such a manner as to have a concentration of 0.021% by weight (equivalent to 0.855 mol/t) with respect to the polyethylene terephthalate resin composition.
    Polycondensation reaction was carried out in the second polycondensation reaction vessel at a temperature of 275°C and at degree of vacuum of 2.2 kPa and in the third polycondensation reaction vessel at a temperature of 280°C and at a degree of vacuum of 0.2 kPa; the resulting product was discharged at the point of time when a melt viscosity equivalent to an intrinsic viscosity of 0.65 was achieved; and the product was made into chips using a strand cutter; to obtain the polyethylene terephthalate resin composition. The obtained polyethylene terephthalate resin composition had good color tone and transparency, a low gelation ratio of 0.9% by weight, and a low ΔCOOH, which was good.
    The obtained polyethylene terephthalate resin composition was dried at 150°C for 3 hours, supplied into an extruder, melt-extruded at 285°C, and cast onto an electrostatically charged cast drum of 20°C, to obtain an unstretched sheet. This unstretched sheet was stretched 3.1-fold in the longitudinal direction using a stretching roll heated to 90°C, then stretched 3.7-fold in the transverse direction at 120°C using a tenter type stretching machine, then heat-fixed at 230°C, and wound on a roll. The film formability was good, and the film defects of the obtained film were favorably acceptable.

    (Examples 2 and 3)



    [0066] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 1 except that the added amount of manganese acetate was changed to 0.014% by weight (equivalent to 0.570 mol/t) and 0.028% by weight (equivalent to 1.14 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the contents of metals were as shown in Table 2. The change in the added amount of manganese acetate increased the gelation ratio of the polyethylene terephthalate resin composition but at an unproblematic level. In Example 3, the increase in the amount of manganese element increased the solution haze, but the film defects were at an unproblematic level.

    (Examples 4 to 6)



    [0067] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 1 except that 0.0046% by weight (equivalent to 0.214 mol/t) of magnesium acetate, 0.00045% by weight (equivalent to 0.059 mol/t) of calcium acetate, and 0.0075% by weight (equivalent to 0.735 mol/t) of lithium acetate with respect to the polyethylene terephthalate resin composition were respectively added to the third polycondensation reaction vessel in such a manner that the contents of metals were as shown in Table 2. In Examples 4, 5, and 6, the addition of the highly active metal catalysts increased the gelation ratio of the polyethylene terephthalate resin composition, and increased the generated amount of linear oligomer, but the film defects were at an unproblematic level.

    (Examples 7 and 8)



    [0068] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 1 except that the added amount of potassium hydroxide was changed to 0.0002% by weight (equivalent to 0.036 mol/t) and 0.0010% by weight (equivalent to 0.18 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the content of potassium element was as shown in Table 2.

    [0069] In Example 7, the amount of potassium element was small, and the melt specific resistance exhibited an increase but at a level unproblematic for a film-forming process. In Example 8, the increase in the amount of potassium element increased the b value of the polyethylene terephthalate resin composition, and increased the largest particle size of the internal particles to 0.3 µm, but the solution haze was 0.9%, which was at an unproblematic level.

    (Example 9)



    [0070] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 1 except that the positions where potassium hydroxide was added were three places: the first esterification reaction vessel, the second esterification reaction vessel, and the first polycondensation reaction vessel. The addition carried out at the three places caused the polyethylene terephthalate resin composition to have a solution haze of 0.8% and caused the largest particle size of the internal particles to be 0.3 µm, which were at an unproblematic level.

    (Examples 10 and 11)



    [0071] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 1; except that the added amount of antimony trioxide was changed to 0.0081% by weight (0.269 mol/t) and 0.0173% by weight (equivalent to 0.575 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the content of antimony element was as shown in Table 2; and except that, in Example 10, the amount of manganese acetate was changed to 0.014% by weight (equivalent to 0.570 mol/t) with respect to the polyethylene terephthalate resin composition. In Example 10 in which the amount of antimony trioxide was reduced, the activity was lowered, and the reaction was carried out with the reaction temperature raised by 1°C, with the result that the b value and COOH terminal group amount of the polyethylene terephthalate resin composition increased but at an unproblematic level. In Example 11, the increase in the amount of antimony element increased the solution haze but at an unproblematic level.

    (Example 12)



    [0072] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 1 except that the added amount of manganese acetate was changed to 0.014% by weight (equivalent to 0.570 mol/t) and the added amount of phosphoric acid was changed to 0.007% by weight (equivalent to 0.714 mol/t) with respect to the polyethylene terephthalate resin composition in such a manner that the contents of manganese element and phosphorus element were as shown in Table 2. The increase in M/P increased the gelation ratio of the polyethylene terephthalate resin composition and the generated amount of linear oligomer, but the film defects were at an unproblematic level.

    (Example 13)



    [0073] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 1 except that the added amount of phosphoric acid was changed to 0.021% by weight (equivalent to 2.14 mol/t) with respect to the polyethylene terephthalate resin composition in such a manner that the content of phosphorus element was as shown in Table 2. The increase in the amount of phosphorus element lowered the M/P and increased the melt specific resistance of the polyethylene terephthalate resin composition but at a level unproblematic for a film-forming process.

    (Example 14)



    [0074] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 1 except that the added amount of manganese acetate was changed to 0.028% by weight (equivalent to 1.14 mol/t) with respect to the polyethylene terephthalate resin composition and the added amount of phosphoric acid was changed to 0.023% by weight (equivalent to 2.38 mol/t) with respect to the polyethylene terephthalate resin composition in such a manner that the contents of manganese element and phosphorus element were as shown in Table 2. The increase in the metal element amount of manganese increased the gelation ratio of the polyethylene terephthalate resin composition and the generated amount of linear oligomer, but the film defects were at an unproblematic level.

    (Examples 15 and 16)



    [0075] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 1 except that the phosphorus compound to be added was changed from phosphoric acid to triethyl phosphonoacetate and trimethyl phosphate respectively. The change in the phosphorus compound increased the gelation ratio of the polyethylene terephthalate resin composition and increased the solution haze, but the film defects were at an unproblematic level.

    (Example 17)



    [0076] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 1 except that the temperature of the third polycondensation reaction vessel was raised by 2°C in order to increase the COOH terminal group. The rise in the reaction temperature increased the b value of the polyethylene terephthalate resin composition to 5.5 and the ΔCOOH thereof to 90 eq/t but at an unproblematic level.

    (Example 18)



    [0077] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 1 except that the place where potassium hydroxide was added was only the first esterification reaction vessel. Adding potassium hydroxide at one place facilitated decomposition reaction, and increased the solution haze and gelation ratio of the polyethylene terephthalate resin composition, but the film defects were at an unproblematic level.

    (Example 19)



    [0078] In the first esterification reaction vessel, slurry of terephthalic acid and ethylene glycol (at an ethylene glycol/terephthalic acid molar ratio of 1.05 to 1.30) was continuously added at a constant flow rate of 8.0 to 8.7 t/hr, and the esterification reaction was carried out at 245 to 255°C with water being distilled out until an esterification reaction rate of 90 to 95% was achieved. A potassium hydroxide solution (0.216% by weight) prepared with water and ethylene glycol mixed thereinto was split and continuously added into the first esterification reaction vessel and the second esterification reaction vessel in such a manner as to have a concentration of 0.0005% by weight (equivalent to 0.09 mol/t) with respect to the polyester resin.

    [0079] In addition, a phosphoric acid aqueous solution was continuously added to the second esterification reaction vessel in such a manner as to have a concentration of 0.014% by weight (equivalent to 1.428 mol/t) with respect to the polyester resin composition.

    [0080]  In the second esterification reaction vessel, the esterification reaction was carried out at 255°C with water being distilled out until an esterification reaction rate of 97% was achieved, whereby the esterification reaction was completed.

    [0081] With regard to polycondensation reaction, the polycondensation reaction was carried out in the first polycondensation reaction vessel at a temperature of 260°C and at a degree of vacuum of 10kPa; antimony trioxide was added in such a manner as to have a concentration of 0.0127% by weight (equivalent to 0.422 mol/t) with respect to the polyester resin; and manganese acetate was added in such a manner as to have a concentration of 0.021% by weight (equivalent to 0.855 mol/t) with respect to the polyester resin composition.

    [0082] Polycondensation reaction was carried out in the second polycondensation reaction vessel at a temperature of 275°C and at degree of vacuum of 2.2 kPa and in the third polycondensation reaction vessel at a temperature of 280°C and at a degree of vacuum of 0.2 kPa until an intrinsic viscosity of interest was achieved by carrying out the polymerization reaction. Then, nitrogen gas was used to bring the polycondensation reaction vessel back to normal pressure; and the reaction product was discharged in strand form into cold water through the die, pelletized in cylindrical form using an extrusion cutter, and preliminarily crystallized using a surface crystallizing device, to obtain the polyethylene terephthalate resin composition. The obtained liquid phase polyethylene terephthalate resin composition had an intrinsic viscosity of 0.50, a cyclic trimeric oligomer content of 1.10% by weight, and a carboxyl terminal group content of 40 eq/t.

    [0083] The liquid phase polyethylene terephthalate resin composition obtained through polycondensation reaction was subjected to solid phase polymerization in nitrogen gas having a dew point of 5°C using a continuous tower dryer at a temperature of 215°C for 18 hours to obtain the polyethylene terephthalate resin composition. The obtained polyethylene terephthalate resin composition had good quality with an intrinsic viscosity of 0.65, a cyclic trimeric oligomer content of 0.30% by weight, a carboxyl terminal group content of 9 eq/t, an antimony element content of 110 ppm, a cyclic trimeric oligomer regeneration rate of 0.007% by weight/minute, a color tone b value of 3.9, and a transparency (solution haze) of 0.9%.

    [0084] The obtained polyethylene terephthalate resin composition was dried at 150°C for 3 hours, supplied into an extruder, melt-extruded at 285°C, and cast onto an electrostatically charged cast drum of 20°C, to obtain an unstretched sheet. This unstretched sheet was stretched 3.1-fold in the longitudinal direction using a stretching roll heated to 90°C, then stretched 3.7-fold in the transverse direction at 120°C using a tenter type stretching machine, then heat-fixed at 230°C, and wound on a roll. The film formability was good, and the deposition characteristic and film defects of the cyclic trimeric oligomer of the obtained film were favorably acceptable.

    (Examples 20 and 21)



    [0085] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 19 except that the solid phase polymerization conditions were changed as shown in Table 5-1. The increase in the heat history increased the b value and gelation ratio of the polyethylene terephthalate resin composition but at an unproblematic level, and the film defects of the obtained film were favorably acceptable.

    (Example 22)



    [0086] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 19 except that the added amounts of manganese acetate, antimony trioxide, and phosphoric acid were changed to 0.014% by weight (equivalent to 0.570 mol/t), 0.0081% by mass (0.269 mol/t), and 0.007% by weight (equivalent to 0.714 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the contents of manganese element, antimony element, and phosphorus element were as shown in Table 2; and except that the solid phase polymerization conditions were changed as shown in Table 5-1. The dew point temperature was high, and the COOH terminal group amount of the polyethylene terephthalate resin composition exhibited an increase but at an unproblematic level, and the film defects of the obtained film were favorably acceptable.

    (Example 23)



    [0087] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 19 except that the added amounts of manganese acetate and phosphoric acid were changed to 0.028% by weight (equivalent to 1.140 mol/t) and 0.013% by weight (1.332 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the contents of manganese element and phosphorus element were as shown in Table 2; and except that the solid phase polymerization conditions were changed as shown in Table 5-1. The increase in the added amount of manganese acetate increased the gelation ratio of the polyethylene terephthalate resin composition and the generated amount of linear oligomer but at an unproblematic level, and the film defects of the obtained film were favorably acceptable.

    (Examples 24 to 27)



    [0088] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 19 except that the added amount of manganese acetate was changed to 0.016% by weight (0.665 mol/t), 0.026% by weight (1.045 mol/t), 0.019% by weight (0.760 mol/t), and 0.023% by weight (0.950 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the contents of manganese element and phosphorus element were as shown in Table 2. The added amount of manganese acetate was changed, but the polyethylene terephthalate resin composition had an unproblematic level of quality, and the film defects of the obtained film were favorably acceptable.

    (Examples 28 and 29)



    [0089] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 19 except that the added amount of potassium hydroxide was changed to 0.0002% by mass (equivalent to 0.036 mol/t) and 0.0010% by mass (equivalent to 0.18 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the content of potassium element was as shown in Table 2. The change in the added amount of potassium hydroxide resulted in exhibiting a difference in the melt specific resistance of the polyethylene terephthalate resin composition but at an unproblematic level, and the film defects of the obtained film were favorably acceptable.

    (Examples 30 to 32)



    [0090] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 19 except that the added amounts of manganese acetate and antimony trioxide were changed to 0.019% by weight (0.760 mol/t) and 0.0173% by mass (equivalent to 0.575 mol/t) in Example 30, 0.019% by weight (0.760 mol/t) and 0.104% by weight (0.345 mol/t) in Example 31, and 0.016% by weight (0.328 mol/t) and 0.150% by weight (0.498 mol/t) in Example 32 respectively with respect to the polyethylene terephthalate resin composition in such a manner that the contents of manganese element and antimony element were as shown in Table 2. The increase in the added amount of antimony trioxide increased the cyclic trimeric oligomer regeneration rate of the polyethylene terephthalate resin composition but at an unproblematic level, and the film defects of the obtained film were favorably acceptable.

    (Examples 33 and 34)



    [0091] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 19 except that the added amount of antimony trioxide was changed to 0.115% by weight (0.383 mol/t) and 0.138% by weight (0.460 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the content of antimony element was as shown in Table 2. The added amount of antimony trioxide was changed, but the polyethylene terephthalate resin composition had an unproblematic level of quality, and the film defects of the obtained film were favorably acceptable.

    (Examples 35 to 38)



    [0092] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 19 except that the added amount of potassium hydroxide was changed to 0.0003% by weight (0.054 mol/t), 0.0008% by weight (0.144 mol/t), 0.0004% by weight (0.072 mol/t), and 0.0006% by weight (0.108 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the content of potassium element was as shown in Table 2. The added amount of potassium hydroxide was changed, but the polyethylene terephthalate resin composition had an unproblematic level of quality, and the film defects of the obtained film were favorably acceptable.

    (Examples 39 to 42)



    [0093] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 19 except that the added amount of phosphoric acid was changed to 0.021% by weight (2.142 mol/t), 0.019% by weight (1.904 mol/t), 0.012% by weight (1.190 mol/t), and 0.016% by weight (1.666 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the content of phosphorus element was as shown in Table 2. The added amount of phosphoric acid was changed, but the polyethylene terephthalate resin composition had an unproblematic level of quality, and the film defects of the obtained film were favorably acceptable.

    (Comparative Examples 1 and 2)



    [0094] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 1 except that the added amount of manganese acetate was changed to 0.009% by weight (equivalent to 0.380 mol/t) and 0.033% by weight (equivalent to 1.33 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the content of manganese element was as shown in Table 8. In Comparative Example 1, the amount of manganese element was small, and the gelation ratio of the polyethylene terephthalate resin composition was 5.6% by weight, which was an inadequate result. In Comparative Example 2, the amount of manganese element was large, and the gelation ratio worsened to 7.2% by weight, which was an inadequate result.

    (Comparative Examples 3 and 4)



    [0095] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 1 except that the added amount of magnesium acetate in place of manganese acetate was changed to 0.0046% by weight (equivalent to 0.214 mol/t) and 0.0368% by weight (equivalent to 1.712 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the content of magnesium element was as shown in Table 8. Using magnesium acetate instead of using a manganese compound resulted in increasing the gelation ratio of the polyethylene terephthalate resin composition, which was an inadequate result. The b value and the generated amount of linear oligomer also resulted in worsening.

    (Comparative Examples 5 and 6)



    [0096] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 1 except that the added amount of calcium acetate in place of manganese acetate was changed to 0.00023% by weight (equivalent to 0.030 mol/t) and 0.0018% by weight (equivalent to 0.236 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the content of calcium element was as shown in Table 8. Adding calcium acetate instead of adding a manganese compound resulted in increasing the gelation ratio of the polyethylene terephthalate resin composition, which was an inadequate result.

    (Comparative Examples 7 and 8)



    [0097] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 1 except that the added amount of lithium acetate in place of manganese acetate was changed to 0.0075% by weight (equivalent to 0.735 mol/t) and 0.06% by weight (equivalent to 5.88 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the content of lithium element was as shown in Table 8. Adding lithium acetate instead of adding a manganese compound resulted in worsening the ΔCOOH and also increased the gelation ratio of the polyethylene terephthalate resin composition, which were inadequate results.

    (Comparative Examples 9 and 10)



    [0098] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 1 except that the added amount of potassium hydroxide was changed to 0.0001% by weight (equivalent to 0.018 mol/t) and 0.0015% by weight (equivalent to 0.27 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the content of potassium element was as shown in Table 8. In Comparative Example 9, the content of potassium hydroxide was small, and thus the melt specific resistance of the polyethylene terephthalate resin composition was worsened, with the result that the film formability was poor. In Comparative Example 10, the content of potassium element was large, and the gelation ratio of the polyethylene terephthalate resin composition was high, which was an inadequate result.

    (Comparative Example 11)



    [0099] Using a batch type of polymerization equipment, the esterification reaction of terephthalic acid and ethylene glycol which have a molar ratio of 1.15 at the reaction start was carried out at 140 to 260°C with water being distilled out. After the esterification reaction was completed, 0.0127% by weight (equivalent to 0.422 mol/t) of antimony trioxide, 0.021% by weight (equivalent to 0.855 mol/t) of manganese acetate, 0.014% by weight (equivalent to 1.428 mol/t) of phosphoric acid, and 0.0005% by weight (equivalent to 0.09mol/t) of potassium hydroxide respectively with respect to the polyethylene terephthalate resin composition were added under normal pressure; subsequently the reaction system was gradually brought down from normal pressure to 100 Pa and heated to 290°C, terminating the polycondensation reaction, to obtain the polyester composition and the film. Adopting the batch type resulted in lowered reaction efficiency accompanied by increased heat history, and increased the gelation ratio of the polyethylene terephthalate resin composition, which was an inadequate result.

    (Comparative Examples 12 and 13)



    [0100] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 1 except that the added amount of antimony trioxide was changed to 0.0069% by weight (0.231 mol/t) and 0.0207% by weight (equivalent to 0.693 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the content of antimony element was as shown in Table 8. In Comparative Example 13, the polymerization activity was reduced, and the increase of 2°C in the reaction temperature increased heat history, exhibiting an increased gelation ratio, a degraded b value, and the like, which were inadequate results. In Comparative Example 14 in which the amount of antimony was increased contrarily, the activity increased, thereby increasing the generated amount of linear oligomer of the polyethylene terephthalate resin composition and also increasing the solution haze, which were inadequate results.

    (Comparative Examples 14 and 15)



    [0101] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 1 except that the added amount of phosphoric acid was changed to 0.005% by weight (equivalent to 0.476 mol/t) and 0.0275% by weight (equivalent to 2.618 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the content of phosphorus element was as shown in Table 8. In Comparative Example 15, the M/P increased, thereby deteriorating the gelation ratio; in Comparative Example 16, the increase in the amount of phosphorus element increased the melt specific resistance of the polyethylene terephthalate resin composition, and increased the solution haze; and thus, the results were inadequate in both Examples.

    (Comparative Example 16)



    [0102] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 19 except that the added amounts of manganese acetate and potassium hydroxide were changed to 0.0015% by mass (equivalent to 0.646 mol/t) and 0.0010% by mass (equivalent to 0.18 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the contents of manganese element and potassium element were as shown in Table 8; except that no split addition of potassium element was carried out; and further except that the solid phase polymerization conditions were changed as shown in Table 11-1. The gelation ratio of the polyethylene terephthalate resin composition was high, and the obtained film had many film defects.

    (Comparative Example 17)



    [0103] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 19 except that the added amounts of magnesium acetate, lithium acetate, and potassium hydroxide, in place of manganese acetate, were changed to 0.041% by mass (equivalent to 1.93 mol/t), 0.006% by mass (equivalent to 0.588 mol/t), and 0.0008% by mass (equivalent to 0.144 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the contents of magnesium element, lithium element, and potassium element were as shown in Table 8; except that no split addition of potassium element was carried out; and further except that no solid phase polymerization was carried out. The gelation ratio and cyclic trimeric oligomer of the polyethylene terephthalate resin composition were high, and the obtained film had many film defects.

    (Comparative Example 18)



    [0104] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 19 except that the added amount of magnesium acetate in place of manganese acetate was changed to 0.061 % by mass (equivalent to 2.87 mol/t) with respect to the polyethylene terephthalate resin composition in such a manner that the content of magnesium element was as shown in Table 8; except that no potassium acetate was added; and further except that the solid phase polymerization conditions were changed as shown in Table 11-1. The gelation ratio of the polyethylene terephthalate resin composition was high, and the obtained film had many film defects.

    (Comparative Example 19)



    [0105] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 19 except that the added amounts of manganese acetate and antimony trioxide were changed to 0.033% by mass (equivalent to 1.33 mol/t) and 0.023% by mass (0.767 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the contents of manganese element and antimony element were as shown in Table 8; and except that no solid phase polymerization was carried out. The gelation ratio and cyclic trimeric oligomer of the polyethylene terephthalate resin composition were high, and the obtained film had many film defects.

    (Comparative Example 20)



    [0106] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 19 except that the added amount of manganese acetate was changed to 0.007% by mass (equivalent to 0.285 mol/t) with respect to the polyethylene terephthalate resin composition in such a manner that the content of manganese element was as shown in Table 8. Because the M/P was low, the melt specific resistance of the polyethylene terephthalate resin composition was high, and the electrostatic casting properties were poor.

    (Comparative Example 21)



    [0107] The polyethylene terephthalate resin composition was obtained in the same manner as in Example 19 except that the added amounts of manganese acetate and antimony trioxide element were changed to 0.037% by mass (equivalent to 1.52 mol/t) and 0.0052% by mass (0.173 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the contents of manganese element and antimony element were as shown in Table 8; and further except that the solid phase polymerization temperature was changed to 222°C. The solid phase polymerization temperature was high, and the polyethylene terephthalate resin composition fused adhesively inside the device, failing to become a film.

    (Comparative Example 22)



    [0108] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 19 except that, in place of manganese acetate, the added amounts of magnesium acetate, lithium acetate, and antimony trioxide were changed to 0.051% by mass (equivalent to 2.35 mol/t), 0.011% by mass (equivalent to 1.029 mol/t), and 0.0087% by mass (equivalent to 0.288 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the contents of magnesium element, lithium element, and antimony element were as shown in Table 8. The gelation ratio of the polyethylene terephthalate resin composition was high, and the obtained film had many film defects.

    (Comparative Example 23)



    [0109] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 19 except that the added amount of potassium hydroxide was changed to 0.0020% by mass (equivalent to 0.36 mol/t) with respect to the polyethylene terephthalate resin composition in such a manner that the content of potassium element was as shown in Table 8. The solution haze of the polyethylene terephthalate resin composition was high. The obtained film had many film defects.

    (Comparative Example 24)



    [0110] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 19 except that the dew point in the solid phase polymerization conditions was changed to 25°C. The color tone of the polyethylene terephthalate resin composition was poor; in addition, the gelation ratio was high; and the obtained film had many film defects.

    (Comparative Example 25)



    [0111] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 19 except that the added amount of calcium acetate in place of manganese acetate was changed to 0.010% by mass (equivalent to 1.36 mol/t) with respect to the polyethylene terephthalate resin composition in such a manner that the content of calcium element was as shown in Table 8. The gelation ratio of the polyethylene terephthalate resin composition was high, and the obtained film had many film defects.

    (Comparative Example 26)



    [0112] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 19 except that the added amounts of manganese acetate, antimony trioxide, and phosphoric acid were changed to 0.033% by mass (equivalent to 1.33 mol/t), 0.014% by mass (equivalent to 0.460 mol/t), and 0.0476% by mass (equivalent to 4.90 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the contents of manganese element, antimony element, and phosphorus element were as shown in Table 8; and except that no potassium acetate was added. The content of cyclic trimeric oligomer of the polyethylene terephthalate resin composition was high, and the obtained film had many film defects. The electrostatic casting properties were poor.

    (Comparative Example 27)



    [0113] The polyethylene terephthalate resin composition and the film were obtained in the same manner as in Example 19 except that the added amounts of manganese acetate, antimony trioxide, and phosphoric acid were changed to 0.033% by mass (equivalent to 1.33 mol/t), 0.069% by mass (equivalent to 0.230 mol/t), and 0.0476% by mass (equivalent to 4.90 mol/t) respectively with respect to the polyethylene terephthalate resin composition in such a manner that the contents of manganese element, antimony element, and phosphorus element were as shown in Table 8; and except that no potassium acetate was added. The content of cyclic trimeric oligomer of the polyethylene terephthalate resin composition was high, and the obtained film had many film defects. The electrostatic casting properties were poor.

    [Table 2]
     Metal Content in Liquid-Phase-Polymenzed Polymer
    AntimonyManganesePotassiumPhosphorusMagnesiumCalciumLithiumTotal of Mg, Ca, LiMn/SbM/P
    ppmppmppmppm0ppmppmppm
    Example 1 110 45 5 30 0 0 0 0 091 091
    Example 2 110 30 5 30 0 0 0 0 0.60 0.63
    Example 3 110 60 5 30 0 0 0 0 121 119
    Example 4 110 4b 5 30 5 0 0 5 091 112
    Example 5 110 45 5 30 0 10 0 10 0.91 1.17
    Example 6 110 45 5 30 0 0 5 5 091 1.28
    Example 7 110 45 2 30 0 0 0 0 091 087
    Example 8 110 45 10 30 0 0 0 0 0.91 0.98
    Example 9 110 45 5 30 0 0 0 0 091 091
    Example 10 70 30 5 30 0 0 0 0 095 0.63
    Example 11 150 45 5 30 0 0 0 0 066 091
    Example 12 110 30 5 15 0 0 0 0 0.60 1.26
    Example 13 110 45 5 45 0 0 0 0 0.91 0.61
    Example 14 110 60 5 50 0 0 0 0 1.21 0.72
    Example 15 110 45 5 30 0 0 0 0 0 91 091
    Example 16 110 45 5 30 0 0 0 0 0.91 0.91
    Example 17 110 45 5 30 0 0 0 0 091 091
    Example 18 110 45 5 30 0 0 0 0 091 091
    Example 19 110 45 5 30 0 0 0 0 0.91 091
    Example 20 110 45 5 30 0 0 0 0 0.91 091
    Example 21 110 45 5 30 0 0 0 0 091 091
    Example 22 70 30 5 15 0 0 0 0 095 126
    Example 23 110 60 5 28 0 0 0 0 121 128
    Example 24 110 35 5 30 0 0 0 0 0.71 0.72
    Example 25 110 55 5 30 0 0 0 0 111 110
    Example 26 110 40 5 30 0 0 0 0 081 082
    Example 27 110 50 5 30 0 0 0 0 101 1.01
    Example 28 110 40 2 30 0 0 0 0 091 0.87
    Example 29 110 45 10 30 0 0 0 0 091 0.98
    Example 30 150 40 b 30 0 0 0 0 059 0.82
    Example 31 90 40 5 30 0 0 0 0 0.99 0.82
    Example 32 130 35 5 30 0 0 0 0 060 072
    Example 33 100 45 5 30 0 0 0 0 100 0.91
    Example 34 120 45 5 30 0 0 0 0 083 0.91
    Example 35 110 45 3 30 0 0 0 0 0.91 0.89
    Example 36 110 45 8 30 0 0 0 0 091 095
    Example 37 110 45 4 30 0 0 0 0 0.91 0.90
    Example 38 110 45 6 30 0 0 0 0 091 092
    Example 39 110 4b 5 45 0 0 0 0 0.91 0.61
    Example 40 110 45 5 40 0 0 0 0 0.91 068
    Example 41 110 45 5 25 0 0 0 0 0.91 1.09
    Example 42 110 4b 5 35 0 0 0 0 0.91 078
    [Table 3]
     Quality of Liquid-Phase-Polymerized Polymer
    Intrinsic Viscosityb ValueMelt Specific ResistanceGelation RatioLargest Particle Size of Internal ParticlesCOOH Terminal GroupΔCOOHSolution HazeGenerated Amount of Linear Oligomer
    dl/g-×108Ω·cm% by weightµmeq/teq/t%µg/g
    Example 1 0.650 3.9 2.5 0.9 0.1 30 60 0.6 180
    Example 2 0.650 4.0 2.9 1.5 0.2 32 68 0.6 179
    Example 3 0.649 4.5 2.3 3.5 0.3 34 72 0.8 203
    Example 4 0.650 5.0 2.3 3.7 0.1 33 78 0.6 190
    Example 5 0.651 5.6 2.2 4.2 0.2 32 80 0.6 195
    Example 6 0.650 5.4 1.9 4.7 0.1 33 81 0.5 188
    Example 7 0.649 4.1 3.4 1.3 0.2 30 63 0.5 183
    Example 8 0.648 4.7 2.6 2.1 0.3 36 65 0.9 199
    Example 9 0.651 3.9 2.5 1.0 0.3 39 61 0.8 182
    Example 10 0.650 4.6 3.0 2.2 0.2 42 60 0.5 189
    Example 11 0.650 4.6 2.9 2.1 0.3 28 72 0.8 205
    Example 12 0.650 4.1 3.2 2.9 0.2 38 74 0.6 199
    Example 13 0.651 4.3 4.0 3.3 0.3 34 67 0.9 180
    Example 14 0.651 4.5 3.9 3.4 0.5 35 68 1.0 182
    Example 15 0.649 4.2 2.9 2.7 0.4 33 65 0.8 190
    Example 16 0.648 4.5 3.2 3.4 0.4 35 63 1.0 192
    Example 17 0.650 5.5 2.5 1.5 0.2 50 90 0.7 210
    Example 18 0.651 5.3 2.6 4.6 0.6 32 70 1.1 198
    [Table 4]
     Film Characteristics
    DefectsElectrostatic Casting Properties
    Example 1 Acceptable Grade 1
    Example 2 Acceptable Grade 1
    Example 3 Acceptable Grade 1
    Example 4 Acceptable Grade 1
    Example 5 Acceptable Grade 1
    Example 6 Acceptable Grade 1
    Example 7 Acceptable Grade 2
    Example 8 Acceptable Grade 1
    Example 9 Acceptable Grade 1
    Example 10 Acceptable Grade 2
    Example 11 Acceptable Grade 1
    Example 12 Acceptable Grade 2
    Example 13 Acceptable Grade 2
    Example 14 Acceptable Grade 2
    Example 15 Acceptable Grade 1
    Example 16 Acceptable Grade 2
    Example 17 Acceptable Grade 1
    Example 18 Acceptable Grade 1

    [Table 5-1]



    [0114] 
    Table 5-1
     Quality of Liquid-Phase-Polymerized PolymerSolid Phase Polymerization Conditions
    Intrinsic ViscositySolution HazeLargest Particle Size of Internal ParticlesCOOH Terminal GroupTemperatureTimeDew Point Temperature
    dl/g%µmeq/t°Chr°C
    Example 19 0.480 0.6 0.10 34 212 40 5
    Example 20 0.480 0.6 0.10 34 210 50 5
    Example 21 0.480 0.6 0.10 34 215 33 5
    Example 22 0.400 0.4 0.20 40 220 23 20
    Example 23 0.520 0.8 0.22 25 200 100 5
    Example 24 0.450 0.6 0.15 28 212 40 5
    Example 25 0.500 0.6 0.18 37 212 40 5
    Example 26 0.460 0.6 0.15 38 212 40 5
    Example 27 0.520 0.6 0.10 31 212 40 b
    Example 28 0.480 0.6 0.10 34 212 40 b
    Example 29 0.480 0.6 0.10 34 212 40 b
    Example 30 0.520 1.0 0.30 32 212 40 5
    Example 31 0.460 0.6 0.20 37 212 40 5
    Example 32 0.480 0.9 0.25 34 212 40 5
    Example 33 0.480 0.8 0.15 34 212 40 5
    Example 34 0.480 1.0 0.18 34 212 40 5
    Example 35 0.480 0.6 0.10 34 212 40 5
    Example 36 0.480 0.6 0.10 34 212 40 5
    Example 37 0.480 0.6 0.10 34 212 40 5
    Example 38 0.480 0.6 0.10 34 212 40 5
    Example 39 0.480 0.6 0.10 34 212 40 5
    Example 40 0.480 0.6 0.10 34 212 40 5
    Example 41 0.480 0.6 0.10 34 212 40 5
    Example 42 0.480 0.6 0.10 34 212 40 5

    [Table 5-2]



    [0115] 
    Table 5-2
     Quality of Solid-Phase-Polymerized Polymer
    Intrinsic Viscosityb ValueMelt Specific ResistanceGelation RatioCOOH Terminal GroupΔCOOHContent of Cyclic Trimeric Oligomer in Resin CompositionCyclic Trimeric Oligomer Regeneration RateGenerated Amount of Linear Oligomer
    dl/g-×108Ω)·cm% by weighteq/teq/t% by weight% by weight/minuteµg/g
    Example 19 0.650 3.9 1.9 2.1 8 60 0.29 0 009 180
    Example 20 0.650 4.1 2.2 2.5 9 60 0.30 0.009 182
    Example 21 0.650 4.1 2.2 2.3 8 60 0.30 0.009 17d
    Example 22 0.650 4.0 2.1 1.5 20 70 0.29 0.009 179
    Example 23 0.650 4.5 2.0 2.3 20 65 0.40 0.009 203
    Example 24 0.650 3.9 1.9 2.1 18 65 0.30 0.009 180
    Example 25 0.650 3.9 1.9 2.1 18 65 0.30 0.009 180
    Example 26 0.650 3.9 1.9 2.1 18 65 0.30 0.010 180
    Example 27 0.650 3.9 1.9 2.1 18 65 0.30 0.010 180
    Example 28 0.650 4.1 2.5 1.3 20 65 0.30 0.010 183
    Example 29 0.650 4.7 2.4 2.1 20 60 0.30 0.010 199
    Example 30 0.650 4.0 2.4 2.2 22 80 0.30 0.015 189
    Example 31 0.650 4.0 2.4 2.2 22 60 0.35 0.010 189
    Example 32 0.650 4.6 2.1 2.1 28 75 0.30 0.012 205
    Example 33 0.650 4.0 2.4 2.2 22 60 0.30 0.010 189
    Example 34 0.650 4.0 2.2 2.1 19 60 0.30 0.010 202
    Example 35 0.600 4.1 1.9 2.9 20 60 0.30 0.009 210
    Example 36 0.600 4.1 1.9 2.9 20 60 0.30 0.009 210
    Example 37 0.600 4.1 1.9 2.9 20 60 0.30 0.009 210
    Example 38 0.600 4.1 1.9 2.9 20 60 0.30 0.009 210
    Example 39 0.600 3.9 2.1 2.1 19 60 0.30 0.009 195
    Example 40 0.600 4.3 2.1 2.5 18 60 0.30 0.009 190
    Example 41 0.600 4.3 2.1 2.5 18 60 0.30 0.010 190
    Example 42 0.600 4.3 2.1 2.5 18 60 0.30 0.010 190

    [Table 6]



    [0116] 
    Table 6
     Film Characteristics
    DefectsContent of Cyclic Trimeric OligomerDeposition Characteristic of Cyclic Trimeric OligomerElectrostatic Casting Properties
    % by weight
    Example 19 Acceptable 0.43 A Grade 1
    Example 20 Acceptable 0.44 A Grade 1
    Example 21 Acceptable 0.44 A Grade 1
    Example 22 Acceptable 0.44 A Grade 1
    Example 23 Acceptable 0.55 B Grade 1
    Example 24 Acceptable 0.44 A Grade 1
    Example 25 Acceptable 0.44 A Grade 1
    Example 26 Acceptable 0.44 A Grade 1
    Example 27 Acceptable 0.44 A Grade 1
    Example 28 Acceptable 0.44 A Grade 2
    Example 29 Acceptable 0.44 A Grade 2
    Example 30 Acceptable 0.44 A Grade 2
    Example 31 Acceptable 0.50 B Grade 2
    Example 32 Acceptable 0.45 B Grade 1
    Example 33 Acceptable 0.44 A Grade 2
    Example 34 Acceptable 0.44 A Grade 1
    Example 35 Acceptable 0.44 A Grade 1
    Example 36 Acceptable 0.44 A Grade 1
    Example 37 Acceptable 0.44 A Grade 1
    Example 38 Acceptable 0.44 A Grade 1
    Example 39 Acceptable 0.44 A Grade 1
    Example 40 Acceptable 0.44 A Grade 1
    Example 41 Acceptable 0.44 A Grade 1
    Example 42 Acceptable 0.44 A Grade 1



    [Table 8]



    [0117] 
    Table 8
     Metal Content in Liquid-Phase-Polymerized Polymer
    AntimonyManganesePotassiumPhosphorusMagnesiumCalciumLithiumTotal of Mg, Ca, LiMn/SbM/P
    ppmppmppmppmppmppmppmppm
    Comparative Example 1 110 20 5 30 0 0 0 0 0.40 0.44
    Comparative Example 2 110 70 5 30 0 0 0 0 1.41 1.38
    Comparative Example 3 110 0 5 30 5 0 0 5 0.00 0.28
    Comparative Example 4 60 0 5 9 40 0 0 40 0.00 5.88
    Comparative Example 5 110 0 5 30 0 5 0 5 0.00 0.19
    Comparative Example 6 110 0 8 30 0 40 0 40 0.00 1.14
    Comparative Example 7 110 0 5 30 0 0 5 5 0.00 0.44
    Comparative Example 8 110 0 5 30 0 0 40 40 0.00 3.04
    Comparative Example 9 110 45 1 30 0 0 0 0 0.91 0.86
    Comparative Example 10 110 45 15 30 0 0 0 0 0.91 1.04
    Comparative Example 11 110 45 5 30 0 0 0 0 0.91 0.91
    Comparative Example 12 60 45 5 30 0 0 0 0 1.66 0.91
    Comparative Example 13 180 45 5 30 0 0 0 0 0.55 0.91
    Comparative Example 14 110 45 5 10 0 0 0 0 0.91 2.74
    Comparative Example 15 110 45 5 55 0 0 0 0 0.91 0.50
    Comparative Example 16 134 34 10 15 0 0 0 0 0.56 1.54
    Comparative Example 17 60 0 8 9 45 0 4 49 0.00 7.72
    Comparative Example 18 10 0 0 65 67 0 0 67 0.00 1.31
    Comparative Example 19 200 70 0 46 0 0 0 0 0.78 0.86
    Comparative Example 20 110 15 5 30 0 0 0 0 0.30 0.35
    Comparative Example 21 45 80 5 30 0 0 0 0 3.94 1.57
    Comparative Example 22 75 0 2 27 55 0 7 62 0.00 3.20
    Comparative Example 23 110 45 20 30 0 0 0 0 0.91 1.11
    Comparative Example 24 110 45 5 30 0 0 0 0 0.91 0.91
    Comparative Example 25 110 45 5 30 0 230 0 230 0.91 6.84
    Comparative Example 26 120 70 0 102 0 0 0 0 1.29 0.39
    Comparative Example 27 60 70 0 102 0 0 0 0 2.59 0.39

    [Table 9]



    [0118] 
    Table 9
     Quality of Liquid-Phase-Polymerized Polymer
    Intrinsic Viscosityb ValueMelt Specific ResistanceGelation RatioLargest Particle Size of Internal ParticlesCOOH Terminal GroupΔCOOHSolution HazeGenerated Amount of Linear Oligomer
    dl/g-×108Ω·cm% by weightµmeq/teq/t%µg/g
    Comparative Example 1 0.649 4.2 4.5 5.6 0.2 30 62 0.5 182
    Comparative Example 2 0.650 6.2 2.3 7.2 0.4 35 72 1.2 215
    Comparative Example 3 0.649 5.5 2.0 10.2 0.3 33 90 0.5 220
    Comparative Example 4 0.648 7.8 1.5 21.3 0.1 34 115 0.5 250
    Comparative Example 5 0.650 5.2 2.2 6.2 0.2 30 85 0.7 193
    Comparative Example 6 0.649 6.5 1.8 13.5 0.4 32 102 0.8 210
    Comparative Example 7 0.651 4.9 0.9 7.0 0.3 33 110 0.7 190
    Comparative Example 8 0.651 6.3 0.3 18.8 0.6 37 120 1.0 220
    Comparative Example 9 0.649 4.6 4.5 1.5 0.1 31 62 0.5 184
    Comparative Example 10 0.649 5.6 1.9 5.2 1.3 35 1.2 1.3 192
    Comparative Example 11 0.650 5.6 2.6 5.1 0.2 36 72 0.7 199
    Comparative Example 12 0.648 8.0 5.2 6.2 0.1 41 115 0.5 210
    Comparative Example 13 0.649 4.0 5.3 5.3 0.6 30 65 1.6 220
    Comparative Example 14 0.650 4.3 2.0 9.2 0.1 34 100 0.5 185
    Comparative Example 15 0.651 4.7 10.0 5.2 0.9 37 75 1.3 180

    [Table 10]



    [0119] 
    Table 10
     Film Characteristics
    DefectsElectrostatic Casting Properties
    Comparative Example 1 Acceptable Grade 2
    Comparative Example 2 Not Acceptable Grade 1
    Comparative Example 3 Not Acceptable Grade 1
    Comparative Example 4 Not Acceptable Grade 1
    Comparative Example 5 Not Acceptable Grade 3
    Comparative Example 6 Not Acceptable Grade 1
    Comparative Example 7 Not Acceptable Grade 1
    Comparative Example 8 Not Acceptable Grade 1
    Comparative Example 9 Acceptable Grade 3
    Comparative Example 10 Acceptable Grade 1
    Comparative Example 11 Acceptable Grade 1
    Comparative Example 12 Not Acceptable Grade 3
    Comparative Example 13 Acceptable Grade 3
    Comparative Example 14 Not Acceptable Grade 1
    Comparative Example 15 Acceptable Grade 4

    [Table 11-1]



    [0120] 
    Table 11-1
     Quality of Liquid-Phase-Polymerized PolymerSolid Phase Polymerization Conditions
    Intrinsic ViscositySolution HazeLargest Particle Size of Internal ParticlesCOOH Terminal GroupTemperatureTimeDew Point Temperature
    dl/g%µmeq/t°Chr°C
    Comparative Example 16 0.500 1.0 0.50 40 212 30 -50
    Comparative Example 17 0.500 0.8 0.50 35 - - -
    Comparative Example 18 0.500 1.1 0.50 28 212 25 -56
    Comparative Example 19 0.500 2.2 0.50 35 - - -
    Comparative Example 20 0.500 0.9 0.10 36 215 35 5
    Comparative Example 21 0.500 0.7 0.10 36 222 20 5
    Comparative Example 22 0.500 0.6 0.10 36 215 35 5
    Comparative Example 23 0.500 1.2 0.10 40 215 35 5
    Comparative Example 24 0.500 0.8 0.10 40 215 35 25
    Comparative Example 25 0.500 2.8 0.10 40 215 35 5
    Comparative Example 26 0.500 0.8 0.40 40 215 35 5
    Comparative Example 27 0.440 0.8 0.40 40 215 35 5

    [Table 11-2]



    [0121] 
    Table 11-2
     Quality of Solid-Phase-Polymerized Polymer
    Intrinsic Viscosityb ValueMelt Specific ResistanceGelation RatioCOOH Terminal GroupΔCOOHContent of Cyclic Trimeric Oligomer in Resin CompositionCyclic Trimeric Oligomer Regeneration RateGenerated Amount of Linear Oligomer
    dl/g-×108Ω·cm% by weighteq/teq/t% by weight% by weight/minuteµg/g
    Comparative Example 16 0.850 6.0 2.1 10.0 25 90 0.28 0.010 300
    Comparative Example 17 - - 0.8 7.0 - - 1.10 - -
    Comparative Example 18 0.780 9.0 1.1 21.0 15 90 0.29 0.010 280
    Comparative Example 19 - - - 15.0 - - 1.12 - -
    Comparative Example 20 0.630 4.0 1.2 2.0 21 90 0.31 0.010 189
    Comparative Example 21 0.650 6.0 2.3 7.0 20 90 0.29 0.010 262
    Comparative Example 22 0.630 6.0 0.7 22.0 21 70 0.28 0.010 323
    Comparative Example 23 0.630 4.0 2.2 2.8 21 90 0.30 0.010 190
    Comparative Example 24 0.580 6.5 2.4 5.5 30 70 0.30 0.010 219
    Comparative Example 25 0.630 4.0 2.4 5.5 21 70 0.30 0.010 219
    Comparative Example 26 0.630 4.0 8.5 5.5 21 70 0.38 0.010 219
    Comparative Example 27 0.560 4.0 9.3 5.5 21 70 0.45 0.010 219
    [Table 12]
    Table 12 
     Film Characteristics
    DefectsContent of Cyclic Trimeric OligomerDeposition Characteristic of Cyclic Trimeric OligomerElectrostatic Casting Properties
    % by weight
    Comparative Example 16 Not Acceptable 0.48 B Grade 1
    Comparative Example 17 Not Acceptable 1.09 C Grade 1
    Comparative Example 18 Not Acceptable 1.13 C Grade 2
    Comparative Example 19 Not Acceptable 1.15 C Grade 2
    Comparative Example 20 Acceptable 0.50 B Grade 4
    Comparative Example 21 - - - -
    Comparative Example 22 Not Acceptable 0.48 B Grade 1
    Comparative Example 23 Acceptable 0.49 B Grade 1
    Comparative Example 24 Not Acceptable 0.47 B Grade 1
    Comparative Example 25 Not Acceptable 0.47 B Grade 1
    Comparative Example 26 Not Acceptable 0.54 B Grade 3
    Comparative Example 27 Not Acceptable 0.56 B Grade 3



    Claims

    1. A polyethylene terephthalate resin composition, having a manganese element content of 30 to 60 ppm, a potassium element content of 2 to 10 ppm, and an antimony element content of 70 to 150 ppm with respect to the total weight of elements of the polyethylene terephthalate resin composition,
    wherein a molar ratio of metal elements to phosphorus element, (M/P = (M1 + M2 / 2) / P), satisfies the following formula:

    (wherein M1 represents the content (mol/t) of a bivalent metal element selected from the group consisting of Mg, Mn, and Ca;

    M2 represents the content (mol/t) of a monovalent metal element selected from the group consisting of Li, Na, and K; and

    P represents the content (mol/t) of phosphorus element.); and

    wherein the composition has a gelation ratio of 5% by weight or less,

    wherein the manganese element content, the potassium element content, the antimony element content, the phosphorus element content and the gelation ratio are measured by methods as set out in the description respectively.


     
    2. The polyethylene terephthalate resin composition according to claim 1, wherein the total content of metal elements: Mg, Ca, and Li measured by a method as set out in the description is less than 0.1 ppm.
     
    3. The polyethylene terephthalate resin composition according to claim 1 or 2, wherein the composition generates linear oligomer in an amount of 210 µg/g or less when melted at 290°C for 20 minutes, wherein the linear oligomer generated is measured by a method as set out in the description.
     
    4. The polyethylene terephthalate resin composition according to claim 1, wherein the composition comprises internal particles whose largest particle diameter measured by a method as set out in the description is 0.3 µm or less, and has 1.0% or less of solution haze.
     
    5. The polyethylene terephthalate resin composition according to claim 1, wherein the content of phosphorus element measured by a method as set out in the description is 15 ppm to 45 ppm.
     
    6. The polyethylene terephthalate resin composition according to claim 1, having a COOH terminal group content of 25 to 40 eq/t, wherein the COOH terminal group amount increased between before and after heat-moisture treatment is 80 eq/t or less, wherein the COOH terminal group content and the COOH terminal group amount are measured by a method as set out in the description.
     
    7. The polyethylene terephthalate resin composition according to claim 1, having an intrinsic viscosity measured by a method as set out in the description of 0.60 to 0.70, a COOH terminal group content measured by a method as set out in the description of 5 to 20 eq/t, and 0.40% by weight or less of cyclic trimeric oligomer measured by a method as set out in the description.
     
    8. A polyester film formed from the polyethylene terephthalate resin composition according to claim 1.
     


    Ansprüche

    1. Polyethylenterephthalatharz-Zusammensetzung mit einem Manganelementgehalt von 30 bis 60 ppm, einem Kaliumelementgehalt von 2 bis 10 ppm und einem Antimonelementgehalt von 70 bis 150 ppm, bezogen auf das Gesamtgewicht von Elementen der Polyethylenterephthalatharz-Zusammensetzung, wobei ein Molverhältnis von Metallelementen zum Phosphor-Element (M/P = (M1 + M2 / 2) / P) die folgende Formel erfüllt:

    (worin M1 für den Gehalt (Mol/t) eines zweiwertigen Metallelements steht, das aus der aus Mg, Mn und Ca bestehenden Gruppe ausgewählt ist;

    M2 für den Gehalt (Mol/t) eines einwertigen Metallelements steht, das aus der aus Li, Na und K bestehenden Gruppe ausgewählt ist; und

    P für den Gehalt (Mol/t) eines Phosphorelements steht); und

    wobei die Zusammensetzung ein Gelierverhältnis von 5 Gew.-% oder weniger aufweist,

    wobei der Gehalt des Manganelements, der Gehalt des Kaliumelements, der Gehalt des Antimonelements, der Gehalt des Phosphorelements und das Gelierverhältnis über Verfahren gemessen werden, die jeweils in der Beschreibung dargelegt sind.


     
    2. Polyethylenterephthalatharz-Zusammensetzung nach Anspruch 1, wobei der Gesamtgehalt der Metallelemente Mg, Ca und Li, der über ein Verfahren wie in der Beschreibung dargelegt gemessen wird, weniger als 0,1 ppm beträgt.
     
    3. Polyethylenterephthalatharz-Zusammensetzung nach Anspruch 1 oder 2, wobei die Zusammensetzung ein lineares Oligomer in einer Menge von 210 µg/g oder weniger erzeugt, wenn diese 20 min lang bei 290 °C geschmolzen wird, wobei das erzeugte lineare Oligomer über ein Verfahren wie in der Beschreibung dargelegt gemessen wird.
     
    4. Polyethylenterephthalatharz-Zusammensetzung nach Anspruch 1, wobei die Zusammensetzung interne Teilchen umfasst, deren größter Teilchendurchmesser, gemessen über ein in der Beschreibung dargelegtes Verfahren, 0,3 µm oder weniger beträgt, und eine Lösungstrübung von 1,0 % oder weniger aufweist.
     
    5. Polyethylenterephthalatharz-Zusammensetzung nach Anspruch 1, wobei der Gehalt des Phosphor-Elements, gemessen über ein in der Beschreibung dargelegtes Verfahren, 15 ppm bis 45 ppm beträgt.
     
    6. Polyethylenterephthalatharz-Zusammensetzung nach Anspruch 1, die einen Gehalt einer endständigen COOH-Gruppe von 25 bis 40 Äq./t aufweist, wobei die Menge der endständigen COOH-Gruppe, die zwischen vor und nach der Wärme-Feuchtigkeitsbehandlung ansteigt, 80 Äq./t oder weniger beträgt, wobei der Gehalt der endständigen COOH-Gruppe und die Menge der endständigen COOH-Gruppe über ein in der Beschreibung dargelegtes Verfahren gemessen werden.
     
    7. Polyethylenterephthalatharz-Zusammensetzung nach Anspruch 1, die eine intrinsische Viskosität, gemessen über ein in der Beschreibung dargelegtes Verfahren, von 0,60 bis 0,70, einen Gehalt einer endständigen COOH-Gruppe, gemessen über ein in der Beschreibung dargelegtes Verfahren, von 5 bis 20 Aq./t und 0,40 Gew.-% oder weniger eines zyklischen trimeren Oligomers, gemessen über ein in der Beschreibung dargelegtes Verfahren, aufweist.
     
    8. Polyesterfolie, gebildet aus einer Polyethylenterephthalatharz-Zusammensetzung nach Anspruch 1.
     


    Revendications

    1. Composition de résine de polyéthylène téréphtalate, ayant une teneur en élément manganèse de 30 à 60 ppm, une teneur en élément potassium de 2 à 10 ppm, et une teneur en élément antimoine de 70 à 150 ppm par rapport au poids total d'éléments de la composition de résine de polyéthylène téréphtalate,
    dans laquelle un rapport molaire d'éléments métalliques à un élément phosphore, (M/P=(M1 + M2/2)/P), satisfait la formule suivante :

    (dans laquelle M1 représente la teneur (mol/t) d'un élément métallique bivalent choisi dans le groupe comprenant Mg, Mn et Ca ;

    M2 représente la teneur (mol/t) d'un élément de métal monovalent choisi dans le groupe comprenant Li, Na et K ; et

    P représente la teneur (mol/t) de l'élément phosphore) ; et

    dans laquelle la composition a un taux de gélification de 5 % en poids ou moins,

    dans laquelle la teneur en élément manganèse, la teneur en élément potassium, la teneur en élément antimoine, la teneur en élément phosphore et le taux de gélification sont mesurés par des procédés tels qu'établis dans la description, respectivement.


     
    2. Composition de résine de polyéthylène téréphtalate selon la revendication 1, dans laquelle la teneur totale en éléments métalliques: Mg, Ca et Li, mesurée par un procédé tel qu'établi dans la description, est inférieure à 0,1 ppm.
     
    3. Composition de résine de polyéthylène téréphtalate selon la revendication 1 ou 2, dans laquelle la composition génère un oligomère linéaire en une quantité de 210 ug/g ou moins lorsqu'elle est fondue à 290°C pendant 20 minutes, dans laquelle l'oligomère linéaire généré est mesuré par un procédé tel qu'établi dans la description.
     
    4. Composition de résine de polyéthylène téréphtalate selon la revendication 1, dans laquelle la composition comprend des particules dont le plus grand diamètre de particule interne mesuré par un procédé tel qu'établi dans la description est de 0,3 µm ou moins, et a 1,0% ou moins de trouble de solution.
     
    5. Composition de résine de polyéthylène téréphtalate selon la revendication 1, dans laquelle la teneur en élément phosphore mesurée par un procédé tel qu'établi dans la description est de 15 ppm à 45 ppm.
     
    6. Composition de résine de polyéthylène téréphtalate selon la revendication 1, ayant une teneur en groupe terminal COOH de 25 à 40 eq/t, dans laquelle la quantité de groupes terminaux COOH augmentée entre avant et après un traitement thermo-hydrique est de 80 eq/t ou moins, dans laquelle la teneur en groupe terminal COOH et la quantité de groupes terminaux COOH sont mesurées par un procédé tel qu'établi dans la description.
     
    7. Composition de résine de polyéthylène téréphtalate selon la revendication 1, ayant une viscosité intrinsèque mesurée par un procédé tel qu'établi dans la description de 0,60 à 0,70, une teneur en groupe terminal COOH mesurée par un procédé tel qu'établi dans la description de 5 à 20 eq/t, et 0,40% en poids ou moins de l'oligomère trimère cyclique, en mesurant via un procédé tel qu'établi dans la description,
     
    8. Film de polyester formé à partir de la composition de résine de polyéthylène téréphtalate selon la revendication 1.
     






    Cited references

    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description




    Non-patent literature cited in the description