JP6131718B2 - Biaxially oriented polyester film and method for producing the same - Google Patents

Description

  The present invention relates to a polyester film having a good balance between durability and processability. More specifically, it has a high property retention rate in a moist and heat resistant environment, and is excellent in film productivity and processability during punching and bending, particularly in applications used under high temperature conditions such as motor insulation paper and solar cell sealing. The present invention relates to a polyester film useful for applications used outdoors such as a stop film, a building material, an automobile material, and the like, and a manufacturing method thereof.

  Polyester resins are excellent in mechanical properties, thermal properties, chemical resistance, electrical properties, and moldability, and are used in various applications. The polyester film made from the polyester resin, especially the biaxially oriented polyester film, has its mechanical properties, electrical properties, etc., and has a copper-clad laminate, solar cell sealing film, adhesive tape, flexible printed circuit board, membrane switch, Used as various industrial materials such as sheet heating elements or electrical insulation materials such as flat cables, magnetic recording materials, capacitor materials, packaging materials, automotive materials, building materials, photographic applications, graphic applications, thermal transfer applications, etc. ing.

  Among these applications, electrical insulation materials used in outdoor and high temperature conditions (eg, solar cell sealing films and motor insulation paper used in harsh environments such as automobiles), automotive materials, building materials, etc. Therefore, it is often used in a harsh environment for a long time. When used in such a harsh environment for a long period of time, the polyester resin has a molecular weight that decreases due to hydrolysis, and the embrittlement progresses, resulting in a decrease in mechanical properties. Therefore, when it is used in a harsh environment for a long period of time or in an application where it is used in a damp state, durability against wet heat is required. For example, in a solar cell sealing application, in order to reduce the power generation cost by improving the service life of the solar cell, it is required to improve the wet heat resistance of the polyester film.

  Therefore, various studies have been made to suppress hydrolysis of the polyester resin. For example, a polycondensation catalyst for a polyester resin is studied (Patent Document 1), or an epoxy compound (Patent Document 2) or a polycarbodiimide (Patent Document 3) is added to improve the heat and moisture resistance of the polyester resin itself. Has been. In addition, a method of improving moisture and heat resistance by intermolecular crosslinking by adding a buffering agent to a polyester resin (Patent Document 4) and further introducing a trifunctional component into the polyester resin has been studied (Patent Document 5).

JP 2010-212272 A JP-A-9-227767 Japanese National Patent Publication No. 11-506487 JP 2008-7750 A JP 2010-248492 A

  However, the method of Patent Document 1 has insufficient hydrolysis resistance. In the techniques of Patent Documents 2 and 3, gelation progresses during film melting and film formation, resulting in poor thickness, filter clogging, and film breakage during biaxially oriented film production, which is resistant to hydrolysis. There is a problem in the film forming process that the orientation necessary for improvement cannot be imparted, or there is a problem that foreign matter remains in the film, resulting in poor quality. In Patent Document 4 containing a buffering agent in the film, the durability of the polyester resin is improved, but it is not sufficient, and the molecular orientation necessary for further improving the hydrolysis resistance is given to the film. When film forming conditions are used, problems such as tearing and unevenness in thickness are likely to occur during biaxially oriented film production, and there are also problems with film cracking and peeling during punching and bending, resulting in productivity and hydrolysis resistance. It was difficult to achieve both. Furthermore, when it has an intermolecular cross-linked structure as in Patent Document 5, the hydrolysis resistance of the film is improved, but the stretchability and workability of the film are further reduced. It was difficult to achieve both productivity / workability and hydrolysis resistance, and the productivity was poor. In addition, the buffer used in Patent Documents 4 and 5 has a problem of being easily aggregated at the time of addition, and these aggregates shorten the filter life in the filtration process, or the minute aggregates that remain without being filtered, Since it remains inside the film as a foreign substance, there is also a problem that the yield is deteriorated as an appearance defect. In recent years, with the progress of yield improvement for cost reduction proceeding, the level of demand for reducing foreign material defects on films has been increasing, and in addition to improving resistance to hydrolysis, improvements in reducing foreign material defects have been required. .

  In view of the problems of the conventional technology, the object of the present invention is to achieve both durability under conditions of high temperature and high humidity and processability at the time of punching and bending. An object of the present invention is to provide a polyester film excellent in durability and productivity that can suppress the occurrence of defects inside the film, and a method for producing the same.

(1). The intrinsic viscosity (IV) of the polyester resin constituting the film is 0.65 to 0.80, the terminal carboxyl group amount is 20 equivalent / t or less, the diethylene glycol content is 2.0% by mass or more and 5.0% by mass or less, and the differential. A biaxially oriented polyester film having a minute endothermic peak temperature Tmeta (° C.) determined by scanning calorimetry (DSC) of 150 ° C. or more and 200 ° C. or less.
(2). The biaxially oriented polyester film according to (1), wherein the polyester resin is obtained using at least a component (A) having a total number of carboxylic acid groups and hydroxyl groups of 3 or more.
(3). The said polyester resin contains 0.1 mol / t or more and 5.0 mol / t or less of alkali metal phosphates, and the foreign material containing the phosphorus component of 100 micrometers or more of long diameters contained in a film is 10 pieces / 1000 cm < ² > or less ( The biaxially oriented polyester film according to 1) or (2).
(4). The biaxially oriented polyester film according to any one of (1) to (3), wherein the thickness is 200 μm or more.
(5). The average ultrasonic conduction velocity of the film is 2.2 km / second or more, and the ratio of the maximum value and the minimum value of the ultrasonic conduction velocity is 1.0 or more and 1.3 or less. Biaxially oriented polyester film.
(6). The biaxially oriented polyester film according to (5), wherein an angle (θ) between the direction in which the ultrasonic conduction velocity of the film exhibits a maximum value and the film longitudinal direction is 10 ° or more and 80 ° or less.
(7). The biaxially oriented polyester film according to any one of (1) to (6), wherein the elongation retention when held at 125 ° C. and 100% RH for 72 hours is 50% or more.
(8). It is a process for producing a biaxially oriented polyester film having a step of melting a polyester resin and molding it into a sheet, and a stretching step in the longitudinal direction and width direction, an intermediate step, and a heat treatment step described in (a) to (c) below. The intrinsic viscosity (IV) of the polyester resin constituting the film is 0.65 to 0.80, the terminal carboxyl group content is 20 equivalent / t or less, and the diethylene glycol content is 2.0 mass% or more and 5.0 mass% or less. And a method for producing a biaxially oriented polyester film having a minute endothermic peak temperature Tmeta (° C.) of 150 ° C. or higher and 200 ° C. or lower.
(A) The film width is stretched 3.5 to 4.5 times in the width direction, and the film width before the start of the width direction stretching process is W0, the film width at the midpoint of the width direction stretching process is W1, and after the end of the width direction stretching process. In the case where the film width at W2 is W2, the step satisfying the following formula (A) 60 ≦ 100 × (W1-W0) / (W2-W0) ≦ 80 Formula (A)
(B) a step of heat-treating the biaxially oriented film at 160 ° C. to 210 ° C. (c) having an intermediate step between the width direction stretching step and the heat treatment step, and the temperature of the intermediate step is the final of the width direction stretching step When the temperature of the section: Ts (° C.) and the first heat treatment process temperature corresponding to the first section of the heat treatment process: Th (° C.), and the time for the film to pass through the intermediate process is Sm (seconds) Step satisfying formula (B) (Th−Ts) / Sm ≦ 50 (Equation (B)
(9). In the step of melting the polyester resin and molding it into a sheet shape, the polyester resin to be used contains the alkali metal phosphate in an amount of 0.1 mol / t or more and 5.0 mol / t or less (8). Production method.
(10). A motor using the biaxially oriented polyester film according to any one of (1) to (7).
(11). (1)-The solar cell using the biaxially-oriented polyester film in any one of (7).

  ADVANTAGE OF THE INVENTION According to this invention, the polyester film which is excellent in the property balance which can be compatible with durability at high temperature, high humidity, and processing appropriateness, such as punching and bending, and also has good productivity can be provided. Such polyester films are used for insulating paper for motors, solar cell encapsulating sheets, copper-clad laminates, adhesive tapes, flexible printed circuit boards, membrane switches, sheet heating elements, flat cables, and other electrically insulating materials, capacitor materials, automobiles. It can be suitably used for applications in which durability and workability such as construction materials and building materials are important.

  In the present invention, the terminal carboxyl group content of the polyester resin constituting the polyester film is required to be 20 equivalent / t or less in order to improve the durability under high temperature and high humidity. A general polyester film is composed of crystalline polyester, and there are crystalline and amorphous parts of the polyester in the film. Moreover, in the polyester film obtained by biaxially stretching such crystalline polyester, there are a portion where the polyester is crystallized by orientation (hereinafter referred to as an orientation crystallized portion) and an amorphous portion. Here, the amorphous part is considered to be in a state where the density is lower than that of the crystal part and the oriented crystal part and the average intermolecular distance is large. When the polyester film is exposed to a moist heat atmosphere, moisture (water vapor) enters the inside through the molecules of the amorphous part having a low density, plasticizes the amorphous part, and increases the mobility of the molecule. Further, moisture (water vapor) promotes hydrolysis of an amorphous part having increased molecular mobility using a proton at the carboxyl group terminal of the polyester as a reaction catalyst. Hydrolyzed polyester with a low molecular weight further increases molecular mobility, and progresses in hydrolysis and crystallization. As a result of this being repeated, embrittlement of the film progresses, and finally, even a slight impact results in a state of breaking. Since such a hydrolysis reaction proceeds using the carboxyl group terminal proton in the polyester resin as a reaction catalyst, the hydrolysis resistance improves as the amount of the terminal carboxyl group in the polyester resin constituting the polyester film decreases. Conceivable. The terminal carboxyl group amount is preferably 15 equivalent / t or less, more preferably 13 equivalent / t or less. Although a lower limit is not specifically limited, It is difficult to make it substantially 1 equivalent / t or less.

  In the present invention, the intrinsic viscosity (IV) of the polyester resin constituting the polyester film is 0.65 or more and 0.80 or less, preferably 0.68 or more and 0.75 or less. When the intrinsic viscosity (IV) is less than 0.65, the molecular chain is short and the molecular mobility in a heat-and-moisture resistant environment is likely to increase, and the hydrolysis resistance is likely to deteriorate due to an increase in the terminal portion. On the other hand, when it exceeds 0.80, the viscosity becomes too high, so that the productivity may be deteriorated such as an increase in breakage during film formation, and the thickness unevenness may be deteriorated.

  In addition, in the melted state when the polyester resin is melt-formed, hydrolysis and thermal decomposition with residual moisture proceed, so the intrinsic viscosity (IV) of the polyester raw material before melt extrusion used as the film raw material constitutes the film. It is preferable to make it higher than the target value of IV in the polyester resin. However, in order to increase the intrinsic viscosity (IV) of the polyester resin of the film raw material, it is necessary to lengthen the solid phase polymerization time during the production of the polyester resin or increase the amount of the catalyst added. It may lead to deterioration. Therefore, even if the intrinsic viscosity (IV) of the polyester resin of the film raw material is higher than the target value of IV in the polyester resin constituting the film, the difference is preferably small. It is preferable that the intrinsic viscosity (IV) of the polyester resin of the film raw material is 0.05 to 0.15 higher than the target value of IV in the polyester resin constituting the film. Further, the amount of terminal carboxyl groups of the polyester raw material is also increased in the melted state during melt film formation, so that it is 2 to 5 equivalents / t lower than the target value of the terminal carboxyl groups in the polyester resin constituting the film. It is preferable to use a value. In order to reduce the degradation of the polyester resin during melting, the moisture content in the polyester resin is reduced to 50 ppm or less in advance by a method such as heating the polyester resin under reduced pressure, or the film is melted into the film. The temperature of the polyester resin at the time of extrusion film formation is set to the melting point (Tm) of the polyester resin + 40 ° C. or less, and the time from landing of the extruder to the casting drum is shortened. Is preferably 5 minutes or less, particularly preferably 3 minutes or less. By these methods, hydrolysis and thermal decomposition of polyester resin during melt film formation are suppressed to reduce the decrease in intrinsic viscosity (IV) and increase in the amount of terminal carboxyl groups, and the polyester film has stable and good hydrolysis resistance. Can be obtained.

  As described above, in order to reduce the amount of terminal carboxyl groups and increase the intrinsic viscosity, solid-state weight that advances polymerization by heating under reduced pressure or a flow of an inert gas such as nitrogen gas after melt polymerization. It is preferable to apply the law. After obtaining a polyester having an intrinsic viscosity of 0.5 or more and 0.6 or less by melt polymerization, solid phase polymerization is preferably performed at a temperature of 190 ° C. or more and lower than the melting point of the polyester under reduced pressure or a flow of nitrogen gas.

  In the present invention, the content of diethylene glycol (DEG) in the polyester resin constituting the polyester film is 2.0% by mass or more and 5.0% by mass or less, preferably 2.0% by mass or more and 4.0% by mass or less. It is. In the present invention, the diethylene glycol (DEG) contained in the polyester resin is determined by the measurement method described later, and is contained alone in the polyester resin, diethylene glycol contained in the polyester resin in a state copolymerized with the polyester chain. Contains both diethylene glycol. When the content of diethylene glycol (DEG) is less than 2.0% by mass, the stretchability in the film production process is deteriorated, and there is a problem of productivity reduction due to film breakage. Problems such as easy cracking may occur, and this tendency is particularly noticeable with thick films having a thickness exceeding 200 μm. Further, when the content of diethylene glycol (DEG) exceeds 5.0% by mass, the melting point of the polyester resin is lowered or the orientation of molecules at the time of stretching is lowered, so that the heat and humidity resistance tends to be lowered. .

  In particular, films with high hydrolysis resistance so far have a high intrinsic viscosity (IV) as described above, which increases the stretching tension, and particularly stress is generated near the edge during stretching in the width direction during production at a wide width. There was a problem that concentrated and easily broken. In addition, in the film with a low amount of terminal carboxyl groups, the interaction within the molecule is weak, and the uniformity of molecular orientation is particularly likely to deteriorate at the center and both ends in the width direction, the tearing during stretching increases, and the film width There is a problem that the difference in characteristics increases depending on the position in the direction. By setting the content of diethylene glycol (DEG) in the above range, the polyester molecule is given adequate flexibility, the film is less likely to break, and the productivity is improved. Since it progresses, adhesive force and adhesion durability can also be improved. In addition, it is possible to improve workability such that the cut surface is less likely to be burred or broken when punching is performed. Furthermore, the polyester film of the present invention in which the DEG content in the polyester resin constituting the polyester film is in the above range and appropriate molecular orientation is imparted not only has good productivity and workability, but also It is also possible to prevent a decrease in durability (humidity heat resistance) under high temperature and high humidity, which has been difficult to achieve. Since the polyester film of the present invention has good stretchability due to the provision of a flexible component, it is possible to take stretching conditions with a high stretching speed, which will be described later, which was impossible because a film breakage has occurred. Since the polyester film obtained using these stretching conditions can increase the molecular orientation of the film, it can improve the durability. In addition, it is possible to reduce the difference in orientation due to the orientation difference between the central portion and the end portion in the width direction and the property difference due to the orientation difference, particularly in wide film formation, along with the improvement in durability (humidity heat resistance) under high temperature and high humidity. It is possible to reduce the characteristic difference in

  In order to make the amount of diethylene glycol (DEG) in the polyester resin constituting the film within the above range, a method of adding diethylene glycol (DEG) as a diol component at the time of polymerization of the polyester resin is the most preferable method. However, since the diethylene glycol component also occurs as a side reaction component of the ethylene glycol component, in order to stabilize the amount of diethylene glycol (DEG) within the above range, the side reaction component during the polymerization reaction can be suppressed and controlled. Necessary. Therefore, as the dicarboxylic acid component, it is preferable to use a raw material in which the terminal is esterified, such as dimethyl terephthalate. For example, when a raw material such as terephthalic acid having a terminal carboxylic acid is used as a starting material, a side reaction in which diol components react with each other easily occurs due to the carboxylic acid component. For example, when ethylene glycol is used as the diol component, diethylene glycol (DEG) is easily generated as a side reaction, and a certain amount of diethylene glycol (DEG) component is introduced into the polyester resin. However, since the amount of diethylene glycol (DEG) generated as a side reaction product is difficult to control, there is a problem that the content increases. Moreover, in order to reduce the amount of terminal carboxyl groups while suppressing the side reaction, a method of gradually adding the diol component according to the reaction so that the diol component does not become excessive with respect to the dicarboxylic acid component during the transesterification reaction. Or a method in which the temperature at the time of adding the diol component is a low temperature condition of 220 ° C. to 240 ° C. is preferable.

In the polyester film of the present invention, the polyester resin constituting the film preferably contains 0.1 to 5.0 mol / t of an alkali metal phosphate. Since alkali metal phosphates dissociate in polyester and show ionicity, protons that act as a catalyst for hydrolysis reaction can be neutralized. As a result, hydrolysis reaction by protons can be suppressed, and the heat and humidity resistance can be improved. Specific examples of the alkali metal phosphate having a buffering action include compounds represented by the following chemical formula (I), from the viewpoint of polymerization reactivity of the polyester resin, heat resistance during melt molding, and heat and humidity resistance. Potassium dihydrogen phosphate and sodium dihydrogen phosphate are particularly preferred examples.
POxHyMz: Chemical formula (I)
(Where x is an integer from 2 to 4, y is 1 or 2, z is 1 or 2, and M is an alkali metal).

  When the content of the alkali metal phosphate in the polyester resin constituting the polyester film of the present invention is less than 0.1 mol / t, sufficient heat-and-moisture resistance may not be obtained. If it exceeds 1, the decomposition reaction may be accelerated by excess alkali metal. The alkali metal phosphate content is more preferably 0.3 mol / t or more and 3.0 mol / t or less, and still more preferably 1.0 mol / t or more and 2.0 mol / t or less. Moreover, since the polyester film of this invention contains 50 mass% or more of the polyester resin containing 0.1-5.0 mol / t of the said alkali metal phosphate, in order to maintain the heat-and-moisture resistance performance of a film. It is preferably 70% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more. When the amount is less than 50% by mass, the heat-and-moisture resistance may be poor. In the present invention, the content of the alkali metal phosphate contained in the polyester resin is the amount of the alkali metal phosphate added during the synthesis of the polyester resin.

  In the polyester resin constituting the polyester film of the present invention, the ratio WA / WP of the alkali metal element content WA (ppm) and the phosphorus element content WP (ppm) is preferably 0.3 or more and 0.7 or less. By adjusting the content within this range, heat resistance stability can be imparted while maintaining the hydrolysis inhibiting effect of the polyester film. In addition, it is particularly preferable to use an alkali metal phosphate and phosphoric acid together as the phosphorus compound because the hydrolysis inhibiting effect can be further enhanced.

In the present invention, the alkali metal phosphate may be added at the time of polymerization of the polyester or at the time of melt molding. However, the alkali metal phosphate may be uniformly dispersed in the film or at the time of polymerization. In order to reduce the amount of terminal carboxyl groups, it is preferable to add at the time of polymerization. When adding at the time of polymerization, the addition time may be any time as long as it is from the end of the esterification reaction or the transesterification reaction at the time of polymerization of the polyester to the beginning of the polycondensation reaction (inherent viscosity is less than 0.3). Can be added. However, alkali metal phosphates may generate foreign substances mainly composed of phosphorus compounds in the polyester resin due to aggregation of the alkali metal phosphates themselves upon addition or polymerisation by reaction. . As a result, the filter in the film forming process may be blocked to reduce productivity, or may remain as a foreign substance in the film, resulting in problems such as deterioration in appearance and deterioration in insulation performance. Therefore, in the polyester film of the present invention, it is preferable that foreign substances containing elemental phosphorus or major axis 100μm is 10 months / 1000 cm ² or less in the film, more preferably 5 months / 1000 cm ² or less, particularly preferably 3/1000 cm ² . In order to reduce the amount of foreign matter containing phosphorus element in the polyester, the alkali metal phosphate is added in advance to a diol component such as ethylene glycol and the concentration is 1% by mass. It is preferable to add as the following solution, and it is more preferable that the concentration is 0.5% by mass or less and the diluted solution is gradually added over 20 minutes or more. Further, when the temperature of the polyester at the time of addition of the alkali metal phosphate exceeds 250 ° C., foreign matter due to the phosphorus compound is likely to be generated. Therefore, the temperature of the polyester at the time of the addition of the alkali metal phosphate is preferably 250 ° C. or less. Preferably it is 210 to 240 degreeC. When the temperature of the polyester when the alkali metal phosphate is added is less than 210 ° C., the dispersibility of the alkali metal phosphate in the polyester resin may deteriorate, which is not preferable. Examples of the method for synthesizing the polyester resin include a method using a dicarboxylic acid compound and a method using a dicarboxylic acid ester compound as a raw material of the dicarboxylic acid component, but a dicarboxylic acid compound (in the case of polyethylene terephthalate). When terephthalic acid) is used as a starting material, aggregation of the alkali metal phosphate tends to occur due to the acid component derived from the dicarboxylic acid compound. Therefore, the dicarboxylic acid component is preferably made from a dicarboxylic acid ester compound (in the case of polyethylene terephthalate, for example, dimethyl terephthalate). In addition, when using a dicarboxylic acid compound as a raw material, the density | concentration of an alkali metal phosphate is 0.5 mass% or less, and the temperature of polyester adds in the range of 210-230 degreeC, The foreign material by a phosphorus compound is added. It is possible to suppress the formation within a practical range. In the transesterification reaction using a dicarboxylic acid ester compound as a raw material, the diol component is mixed so as to have a molar ratio of 1.1 to 1.3 times the dicarboxylic acid component, and the start temperature of the transesterification reaction is 250. After promoting the initial reaction in the range of ˜270 ° C., the transesterification reaction end temperature is in the range of 220 ° C. to 240 ° C., and the diol component finally has a molar ratio of 1.5 to 2.0 times with respect to the dicarboxylic acid component. It is preferable to add a mixture of ethylene glycol and diethylene glycol during the transesterification reaction so that the reactivity is improved and the productivity of the polyester resin can be improved, and the amount of DEG contained in the polyester resin is controlled. This is preferable because it becomes easier.

  As the polycondensation catalyst for the polyester resin of the present invention, conventional antimony compounds, germanium compounds, and titanium compounds can be used. When using an antimony compound and / or a germanium compound, the sum of the antimony element and germanium element is preferably 50 ppm to 500 ppm from the viewpoint of polycondensation reactivity and solid phase polymerization reactivity, and more preferably 50 to 300 ppm. Is preferable from the viewpoint of heat resistance and hydrolysis resistance. If it exceeds 500 ppm, the polycondensation reactivity and solid-phase polymerization reactivity will improve, but the decomposition reaction during remelting will also be accelerated, leading to an increase in carboxyxyl end groups and a decrease in heat resistance and hydrolysis resistance. It may become. Examples of the antimony compound and the germanium compound that are preferably used include antimony pentoxide, antimony trioxide, and germanium dioxide, which can be used depending on the purpose. For example, the germanium compound has the best color tone, and the antimony compound has the best solid-phase polymerization reactivity. In consideration of the environment, when producing non-antimony system, a titanium catalyst is preferable in that the reactivity of polycondensation reaction or solid phase polymerization is improved. Furthermore, it is preferable to add a manganese compound in the range of 100 to 300 ppm because hydrolysis resistance is improved. This is presumably because manganese has high hydration energy and low affinity with water in the polyester film, so that the hydrolysis reaction does not proceed easily. When it is less than 100 ppm, the hydrolysis inhibiting effect is insufficient, and when it exceeds 300 ppm, the hydrolysis resistance tends to deteriorate.

  The polyester resin constituting the polyester film of the present invention is a polyester obtained using a dicarboxylic acid component and a diol component as main raw materials.

  Examples of the dicarboxylic acid component used in the present invention include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimer acid, eicosandioic acid, pimelic acid, azelaic acid, methylmalonic acid Aliphatic dicarboxylic acids such as ethylmalonic acid, adamantane dicarboxylic acid, norbornene dicarboxylic acid, isosorbide, cyclohexanedicarboxylic acid, decalin dicarboxylic acid, and the like, terephthalic acid, isophthalic acid, phthalic acid, 1,4- Naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 4,4′-diphenyl dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 5-sodium sulfo Isophthalic acid, Fe Toluene boys carboxylic acid, anthracene dicarboxylic acid, phenanthrene carboxylic acid, 9,9'-bis (4-carboxyphenyl) dicarboxylic acids such as fluorene acids and aromatic dicarboxylic acids, or there may be mentioned an ester derivative thereof is not limited thereto. Also preferred are those obtained by adding oxyacids such as l-lactide, d-lactide, hydroxybenzoic acid, and derivatives thereof, or a combination of a plurality of oxyacids to the carboxy terminus of the dicarboxylic acid component described above. Used. Moreover, these may be used independently or may be used in multiple types as needed.

  Examples of the diol component used in the present invention include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, and the like. Aliphatic diols, cycloaliphatic dimethanol, spiroglycol, isosorbide and other alicyclic diols, bisphenol A, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 9,9'-bis (4- Examples thereof include, but are not limited to, diols such as hydroxyphenyl) fluorene and aromatic diols, and those in which a plurality of the above diols are linked. Moreover, these may be used independently or may be used in multiple types as needed.

  Moreover, it is preferable to use further the component (A) whose sum total of a carboxylic acid component and a hydroxyl component is 3 or more for the polyester resin of this invention. The addition amount is preferably 0.005 mol% or more and 2.0 mol% or less when the total amount of monomer raw materials for synthesizing the polyester resin is 100 mol%. Examples of the component (A) in which the total number of carboxylic acid groups and hydroxyl groups is 3 or more include, as trifunctional aromatic carboxylic acid components, trimesic acid, trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, anthracentricarboxylic Examples of the trifunctional aliphatic carboxylic acid component include methanetricarboxylic acid, ethanetricarboxylic acid, propanetricarboxylic acid, and butanetricarboxylic acid. Examples of the component (A) having 3 or more hydroxyl groups include Examples thereof include hydroxybenzene, trihydroxynaphthalene, trihydroxyanthracene, trihydroxychalcone, trihydroxyflavone, trihydroxycoumarin, and pentaerythritol.

  Furthermore, it is also possible to contain a terminal carboxyl group sealing agent such as an epoxy compound, a carbodiimide compound, or an oxazoline compound to the extent that the effects of the present invention are not impaired.

  Moreover, in the polyester resin which comprises the polyester film of this invention, 90 mol% or more and 100 mol% or less of the ratio of the aromatic dicarboxylic acid component in all the dicarboxylic acid components in polyester are preferable. More preferably, it is 95 mol% or more and 100 mol%. More preferably, it is 98 mol% or more and 100 mol% or less, particularly preferably 99 mol% or more and 100 mol% or less, and most preferably 100 mol%, that is, all dicarboxylic acid components should be aromatic dicarboxylic acid components. If it is less than 90 mol%, the heat and moisture resistance and heat resistance may decrease. In the polyester film of the present invention, by making the ratio of the aromatic dicarboxylic acid component in the total dicarboxylic acid component in the polyester 90 mol% or more and 100 mol% or less, it becomes possible to achieve both heat and moisture resistance and heat resistance. .

  The polyester resin which comprises the polyester film of this invention makes the repeating unit which consists of a dicarboxylic acid component and a diol component the main repeating unit. The main repeating units consisting of a dicarboxylic acid component and a diol component are ethylene terephthalate, ethylene-2,6-naphthalene dicarboxylate, propylene terephthalate, butylene terephthalate, 1,4-cyclohexylenedimethylene terephthalate, ethylene-2,6-naphthalene. What consists of a dicarboxylate and these mixtures is used suitably. In addition, the main repeating unit here represents that it is 70 mol% or more of all the repeating units. More preferably, it is 80 mol% or more, More preferably, it is 90 mol% or more. Furthermore, it is preferable that ethylene terephthalate, ethylene-2,6-naphthalenedicarboxylate, and a mixture thereof are main repeating units in that they can be easily polymerized at low cost and have excellent heat resistance. . In this case, when more ethylene terephthalate is used as a structural unit, a cheap and versatile film having heat and heat resistance can be obtained, and more ethylene-2,6-naphthalenedicarboxylate is used as a structural unit. When used, the film can be made more excellent in heat and moisture resistance.

  Further, in the polyester resin constituting the polyester film of the present invention, various additives such as antioxidants, heat stabilizers, weathering stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic Fine particles, fillers, antistatic agents, nucleating agents, cross-linking agents, etc. may be added to such an extent that the properties are not deteriorated. In particular, it is preferable to contain inorganic particles such as titanium dioxide having a high concealment property or an ultraviolet absorber in the polyester film in order to impart ultraviolet cut ability, and in particular, titanium dioxide has a high concealability and high reflectance. When used as a solar cell sealing film, the internal wiring is less visible, or when used as a back side sealing film, it contributes to improving power generation efficiency by reflecting light that was not used for power generation. Is preferable.

  Titanium dioxide includes titanium dioxide having anatase and rutile crystal structures, but the rutile type has a higher refractive index because the crystal structure is denser than the anatase type. Therefore, the titanium dioxide used in the present invention is preferably rutile titanium dioxide from the viewpoint that a concealing effect due to high reflection action can be obtained.

  As a production method of the titanium dioxide particles, mainly a sulfuric acid method and a chlorine method are exemplified. In the sulfuric acid process, ilmenite ore is dissolved in concentrated sulfuric acid, iron is separated as iron sulfate, and the solution is hydrolyzed to precipitate and separate titanium as a hydroxide. Next, titanium dioxide can be obtained by baking this hydroxide with a high-temperature rotary keeln or the like. On the other hand, in the chlorine process, rutile ore is used as a raw material and reacted with chlorine gas and carbon at a high temperature of about 1,000 ° C. to produce titanium tetrachloride. Then, titanium tetrachloride is separated and oxidized while being injected at high speed. By doing so, titanium dioxide can be obtained. Compared to the sulfuric acid process, titanium dioxide produced by the chlorine process is synthesized by a gas phase reaction involving only gas, so there are few impurities such as vanadium, iron, and manganese, and high purity titanium dioxide is used. It can be obtained and is particularly preferred.

  The titanium dioxide used in the present invention is preferably surface-treated in order to suppress the photocatalytic activity of titanium dioxide or to improve the dispersibility in the polyester resin. In order to suppress the photocatalytic activity, for example, a method of coating the surface with an inorganic oxide such as silica or alumina can be mentioned. In order to improve dispersibility, for example, a method of surface treatment with a siloxane compound or a polyol can be used.

  The particle size of titanium dioxide used in the present invention is preferably 0.1 μm to 0.5 μm. The wavelength at which the light reflection ability of titanium dioxide is maximized is about twice the wavelength of the titanium dioxide particle size, and if the titanium dioxide particle size is in the above range, the reflection efficiency in the visible light region is increased. For example, when used as a sealing film for solar cells, the power generation efficiency is improved, which is preferable. The particle size of titanium dioxide is particularly preferably 0.2 μm to 0.4 μm. When the particle diameter of titanium dioxide is less than 0.1 μm, the titanium dioxide particles tend to aggregate and tend to be difficult to disperse, and when it exceeds 0.5 μm, the reflection efficiency in the visible light region tends to decrease. The average particle diameter of the titanium dioxide particles referred to here means that the laminated film was incinerated and then observed with a scanning electron microscope (SEM) at a magnification of 20,000 times. The number average particle diameter was obtained.

  As a quantity of the titanium dioxide particle contained in the polyester resin which comprises the polyester film of this invention, 2-25 mass% is preferable, More preferably, it is 3-20 mass%. When the content is less than 2% by mass, the concealing property may be insufficient. When the content exceeds 25% by mass, film breakage may easily occur during stretching, or the heat and moisture resistance may be reduced. In the polyester film of the present invention, the polyester film is coextruded and laminated in the thickness direction, and one surface side thereof has an ultraviolet ray containing 10 to 25% by weight of titanium dioxide particles as a blocking functional layer, and the other side. By making the amount of titanium dioxide particles 2 to 8% by mass on the surface side and making it a layer intended to maintain durability in a humid heat environment, it is possible to achieve both high UV durability and high moisture resistance. Therefore, it is preferable. At this time, when the ratio of the thickness of the layer containing 10 to 25% by weight of the titanium dioxide particles and the layer containing 2 to 8% by weight of the titanium dioxide particles is 1:10 to 1: 5, the ultraviolet durability is high. It is possible to achieve a good balance between moisture and heat resistance, which is more preferable. In addition, when the titanium-type compound which has normal photocatalytic reactivity is contained in a polyester film, the hydrolysis of a polyester film is accelerated | stimulated from the height of the catalytic activity, and durability in a humid heat environment falls. However, even when the polyester film of the present invention contains a titanium-based compound (titanium-based particles), it becomes possible to maintain high moisture and heat resistance.

  Further, preferable examples of the ultraviolet absorber usable in the present invention include salicylic acid compounds, benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, benzoxazinone compounds, and cyclic imino ester compounds. However, benzoxazinone compounds are most preferable from the viewpoint of dispersibility. These compounds can be used alone or in combination of two or more. In addition, stabilizers such as HALS and antioxidants can be used in combination, and it is particularly preferable to use a phosphorus-based antioxidant in combination.

  The polyester film of the present invention is a biaxially oriented polyester film. The term “biaxial orientation” as used herein refers to a pattern showing a biaxial orientation pattern by wide-angle X-ray diffraction. A biaxially oriented polyester film can be generally obtained by stretching an unstretched polyester sheet in the sheet longitudinal direction and width direction, and then performing a heat treatment to complete crystal orientation.

  The polyester film of the present invention preferably has an average conduction velocity of 2.2 km / second or more. The ratio of the maximum value and the minimum value of the ultrasonic conduction velocity of the film is preferably 1.0 or more and 1.3 or less. In the present invention, the average ultrasonic conduction velocity of the film refers to the ultrasonic conduction velocity measured by the measurement method described later, with the longitudinal direction of the polyester film as the reference (0 °), and the film is rotated about the perpendicular of the film. 16 points are measured every 11.25 ° from 0 ° to 180 °, and the average value of the obtained values is shown. In the present invention, the ratio of the maximum value and the minimum value of the ultrasonic conduction velocity of the film is the minimum value of the ultrasonic conduction velocity calculated from the measurement result of the average ultrasonic conduction velocity of the film. Indicates the divided value (maximum value / minimum value). The ultrasonic conduction velocity of the film is an index related to the orientation of the polyester chain constituting the polyester film, and the higher the ultrasonic conduction velocity, the stronger the orientation of the polyester chain in that direction. As described above, when the polyester film is exposed to a moist heat atmosphere, moisture (water vapor) enters the interior through the molecules of the amorphous part having a low density, plasticizing the amorphous part, and increasing the molecular mobility. However, when the molecular orientation is strong, the mobility of the amorphous part is limited, so that it is possible to improve the durability in a humid heat environment. Therefore, when the average ultrasonic conduction velocity of the film is less than 2.2 km / second, the moist heat resistance tends to deteriorate. The average ultrasonic conduction velocity is preferably 2.25 km / second or more, more preferably 2.3 km / second or more. In addition, when the ratio between the maximum value and the minimum value of the ultrasonic conduction velocity exceeds 1.3, the difference in moisture and heat resistance performance depending on the direction becomes large and the balance deteriorates, and in particular, the moisture and heat resistance becomes weak in the direction of the minimum value. It is not preferable. The ratio between the maximum value and the minimum value of the ultrasonic conduction velocity is more preferably 1.0 or more and 1.25 or less.

  In the polyester film of the present invention, the angle (θ) of the acute angle (0 ° or more and 90 ° or less) of the angle formed between the direction in which the ultrasonic conduction velocity of the film shows the maximum value and the film longitudinal direction (hereinafter, (It may be referred to as misalignment of the orientation angle), but even at a position away from the central portion in the width direction of the film such that it is 10 ° or more, it is possible to maintain a state where the difference in wet heat resistance performance depending on the in-plane direction is small. it can. The direction in which the ultrasonic conduction velocity exhibits the maximum value is the direction in which the orientation of the biaxially oriented polyester film is the strongest (the long axis direction (hereinafter, the direction with the stronger orientation of the two orientation axes of the biaxially oriented polyester film). The major axis and the weaker orientation are referred to as minor axes)), and the angle (θ) represents the angle formed by the major axis direction and the longitudinal direction of the film. In addition, in the center part in the width direction in the intermediate product of the biaxially oriented polyester film that is not cut in the width direction after film production, the orientation axis of the film is usually two directions of the longitudinal direction and the width direction. Which direction is the major axis and which is the minor axis depends on the film production method. When the draw ratio in the longitudinal direction of the film is higher than the width direction of the film, the major axis of orientation is the longitudinal direction, and the direction showing the maximum value of the ultrasonic conduction velocity is also the longitudinal direction of the film. In this case, the angle (θ) is 0 ° in the central portion in the film width direction. As the distance from the central portion in the film width direction increases, the major axis is displaced due to the bowing phenomenon or the like, and when the major axis is displaced by 10 °, the angle (θ) is 10 °. On the other hand, when the draw ratio in the width direction of the film is higher than the longitudinal direction of the film, the major axis of orientation is the width direction, and the direction showing the maximum value of the ultrasonic conduction velocity is also the width direction of the film. In this case, the angle (θ) is 90 ° at the central portion in the film width direction. As the distance from the center in the film width direction increases, the major axis shifts due to the bowing phenomenon or the like, and when the major axis shifts by 10 °, the angle (θ) becomes 80 °. In recent years, in order to improve productivity, the biaxially oriented polyester film that is the final product is manufactured from a biaxially oriented polyester film with a wide width to obtain an intermediate product. A method of cutting out dozens is performed. At the center in the width direction of the intermediate product, as described above, the angle (θ) when the orientation is high in the film longitudinal direction is 0 °, and the angle (θ) when the orientation is high in the film width direction is 90 °. As the polyester film moves away from the central portion in the width direction (approaching the end portion), a misalignment of the orientation angle generally occurs due to the bowing phenomenon. When the orientation in the film longitudinal direction is high, the angle (θ) increases from 0 °, and when the orientation in the film width direction is high, the angle (θ) decreases from 90 °. As described above, the orientation angle shift occurs, the orientation difference between the major axis direction and the minor axis direction increases, and the characteristic difference depending on the direction in the film plane also increases. As described above, the biaxially oriented polyester film of the present invention has an alignment axis misalignment of 10 ° or more, that is, an angle (θ) of 10 ° or more and 80 ° or less, and further an alignment axis misalignment of 20 ° or more, that is, an angle (θ ) Is 20 ° or more and 60 ° or less in the width direction end position, as described above, the difference in the in-plane ultrasonic conductivity is small, that is, the orientation difference is kept small, so that the moisture and heat resistance performance is maintained. It is possible to reduce the difference due to the direction of the. If the angle (θ) is more than 40 ° and less than 50 °, there may be a tendency that the half-elongation tends to increase or the difference in shrinkage rate in the oblique direction increases.

  In addition, as described above, the durability (wet heat resistance and thermal stability) of the film can be improved by increasing the intrinsic viscosity (IV) of the polyester resin constituting the film and decreasing the amount of terminal carboxyl groups. In addition, the processability of the film can be improved by adjusting the DEG amount in the polyester resin constituting the film to an appropriate amount. However, further improvements in durability and workability are required for insulating paper for motors and films for sealing solar cells. For this reason, the polyester resin constituting the polyester film of the present invention needs to have a minute endothermic peak temperature (Tmeta) determined by differential scanning calorimetry (DSC) of 150 ° C. or higher and 200 ° C. or lower. The intrinsic viscosity (IV) of the polyester resin constituting the polyester film is 0.65 to 0.80, the terminal carboxyl group amount is 20 equivalent / t or less, and the diethylene glycol content is 2.0 mass% or more and 5.0 mass% or less. And if the endothermic peak temperature (Tmeta) required by differential scanning calorimetry (DSC) of the polyester resin constituting the polyester film is 150 ° C. or higher and 200 ° C. or lower, durability (moisture and heat resistance, thermal stability), processing A film having dramatically improved properties can be obtained. This effect is estimated to be obtained by the following mechanism. Tmeta is a value corresponding to the amount of heat applied to the film in the heat treatment step, and the higher the value, the higher the temperature and the longer the heat treatment. In the process for producing a biaxially oriented film, the heat treatment step applies heat to the biaxially oriented film, thereby increasing the crystallinity of the polyester molecules in the film and imparting thermal stability and the like. In this step, the molecular regularity of part of the amorphous component is relaxed simultaneously with the crystal growth in the molecule. It is considered that the film orientation and wet heat resistance are affected by the relaxation of the orientation of the amorphous part. When extremely high durability (moisture heat resistance, thermal stability) and workability are required as in the present invention, it is necessary to control the Tmeta value within the above range. When Tmeta is less than 150 ° C., the progress of crystallization is insufficient and thermal stability, chemical resistance, and workability may be inferior. When Tmeta exceeds 200 ° C., the heat and moisture resistance is deteriorated. Tmeta is preferably 160 ° C. or higher and 190 ° C. or lower. A method for setting Tmeta in the above range is not particularly limited, but it is preferable to perform a heat treatment at a temperature of 160 ° C. to 210 ° C. for 5 seconds to 60 seconds.

  When heat treatment is performed as described above or when a lot of DEG components are contained, the molecular orientation generally decreases, but by applying the manufacturing method shown below, the orientation in the film can be maintained, Even at a position where the orientation axis is deviated by 10 ° or more, the average ultrasonic conduction velocity and the maximum / minimum value of the ultrasonic conduction velocity can be controlled within the above ranges, which is preferable.

  It is preferable to have the process of extending | stretching 3.0 to 4.5 times in a longitudinal direction as a manufacturing method of the polyester film of this invention. The film temperature during stretching in the longitudinal direction is preferably Tg or more and Tg + 40 ° C. or less, more preferably Tg + 10 ° C. or more and Tg + 30 ° C. or less when the glass transition temperature of the polyester resin is Tg (° C.).

As a method for producing the polyester film of the present invention, the stretch amount is 3.5 to 4.5 times in the width direction, and the stretch amount at the midpoint of the width direction stretch step is 60 to 80 of the stretch amount at the end of the width direction stretch step. % Is preferable. When the stretching amount at the midpoint of the width direction stretching step is 60 to 80% of the stretching amount at the end of the width direction stretching step, the film width before starting the width direction stretching step is W0, When the film width at the intermediate point is W1 and the film width at the end of the width direction stretching step is W2, the following formula (A) is satisfied.
60 <= 100 * (W1-W0) / (W2-W0) <= 80 ... Formula (A).

Further, there is an intermediate step between the width direction stretching step and the heat treatment step, and the atmosphere temperature of the intermediate step is the first temperature corresponding to the atmospheric temperature: Ts (° C.) in the final section of the width direction stretching step and the first section of the heat treatment step. It is preferable that the following formula (B) is satisfied when the atmosphere temperature of the heat treatment process: Th (° C.) and the time during which the film passes through the intermediate process is Sm (seconds). The atmosphere temperature in the intermediate process is preferably a temperature close to the middle of Th and Ts from the viewpoint of ease of temperature control, ((Ts + Th) / 2) −20 (° C.) or more, ((Ts + Th) / 2) It is still more preferable that it is +20 (degreeC) or less. Also, in the intermediate process, part of hot air blown to the film in the stretching process and heat treatment process may flow in and the temperature may become unstable, so the exhaust process can keep the temperature more stable. Therefore, it is preferable.
(Th-Ts) / Sm <= 50 ... Formula (B).

  In addition, the heat treatment process here refers to the process which advances crystallization by heating a film using heating means, such as a means to blow the hot air heated to the film, and a radiation heater. In the heat treatment step, as described above, it is preferable to perform the treatment at 160 ° C. or more and 210 ° C. or less for 5 seconds or more and 60 seconds or less.

  The intermediate step in the present invention is located in the middle of the width direction stretching step and the heat treatment step, does not have a means for heating the film, and both ends in the width direction without changing the dimension of the film in the longitudinal direction and the width direction. This refers to the process of conveying while holding. In order to suppress temperature fluctuation in the intermediate process, it is preferable that the periphery is surrounded by a heat insulating wall or the like. The atmospheric temperature in the intermediate step is preferably a temperature between Th and Ts, more preferably ((Ts + Th) / 2) −20 (° C.) or more and ((Ts + Th) / 2) +20 (° C.) or less.

  In the production of a biaxially stretched film, the film on the heat treatment process side is in the width direction stretch side in the width direction center part where the film is not held by the stretching tension at the time of width direction stretching in the film width direction stretching to the heat treatment process. Therefore, a bowing phenomenon occurs in which the orientation angle shifts in an oblique direction as it goes to the end in the width direction. Due to this phenomenon, the difference in the direction of the polyester molecular orientation in the film plane increases toward the end in the width direction. As described above, unevenness in molecular orientation is not preferable because it affects the durability of the film in a moist heat environment. By having the width direction stretching step and the intermediate step, the stretching tension at the time of width direction stretching becomes difficult to propagate to the heat treatment step, and distortion of the film orientation axis can be suppressed. When the stretching ratio in the width direction is less than 3.5 times, when the stretching amount at the midpoint of the width direction stretching step is less than 60% of the stretching amount at the end of the width direction stretching step, or (Th-Ts ) When the value of / Sm exceeds 50, the effect of improving the distortion of the film orientation axis becomes insufficient, and the ratio of the maximum value and the minimum value of the ultrasonic conduction velocity of the film at the end in the width direction exceeds 1.3. There is. When the stretching ratio in the width direction exceeds 4.5 times, or when the stretching amount at the midpoint of the stretching direction in the width direction exceeds 80% of the stretching amount at the end of the stretching process in the width direction, the film breaks during stretching. It is likely to occur and productivity may be inferior. Furthermore, the value of (Th−Ts) / Sm is preferably less than 40, and particularly preferably less than 30. Moreover, about the temperature of the width direction extending | stretching process, Tg or more and Tg + 40 degrees C or less are preferable, More preferably, they are Tg + 10 degreeC or more and Tg + 30 degrees C or less. In addition, the heat treatment process is divided into a plurality of processes, and the method of lowering the temperature Th in the first process corresponding to the first section and increasing the temperature step by step reduces the influence of bowing, while allowing the treatment at an appropriate heat treatment temperature. This is particularly preferable because it can be carried out.

  In order to reduce the production cost of the film, for example, it is necessary to produce a biaxially oriented polyester film with a wide width such that the film width exceeds 2 m. Since the orientation axis at the part position is inclined, it is particularly preferable to use the above production method when producing such a wide film. In addition, when applying conditions such as the above stretching speed is high, generally the load during stretching to the film is large, especially when using a polyester resin having a high intrinsic viscosity for maintaining durability, There is a problem that film breakage increases. However, the polyester film of the present invention can be produced without deteriorating productivity by using a means such as adjusting the amount of diethylene glycol (DEG) in the film to an appropriate amount as described above. It became.

  The polyester film of the present invention preferably has an elongation retention of 50% or more when held at a temperature of 125 ° C. and a humidity of 100% Rh for 72 hours, more preferably 60% or more. In the present invention, the elongation retention rate of 50% or more means that the elongation retention rate is 50% or more in both the directions in which the ultrasonic conduction velocity is maximum and the minimum direction. Represents. When a film is used, a force is often applied in all directions of the film. When the heat and humidity resistance in a specific direction is poor, the film is likely to crack or break from that direction. Therefore, a film having the above-described elongation retention rate in a direction in which the polyester molecular chain orientation is low, that is, the ultrasonic conduction speed is minimum, that is, the direction most disadvantageous in wet heat resistance is preferable because it has high durability. When the elongation retention is less than 50%, there may be a problem that the film deteriorates and breaks or breaks during long-term use.

  The thickness of the polyester film of the present invention is preferably 200 μm or more and 500 μm or less. If the film thickness is less than 200 μm, the film will become weak. For example, when used as an insulating paper for a motor, the shape retention will deteriorate and the film will be broken when inserted into a motor. May be inferior. On the other hand, when it is thicker than 500 μm, it tends to be difficult to achieve both heat resistance and productivity, such as being easily broken in the film stretching process. A thick film of 200 μm or more is easily deteriorated in stretchability and workability because it is thick, and it is difficult to maintain productivity and workability as compared with a film of less than 200 μm. This makes it possible to maintain productivity and workability.

  Next, although an example is demonstrated about the manufacturing method of the polyester film of this invention, this invention is limited to only the thing obtained by this example, and is not interpreted.

  First, as an example of the polymerization step, the polyester resin production method includes a first step of performing an esterification reaction or a transesterification reaction, a second step of adding an additive such as an alkali metal phosphate, and a polymerization reaction. It can be manufactured by the third step, and if necessary, a fourth step for performing a solid phase polymerization reaction may be added.

  In the first step, dimethyl terephthalate as the dicarboxylic acid component, and a mixture of ethylene glycol and diethylene glycol as the diol component, the molar ratio of the diol component is 1.1 to 1.3 times the molar ratio of the dicarboxylic acid component. After mixing, a known polymerization catalyst such as antimony trioxide and a manganese-based metal catalyst are added at a temperature of 220 to 270 ° C., and a mixture of ethylene glycol and diethylene glycol is added to the final diol component and dicarboxylic acid. The transesterification reaction is carried out while adding the acid component in a molar ratio of 1: 1.5 to 1: 2.0.

  The second step is a step of adding an additive such as an alkali metal phosphate after the transesterification reaction is substantially completed until the intrinsic viscosity reaches 0.3. The alkali metal phosphate is mixed in such a ratio that the ratio of phosphoric acid, the amount of alkali metal element and the amount of phosphorus element is in the range of 0.3 to 0.7, and further diluted with ethylene glycol to a concentration of 1% by mass or less. Added. It is more preferable to adjust the pH of the mixed dilution at this time to an acidity of 4.0 or more and 6.0 or less from the viewpoint of suppressing the generation of foreign matter. Further, the alkali metal phosphate is preferably added in such a manner that the temperature of the polyester at the time of addition is 240 ° C. or less and the addition time is 20 minutes or more, from the viewpoint of suppressing foreign matter formation. Moreover, you may add a trace amount alkali compounds, such as potassium hydroxide, as a method of reducing the carboxyl group terminal number of polyester obtained by superposition | polymerization.

  In the third step, the polymerization reaction can be performed by a known method. In order to further reduce the amount of terminal carboxyl groups of the polyester obtained by polycondensation in the range of 20 equivalent / t or less and to increase the intrinsic viscosity of the polyester, after the above polymerization, as the fourth step, 190 ° C. or higher It is preferable to perform so-called solid-state polymerization, in which heating is performed under reduced pressure or a flow of an inert gas such as nitrogen gas at a temperature lower than the melting point of the polyester. In this case, after polymerizing the polyester having an intrinsic viscosity of 0.5 or more and 0.6 or less in the third step, the fourth step is performed at a temperature of 190 ° C. or more and lower than the melting point of the polyester, under reduced pressure or inert such as nitrogen gas. Solid-phase polymerization is preferably performed by heating in a gas flow. If the intrinsic viscosity of the polyester obtained in the third step is less than 0.5, the chip is easily cracked and the shape becomes non-uniform, resulting in unevenness in the degree of polymerization of the polyester obtained by solid phase polymerization in the fourth step. May occur. Moreover, when the intrinsic viscosity of the polyester obtained in the third step is larger than 0.6, the thermal deterioration in the third step becomes severe, and as a result, the amount of terminal carboxyl groups of the obtained polyester is increased and formed into a film. Since hydrolysis resistance may fall, it is not preferable. By setting the intrinsic viscosity of the polyester obtained in the third step to 0.5 or more and 0.6 or less, a polyester having a uniform intrinsic viscosity is maintained in a state where the number of carboxyl group terminals is kept low when solid-phase polymerization is performed. Can be obtained. As a result, it is possible to further improve the hydrolysis resistance when the film is formed.

  Next, it illustrates about the method of manufacturing a polyester film using the obtained polyester resin.

  The polyester resin obtained by the above method is heated under vacuum and dried so that the inherent moisture content is 50 ppm or less. Drying is preferably performed at a vacuum degree of 3 kPa or less and a temperature of 160 ° C. or more for 3 hours or more. Next, the dried polyester resin is melted at 260 to 300 ° C. with an extruder, foreign matter is filtered with a filter, and then extruded into a sheet form from a T-shaped die. The surface temperature is 10 to 60 ° C. using an electrostatic application casting method. It is wound around a mirror casting drum and cooled and solidified to obtain an unstretched film. In order to suppress hydrolysis of the polyester resin in this step and prevent a decrease in intrinsic viscosity (IV) and an increase in the amount of terminal carboxyl groups, the moisture content of the polyester resin supplied to the extruder should be reduced as much as possible. Is preferred. Further, it is preferable that the time from the extrusion of the resin from the extruder to the landing on the casting drum is as short as possible. As a guideline, it is preferably 10 minutes or less, more preferably 5 minutes or less, and particularly preferably 3 minutes or less.

  After preheating this unstretched film with a roll heated to 70 to 100 ° C., it is stretched 3.0 to 4.5 times in the longitudinal direction while being heated to a temperature of 90 to 120 ° C. using a radiation heater or the like, and uniaxial. An oriented film is obtained. Further, the film is guided to an oven while being fixed with clips at both ends and heated at a temperature of 70 to 150 ° C, and continuously stretched 3.5 to 4.5 times in the width direction in a heating zone of 70 to 150 ° C. Subsequently, heat treatment is performed in a heating zone at 160 to 210 ° C. for 5 to 60 seconds, and a biaxially oriented polyester film having crystal orientation completed is obtained through a cooling zone at 100 to 200 ° C. In addition, you may perform a 3-12% relaxation process as needed during the said heat processing. In the stretching process in the width direction, the stretching amount at the midpoint of the stretching process in the width direction is 60 to 80% of the stretching amount at the end of the stretching process in the width direction, and between the stretching process in the width direction and the heat treatment process. In addition, there is no means for heating the film, and there is an intermediate process that conveys the film while holding both ends in the width direction without changing the dimension of the film in both the longitudinal direction and the width direction. It is preferable that the temperature change amount (° C.) is 50 ° C./second or less because distortion of the alignment axis due to bowing can be suppressed.

  In addition, simultaneous biaxial stretching can also be used for biaxial stretching. Moreover, after extending | stretching a longitudinal direction and the width direction, you may re-extend to both the direction of a longitudinal direction and the width direction, or any one direction before a heat treatment process. After cutting the end of the obtained biaxially oriented laminated polyester film, it is made into a winding intermediate product, then cut to a desired width using a slitter, and then wound around a cylindrical core to obtain a polyester film roll having a desired length. be able to. In addition, you may give an embossing process to both ends of a film for winding-up improvement at the time of winding.

  The polyester film of the present invention thus obtained is an excellent film having very high moisture and heat resistance and good workability and productivity, particularly for insulating paper for motors and solar cell sealing. Suitable as a film.

[Measurement method of physical properties]
Hereinafter, the configuration and effects of the present invention will be described more specifically with reference to examples. In addition, this invention is not limited to the following Example. Prior to describing each example, a method for measuring various physical properties will be described.

(1) Diethylene glycol (DEG) content 1.0 g of a measurement sample (polyester resin or polyester film) was hydrolyzed at 260 ° C. using 2.5 mL of monoethanolamine as a solvent. Next, 10 mL of methanol was added, cooled, neutralized with terephthalic acid, centrifuged, and then the supernatant was measured for diethylene glycol (DEG) content by gas chromatography (GC-14A, manufactured by Shimadzu Corporation). In addition, since additional components, such as inorganic particles, settle as an insoluble substance during centrifugation, the sedimented components were filtered and weighed, and the weight was subtracted from the measured sample weight to correct the measured sample weight.

(2) Intrinsic viscosity (IV)
A polyester resin or a polyester film was dissolved in 100 mL of orthochlorophenol (solution concentration C = 1.2 g / mL), and the viscosity of the solution at 25 ° C. was measured using an Ostwald viscometer. Similarly, the viscosity of the solvent was measured. Using the obtained solution viscosity and solvent viscosity, [η] was calculated by the following formula (C), and the obtained value was used as the intrinsic viscosity (IV).
ηsp / C = [η] + K [η] ² · C Formula (C)
(Where ηsp = (solution viscosity / solvent viscosity) −1, K is a Huggins constant (assuming 0.343)
It is. ).

  If there is insoluble matter such as inorganic particles in the solution in which the polyester resin or polyester film is dissolved, the solution is filtered and weighed, and the value obtained by subtracting the weight of the filtrate from the measured sample weight The following correction was made.

(3) Amount of terminal carboxyl group The amount was measured according to the following method in accordance with the method of Malice (reference MJ Malice, F. Huizinga. Anal. Chim. Acta, 22 363 (1960)).
2 g of polyester resin or polyester film was dissolved in 50 mL of o-cresol / chloroform (weight ratio 7/3) at a temperature of 80 ° C., titrated with a 0.05 N KOH / methanol solution, the terminal carboxyl group concentration was measured, / Indicated by the value of polyester 1t. In addition, the indicator at the time of titration used phenol red, and the place where it changed from yellowish green to light red was set as the end point of titration.

  If there is insoluble matter such as inorganic particles in the solution in which the polyester resin or polyester film is dissolved, the solution is filtered and weighed, and the value obtained by subtracting the weight of the filtrate from the measured sample weight The following correction was made.

(4) Alkali metal element content Quantification was performed by atomic absorption spectrometry (manufactured by Hitachi, Ltd .: polarized Zeeman atomic absorption photometer 180-80, frame: acetylene-air).

(5) Phosphorus element and manganese element content Measured using a wavelength dispersive X-ray fluorescence spectrometer (model number: ZSX100e) manufactured by Rigaku Corporation.

(6) Number of foreign substances containing phosphorus element Using a three-wavelength fluorescent lamp as a light source, the film was inspected 1000 cm ² with transmitted light and reflected light, and the observed foreign substances were marked to collect samples. At this time, the distance between the light source and the film was adjusted so that the amount of light at the film position was 1000 lux. The obtained foreign material sample was observed with an optical microscope (magnification 100 times) and measured in the direction in which the size of the foreign material was the largest, and was taken as the long diameter of the foreign material. In addition, an energy dispersive X-ray analyzer (EDX) EMAX-7000 (manufactured by Horiba, Ltd.) was attached to a scanning electron microscope (SEM) S-4300A (manufactured by Hitachi, Ltd.) as a foreign material sample. Elemental analysis of the foreign matter portion was performed using an apparatus, the presence or absence of phosphorus element was measured, and the number of foreign matters containing phosphorus element having a major axis of 100 μm or more was counted.

(7) Ultrasonic conduction velocity of the film and the angle (θ) between the direction in which the ultrasonic conduction velocity exhibits the maximum value and the longitudinal direction of the film
A film sample of 300 mm in the width direction and 300 mm in the longitudinal direction is collected from the center and the endmost rolls of the middle roll, and 300 mm in the longitudinal direction from each roll, and is manufactured by Nomura Shoji Co., Ltd. SONIC SHEEET TESTER SST-4000. The longitudinal direction of the polyester film is taken as the reference (0 °), and the film is rotated around the normal of the film. The ultrasonic conduction velocity (km / sec) is increased from 0 ° to 180 ° every 11.25 ° to 16 °. Point measurement was performed, and an average value of the obtained values was calculated. Further, a value obtained by dividing the maximum value of the ultrasonic conduction velocity calculated from the measurement result by the minimum value (maximum value / minimum value) was defined as the ratio between the maximum value and the minimum value of the ultrasonic conduction velocity. In addition, the measurement of the ultrasonic conduction velocity is performed on both sides of the film, and after calculating the average value of the ultrasonic conduction velocity and the (maximum value / minimum value) on each surface, the average value of the surfaces on both sides is calculated. The average value of the ultrasonic conduction velocity of the film and (maximum value / minimum value) were used. Moreover, the angle (θ) formed by the direction in which the ultrasonic conduction velocity calculated from the measurement result shows the maximum value and the film longitudinal direction was calculated. The angle (θ) refers to the acute angle (0 ° or more and 90 ° or less) of the angle formed between the direction in which the ultrasonic conduction velocity has the maximum value and the film longitudinal direction.

(8) Moisture and heat resistance evaluation (elongation retention)
Cut the film from the center roll and endmost roll of the middle roll, and the width direction center of each roll, and the direction of the maximum value and the minimum value of the ultrasonic conduction velocity measured in (7) are long. A sample for measuring elongation was cut out in a strip shape with a width of 10 mm and a length of 250 mm in each direction so as to be in the horizontal direction. The cut out sample was subjected to a treatment for 72 hours in an environment with a temperature of 125 ° C. and a humidity of 100 RH% using an advanced accelerated life test apparatus EHS-221 (manufactured by Espec). The elongation of the film before and after the treatment was measured using Tensilon under conditions of an original length (distance between chucks) of 100 mm and a pulling speed of 200 mm / min. In addition, about the elongation, it was set as the average value measured by N = 5, respectively. About the obtained film elongation, the value which remove | divided the elongation after a process by the elongation before a process was made into the elongation retention in wet-heat-resistant evaluation, and it determined on the following references | standards. B or more is a practical range.

S: The elongation retention is 60% or more A: The elongation retention is 50% or more and less than 60% B: The elongation retention is 30% or more and less than 50% C: The elongation retention is less than 30% (9) Transmission Optical Density The transmission optical density of the polyester film was calculated from the incident light flux and the transmitted light flux according to JIS K7605 (1976) using an optical densitometer (TR524 manufactured by Macbeth). A Visual filter was used as a filter at the time of measurement.

(10) Film-forming property Judgment was made according to the following criteria using a calculated value obtained by converting the number of tears when the film was formed under the conditions of Examples and Comparative Examples per day. B or more is a practical range.

S: No more than 1 break per day A: No more than 2 breaks per day B: No more than 2 breaks per day C: No more than 3 breaks per day Over.

(11) Workability (punchability)
Three of the obtained films were overlapped and punched with a Thomson punching cutter, and the cut surface was visually observed and judged according to the following criteria. B or more is a practical range.

S: No burrs or whiskers are observed A: Burrs and whiskers are less than 1 per 0.3 m length of cut surface B: Burrs and whiskers exceed 1 per 0.3 m length of cut surface 3 or less C: Burrs and whiskers exceed 3 per 0.3 m length of the cut surface.

(12) Minute endothermic peak temperature (Tmeta)
The film was measured with a differential scanning calorimeter (DSC Q100 manufactured by TA Instruments) at a temperature rising rate of 20 ° C./min in the range of 30 ° C. to 280 ° C. The minute endothermic peak temperature before the polyester crystal melting peak in the differential scanning calorimetry chart obtained by this measurement was defined as Tmeta (° C.). Tmeta appears as a history of the heat treatment temperature for the polyester film.

  The adjustment method of resin etc. used in each example and comparative example is shown as a reference example.

Reference Example 1 Preparation of Polyester Resin 1 As the first step, 100 parts by mass of dimethyl terephthalate, 37.35 parts by mass of ethylene glycol, and 1.05 parts by mass of diethylene glycol were mixed at a temperature of 260 ° C. in a nitrogen atmosphere. Thereafter, the temperature was lowered to 225 ° C., 0.068 parts by mass of manganese acetate tetrahydrate and 0.029 parts by mass of antimony trioxide were added and then stirred, and further 15.58 parts by mass of ethylene glycol and 0.42 parts of diethylene glycol. Part of the mixture was gradually added over 2 hours while distilling methanol to complete the transesterification reaction. As the second step, after completion of the transesterification reaction, the temperature of the polyester in the reaction system is set to 225 ° C., 0.015 part by mass of phosphoric acid (corresponding to 1.5 mol / t) and sodium dihydrogen phosphate dihydrate 0 An ethylene glycol solution (phosphorus compound concentration 0.4 mass%) in which 0.027 mass parts (equivalent to 1.5 mol / t) was dissolved in 6.8 mass parts of ethylene glycol was added. Subsequently, as a third step, the polymerization reaction was carried out under a reduced pressure at a final temperature of 285 ° C. and a pressure of 13 Pa to obtain a polyester having an intrinsic viscosity of 0.54 and a terminal carboxyl group content of 17 equivalents / t. Further, as a fourth step, the obtained polyethylene terephthalate was dried and crystallized at 160 ° C. for 6 hours, and then subjected to solid phase polymerization at 230 ° C. for 10 hours under a reduced pressure of 65 Pa to obtain an intrinsic viscosity (IV ) 0.82, a terminal carboxyl group content of 9.7 equivalent / t, a diethylene glycol content of 3.00 mass%, a melting point of 260 ° C., and a glass transition temperature of Tg of 81 ° C. were obtained.

[Reference Example 2] Preparation of polyester resins 2 to 24 Polyester resins were obtained using the same method as in Reference Example 1 except that the conditions shown in Table 1-1 and Table 1-2 were used. For polyester resin 5, 85.6 parts by mass of terephthalic acid instead of 100 parts by mass of dimethyl terephthalate, and for polyester resins 15 and 16, dihydrogen phosphate instead of sodium dihydrogen phosphate dihydrate. Potassium was used. Moreover, about polyester resin 6,7,22, solid phase polymerization time was adjusted so that a 4th process might become the intrinsic viscosity shown to Table 1-1, Table 1-2. Further, for the polyester resin 23, the polyester in the third step was made to have an intrinsic viscosity of 0.50 and the terminal carboxyl group amount was 27 equivalents / t, and then solid phase polymerization was carried out until the intrinsic viscosity became 0.73 in the fourth step. . Further, for polyester resins 8 and 9, trimellitic acid is used as component (A) having a total number of carboxylic acid groups and hydroxyl groups of 3 or more, and for polyester resin 10, pentaerythritol is used as a monomer raw material for synthesizing polyester. When the total was 100 mol%, the amount was added so as to be the amount shown in Table 1-1.
The results of evaluating the properties of the obtained polyester are shown in Table 1-1 and Table 1-2.

[Reference Example 3] Preparation of Silicon Dioxide-Containing Polyester Resin A To 95 parts by mass of the polyester resin 1 obtained in Reference Example 1, 5 parts by mass of silicon dioxide particles having an average particle size of 4.3 μm was 290 by a twin screw extruder. The mixture was kneaded at 0 ° C. to obtain a silicon dioxide-containing polyester resin A.

[Reference Example 4] Preparation of Rutile Titanium Dioxide-Containing Polyester Resin B To 50 parts by mass of the polyester resin 1 obtained in Reference Example 1, 2 parts by mass of 50 parts by mass of chlorine method rutile type titanium dioxide particles having an average particle size of 0.3 μm. The mixture was kneaded at 290 ° C. with a screw extruder to obtain a rutile-type titanium dioxide-containing polyester resin B.

[Example 1]
A mixture of 99.5 parts by mass of polyester resin 1 prepared according to Reference Example and 0.5 parts by mass of silicon dioxide-containing polyester resin A was dried at a temperature of 170 ° C. for 4 hours under a reduced pressure of 1 kPa, and then extruded. The melt was extruded at 285 ° C.

  After filtering with stainless steel fiber sintered and compressed through a filter with an average opening of 60 μm, it is extruded into a sheet form from a T-shaped die, wound around a mirror casting drum having a surface temperature of 20 ° C. using an electrostatic application casting method, and cooled and solidified. I was damned. This unstretched film was preheated to 85 ° C. with a preheating roll, and then stretched 3.3 times in the longitudinal direction using the difference in peripheral speed between the rolls while heating up to 100 ° C. using a radiation heater from above and below. It cooled to 25 degreeC with the cooling roll, and was set as the uniaxially oriented (uniaxial stretching) film.

  Next, a uniaxially oriented (uniaxially stretched) film is gripped with a clip, preheated with hot air of 100 ° C. in an oven, and continuously stretched 3.8 times in the width direction while continuously heated with 120 ° C. hot air in a stretching process. did. In addition, about extending | stretching of the width direction, it set so that the draw ratio in the intermediate point of an extending process shall be 3.0 time, and 71% of width direction extending | stretching may be completed at an intermediate point. The obtained biaxially oriented (biaxially stretched) film is led to a heat treatment step through an intermediate step, and the first heat treatment is carried out with hot air at 170 ° C. for 3.5 seconds, and the second heat treatment is carried out with hot air at 187 ° C. for 20 seconds. Processing was performed for seconds. In the intermediate process, the periphery was surrounded by a heat insulating wall, and heating with hot air or the like was not performed. Only the exhaust in the process was performed, and the ambient temperature was adjusted to 140 ° C. Further, the film passing time in the intermediate process was 3.5 seconds. The film subjected to the heat treatment step was subjected to a 5% relaxation treatment in the width direction at 180 ° C. and subsequently cooled to 80 ° C. Then, the film was drawn out from the oven, wound up after removing both ends in the width direction, A polyester film intermediate roll having a width of 250 μm and a width of 5.4 m was obtained. The characteristics of the obtained polyester film are shown in Table 3-1 and Table 4-1.

  Further, the obtained polyester film intermediate roll was cut with a slitter so that the intermediate roll had a width of 1000 mm × 5, and was wound around a core having an inner diameter of 152.5 mm and an outer diameter of 167 mm to obtain a laminated polyester film roll.

  The obtained film had a high heat and humidity resistance regardless of the direction at both the center and the end of the intermediate roll, and was a film having excellent durability. In addition, it is a biaxially oriented polyester film with excellent productivity and workability that has no film breakage and no burrs on the cut end face, despite the film formation under stretching conditions for molecular orientation control. It was.

[Examples 2 to 30]
Biaxially oriented polyester films were obtained in the same manner as in Example 1 except that the raw materials and film forming conditions in Table 2-1 and Table 2-2 were applied. The properties of the obtained film are shown in Table 3-1, Table 3-2, Table 4-1, and Table 4-2.

[Example 31]
A mixture of 95 parts by weight of polyester resin 1 prepared according to the reference example and 5 parts by weight of rutile-type titanium dioxide-containing polyester resin B was dried at a temperature of 170 ° C. for 4 hours under a reduced pressure of 1 kPa, Then, melt extrusion was performed at 285 ° C. Also, a mixture of 60 parts by mass of polyester resin 1 prepared according to the reference example and 40 parts by mass of rutile-type titanium dioxide-containing polyester resin B was dried at a temperature of 170 ° C. for 4 hours under a reduced pressure of 1 kPa, and then an extruder. B was supplied to B and melt extrusion was performed at 285 ° C. The molten resin extruded from the extruder A and the molten resin extruded from the extruder B are each filtered through a filter having an average opening of 60 μm obtained by sintering and compressing stainless steel fibers, and then two layers in the thickness direction using a feed block. And then extruded into a sheet form from a T-shaped die, wound around a mirror casting drum having a surface temperature of 20 ° C. using an electrostatic application casting method, and solidified by cooling. By using the same method as in Example 1 for the obtained unstretched sheet, a laminated biaxially oriented polyester film in which the resin on the extruder A side: the resin on the extruder B side was laminated 6: 1 in the thickness direction Got. The characteristics of the obtained film are shown in Table 3-2 and Table 4-2.

[Example 32]
Example 1 except that the width of the intermediate roll (intermediate product) was 3.4 m, and the intermediate roll was wound around a core having an inner diameter of 152.5 mm and an outer diameter of 167 mm while being cut with a slitter to a width of 1000 mm × 3. In the same manner as above, a laminated biaxially oriented polyester film was obtained. Of the three film rolls obtained, the central part and the end part were evaluated. The results are shown in Table 3-3 and Table 4-3.

[Example 33]
Laminated biaxially oriented polyester in the same manner as in Example 1 except that an intermediate roll (intermediate product) was cut with a slitter to a width of 1250 mm × 4 and wound on a core having an inner diameter of 152.5 mm and an outer diameter of 167 mm. A film was obtained. Of the four film rolls obtained, the second end from the end and the end (indicated in the table as the center) were evaluated. The results are shown in Table 3-3 and Table 4-3.

[Example 34]
Applying the raw materials and film forming conditions shown in Table 2-3, the intermediate roll (intermediate product) has a width of 3.4 m, and the intermediate roll is cut by a slitter so that the width becomes 1000 mm × 3. A laminated biaxially oriented polyester film was obtained in the same manner as in Example 1 except that it was wound around a core having an outer diameter of 167 mm. Of the three film rolls obtained, the central part and the end part were evaluated. The results are shown in Table 3-3 and Table 4-3.

[Comparative Examples 1-8]
A biaxially oriented polyester film was obtained in the same manner as in Example 1 except that the raw materials and film forming conditions shown in Table 2-3 were applied. The characteristics of the obtained film are shown in Tables 3-3 and 4-3.

[Summary of results]
It is composed of a polyester resin having a terminal carboxyl group amount of 20 equivalent / t or less, an intrinsic viscosity (IV) of 0.65 to 0.80, and a diethylene glycol amount of 2.0 to 5.0% by mass, and an ultrasonic conduction velocity. In the polyester film having an average value of 2.2 km / sec or more and a Tmeta value of 150 ° C. or more and 200 ° C. or less, all of the heat resistance and productivity / workability were satisfactory.

  In Comparative Examples 1 and 2 where the diethylene glycol (DEG) content is below the above range, the film formation stability and processability are poor, and in Comparative Example 3 where the diethylene glycol (DEG) content is above the above range, the heat and humidity resistance is poor. It was. Comparative Examples 4 and 5 in which the intrinsic viscosity is out of range, Comparative Example 6 in which the amount of terminal carboxyl groups is out of range, and Comparative Examples 7 and 8 in which the Tmeta value is out of range are durability in a humid heat environment, or Either productivity or workability was bad.

  Furthermore, about Examples 10-12 which have a component (A) whose sum total of the number of carboxylic acid groups and the number of hydroxyl groups is 3 or more, it became a result that heat-and-moisture resistance improved more.

  When the polyester resin constituting the film contains 0.1 to 5.0 mol / t of an alkali metal phosphate, compared to the case where it is not contained (for example, comparison between Example 1 and Example 22). The heat and humidity resistance was improved without deteriorating other characteristics, which was a favorable result. In addition, for the foreign matter generated by containing the alkali metal phosphate, the temperature of the polyester at the time of addition of the alkali metal phosphate during polymerization of the polyester resin and the concentration of the alkali metal phosphate in the ethylene glycol are within a preferable range. However, in Example 28 where the temperature at the time of addition was high and Example 29 where the concentration at the time of addition was high, there was a tendency for foreign matter to increase. Moreover, the tendency for the amount of foreign matter containing phosphorus to increase was also observed in Example 5 in which terephthalic acid was used as a starting material during polymerization of the polyester resin.

  As the film characteristics, when the average value of the ultrasonic conduction velocity was 2.2 km / second or more, the wet heat resistance was further improved, but the ratio of the maximum value to the minimum value was 1.0 to 1. .3, the orientation axis is shifted by 10 ° or more, that is, the variation due to the direction of the moisture and heat resistance is reduced even at the end position where the angle θ is in the range of 10 ° to 80 °. Particularly favorable results were obtained. Since these have a stretching process and an intermediate process, it has become possible to satisfy the above characteristics even at the end position when a wide film having a width of 5 m is manufactured as a product portion.

  Moreover, about Example 30 and 31, the concealability of a film and ultraviolet durability have improved by containing a rutile type titanium dioxide, especially in the case of the use used outdoors, such as a solar cell sealing film use Is preferred. Further, Example 31 has a structure in which a layer containing a large amount of rutile titanium dioxide and a layer containing a small amount of rutile titanium dioxide are laminated in the thickness direction, and high moisture and heat resistance is maintained even when containing titanium dioxide having a high catalytic activity. It was a very favorable result.

  The durable polyester film according to the present invention is a film excellent in durability under high temperature and high humidity, processability at the time of punching and bending, and excellent in property balance with good productivity. Applications used under high temperature conditions such as solar cell sealing films, building materials, automotive materials, etc., applications used outdoors, copper-clad laminates, adhesive tapes, flexible printed circuit boards, membrane switches, planar shapes It can be suitably used for applications where durability is important, such as heating elements or flat cables.

Claims (11)

The intrinsic viscosity (IV) of the polyester resin constituting the film is 0.65 to 0.80, the terminal carboxyl group amount is 20 equivalent / t or less, the diethylene glycol content is 2.0% by mass or more and 5.0% by mass or less, and the differential. A biaxially oriented polyester film having a minute endothermic peak temperature Tmeta (° C.) determined by scanning calorimetry (DSC) of 150 ° C. or more and 200 ° C. or less. The biaxially oriented polyester film according to claim 1, wherein the polyester resin is obtained by using at least a component (A) having a total number of carboxylic acid groups and hydroxyl groups of 3 or more. The polyester resin contains 0.1 mol / t or more and 5.0 mol / t or less of an alkali metal phosphate, and 10/1000 cm ² or less of foreign matters containing a phosphorus component having a major axis of 100 μm or more contained in the film. Item 3. The biaxially oriented polyester film according to item 1 or 2. The biaxially oriented polyester film according to any one of claims 1 to 3, wherein the thickness is 200 µm or more. The average ultrasonic conduction velocity of the film is 2.2 km / sec or more, and the ratio between the maximum value and the minimum value of the ultrasonic conduction velocity is 1.0 or more and 1.3 or less. Axial-oriented polyester film. The biaxially oriented polyester film according to claim 5, wherein an angle (θ) between a direction in which the ultrasonic conduction velocity of the film exhibits a maximum value and a film longitudinal direction is 10 ° or more and 80 ° or less. The biaxially oriented polyester film according to any one of claims 1 to 6, which has an elongation retention rate of 50% or more when held at 125 ° C and 100% RH for 72 hours. A method for producing a biaxially oriented polyester film comprising a step of melting a polyester resin and molding it into a sheet, and a stretching step, an intermediate step, and a heat treatment step described in (1) to (3) below, and constituting the film The polyester resin has an intrinsic viscosity (IV) of 0.65 to 0.80, a terminal carboxyl group content of 20 equivalent / t or less, a diethylene glycol content of 2.0% by mass or more and 5.0% by mass or less, and a minute endotherm. The manufacturing method of the biaxially-oriented polyester film whose peak temperature Tmeta (degreeC) is 150 degreeC or more and 200 degrees C or less.
(1) The film width is stretched 3.5 to 4.5 times in the width direction and the film width before the start of the width direction stretching process is W0, the film width at the midpoint of the width direction stretching process is W1, and after the end of the width direction stretching process. In the case where the film width at W2 is W2, the step satisfying the following formula (A) 60 ≦ 100 × (W1-W0) / (W2-W0) ≦ 80 Formula (A)
(2) Step of heat-treating biaxially oriented film at 160 ° C. or higher and 210 ° C. or lower (3) There is an intermediate step between the width direction stretching step and the heat treatment step, and the temperature of the intermediate step is the final of the width direction stretching step When the temperature of the section: Ts (° C.) and the first heat treatment process temperature corresponding to the first section of the heat treatment process: Th (° C.), and the time for the film to pass through the intermediate process is Sm (seconds) Step satisfying formula (B) (Th−Ts) / Sm ≦ 50 (Equation (B) The biaxially oriented polyester film according to claim 8, wherein the polyester resin used contains 0.1 to 5.0 mol / t of an alkali metal phosphate in the step of melting and molding the polyester resin into a sheet. Production method. A motor using the biaxially oriented polyester film according to claim 1. A solar cell using the biaxially oriented polyester film according to claim 1.