JPWO2015046121A1 - Polyester film and method for producing polyester film, polarizing plate and image display device - Google Patents

Abstract

Using a tenter-type stretching device that has a clip that runs along a pair of rails installed on both sides of the film transport path, it includes a step of laterally stretching while gripping the unstretched polyester film with the clip. The method for producing a polyester film in which the film film surface temperature when the polyester film is opened later is controlled to 50 to 120 ° C. can greatly reduce the film breakage in the vicinity of the film opening from the clip at the tenter outlet. A polyester film having good surface flatness can be produced; a polyester film; a polarizing plate; an image display device.

Description

  The present invention relates to a polyester film and a method for producing the same, a polarizing plate, and an image display device. In particular, a method for producing a preferably uniaxially oriented polyester film, a polyester film produced by the method for producing a polyester film, a polarizing plate and an image containing the polyester film, which are preferably used as a liquid crystal display substrate for optical film applications The present invention relates to a display device.

  Image display devices such as liquid crystal display (LCD), plasma display (PDP), electroluminescence display (OELD or IELD), field emission display (FED), touch panel, and electronic paper have a polarizing plate on the display screen side of the image display panel. Has been placed. For example, a liquid crystal display device has low power consumption, and its application is expanding year by year as a space-saving image display device. Conventionally, a liquid crystal display device has a major drawback that the viewing angle dependency of a display image is large. However, a wide viewing angle liquid crystal mode such as a VA mode and an IPS mode has been put into practical use. The demand for liquid crystal display devices is rapidly expanding even in the market where such images are required.

A polarizing plate used in a liquid crystal display device is generally composed of a polarizer made of a polyvinyl alcohol film or the like on which iodine or dye is adsorbed and oriented, and a transparent protective film (polarizing plate protective film) on both sides of the polarizer. It has a configuration. For convenience, the protective film on the surface (the side opposite to the display side) to be bonded to the liquid crystal cell is called an inner film, and the opposite side (display side) is called an outer film. Polyester, polycarbonate resin, and the like have advantages such as low cost, high mechanical strength, low moisture permeability, and the like, and are expected to be used as outer films.
In recent years, a uniaxially oriented polyester film is increasingly used as a base material for liquid crystal displays (such as a protective film for a polarizing plate) in place of a conventional biaxially oriented polyester resin film. For example, as a polarizing plate protective film with improved rainbow unevenness, Re = 3000 to 30000 nm, Re / Rth ≧ 0.2 uniaxially or biaxially oriented polyester film is used as a polarizer protective film, so that rainbow unevenness can be visually recognized. An example is known in which rainbow unevenness is eliminated by making it inconspicuous to the extent that it cannot be performed (see Patent Document 1). Patent Document 1 also describes that the mechanical strength in the direction orthogonal to the orientation direction is significantly reduced in a complete uniaxial (uniaxial symmetry) film.
The uniaxially or biaxially oriented polyester resin film having the optical properties as described above is produced by laterally uniaxially stretching at least an unstretched film while holding it with a clip using a tenter type stretching device.

On the other hand, when a film is stretched laterally using a tenter type stretching apparatus, a method for improving a failure in the vicinity of the clip is known when the film is gripped and released by a tenter clip.
In Patent Document 2, when a uniaxially oriented polyester film is produced by laterally uniaxially stretching an unstretched PET film, it is easily stretched along the orientation direction of the film because it is stretched only in the direction perpendicular to the film transport direction. Paying attention to that, when the film is released from the clip, the tenter rail width when releasing the film from the clip is expanded in the range of 0.1 to 10% of the minimum rail width after the heat setting zone. A method for suppressing breakage is described.

JP 2012-256014 A Patent No. 5021453

However, in the method for producing a uniaxially oriented polyester resin film described in Patent Documents 1 and 2, the present inventors have examined and found that breakage easily occurs when the film is released from the clip. In particular, as described in Patent Document 2, it has been found that the breakage of the tenter outlet cannot be completely eliminated simply by widening the rail width when the film after transverse stretching is opened from the clip. Moreover, it discovered newly that the film flatness will deteriorate remarkably on the manufacturing conditions as described in Example 1 of patent document 2. FIG.
The problem to be solved by the present invention is a method for producing a polyester film capable of producing a polyester film having extremely good film surface flatness, which can extremely reduce the film breakage in the vicinity of the film opening from the clip at the tenter outlet. Can be provided.

As a result of intensive studies by the inventor in order to solve the above problems, the film is oriented only in the horizontal direction, so the breaking strength in the vertical direction is weak, and the film breaks in the lateral direction around the clip separation part at the tenter outlet. There were many problems and it was found that stable production was difficult.
As a result of examining the above problems, if the film film surface temperature at the opening part of the film from the clip is too low near the tenter outlet, the film released from the clip acts on the film released from the clip due to cooling of the film. Was found to break. Furthermore, it was found that if the film surface temperature at the opening portion of the film from the clip is too high near the exit of the tenter, the film released from the clip is greatly shrunk and the flatness of the film is significantly deteriorated.
On the other hand, by controlling the film film surface temperature when releasing the polyester film after transverse stretching from the clip within a specific range, the film breakage in the vicinity of the open part of the film from the clip at the tenter outlet is extremely reduced. It has been found that it is possible to provide a method for producing a polyester film that can be reduced and that can produce a polyester film having a good film surface flatness, and that the above-mentioned problems can be solved.
That is, the said subject is solved by this invention of the following structures.

[1] including a step of laterally stretching an unstretched polyester film while holding the unstretched polyester film with the above-described clip using a tenter-type stretching device having a clip that travels along a pair of rails installed on both sides of the film conveyance path. ,
The manufacturing method of the polyester film which controls the film film surface temperature when releasing the polyester film after the above-mentioned transverse stretching from the above-mentioned clip to 50-120 degreeC.
[2] The method for producing a polyester film according to [1] is that the polyester film after the transverse stretching described above is released from the clip described above, and then 500 to 5000 kN / m with respect to the polyester film opened from the clip. It is preferable to apply a tension per cross-sectional area of the film in the film transport direction ² .
[3] In the method for producing a polyester film according to [1] or [2], the distance between a pair of rails when the polyester film after the transverse stretching is released from the clip is set as the transverse stretching zone. It is preferable to make it wide in the range of 0.1 to 5% with respect to the shortest distance between the pair of rails thereafter.
[4] The method for producing a polyester film according to any one of [1] to [3], wherein the polyester film after the transverse stretching described above is released before the polyester film after the transverse stretching is released from the clip. It is preferable to include a heat setting step of heating the film to the maximum temperature in the tenter.
[5] The method for producing a polyester film according to [4] includes a step of cooling the heat-fixed polyester film before releasing the heat-fixed polyester film from the clip. preferable.
[6] In the method for producing a polyester film according to any one of [1] to [5], the refractive index in the longitudinal direction of the unstretched polyester film is 1.590 or less, and
The crystallinity of the unstretched polyester film is preferably 5% or less.
[7] In the method for producing a polyester film according to any one of [1] to [6], the unstretched polyester film preferably includes a polyethylene terephthalate resin as a main component.
[8] A polyester film produced by the method for producing a polyester film according to any one of [1] to [7].
[9] The polyester film according to [8] preferably has a heat shrinkage rate of 3% or less in the longitudinal direction after heating the above-described polyester film at 150 ° C. for 30 minutes.
[10] The polyester film according to [8] or [9] has a film thickness of 20 to 150 μm,
The in-plane direction retardation Re is 3000 to 30000 nm,
The thickness direction retardation Rth is 3000 to 30000 nm,
It is preferable that the Re / Rth ratio is 0.5 to 2.5.
[11] The polyester film according to any one of [8] to [10] is preferably uniaxially oriented.
[12] The polyester film according to [11] has a refractive index in the longitudinal direction of the polyester film of 1.590 or less, and
It is preferable that the degree of crystallinity of the polyester film exceeds 5%.
[13] A polarizing plate comprising a polarizer and the polyester film according to any one of [8] to [12].
[14] An image display device comprising the polyester film according to any one of [8] to [12] or the polarizing plate according to [13].

  According to the present invention, it is possible to provide a method for producing a polyester film capable of producing a polyester film that can extremely reduce film breakage in the vicinity of an open portion of the film from a clip at a tenter outlet and that has good flatness on the film surface. it can.

Hereinafter, the polyester film of the present invention, the production method thereof, the polarizing plate and the image display device will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Production method of polyester film]
The polyester film manufacturing method of the present invention (hereinafter also referred to as the manufacturing method of the present invention) uses a tenter type stretching apparatus having clips that run along a pair of rails installed on both sides of a film transport path. The method includes a step of transverse stretching while holding the stretched polyester film with a clip, and the film film surface temperature when the polyester film after transverse stretching is released from the clip is controlled to 50 to 120 ° C.
With such a configuration, the method for producing a polyester film of the present invention can produce a polyester film with extremely low film breakage in the vicinity of the open portion of the film from the clip at the tenter outlet and good film surface flatness. .
Hereinafter, the preferable aspect of the manufacturing method of this invention is demonstrated.

<Preparation of unstretched polyester film>
(1) Polyester resin:
The unstretched polyester film preferably contains a polyester resin as a main component and a polyethylene terephthalate resin as a main component. A main component means the component which occupies 50 mass% or more of a film. As the polyester resin, those having the composition of [0042] of WO2012 / 157762 are preferably used.
As the polyester, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polycyclohexanedimethylene terephthalate (PCT), etc. can be used, but PET and PEN are more preferable because of cost and heat resistance. More preferably, it is PET (PEN tends to have a small Re / Rth).
Polyester is most preferably polyethylene terephthalate, but polyethylene naphthalate can also be preferably used. For example, those described in JP-A-2008-39803 can be preferably used.

  Polyethylene terephthalate is a polyester having a structural unit derived from terephthalic acid as a dicarboxylic acid component and a structural unit derived from ethylene glycol as a diol component, and 80 mol% or more of all repeating units are preferably ethylene terephthalate. The structural unit derived from other copolymerization components may be included. Other copolymer components include isophthalic acid, p-β-oxyethoxybenzoic acid, 4,4′-dicarboxydiphenyl, 4,4′-dicarboxybenzophenone, bis (4-carboxyphenyl) ethane, adipic acid , Dicarboxylic acid components such as sebacic acid, 5-sodium sulfoisophthalic acid, 1,4-dicarboxycyclohexane, propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexanediol, bisphenol A ethylene oxide adduct, polyethylene glycol And diol components such as polypropylene glycol and polytetramethylene glycol. These dicarboxylic acid components and diol components can be used in combination of two or more if necessary. It is also possible to use an oxycarboxylic acid such as p-oxybenzoic acid in combination with the carboxylic acid component or diol component. As another copolymer component, a dicarboxylic acid component and / or a diol component containing a small amount of an amide bond, a urethane bond, an ether bond, a carbonate bond, or the like may be used. Polyethylene terephthalate can be produced by a direct polymerization method in which terephthalic acid and ethylene glycol and, if necessary, other dicarboxylic acid and / or other diol are directly reacted, dimethyl ester of terephthalic acid and ethylene glycol, and necessary Depending on the above, any production method such as a so-called transesterification method in which a dimethyl ester of another dicarboxylic acid and / or another diol is transesterified can be applied.

(1-1) Intrinsic viscosity The intrinsic viscosity IV of the polyester resin is preferably 0.5 or more and 0.9 or less, more preferably 0.52 or more and 0.8 or less, and further preferably 0.54 or more and 0.7 or less. . In order to obtain such an IV, solid phase polymerization may be used in combination with the melt polymerization described later when the polyester resin is synthesized.

(1-2) Acetaldehyde content The polyester resin preferably has an acetaldehyde content of 50 ppm or less. More preferably, it is 40 ppm or less, Most preferably, it is 30 ppm or less. Acetaldehyde easily causes a condensation reaction between acetaldehydes, and water is generated as a side reaction product, which may cause hydrolysis of the polyester. The lower limit of the acetaldehyde content is practically about 1 ppm. In order to keep the acetaldehyde content in the above range, keep the oxygen concentration in each step such as melt polymerization and solid phase polymerization at the time of resin production, keep the oxygen concentration at the time of resin storage and drying, at the time of film production Methods such as lowering the heat history applied to the resin by an extruder, melt piping, die, etc., or preventing local strong shearing by the screw configuration of the extruder during melting, etc. can be employed.

(1-3) Catalyst For the polymerization of the polyester resin, Sb, Ge, Ti, Al-based catalysts are used, preferably Sb, Ti, Al-based catalysts, and more preferably Al-based catalysts.
That is, it is preferable that the polyester resin used as the raw material resin is polymerized using an aluminum catalyst.
By using an Al-based catalyst, it becomes easier for Re to be expressed than when other catalysts (for example, Sb, Ti) are used, and PET can be thinned. That is, it means that the Al-based catalyst is more easily oriented. This is presumed to be due to the following reasons.
Since the Al-based catalyst has a lower reactivity (polymerization activity) than Sb and Ti, the reaction is mild, and a by-product (diethylene glycol unit: DEG) is hardly generated.
As a result, the regularity of PET increases, and it is easy to align and to express Re.
(1-3-1) Al-based catalyst As the Al-based catalyst, those described in [0013] to [0148] of WO2011 / 040161 ([0021] to [0123] of US2012 / 0183761) are incorporated. The contents described in these publications are incorporated in the present specification.
Although there is no restriction | limiting in particular as a method of superposing | polymerizing a polyester resin using Al type catalyst, Specifically, [0091]-[0094] of WO2012 / 008488 ([0144]-[ 0153]) can be used to polymerize according to these publications, and the contents described in these publications are incorporated herein.
Such Al-based catalysts include, for example, [0052] to [0054], [0099] to [0104] of JP2012-122051 ([0045] to [0047], [0091] of WO2012 / 029725. To [0096]) can be prepared according to these publications, and the contents described in these publications are incorporated herein. The amount of the Al-based catalyst is preferably 3 to 80 ppm, more preferably 5 to 60 ppm, and still more preferably 5 to 40 ppm as the amount of Al element with respect to the mass of the polyester resin.

(1-3-2) Sb-based catalyst:
As the Sb-based catalyst, those described in [0050], [0052] to [0054] of JP 2012-41519 A can be used.
Although there is no restriction | limiting in particular as a method of superposing | polymerizing a polyester resin using a Sb type | system | group catalyst, Specifically, it can superpose | polymerize according to [0086]-[0087] of WO2012 / 157762.

  It is also preferable to add a known additive to the unstretched polyester film used for the polyester film of the present invention. Examples thereof include ultraviolet absorbers, particles, lubricants, antiblocking agents, heat stabilizers, antioxidants, antistatic agents, light resistance agents, impact resistance improvers, lubricants, dyes, pigments and the like. However, since the polyester film generally requires transparency, it is preferable to keep the additive amount to a minimum.

(1-4-1)
The unstretched polyester film used for the polyester film of the present invention can contain an ultraviolet absorber in order to prevent the liquid crystal of the liquid crystal display from being deteriorated by ultraviolet rays. The ultraviolet absorber is not particularly limited as long as it is a compound having ultraviolet absorbing ability and can withstand the heat applied in the production process of the polyester film.
As the ultraviolet absorber, there are an organic ultraviolet absorber and an inorganic ultraviolet absorber. From the viewpoint of transparency, an organic ultraviolet absorber is preferable. Those described in [0057] of WO2012 / 157762 and cyclic iminoester-based ultraviolet absorbers described later can be used.

  Examples of the cyclic imino ester-based ultraviolet absorber include, but are not limited to, 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1-benzoxazine-4, for example. -One, 2-phenyl-3,1-benzoxazin-4-one, 2- (1- or 2-naphthyl) -3,1-benzoxazin-4-one, 2- (4-biphenyl) -3, 1-benzoxazin-4-one, 2-p-nitrophenyl-3,1-benzoxazin-4-one, 2-m-nitrophenyl-3,1-benzoxazin-4-one, 2-p-benzoyl Phenyl-3,1-benzoxazin-4-one, 2-p-methoxyphenyl-3,1-benzoxazin-4-one, 2-o-methoxyphenyl-3,1-benzoxazin-4-one, -Cyclohexyl-3,1-benzoxazin-4-one, 2-p- (or m-) phthalimidophenyl-3,1-benzoxazin-4-one, N-phenyl-4- (3,1-benzoxazine -4-On-2-yl) phthalimide, N-benzoyl-4- (3,1-benzoxazin-4-one-2-yl) aniline, N-benzoyl-N-methyl-4- (3,1- Benzoxazin-4-one-2-yl) aniline, 2- (p- (N-methylcarbonyl) phenyl) -3,1-benzoxazin-4-one, 2,2′-bis (3,1-benzo Oxazin-4-one), 2,2′-ethylenebis (3,1-benzoxazin-4-one), 2,2′-tetramethylenebis (3,1-benzoxazin-4-one), 2, 2'-Decame Renbis (3,1-benzoxazin-4-one, 2,2 '-(1,4-phenylene) bis (4H-3,1-benzoxazin-4-one) [In addition, 2,2'-p- Phenylenebis (3,1-benzoxazin-4-one)], 2,2′-m-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4 ′) -Diphenylene) bis (3,1-benzoxazin-4-one), 2,2 '-(2,6- or 1,5-naphthylene) bis (3,1-benzoxazin-4-one), 2, 2 '-(2-methyl-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2'-(2-nitro-p-phenylene) bis (3,1-benzoxazine-4 -One), 2,2 '-(2-chloro-p-phenylene) bis (3 , 1-benzoxazin-4-one), 2,2 ′-(1,4-cyclohexylene) bis (3,1-benzoxazin-4-one), 1,3,5-tri (3,1- Benzoxazin-4-on-2-yl) benzene, 1,3,5-tri (3,1-benzoxazin-4-on-2-yl) naphthalene, 2,4,6-tri (3,1- Benzoxazin-4-one-2-yl) naphthalene, 2,8-dimethyl-4H, 6H-benzo (1,2-d; 5,4-d ′) bis (1,3) -oxazine-4,6 -Dione, 2,7-dimethyl-4H, 9H-benzo (1,2-d; 4,5-d ') bis (1,3) -oxazine-4,9-dione, 2,8-diphenyl-4H , 8H-Benzo (1,2-d; 5,4-d ′) bis (1,3) -oxazine-4,6-dio 2,7-diphenyl-4H, 9H-benzo (1,2-d; 4,5-d ′) bis (1,3) -oxazine-4,6-dione, 6,6′-bis (2- Methyl-4H, 3,1-benzoxazin-4-one), 6,6′-bis (2-ethyl-4H, 3,1-benzoxazin-4-one), 6,6′-bis (2- Phenyl-4H, 3,1-benzoxazin-4-one), 6,6′-methylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6′-methylenebis (2- Phenyl-4H, 3,1-benzoxazin-4-one), 6,6′-ethylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6′-ethylenebis ( 2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6′- Tylene bis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6′-butylene bis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6′- Oxybis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6′-oxybis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6′- Sulfonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6′-sulfonylbis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6 '-Carbonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-carbonylbis (2-phenyl-4H, 3,1-benzoxazin-4-one), 7 , 7'-methylenebis (2 -Methyl-4H, 3,1-benzoxazin-4-one), 7,7'-methylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one), 7,7'-bis (2 -Methyl-4H, 3,1-benzoxazin-4-one), 7,7'-ethylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7'-oxybis ( 2-methyl-4H, 3,1-benzoxazin-4-one), 7,7′-sulfonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7′-carbonyl Bis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,7′-bis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,7′- Bis (2-phenyl-4H, 3,1-benzoxazine-4 ON, 6,7′-methylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,7′-methylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one) ) And the like.

  Among the above compounds, when considering the color tone, a benzoxazinone-based compound which is difficult to be yellowed is preferably used. As an example thereof, a compound represented by the following general formula (1) is more preferably used. It is done.

In the general formula (1), R represents a divalent aromatic hydrocarbon group, and X ¹ and X ² are each independently selected from hydrogen or the following functional group group, but are not necessarily limited thereto. Absent.

  Functional group: alkyl group, aryl group, heteroaryl group, halogen, alkoxyl group, aryloxy group, hydroxyl group, carboxyl group, ester group, nitro group.

  Among the compounds represented by the general formula (1), 2,2 ′-(1,4-phenylene) bis (4H-3,1-benzoxazin-4-one) is particularly preferable in the present invention.

  The amount of the ultraviolet absorber to be contained in the polyester film of the present invention is usually 10.0% by mass or less, preferably 0.3 to 3.0% by mass. When an ultraviolet absorber in an amount exceeding 10.0% by mass is contained, the ultraviolet absorber may bleed out on the surface, which may cause deterioration of surface functionality such as adhesion deterioration.

  In addition, in the case of the polyester film of the present invention having a multilayer structure, the film having at least a three-layer structure is preferable, and the ultraviolet absorber is preferably blended in the intermediate layer. By blending an ultraviolet absorber in the intermediate layer, this compound can be prevented from bleeding out to the film surface, and as a result, characteristics such as film adhesion can be maintained.

  For these formulations, the master batch method described in [0050] to [0051] of WO2011 / 162198 can be used.

(1-4-2) Other additives Other additives may be used for the unstretched polyester film used in the polyester film of the present invention, for example, those described in [0058] of WO2012 / 157762. The contents described in these publications are incorporated herein by reference.

(2) Melt kneading:
The unstretched polyester film is preferably formed into a film by melt-extruding a polyester resin.
It is preferable to dry the polyester resin or the master batch of the polyester resin and additive produced by the above-described master batch method to a moisture content of 200 ppm or less, and then introduce the melt into a single or twin screw extruder and melt it. At this time, in order to suppress degradation of the polyester, it is also preferable to melt in nitrogen or vacuum. Detailed conditions can be carried out according to these publications with the aid of Patent Nos. 4926661 [0051] to [0052] (US2013 / 0100378 [0085] to [0086]), and are described in these publications. The contents are incorporated herein. Furthermore, it is also preferable to use a gear pump in order to increase the delivery accuracy of the molten resin (melt). It is also preferable to use a 3 μm to 20 μm filter for removing foreign substances.

(3) Extrusion, coextrusion:
Although it is preferable to extrude the melt containing the polyester resin melt-kneaded from the die, it may be extruded as a single layer or as a multilayer. When extruding in multiple layers, for example, a layer containing an ultraviolet grade agent (UV agent) and a layer not containing it may be laminated. In addition to suppressing deterioration, it is preferable to suppress bleeding out of the UV agent.
The bleed-out UV agent is undesirably easily transferred to a pass roll in the film-forming process, increasing the coefficient of friction between the film and the roll, and causing scratches.
When the polyester film is produced by being extruded in multiple layers, the preferred inner layer thickness (ratio to the total layer) of the resulting polyester film is preferably 50% or more and 95% or less, more preferably 60% or more and 90% or less, Preferably they are 70% or more and 85% or less. Such lamination can be performed by using a feed block die or a multi-manifold die.

(4) Cast:
According to [0059] of JP 2009-269301 A, it is preferable to extrude the melt extruded from the die onto a casting drum and cool and solidify to obtain an unstretched polyester film (raw fabric).
In the production method of the present invention, the refractive index in the longitudinal direction of the unstretched polyester film is preferably 1.590 or less, more preferably 1.585 or less, and further preferably 1.580 or less.
In the production method of the present invention, the crystallinity of the unstretched polyester film is preferably 5% or less, more preferably 3% or less, and even more preferably 1% or less. In addition, the crystallinity degree of the unstretched polyester film here means the crystallinity degree of the center part of a film width direction.
When adjusting the degree of crystallinity, the temperature of the end of the casting drum may be lowered, or air may be blown onto the cast drum.
The crystallinity can be calculated from the film density. That is, the density X (g / ^cm 3) of the film density at a crystallinity of ^{0% Y = 1.335g / cm 3} , using density Z = 1.501g / cm ³ at 100% crystalline below The crystallinity (%) can be derived from the calculation formula.
Crystallinity = {Z × (XY)} / {X × (ZY)} × 100
The density can be measured according to JIS K7112.

(5) Formation of polymer layer (adhesive layer):
On the melt-extruded unstretched polyester film, a polymer layer (preferably an easy-adhesion layer) may be formed by coating before or after stretching described later.
Examples of the polymer layer generally include a functional layer that the polarizing plate may have, and among them, it is preferable to form an easy adhesion layer as the polymer layer. The easy-adhesion layer can be applied by the method described in [0062] to [0070] of WO2012 / 157762.

<Horizontal stretching>
The production method of the present invention uses a tenter-type stretching device having a clip that travels along a pair of rails installed on both sides of a film conveyance path, and horizontally stretches the unstretched polyester film while holding the clip with the clip. The film surface temperature when opening the polyester film after transverse stretching from the clip is controlled to 50 to 120 ° C.

  There is no restriction | limiting in particular as a tenter type extending | stretching apparatus which has a clip which drive | works along a pair of rail installed in the both sides of a film conveyance path. A pair of endless rails is usually used as the pair of rails.

In the method for producing a polyester film of the present invention, the extruded film is stretched transversely. Transverse stretching is performed in a direction perpendicular to the film transport direction while transporting an unstretched polyester film along the film transport path.
By stretching, retardation Re in the in-plane direction of the film (hereinafter also referred to as the in-plane direction) can be greatly expressed. In particular, in order to achieve a polyester film satisfying the ranges of Re, Rth, and Re / Rth described later, at least lateral stretching is performed. When the longitudinal stretching is performed thereafter, the stretching ratio of the lateral stretching may be increased among the longitudinal and lateral stretching ratios, and the stretching may be performed unbalanced.

  The stretching temperature in the stretching step is preferably 70 ° C. or higher and 170 ° C. or lower, more preferably 80 ° C. or higher and 160 ° C. or lower, and further preferably 90 ° C. or higher and 150 ° C. or lower. The stretching temperature here refers to an average temperature from the start to the end of stretching.

  That is, it can be achieved by gripping both ends of the film with clips and widening between the clips while heating. The transverse draw ratio is preferably 2 to 5.5 times, more preferably 2.5 to 5 times, and particularly preferably 3 to 4.5 times.

<Heat setting>
The production method of the present invention preferably includes a heat setting step of heating the polyester film after transverse stretching to the maximum temperature in the tenter before releasing the polyester film after transverse stretching from the clip.
In order to promote crystallization after stretching, it is preferable to perform a heat treatment called “heat setting”. This can be performed at a temperature exceeding the stretching temperature to promote crystallization and increase the strength of the film.
In heat setting, volume shrinks due to crystallization.
As a heat fixing method, several slits for sending hot air to the extending portion are provided in parallel to the width direction. This can be achieved by making the temperature of the gas blown out from the slit higher than the stretched portion. Further, a heat source (IR heater, halogen heater, etc.) may be installed near the drawing (part) exit to raise the temperature.

  A preferable temperature for heat setting is 100 ° C. or more and 250 ° C. or less, and more preferably 150 ° C. or more and 245 ° C. or less.

At this time, it is preferable to relax (shrink the film) simultaneously with the heat treatment, and it is preferable to perform at least one of TD (transverse direction) and MD (vertical direction).
Such relaxation can be achieved, for example, by using a pantograph-like chuck for the tenter, reducing the interval between the pantographs, and driving the click on the electromagnet to reduce the speed.
Longitudinal relaxation is preferably performed at 120 ° C. or higher and 230 or lower, more preferably 130 ° C. or higher and 220 ° C. or lower, and further preferably 140 ° C. or higher and 210 ° C. or lower from the viewpoint of suppression of scratches. Longitudinal relaxation also has the effect of increasing Re / Rth in widthwise stretching. This is because loosening the longitudinal direction during transverse stretching facilitates lateral orientation and easily increases Re. The amount of relaxation is preferably 1% or more and 10% or less from the viewpoint of suppressing generation of scratches on the polyester film, more preferably 2% or more and 8% or less, and even more preferably 3% or more and 7%. % Or less. If it is more than the lower limit value of this preferable range, the above-mentioned effect is difficult to occur and scratches are hardly generated. On the other hand, if it is less than or equal to the upper limit of this preferred range, it will be difficult for slack to occur, it will be difficult to come into contact with a stretching machine, and scratches will not easily occur.

The lateral relaxation temperature is preferably in the range of the above-mentioned heat setting temperature, and may be the same as that of heat setting, or may be high or low.
The lateral relaxation amount is preferably in the same range as the longitudinal relaxation amount. Lateral relaxation can be achieved by reducing the width of the widened click.

  By the above stretching and heat setting, Re, Rth and Re / Rth of the polyester film of the present invention can be easily achieved. That is, it is easy to form the polyester film of the present invention that exhibits the effect of reducing rainbow unevenness by performing stretching and heat setting by these methods.

<Cooling>
It is preferable that the manufacturing method of this invention includes the process of cooling the polyester film after heat setting, before releasing the polyester film after heat setting from a clip. From the viewpoint of easily reducing the temperature of the clip when the polyester film after stretching, preferably the heat-set polyester film is cooled before being released from the clip, when the polyester film after transverse stretching is released from the clip, preferable.
The cooling temperature of the polyester film after heat setting is preferably 80 ° C. or less, more preferably 70 ° C. or less, and particularly preferably 60 ° C. or less.
Specific examples of the method for cooling the polyester film after heat setting include a method in which cold air is applied to the polyester film.

<Release film from clip>
In the production method of the present invention, the film film surface temperature when the polyester film after transverse stretching is released from the clip is controlled to 50 to 120 ° C. When it is 50 ° C. or higher, the film is difficult to break at the tenter exit. When the temperature is 120 ° C. or lower, the film does not shrink too much after the clip is released, and the flatness of the film becomes good.
The film film surface temperature when opening the polyester film after transverse stretching from the clip is preferably 55 ° C. or higher and 110 ° C. or lower, and more preferably 60 ° C. or higher and 100 ° C. or lower.

In the production method of the present invention, the distance between the pair of rails when the polyester film after transverse stretching is released from the clip is 0.1 to 5% of the shortest distance between the pair of rails after the transverse stretching zone. It is preferable to widen the range. TD direction when the range in which the distance between the pair of rails when the polyester film after transverse stretching is released from the clip is wider than the shortest distance between the pair of rails after the transverse stretching zone is 0.1% or more It becomes easy to suppress breakage. When the distance between the pair of rails when the polyester film after transverse stretching is released from the clip is 5% or less relative to the distance between the shortest pair of rails after the transverse stretching zone is 5% or less, It becomes easy to suppress breakage.
The distance between the pair of rails when the polyester film after transverse stretching is released from the clip may be widened in a range of 0.2% to 4% with respect to the shortest distance between the pair of rails after the transverse stretching zone. More preferably, it is more preferable to widen in the range of 0.3% to 3.5%, and most preferably in the range of 0.3% to 3%.

  The thickness of the polyester film after completion of film formation (after the transverse stretching and the step of releasing from the clip) is preferably 20 to 150 μm, more preferably 30 to 130 μm, and still more preferably 35 to 110 μm. The reason why this range is preferable is the same as the reason why the thickness of the polyester film of the present invention is preferably within this range.

<Recovery of film, slit, winding>
After the transverse stretching and the step of releasing from the clip, the film is trimmed, slit, and thickened as necessary, and wound for recovery.
In the production method of the present invention, the film width after being released from the clip is preferably 1 to 8 m from the viewpoint of efficiently ensuring the film product width and the apparatus size is not excessive, and more preferably 2 to 6 m. It is preferably 3 to 5 m. An optical film requiring accuracy is usually formed with a thickness of less than 3 m, but in the present invention, it is preferable to form a film with a wide width as described above.
In addition, such a wide-film-formed film is preferably slit into 2 or more, 6 or less, more preferably 2 or more and 5 or less, and even more preferably 3 or more and 4 or less, and the film may be wound up. .

Moreover, after slitting, it is preferable to process the thickness at both ends (providing knurling).
The winding is preferably performed at a diameter of not less than 1000 m and not more than 10000 m on a core having a diameter of not less than 70 mm and not more than 600 mm.

In the production method of the present invention, after releasing the polyester film after transverse stretching from the clip, the tension per cross-sectional area of the film in the film transport direction of 500 to 5000 kN / m ² is applied to the polyester film after opening from the clip. It is preferable to apply. When the tension per cross-sectional area of the film in the film transport direction applied to the polyester film after opening from the clip is 500 kN / m ² or more, the film does not loosen, the film flatness is improved, and the film surface Failures such as scratches can be improved. When the tension per cross-sectional area of the film in the film transport direction applied to the polyester film after being released from the clip is 5000 kN / m ² or more, the film is difficult to break.
800 kN / m ^{2 to} 4000 kN / m ² is more preferable as the tension (winding tension) per cross-sectional area of the film in the film conveyance direction applied to the polyester film after being released from the clip, and 1000 kN / m ^{2 to} 3000 kN. / M ² is more preferable.

Examples of a method for applying tension per cross-sectional area of the film in the film transport direction include a method for controlling the winding tension. Winding tension can be adjusted by adjusting the weight of the weight of the dancer roll by installing a dancer roll upstream of the winder, or by installing a tension meter on the upstream side of the winder. Thus, it can be controlled by a method of adjusting the winding speed.
The tension (winding tension) applied to the polyester film after being released from the clip can be appropriately adjusted according to the target winding tension and the thickness and width of the film.

  It is also preferable to bond a masking film before winding.

[Polyester film]
The polyester film of the present invention is a polyester film produced by the method for producing a polyester film of the present invention.

<Characteristics of polyester film>
-Thermal shrinkage in the longitudinal direction-
The heat shrinkage (MD heat shrinkage) in the longitudinal direction (MD direction) after heating the polyester film of the present invention at 150 ° C. for 30 minutes is preferably 3% or less, more preferably 2.5% or less, and 2% or less. Is more preferable, and 1.5% or less is most preferable.
If the polyester film of the present invention has a heat shrinkage in the longitudinal direction after heating at 150 ° C. for 30 minutes of 3% or less, the film is less likely to wrinkle in subsequent processing steps such as polarizing plate processing, and the film is warped. It is hard to occur.

-Phase difference-
The polyester film of the present invention has an in-plane retardation Re of preferably 3000 to 30000 nm, more preferably 3500 to 25000 nm, and still more preferably 4000 to 20000 nm. When Re is less than 3000 nm, color unevenness on the screen is less likely to occur when a panel is used, which is preferable. In principle, it is difficult to produce a film exceeding 30000 nm. Even if Re of the polyester film exceeds 30000 nm, the effect of reducing rainbow unevenness is only saturated, and the effect of the present invention can be obtained.
Rainbow spot appears when observing light incident obliquely from a backlight source on a polarizing plate having a large birefringence, specifically, a polymer film having Re of 500 nm or more and less than 3000 nm as a protective film. This is conspicuous in a liquid crystal display device including a bright line spectrum and having a light source such as a cold cathode tube as a backlight.
Here, when a white light source having a continuous emission spectrum is used as a backlight light source, it is preferable that the Re of the polyester film of the present invention is in the above range because rainbow unevenness is hardly visible.

  The polyester film of the present invention has a thickness direction retardation Rth of preferably 3000 to 30000 nm, more preferably 3500 to 25000 nm, and still more preferably 4000 to 20000 nm. In principle, it is difficult to make a film with Rth below 3000 nm. When it is 30000 nm or less, color unevenness on the screen hardly occurs when a panel is used, which is preferable.

  In the polyester film of the present invention, the ratio (Re / Rth) of the in-plane retardation Re and the thickness direction retardation Rth is preferably 0.5 to 2.5, more preferably 0.6 to 2.2, 0.7-2.0 is still more preferable. When Re / Rth is 0.5 or more, color unevenness hardly occurs on the screen when the polyester film of the present invention is incorporated as a polarizing plate protective film in a liquid crystal panel, which is preferable. In principle, it is difficult to make a film exceeding 2.5. Moreover, even if Re / Rth exceeds 1.2, the effect of reducing the viewing angle dependency of rainbow spot is only saturated, and if Re / Rth is 1.2 or less, there is little decrease in mechanical properties, and there is no scratch. It is difficult to generate and is preferable.

Rainbow spot unevenness can also be reduced by setting the Nz value representing the relationship between Re and Rth to an appropriate value, and the absolute value of the Nz value is 2.0 or less due to the effect of reducing rainbow-like unevenness and manufacturing suitability. It is preferably 0.5 to 2.0, more preferably 0.5 to 1.5.
Since iridescent unevenness is caused by incident light, it is usually observed during white display.
The in-plane retardation value Re of the polyester film of the present invention is represented by the following formula (4).

Re = (nx−ny) × y ₁ (4)
Here, nx is the refractive index in the in-plane slow axis direction of the polyester film, ny is the refractive index in the in-plane fast axis direction (direction perpendicular to the in-plane slow axis direction) of the polyester film, and y ₁ is the thickness of the polyester film.

  The retardation Rth in the thickness direction of the polyester film of the present invention is represented by the following formula (5).

Rth = {(nx + ny) / 2−nz} × y ₁ (5)
Here, nz is the refractive index in the thickness direction of the polyester film.

  In addition, Nz value of a polyester film is represented by following formula (6).

Nz = (nx−nz) / (nx−ny) (6)

In this specification, Re, Rth, and Nz at a wavelength λnm can be measured as follows.
Using two polarizing plates, the orientation axis direction of the polyester film was determined, and a 4 cm × 2 cm rectangle was cut out so that the orientation axis directions were perpendicular to each other, and used as a measurement sample. For this sample, the biaxial refractive index (Nx, Ny) perpendicular to each other and the refractive index (Nz) in the thickness direction were determined by an Abbe refractometer (NAGO-4T, measurement wavelength 589 nm, manufactured by Atago Co., Ltd.). The absolute value of the refractive index difference (| Nx−Ny |) was defined as the refractive index anisotropy (ΔNxy). The thickness y ₁ (nm) of the polyester film was measured using an electric micrometer (manufactured by Fine Reef, Millitron 1245D), and the unit was converted to nm. Measured Nx, Ny, Nz, Re from the value of _{y 1,} Rth, Nz was calculated.

The above Re and Rth can be adjusted by the type of polyester resin used in the film, the amount of the polyester resin and the additive, the addition of the retardation enhancer, the film thickness, the stretching direction and the stretching ratio of the film, and the like. .
Although there is no restriction | limiting in particular in the method of controlling the polyester film of this invention to the range of said Re and Rth, For example, it can achieve by the extending | stretching method.

-Film thickness-
20-150 micrometers is preferable, as for the thickness of the polyester film of this invention, 30-130 micrometers is more preferable, and 35-110 micrometers or less are still more preferable. When the thickness is 20 μm or more, color unevenness is unlikely to occur on the panel, which is preferable. If it exceeds 150 μm, the cost is high and the profitability is not suitable.

The polyester film of the present invention is preferably uniaxially oriented. Specifically, the polyester film of the present invention preferably has a longitudinal refractive index of 1.590 or less and a crystallinity of more than 5%.
The preferable range of the refractive index in the longitudinal direction of the polyester film of the present invention is the same as the preferable range of the refractive index in the longitudinal direction of the unstretched polyester film.
The degree of crystallinity of the polyester film of the present invention is preferably 5% or more, more preferably 20% or more, and still more preferably 30% or more.

<Layer structure of polyester film, surface treatment>
The polyester film of the present invention contains a polyester resin.
The polyester film of the present invention may be a single layer film having a polyester resin as a main component or a multilayer film having at least one layer having a polyester resin as a main component. Moreover, the surface treatment may be performed on both surfaces or one surface of these single layer films or multilayer films, and this surface treatment is performed by corona treatment, saponification treatment, heat treatment, ultraviolet irradiation, electron beam irradiation, or the like. Modification may be sufficient, and thin film formation by application | coating, vapor deposition, etc. of a polymer, a metal, etc. may be sufficient. The mass ratio of the polyester resin in the entire film is usually 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more.

[Polarizer]
The polyester film of the present invention can be used as a polarizing plate protective film.
The polarizing plate of the present invention includes a polarizer having polarizing performance and the polyester film of the present invention. The polarizing plate of the present invention may further contain a polarizing plate protective film such as a cellulose acylate film in addition to the polyester film of the present invention.

  The shape of the polarizing plate was not only a polarizing plate in the form of a film piece cut to a size that can be incorporated into a liquid crystal display device as it is, but also produced in a long shape by continuous production and rolled up into a roll shape. A polarizing plate of an embodiment (for example, an embodiment having a roll length of 2500 m or more or 3900 m or more) is also included. In order to use for a large-screen liquid crystal display device, the width of the polarizing plate is preferably 1470 mm or more.

  As described in [0025] of WO2011 / 162198, a polarizer comprising PVA and the polyester film of the present invention can be bonded to prepare a polarizing plate. Under the present circumstances, it is preferable to make the said easily bonding layer contact PVA. Furthermore, it is also preferable to combine with a protective film having retardation as described in [0024] of WO2011 / 162198.

[Image display device]
The polyester film of this invention can be used for an image display apparatus, and the polarizing plate containing the polyester film of this invention can be used as a polarizing plate of an image display apparatus.
The image display device of the present invention includes the polyester film of the present invention or the polarizing plate of the present invention.
In a preferred embodiment of the polyester film of the present invention, film scratches are also small. In the preferred embodiment of the image display device of the present invention using such a preferred embodiment of the polyester film of the present invention, there are few bright spots due to film scratches.
Examples of the image display device include a liquid crystal display (LCD), a plasma display (PDP), an electroluminescence display (OELD or IELD), a field emission display (FED), a touch panel, and electronic paper. These image display devices preferably include the polarizing plate of the present invention on the display screen side of the image display panel.

  As a method for bonding the polarizing plate to an image display device such as a liquid crystal display device, a known method can be used. In addition, a roll-to-panel manufacturing method can be used, which is preferable for improving productivity and yield. The roll-to-panel manufacturing method is described in JP2011-48381, JP2009-175653, JP4628488, JP4729647, WO2012 / 014602, WO2012 / 014571, and the like. It is not limited.

In the image display device, it is preferable to use a light source having an emission spectrum having a continuous emission spectrum as the light source.
This is because it becomes easy to eliminate rainbow unevenness as described in [0019] to [0020] of WO2011 / 162198.
As a light source used in the image display device, the one described in [0013] of WO2011 / 162198 is used. On the other hand, the light source described in [0014] to [0015] of WO2011 / 162198 is not a continuous light source and is not preferable.
When the image display device is an LCD, a configuration described in [0011] to [0012] of WO2011 / 162198 can be used as the liquid crystal display device (LCD).
The liquid crystal display device using the polyester film of the present invention and / or the polarizing plate of the present invention is preferably one using a white light source having a continuous emission spectrum, whereby a discontinuous (bright line) light source is used. Rainbow unevenness can be reduced more effectively. This is due to the same reason as described above, with the reason described in [0015] to [0027] of Patent No. 4888853 ([0029] to [0041] of US2012 / 0229732). The contents described in these publications are incorporated herein.
The liquid crystal display device preferably includes the polarizing plate of the present invention and a liquid crystal display element. Here, the liquid crystal display element is typically a liquid crystal panel having a liquid crystal cell in which liquid crystal is sealed between upper and lower substrates and displaying an image by changing the alignment state of the liquid crystal by applying a voltage. The polarizing plate of the present invention can be applied to various known displays such as a display panel, a CRT display, and an organic EL display. Thus, when the polarizing plate which has a polyester film of this invention with high retardation is applied to a liquid crystal display element, the curvature of a liquid crystal display element can be prevented.

  Here, the iridescent color spots are caused by the retardation of the polyester film having a high retardation and the emission spectrum of the backlight light source. Conventionally, a fluorescent tube such as a cold cathode tube or a hot cathode tube is used as a backlight source of a liquid crystal display device. The spectral distribution of a fluorescent lamp such as a cold cathode tube or a hot cathode tube shows an emission spectrum having a plurality of peaks, and these discontinuous emission spectra are combined to obtain a white light source. When light passes through a film having a high retardation, the transmitted light intensity varies depending on the wavelength. For this reason, when the backlight light source has a discontinuous emission spectrum, only a specific wavelength is strongly transmitted, and a rainbow-like color spot is generated.

  When the image display device is a liquid crystal display device, it is preferable to include a backlight light source and a liquid crystal cell disposed between two polarizing plates as constituent members. Moreover, you may have suitably other structures other than these, for example, a color filter, a lens film, a diffusion sheet, an antireflection film etc. suitably.

The configuration of the backlight may be an edge light method using a light guide plate, a reflection plate, or the like, or a direct type, but in the present invention, white is used as the backlight light source of the liquid crystal display device. It is preferable to use a light emitting diode (white LED) from the viewpoint of improving rainbow unevenness. In the present invention, the white LED is an element that emits white by combining a phosphor with a phosphor system, that is, a light emitting diode that emits blue light or ultraviolet light using a compound semiconductor. Examples of the phosphor include yttrium / aluminum / garnet yellow phosphor and terbium / aluminum / garnet yellow phosphor. In particular, white light-emitting diodes, which are composed of light-emitting elements that combine blue light-emitting diodes using compound semiconductors with yttrium, aluminum, and garnet-based yellow phosphors, have a continuous and broad emission spectrum and are also efficient in light emission. Since it is excellent, it is suitable as a backlight light source of the image display device of the present invention. Here, the continuous emission spectrum means that there is no wavelength at which the light intensity becomes zero at least in the visible light region. Further, since the white LED with low power consumption can be widely used according to the present invention, an effect of energy saving can be achieved.
The mechanism by which the occurrence of rainbow-like color spots is suppressed by the above embodiment is described in International Publication No. WO2011 / 162198, and the contents of this publication are incorporated in the present invention.

When the image display device of the present invention is a liquid crystal display device, the arrangement of the polarizing plate of the present invention is not particularly limited. The polarizing plate of the present invention is preferably used as a polarizing plate for the viewing side in a liquid crystal display device.
The arrangement of the polyester film of the present invention having a high retardation in the in-plane direction is not particularly limited, but is arranged on the polarizing plate arranged on the incident light side (light source side), the liquid crystal cell, and the outgoing light side (viewing side). In the case of a liquid crystal display device provided with a polarizing plate, the polarizer protective film on the incident light side of the polarizing plate arranged on the incident light side, or the polarizer on the outgoing light side of the polarizing plate arranged on the outgoing light side The protective film is preferably the polyester film of the present invention having a high in-plane retardation. A particularly preferred embodiment is an embodiment in which the polarizer protective film on the exit light side of the polarizing plate arranged on the exit light side is the polyester film of the present invention having a high retardation in the in-plane direction. When a polyester film having a high retardation in the in-plane direction is disposed at a position other than the above, the polarization characteristics of the liquid crystal cell may be changed. Since the polyester film of the present invention having a high retardation in the in-plane direction is preferably used in a place where no polarizing property is required, it is preferably used as a protective film for the polarizing plate at such a specific position.

The liquid crystal cell of the liquid crystal display device preferably has a liquid crystal layer and two glass substrates provided on both sides of the liquid crystal layer. The thickness of the glass substrate is preferably 0.5 mm or less, more preferably 0.4 mm or less, and particularly preferably 0.3 mm or less.
The liquid crystal cell of the liquid crystal display device is preferably IPS mode, VA mode, or FFS mode.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Example 1]
<Synthesis of raw material polyester>
(Raw material polyester 1)
As shown below, terephthalic acid and ethylene glycol are directly reacted to distill off water, esterify, and then, using a direct esterification method in which polycondensation is performed under reduced pressure, raw polyester 1 ( Sb catalyst system PET) was obtained.

(1) Esterification reaction In a first esterification reactor, 4.7 tons of high-purity terephthalic acid and 1.8 tons of ethylene glycol are mixed over 90 minutes to form a slurry, and continuously at a flow rate of 3800 kg / h. It supplied to the 1st esterification reaction tank. Further, an ethylene glycol solution of antimony trioxide was continuously supplied, and the reaction was carried out at a reaction vessel temperature of 250 ° C. with stirring and an average residence time of about 4.3 hours. At this time, antimony trioxide was continuously added so that the amount of Sb added was 150 ppm in terms of element.

  This reaction product was transferred to a second esterification reaction vessel, and reacted with stirring at a temperature in the reaction vessel of 250 ° C. and an average residence time of 1.2 hours. To the second esterification reaction tank, an ethylene glycol solution of magnesium acetate and an ethylene glycol solution of trimethyl phosphate are continuously supplied so that the added amount of Mg and the added amount of P are 65 ppm and 35 ppm in terms of element, respectively. did.

(2) the polycondensation reaction above-obtained esterification reaction product supplied to the first polycondensation reaction vessel continuously stirring, the reaction temperature 270 ° C., the reaction vessel pressure 20 torr (2.67 × 10 ^{- 3} MPa) and polycondensation with an average residence time of about 1.8 hours.

Further, it was transferred to the second double condensation reaction tank, and while stirring in this reaction tank, the reaction tank temperature was 276 ° C., the reaction tank pressure was 5 torr (6.67 × 10 ⁻⁴ MPa), and the residence time was about 1.2 hours. The reaction (polycondensation) was performed under the conditions.

Subsequently, it was further transferred to the third triple condensation reaction tank. In this reaction tank, the reaction tank temperature was 278 ° C., the reaction tank internal pressure was 1.5 torr (2.0 × 10 ⁻⁴ MPa), and the residence time was 1.5 hours. The reaction product (polyethylene terephthalate (PET)) was obtained by reaction (polycondensation) under the following conditions.

  Next, the obtained reaction product was discharged into cold water in a strand form and immediately cut to prepare polyester pellets (cross section: major axis: about 4 mm, minor axis: about 2 mm, length: about 3 mm).

  The obtained polymer had IV = 0.63. This polymer was designated as raw material polyester 1 (hereinafter abbreviated as PET1).

<Manufacture of polyester film>
-Film forming process-
The raw material polyester 1 (PET1) was dried to a moisture content of 20 ppm or less and then charged into the hopper 1 of a single-screw kneading extruder 1 having a diameter of 50 mm. The raw material polyester 1 was melted at 300 ° C. and extruded from a die through a gear pump and a filter (pore diameter: 20 μm) under the following extrusion conditions.
The molten resin was extruded from the die under the conditions that the pressure fluctuation was 1% and the temperature distribution of the molten resin was 2%. Specifically, the back pressure was increased by 1% with respect to the average pressure in the barrel of the extruder, and the piping temperature of the extruder was heated at a temperature 2% higher than the average temperature in the barrel of the extruder.
The molten resin extruded from the die was extruded onto a cooling cast drum set at a temperature of 25 ° C., and was brought into close contact with the cooling cast drum using an electrostatic application method. It peeled using the peeling roll arrange | positioned facing the cooling cast drum, and the unstretched polyester film 1 was obtained.

  The obtained unstretched polyester film 1 had an intrinsic viscosity IV = 0.62, a refractive index in the longitudinal direction of 1.573, and a crystallinity of 0.2%.

IV is obtained by dissolving the unstretched polyester film 1 in a 1,1,2,2-tetrachloroethane / phenol (= 2/3 [mass ratio]) mixed solvent, and from the solution viscosity at 25 ° C. in the mixed solvent. Asked.
The refractive index of the unstretched polyester film was measured by the following method.
Using two polarizing plates, the orientation axis direction of the unstretched polyester film was determined, and a 4 cm × 2 cm rectangle was cut out so that the orientation axis directions were perpendicular to each other, and used as a measurement sample. For this sample, the biaxial refractive index (Nx, Ny) perpendicular to each other and the refractive index (Nz) in the thickness direction were determined by an Abbe refractometer (NAR-4T, measurement wavelength 589 nm, manufactured by Atago Co., Ltd.).
The crystallinity of the unstretched polyester film was measured by the following method.
The crystallinity can be calculated from the density of the film. That is, the density X (g / ^cm 3) of the film density at a crystallinity of ^{0% Y = 1.335g / cm 3} , using density Z = 1.501g / cm ³ at 100% crystalline below The crystallinity (%) can be derived from the calculation formula.
Crystallinity = {Z × (XY)} / {X × (ZY)} × 100
The density was measured according to JIS K7112.

-Transverse stretching process-
The unstretched polyester film 1 was guided to a tenter (transverse stretching machine), and was stretched laterally by the following method and conditions while holding the end of the film with a clip.

(Preheating part)
The preheating temperature was 90 ° C., and heating was performed to a temperature at which stretching was possible.

(Extension part)
The preheated unstretched polyester film 1 was stretched in the width direction using a tenter under the following conditions.
<Condition>
-Transverse stretching temperature (average temperature during transverse stretching): 90 ° C
・ Horizontal stretch ratio: 4.3 times

(Heat fixing part)
Next, a heat setting treatment was performed while controlling the film surface temperature of the polyester film within the following range.
<Condition>
・ Heat setting temperature: 180 ℃
・ Heat setting time: 15 seconds

(Heat relaxation part)
The polyester film after heat setting was heated to the following temperature to relax the film.
-Thermal relaxation temperature: 170 ° C
-Thermal relaxation rate: TD direction (film width direction) 2%

(Cooling section)
Next, the polyester film after heat relaxation was cooled at a cooling temperature of 85 ° C. Cooling temperature means the film film surface temperature in a cooling part, and actually cooled by applying 80 degreeC cold wind to a polyester film.
Also in the other Examples and Comparative Examples, the cooling temperature was set to the same value as the film film surface temperature when the clip opened the film.

(Open film)
Furthermore, the distance between the pair of rails when the clip opens the film is increased by 1.5% with respect to the shortest part of the distance between the pair of rails in the process downstream of the transverse stretching process in the tenter. The polyester film after transverse stretching was opened.
The film width when the clip opened the film was 3.5 m.
The film surface temperature when the clip opened the film was 85 ° C. The film film surface temperature when the clip opened the film was measured with a radiation thermometer (manufactured by Hayashi Denko, model number: RT61-2, used at an emissivity of 0.95).

(Recovery of film)
After cooling and releasing the film from the clip, both ends of the polyester film were trimmed (ear cut) by 20 cm. Then, after extruding (knurling) with a width of 10 mm at both ends, it was wound up with a tension of 350 N.
After releasing the laterally stretched polyester film from the clip, the cross-sectional area of the film before trimming was determined to be 2.275 × 10 ⁻⁴ m ² from a width of 3.5 m and a thickness of 65 × 10 ⁻⁶ m. Based on the winding tension of 350 N, the tension (winding tension) per unit cross-sectional area of the polyester film after being released from the clip in the film transport direction was calculated as 1538 kN / m ² .
The winding tension was adjusted by changing the weight of the weight of the dancer roll installed on the upstream side of the winder.
As described above, the polyester film of Example 1 having a thickness of 65 μm was manufactured.

(Production of polarizing plate and liquid crystal display device)
Using the polyester film of Example 1, the polarizing plate and liquid crystal display device of Example 1 were produced.

  According to [0225] of JP2011-59488A, a polarizer containing PVA was prepared.

  The following cellulose acylate film was immersed in an alkaline aqueous solution and saponified according to [0275] of Japanese Patent No. 4438270 ([0393] of US2007 / 0178252, the contents described in these publications are incorporated in the present specification). .

  Preparation of a cellulose acylate film in the same manner as [0199] to [0202] of Japanese Patent No. 4731143 ([0412] to [0416] of US2008 / 0158483, the contents described in these publications are incorporated in the present specification) did.

The above polarizer is sandwiched between the polyester film of each example and comparative example and the saponified cellulose acylate, and an aqueous PVA solution (fully saponified PVA5) is placed between the polarizer / polyester and between the cellulose acylate / polarizer. % Aqueous solution) was applied, these were pressure-bonded with a nip roll and bonded together, and then dried at 70 ° C. for 10 minutes to obtain a polarizing plate.
The obtained polarizing plate was used as the polarizing plate of Example 1.

The obtained two pairs of polarizing plates have the polyester film outside with respect to the liquid crystal cell, the absorption axis of the polarizer is orthogonally arranged, and a continuous light source (white LED) or a discontinuous light source (cold cathode tube) as a backlight. It was incorporated in a liquid crystal display device, and the light transmittance was adjusted to 50%.
The obtained liquid crystal display device was used as the image display device of Example 1.

[Examples 2 to 5, Comparative Examples 2 and 3]
In Example 1, the temperature of the cold air in the cooling unit and the air volume were changed, and the film surface temperature when the clip opened the film was changed to the temperature shown in Table 1 below.
Others were carried out in the same manner as in Example 1, and polyester films, polarizing plates and image display devices of Examples 2 to 5 and Comparative Examples 2 and 3 were produced.

[Examples 6 to 9]
In Example 1, the tension at the time of winding was changed to the value described in Table 1 below, and the tension per unit cross-sectional area of the polyester film after being released from the clip per unit cross-sectional area of the film in the film transport direction was as follows. The values were changed to those shown in Table 1.
Others were carried out similarly to Example 1, and manufactured the polyester film, polarizing plate, and image display apparatus of Examples 6-9.

[Examples 10 and 11]
In Example 1, with respect to the shortest portion of the distance between the pair of rails in each step downstream of the transverse stretching step in the tenter, the expansion ratio of the distance between the pair of rails when the clip opens the film Changes were made as described in Table 1 below.
Others were carried out similarly to Example 1, and manufactured the polyester film of Example 10 and 11, a polarizing plate, and an image display apparatus.

[Example 12]
An unstretched polyester film 1A in which the width of the unstretched polyester film 1 was cut to 12/35 times was prepared.
In Example 1, instead of the unstretched polyester film 1, the unstretched polyester film 1A was used, the tension at the time of winding was changed to the values shown in Table 1 below, and the unit cross-sectional area of the polyester film after being released from the clip The tension per cross-sectional area of the film in the film conveyance direction was changed to the values shown in Table 1 below.
Others were carried out similarly to Example 1, and manufactured the polyester film of Example 12, a polarizing plate, and an image display apparatus.

[Examples 13 and 14]
In Example 1, an unstretched polyester film in which the thickness of the unstretched polyester film 1 was adjusted so that the film thickness after lateral stretching was as shown in Table 1 below without changing the lateral stretch ratio was used. .
Furthermore, the tension at the time of winding is changed to the value described in Table 1 below, and the tension per unit cross-sectional area of the polyester film after being released from the clip per unit cross-sectional area of the film in the film transport direction is shown in Table 1 below. Changed to the stated value.
Others were carried out similarly to Example 1, and manufactured the polyester film of Example 13 and 14, a polarizing plate, and an image display apparatus.

[Example 15]
(Raw material polyester 2)
10 parts by weight of the dried UV absorber (2,2 ′-(1,4-phenylene) bis (4H-3,1-benzoxazin-4-one), 90 parts by weight of PET1 (IV = 0.63) The mixture was mixed and pelletized in the same manner as the production of PET1 using a kneading extruder to obtain a raw material polyester 2 containing an ultraviolet absorber (hereinafter abbreviated as PET2).

-Film forming process-
After drying 90 parts by mass of the raw material polyester 1 (PET1) and 10 parts by mass of the raw material polyester 2 (PET2) containing an ultraviolet absorber to a moisture content of 20 ppm or less, the hopper 1 of the uniaxial kneading extruder 1 having a diameter of 50 mm is used. And melted at 300 ° C. with the extruder 1. Extrusion was performed from a die through a gear pump and a filter (pore diameter: 20 μm) under the following extrusion conditions.
The molten resin was extruded from the die under the conditions that the pressure fluctuation was 1% and the temperature distribution of the molten resin was 2%. Specifically, the back pressure was increased by 1% with respect to the average pressure in the barrel of the extruder, and the piping temperature of the extruder was heated at a temperature 2% higher than the average temperature in the barrel of the extruder.
The molten resin extruded from the die was extruded onto a cooling cast drum set at a temperature of 25 ° C., and was brought into close contact with the cooling cast drum using an electrostatic application method. It peeled off using the peeling roll arrange | positioned facing the cooling cast drum, and the unstretched polyester film 2 was obtained.
The obtained unstretched polyester film 2 had an intrinsic viscosity IV = 0.61, a refractive index in the longitudinal direction of 1.574, and a crystallinity of 0.1%.

The obtained unstretched polyester film 2 was horizontally stretched under the same conditions as in Example 1 to produce a polyester film of Example 15 having a thickness of 65 μm.
A polarizing plate and an image display device of Example 15 were produced in the same manner as Example 1 except that the polyester film of Example 15 was used.

[Example 16]
-Film forming process-
After drying 90 parts by mass of the raw material polyester 1 (PET1) and 10 parts by mass of the raw material polyester 2 (PET2) containing an ultraviolet absorber to a moisture content of 20 ppm or less, the hopper 1 of the uniaxial kneading extruder 1 having a diameter of 50 mm is used. And melted to 300 ° C. with the extruder 1 (intermediate layer II layer). Moreover, after drying PET1 to a water content of 20 ppm or less, it was put into a hopper 2 of a single screw kneading extruder 2 having a diameter of 30 mm and melted at 300 ° C. by the extruder 2 (outer layer I layer, outer layer III layer). After these two types of polymers are respectively passed through a gear pump and a filter (pore diameter 20 μm), the polymer extruded from the extruder 1 in the two-type three-layer confluence block is transferred to the intermediate layer (II layer) from the extruder 2. The extruded polymer was laminated so as to be outer layers (I layer and III layer), and extruded from a die into a sheet.
The molten resin was extruded from the die under the conditions that the pressure fluctuation was 1% and the temperature distribution of the molten resin was 2%. Specifically, the back pressure was increased by 1% with respect to the average pressure in the barrel of the extruder, and the piping temperature of the extruder was heated at a temperature 2% higher than the average temperature in the barrel of the extruder.
The molten resin extruded from the die was extruded onto a cooling cast drum set at a temperature of 25 ° C., and was brought into close contact with the cooling cast drum using an electrostatic application method. It peeled off using the peeling roll arrange | positioned facing the cooling cast drum, and the unstretched polyester film 3 was obtained. At this time, the discharge amount of each extruder was adjusted so that the ratio of the thicknesses of the I layer, the II layer, and the III layer was 10:80:10.
The obtained unstretched polyester film 3 had an intrinsic viscosity IV = 0.61, a refractive index in the longitudinal direction of 1.574, and a crystallinity of 0.2%. In addition, the intrinsic viscosity, the refractive index in the longitudinal direction, and the crystallinity of the unstretched polyester film 3 that is a three-layer laminate can also be measured by the same method as in Example 1.

The obtained unstretched polyester film 3 was transversely stretched under the same conditions as in Example 1 to produce a polyester film of Example 16 having a thickness of 65 μm.
A polarizing plate and an image display device of Example 16 were produced in the same manner as in Example 1 except that the polyester film of Example 16 was used.

[Comparative Example 1]
In Example 1, the temperature of the cold air in the cooling unit and the air volume were changed, and the film surface temperature when the clip opened the film was changed to the temperature shown in Table 1 below.
Furthermore, the tension at the time of winding is changed to the value described in Table 1 below, and the tension per unit cross-sectional area of the polyester film after being released from the clip per unit cross-sectional area of the film in the film transport direction is shown in Table 1 below. Changed to the stated value.
Others were carried out similarly to Example 1, and manufactured the polyester film, polarizing plate, and image display apparatus of the comparative example 1.

[Comparative Example 4]
In Comparative Example 4, a polyester film of Comparative Example 4 was produced according to Example 1 of Japanese Patent No. 5021453. In addition, as a result of providing the cooling zone of 150 degreeC after heat setting according to Example 1 of patent 5021453, the film film surface temperature when a clip open | releases a film became 145 degreeC.
A polarizing plate and an image display device of Comparative Example 4 were produced in the same manner as in Example 1 except that the polyester film of Comparative Example 4 was used.

[Evaluation]
(Re, Rth, Re / Rth)
Re and Rth were measured by the method described in JP-A-2012-256057 [0054] to [0055] for each example and comparative example film, and the values of Re, Rth, and Re / Rth were determined. It described in Table 1.

(MD thermal shrinkage)
Samples of 350 mm in the longitudinal (MD) direction and 50 mm in the width direction of the polyester films of each Example and Comparative Example were cut out, marked at 300 mm intervals near both ends in the longitudinal direction of the samples, and adjusted to a temperature of 150 ° C. One end was fixed in the oven and left free for 30 minutes. The distance between the gauge points was measured in the take-out chamber (this length is assumed to be S), and the heat shrinkage rate (MD heat shrinkage rate) in the longitudinal direction after heating at 150 ° C. for 30 minutes according to the following formula was obtained. .
MD direction thermal shrinkage (%) = (300−S) / 300 × 100%

(Tenter outlet break)
The polyester film of each Example and Comparative Example was formed into 10,000 m or more, and the number of times the film was broken at the clip opening portion was measured.
The term “break” refers to a scratch having a length of 50 mm or more and penetrating in the film thickness direction. Further, the direction of the scratch was not limited, and both the scratch in the TD direction and the scratch in the MD direction were included in the break when penetrating in the film thickness direction.
The results evaluated according to the following criteria are shown in Table 1 below.
A: No base breakage of 10,000 m or more.
B: There are 1 to 5 breaks at 10,000 m.
C: Breaked 6 to 10 times at 10,000 m.
D: There are breaks 11 times or more at 10000 m.

(Film flatness)
The polyester film flatness of each Example and Comparative Example was observed visually.
The results evaluated according to the following criteria are shown in Table 1 below.
A: Very good.
B: Good.
C: Within tolerance.
D: There is a problem.

(Film scratch)
The number of bright spots was visually measured for the image table values of each Example and Comparative Example, and based on the result, the number of film scratches per unit area of the polyester film of each Example and Comparative Example was determined.
The results evaluated according to the following criteria are shown in Table 1 below.
A: There are 0 scratches in 1 m ² that become bright spots when incorporated in an LCD.
B: One or two scratches within 1 m ² that become bright spots when incorporated in an LCD.
C: 3 to 5 scratches in 1 m ² that become bright spots when incorporated in an LCD.
D: Six or more scratches within 1 m ² that become bright spots when incorporated in an LCD.

From Table 1 above, when the method for producing a polyester film of the present invention is used, the film breakage in the vicinity of the open portion of the film from the clip at the tenter outlet can be extremely reduced, and a polyester film with excellent film surface flatness can be produced. I knew it was possible.
On the other hand, from Comparative Examples 1 and 2, when the film film surface temperature when the clip opens the film is lower than the lower limit of the present invention, there are many problems of breakage in the vicinity of the open portion of the film from the clip at the tenter outlet. It was found that stable production was not possible.
From Comparative Example 3 and Comparative Example 4 carried out according to Example 1 of Japanese Patent No. 5021453, when the film surface temperature when the clip opens the film exceeds the upper limit of the present invention, the plane of the film surface It has been found that the characteristics are significantly deteriorated.
In addition, the refractive index of the longitudinal direction of the polyester film manufactured with the manufacturing method of the polyester film of this invention is 1.590 or less in all, and crystallinity exceeds all 5% that unstretched polyester film 1 It confirmed by the method similar to 3.
Moreover, it confirmed that the polyester film manufactured with the manufacturing method of the polyester film of this invention was uniaxially oriented with the following method.
That is, the refractive index in the longitudinal direction, the width direction, and the thickness direction is measured with an Abbe refractometer, the refractive index in the longitudinal direction is 1.590 or less, the refractive index in the width direction is sufficiently large, and the thickness By confirming that the refractive index in the direction was sufficiently smaller than that, it was confirmed that the polyester film was uniaxially oriented.

(Evaluation of rainbow unevenness)
In addition, for the image display device of each example, a continuous light source (white LED) and a discontinuous light source (cold cathode tube) are used from one side, light is incident, and the number of rainbows generated visually through polarized sunglasses from the opposite side. The rainbow spot was evaluated by counting.
In the image display device of each example, rainbow unevenness did not occur at normal humidity of 25 degrees and relative humidity of 50%.
Note that the rainbow unevenness was observed both from the normal direction of the polarizing plate and from the oblique direction (45 ° from the normal line).

Claims (14)

Using a tenter-type stretching device having a clip that travels along a pair of rails installed on both sides of the film conveyance path, including a step of laterally stretching while gripping the unstretched polyester film with the clip,
The manufacturing method of the polyester film which controls the film film surface temperature when opening the polyester film after the said horizontal stretching from the said clip to 50-120 degreeC. The polyester film after the transverse stretching is released from the clip, and then the tension per film cross-sectional area in the film conveyance direction of 500 to 5000 kN / m ² is applied to the polyester film after the release from the clip. The manufacturing method of the polyester film of description.   The distance between the pair of rails when the polyester film after the transverse stretching is released from the clip is widened in a range of 0.1 to 5% with respect to the shortest distance between the pair of rails after the transverse stretching zone. The manufacturing method of the polyester film of Claim 1 or 2.   The heat setting process which heats the polyester film after the transverse stretching to the highest temperature in the tenter before releasing the polyester film after the transverse stretching from the clip. A method for producing a polyester film.   The manufacturing method of the polyester film of Claim 4 including the process of cooling the polyester film after the said heat setting before releasing the polyester film after the said heat setting from the said clip. The refractive index in the longitudinal direction of the unstretched polyester film is 1.590 or less, and
The method for producing a polyester film according to any one of claims 1 to 5, wherein the crystallinity of the unstretched polyester film is 5% or less.   The method for producing a polyester film according to claim 1, wherein the unstretched polyester film contains a polyethylene terephthalate resin as a main component.   The polyester film manufactured with the manufacturing method of the polyester film as described in any one of Claims 1-7.   The polyester film according to claim 8, wherein the polyester film has a heat shrinkage in the longitudinal direction of 3% or less after being heated at 150 ° C. for 30 minutes. The film thickness is 20 to 150 μm,
The in-plane direction retardation Re is 3000 to 30000 nm,
The thickness direction retardation Rth is 3000 to 30000 nm,
The polyester film according to claim 8 or 9, wherein the Re / Rth ratio is 0.5 to 2.5.   It is a uniaxial orientation, The polyester film as described in any one of Claims 8-10. The refractive index in the longitudinal direction of the polyester film is 1.590 or less, and
The polyester film according to claim 11, wherein the crystallinity of the polyester film exceeds 5%.   The polarizing plate containing a polarizer and the polyester film as described in any one of Claims 8-12.   An image display apparatus provided with the polyester film as described in any one of Claims 8-12, or the polarizing plate of Claim 13.