JP2022153484A - Liquid crystal display device, polarization plate and polarizer protective film - Google Patents
Liquid crystal display device, polarization plate and polarizer protective film Download PDFInfo
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- JP2022153484A JP2022153484A JP2022113822A JP2022113822A JP2022153484A JP 2022153484 A JP2022153484 A JP 2022153484A JP 2022113822 A JP2022113822 A JP 2022113822A JP 2022113822 A JP2022113822 A JP 2022113822A JP 2022153484 A JP2022153484 A JP 2022153484A
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- film
- polyethylene terephthalate
- protective film
- liquid crystal
- polarizer protective
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract
Description
本発明は、液晶表示装置、偏光板および偏光子保護フィルムに関する。 The present invention relates to a liquid crystal display device, a polarizing plate and a polarizer protective film.
液晶表示装置（ＬＣＤ）に使用される偏光板は、通常ポリビニルアルコール（ＰＶＡ）などにヨウ素を染着させた偏光子を２枚の偏光子保護フィルムで挟んだ構成であり、偏光子保護フィルムとしては主にトリアセチルセルロース（ＴＡＣ）フィルムが用いられている。近年、ＬＣＤの薄型化に伴い、偏光板の薄層化が求められるようになっている。しかし、このために保護フィルムとして用いられているＴＡＣフィルムの厚みを薄くすると、充分な機械強度を得ることが出来ず、また透湿性が悪化するという問題が発生する。また、ＴＡＣフィルムは非常に高価であり、安価な代替素材としてポリエステルフィルムが提案されているが（特許文献１～３）、虹状の色斑が観察されるという問題があった。 A polarizing plate used in a liquid crystal display (LCD) generally has a structure in which a polarizer made of polyvinyl alcohol (PVA) dyed with iodine is sandwiched between two polarizer protective films. mainly uses triacetyl cellulose (TAC) film. In recent years, along with the thinning of LCDs, thinning of polarizing plates is required. However, if the thickness of the TAC film used as the protective film is reduced for this reason, there arises a problem that sufficient mechanical strength cannot be obtained and moisture permeability is deteriorated. In addition, TAC film is very expensive, and polyester film has been proposed as an inexpensive alternative material (Patent Documents 1 to 3), but there is a problem that rainbow-like color spots are observed.
偏光子の片側に複屈折性を有する配向ポリエステルフィルムを配した場合、バックライトユニット、または、偏光子から出射した直線偏光はポリエステルフィルムを通過する際に偏光状態が変化する。透過した光は配向ポリエステルフィルムの複屈折と厚さの積であるリタデーションに特有の干渉色を示す。そのため、光源として冷陰極管や熱陰極管など不連続な発光スペクトルを用いると、波長によって異なる透過光強度を示し、虹状の色斑となる（参照：第１５回マイクロオプティカルカンファレンス予稿集、第３０～３１項）。 When an oriented polyester film having birefringence is arranged on one side of the polarizer, the polarization state of the linearly polarized light emitted from the backlight unit or the polarizer changes when passing through the polyester film. The transmitted light exhibits an interference color characteristic of the retardation, which is the product of the birefringence and thickness of the oriented polyester film. Therefore, when a discontinuous emission spectrum such as a cold-cathode tube or a hot-cathode tube is used as a light source, the intensity of transmitted light varies depending on the wavelength, resulting in rainbow-like color spots. 30-31).
上記の問題を解決する手段として、バックライト光源として白色発光ダイオードのような連続的で幅広い発光スペクトルを有する白色光源を用い、更に偏光子保護フィルムとして一定のリタデーションを有する配向ポリエステルフィルムを用いることが提案されている（特許文献４）。白色発光ダイオードは、可視光領域において連続的で幅広い発光スペクトルを有する。そのため、複屈折体を透過した光による干渉色スペクトルの包絡線形状に着目すると、配向ポリエステルフィルムのリタデーションを制御することで、光源の発光スペクトルと相似なスペクトルを得ることが可能となり、これにより虹斑を抑制することを可能とした。 As a means for solving the above problems, it is possible to use a white light source having a continuous and broad emission spectrum such as a white light emitting diode as a backlight source, and use an oriented polyester film having a certain retardation as a polarizer protective film. It has been proposed (Patent Document 4). A white light emitting diode has a continuous and broad emission spectrum in the visible light region. Therefore, focusing on the envelope shape of the interference color spectrum due to the light transmitted through the birefringent material, it is possible to obtain a spectrum similar to the emission spectrum of the light source by controlling the retardation of the oriented polyester film. It made it possible to suppress the spots.
液晶表示装置のバックライト光源として、青色発光ダイオードとイットリウム・アルミニウム・ガーネット系黄色蛍光体（ＹＡＧ系黄色蛍光体）とを組み合わせた発光素子からなる白色発光ダイオード（白色ＬＥＤ）が、従来から広く用いられている。この白色光源の発光スペクトルは、可視光領域で幅広いスペクトルを有しているとともに、発光効率にも優れるため、バックライト光源として汎用されている。しかし、この白色ＬＥＤをバックライト光源とした液晶表示装置では、人間の目が認識可能なスペクトルの２０％程度しか色を再現することが出来ない。 As a backlight source for a liquid crystal display device, a white light-emitting diode (white LED) composed of a light-emitting element combining a blue light-emitting diode and an yttrium-aluminum-garnet-based yellow phosphor (YAG-based yellow phosphor) has been widely used. It is Since the emission spectrum of this white light source has a wide spectrum in the visible light region and is excellent in emission efficiency, it is widely used as a backlight source. However, in a liquid crystal display device using this white LED as a backlight source, only about 20% of the spectrum recognizable by the human eye can be reproduced.
一方、近年の色域拡大要求の高まりから、白色光源の発光スペクトルが、Ｒ（赤）、Ｇ（緑）、Ｂ（青）の各波長領域に、それぞれ明確なピーク形状を有する広色域化対応の液晶表示装置が開発されている。例えば、量子ドット技術を利用した白色光源、励起光によりＲ（赤）、Ｇ（緑）の領域に明確な発光ピークを有する蛍光体と青色ＬＥＤを用いた蛍光体方式の白色ＬＥＤ光源、３波長方式の白色ＬＥＤ光源等、様々な種類の光源を用いた、広色域化対応の液晶表示装置が開発されている。量子ドット技術を利用した白色光源をバックライト光源とする液晶表示装置の場合、人間の目が認識可能なスペクトルの６０％以上の色を再現することが可能になると言われている。 On the other hand, due to the increasing demand for expanding the color gamut in recent years, the emission spectrum of the white light source has a wide color gamut with distinct peak shapes in each wavelength region of R (red), G (green), and B (blue). A corresponding liquid crystal display device has been developed. For example, a white light source using quantum dot technology, a phosphor-type white LED light source using blue LEDs and phosphors that have clear emission peaks in the R (red) and G (green) regions of excitation light, and three wavelengths. Wide color gamut compatible liquid crystal display devices using various types of light sources such as white LED light sources have been developed. In the case of a liquid crystal display device using a white light source using quantum dot technology as a backlight source, it is said that colors of 60% or more of the spectrum that can be recognized by the human eye can be reproduced.
これらの白色光源は、いずれも従来のＹＡＧ系黄色蛍光体を用いた白色発光ダイオードからなる光源と比較してピークの半値幅が狭く、リタデーションを有するポリエチレンテレフタレート系樹脂フィルムを偏光板の構成部材である偏光子保護フィルムとして用いた場合に、光源の種類によっては虹斑が発生する場合があることが新たにわかった。 All of these white light sources have a narrow peak half-value width compared to a light source composed of a white light emitting diode using a conventional YAG-based yellow phosphor, and a polyethylene terephthalate-based resin film having retardation is used as a constituent member of the polarizing plate. It was newly found that when used as a certain polarizer protective film, iridescence may occur depending on the type of light source.
また、偏光子保護フィルムのさらなる薄膜化の要望が強くなっており、そのような場合にも、表示画面を斜め方向から観察した場合の虹斑をより抑制することのできるポリエチレンテレフタレート系樹脂フィルム（偏光子保護フィルム）を提供することが求められている。 In addition, there is a strong demand for further thinning of the polarizer protective film, and even in such cases, a polyethylene terephthalate resin film ( It is required to provide a polarizer protective film).
すなわち、本発明では、広色域化対応の液晶表示装置の偏光子保護フィルムとしてポリエチレンテレフタレート系樹脂フィルムを使用した場合や、偏光子保護フィルムを薄膜化した場合にも、虹斑の発生を抑制できる、偏光子保護フィルム、それを含む偏光板及び液晶表示装置を提供することを課題とする。 That is, in the present invention, even when a polyethylene terephthalate-based resin film is used as a polarizer protective film for a liquid crystal display device compatible with a wide color gamut, or when the polarizer protective film is made thinner, the occurrence of iridescence is suppressed. An object of the present invention is to provide a polarizer protective film, a polarizing plate including the same, and a liquid crystal display device.
本発明者らは、鋭意検討した結果、ポリエチレンテレフタレート系樹脂フィルムが特定範囲のリタデーションを有していることに加え、Ｘ線回折で測定した結晶の（１００）面のフィルム面に対する配向度が低いほど虹斑抑制に効果的であることを見出した。 As a result of intensive studies, the present inventors have found that the polyethylene terephthalate-based resin film has a retardation within a specific range, and that the (100) plane of the crystal measured by X-ray diffraction has a low degree of orientation with respect to the film plane. It was found to be as effective as iris suppression.
代表的な本発明は、以下の通りである。
項１．
ポリエチレンテレフタレート系樹脂フィルムからなる偏光子保護フィルムであって、前記ポリエチレンテレフタレート系樹脂フィルムは下記の（１）及び（２）を満たすことを特徴とする偏光子保護フィルム。
（１）ポリエチレンテレフタレート系樹脂フィルムが３０００ｎｍ以上３００００ｎｍ以下のリタデーションを有する
（２）Ｘ線回折で測定した結晶の（１００）面のフィルム面に対する配向度が０．７０以下である
項２．
前記ポリエチレンテレフタレート系樹脂フィルムは、遅相軸方向に測定した結晶の（－１０５）面の結晶サイズが３６Å以上である、項１に記載の偏光子保護フィルム。
項３．
偏光子の少なくとも一方の面に項１又は２に記載の偏光子保護フィルムが積層された偏光板。
項４．
バックライト光源、２つの偏光板、及び前記２つの偏光板の間に配された液晶セルを有する液晶表示装置であって、
前記２つの偏光板のうち、少なくとも一方が項３に記載の偏光板である、液晶表示装置。
A typical present invention is as follows.
Section 1.
A polarizer protective film comprising a polyethylene terephthalate-based resin film, wherein the polyethylene terephthalate-based resin film satisfies the following (1) and (2).
(1) The polyethylene terephthalate-based resin film has a retardation of 3000 nm or more and 30000 nm or less.
Item 2. The polarizer protective film according to Item 1, wherein the polyethylene terephthalate-based resin film has a crystal size of 36 Å or more on the (−105) plane of crystals measured in the slow axis direction.
Item 3.
A polarizing plate comprising a polarizer and the polarizer protective film according to Item 1 or 2 laminated on at least one surface of the polarizer.
Section 4.
A liquid crystal display device comprising a backlight source, two polarizing plates, and a liquid crystal cell arranged between the two polarizing plates,
Item 3. A liquid crystal display device, wherein at least one of the two polarizing plates is the polarizing plate according to item 3.
本発明の液晶表示装置、偏光板および偏光子保護フィルムであれば、偏光子保護フィルムとしてのポリエチレンテレフタレート系樹脂フィルムを、広色域化対応の液晶表示装置に使用した場合や、薄膜化した場合にも、表示画面への虹斑の発生を抑制することができる。 If the liquid crystal display device, the polarizing plate and the polarizer protective film of the present invention, the polyethylene terephthalate-based resin film as the polarizer protective film is used in a liquid crystal display device compatible with widening the color gamut, or when it is thinned. Also, it is possible to suppress the occurrence of iridescence on the display screen.
１．偏光子保護フィルム
本発明の偏光子保護フィルムに用いられるポリエチレンテレフタレート系樹脂フィルムは、３０００ｎｍ以上３００００ｎｍ以下のリタデーション（Ｒｅ、面内リタデーション）を有することが好ましい。リタデーションが３０００ｎｍ未満では、偏光子保護フィルムとして用いた場合、斜め方向から観察した時に強い干渉色を呈し、良好な視認性を確保することができない。好ましいリタデーションの下限値は４０００ｎｍ、次に好ましい下限値は５０００ｎｍ、より好ましい下限値は６０００ｎｍである。
1. Polarizer Protective Film The polyethylene terephthalate-based resin film used for the polarizer protective film of the present invention preferably has a retardation (Re, in-plane retardation) of 3000 nm or more and 30000 nm or less. If the retardation is less than 3000 nm, when used as a polarizer protective film, it exhibits a strong interference color when observed from an oblique direction, and good visibility cannot be ensured. A preferable lower limit of retardation is 4000 nm, a second preferable lower limit is 5000 nm, and a more preferable lower limit is 6000 nm.
一方、リタデーションの上限は３００００ｎｍが好ましく、より好ましい上限は１００００ｎｍである。３００００ｎｍの上限を著しく超えると更なる視認性の改善効果は実質的に得られないばかりか、フィルムの厚みも相当に厚くなり、工業材料としての取り扱い性が低下するので好ましくない。 On the other hand, the upper limit of retardation is preferably 30000 nm, more preferably 10000 nm. If the upper limit of 30,000 nm is remarkably exceeded, not only is it not possible to substantially obtain a further effect of improving visibility, the thickness of the film becomes considerably thick, and the handleability as an industrial material deteriorates, which is not preferable.
フィルム面内における屈折率差（遅相軸方向の屈折率－進相軸方向の屈折率）は、０．０８以上が好ましく、より好ましくは０．０９以上、さらに好ましくは０．１０以上である。前記屈折率差の上限は０．１５以下が好ましい。一方向に強く延伸され、フィルム面内における屈折率差が大きいほうが、虹斑をより抑制する観点から好ましい。 The refractive index difference in the plane of the film (refractive index in the slow axis direction - refractive index in the fast axis direction) is preferably 0.08 or more, more preferably 0.09 or more, and still more preferably 0.10 or more. . The upper limit of the refractive index difference is preferably 0.15 or less. Strong stretching in one direction and a large refractive index difference in the film plane are preferred from the viewpoint of further suppressing iridescence.
なお、本発明のリタデーションは、フィルム面内における２軸方向の屈折率とフィルム厚みを測定して求めることもできるし、ＫＯＢＲＡ－２１ＡＤＨ（王子計測機器株式会社）といった市販の自動複屈折測定装置を用いて求めることもできる。フィルム面内における２軸方向の屈折率は、アッベ屈折率計（アタゴ社製、ＮＡＲ－４Ｔ、測定波長５８９ｎｍ）によって求めることができる。 The retardation of the present invention can be obtained by measuring the refractive index in the biaxial direction and the film thickness in the plane of the film, or by using a commercially available automatic birefringence measuring device such as KOBRA-21ADH (Oji Scientific Instruments Co., Ltd.). It can also be obtained by using The biaxial refractive index in the plane of the film can be determined by an Abbe refractometer (NAR-4T manufactured by Atago Co., Ltd., measuring wavelength 589 nm).
本発明の偏光子保護フィルムに用いるポリエチレンテレフタレート系樹脂フィルムは、特定範囲のリタデーションを有することに加え、Ｘ線回折で測定した結晶の（１００）面のフィルム面に対する配向度が０．７０以下であることが斜め方向から観察される虹斑を抑制する観点から好ましい。ポリエチレンテレフタレート系樹脂フィルムの結晶の（１００）面のフィルム面に対する配向度は０．７０以下が好ましく、より好ましくは０．６５以下であり、より好ましくは０．６０以下であり、より好ましくは０．５９以下であり、さらに好ましくは０．５８以下である。下限は０．４０が好ましい。結晶の（１００）面のフィルム面に対する配向度は、ポリエチレンテレフタレート系樹脂フィルムの結晶の分子鎖方向（ｃ軸）まわりの配向を示す指標であり、この値が低いほどｃ軸まわりの配向がランダムであることを表している。このｃ軸まわりの配向がランダムであるほど、斜め方向から観察される虹斑が抑制される。 The polyethylene terephthalate-based resin film used in the polarizer protective film of the present invention has a retardation within a specific range, and the degree of orientation of the crystal (100) plane with respect to the film plane measured by X-ray diffraction is 0.70 or less. It is preferable from the viewpoint of suppressing iridescence observed from an oblique direction. The degree of orientation of the (100) plane of the crystals of the polyethylene terephthalate resin film with respect to the film plane is preferably 0.70 or less, more preferably 0.65 or less, more preferably 0.60 or less, and more preferably 0. 0.59 or less, more preferably 0.58 or less. The lower limit is preferably 0.40. The degree of orientation of the (100) plane of the crystal with respect to the film plane is an index indicating the orientation around the molecular chain direction (c-axis) of the crystal of the polyethylene terephthalate-based resin film, and the lower this value, the more random the orientation around the c-axis. It means that The more random the orientation around the c-axis, the more suppressed the iridescence observed from an oblique direction.
結晶の（１００）面のフィルム面に対する配向度は、Ｘ線回折装置（株式会社リガク社製、ＲＩＮＴ２１００ＰＣ）を用いて、極点測定により得られた回折強度の遅相軸方向を軸とした半値幅を用いて、（１８０－半値幅）／１８０と定義されるパラメーターである。ただし、半値幅の単位は度である。フィルムの遅相軸方向は、分子配向計（王子計測器株式会社製、ＭＯＡ－６００４型分子配向計）を用いて、求めることができる。配向度の測定に関する詳細は実施例で後述する。 The degree of orientation of the (100) plane of the crystal with respect to the film plane is the half width of the diffraction intensity obtained by pole measurement using an X-ray diffractometer (manufactured by Rigaku Co., Ltd., RINT2100PC), with the slow axis direction as the axis. is a parameter defined as (180-half width)/180. However, the unit of the half width is degrees. The slow axis direction of the film can be determined using a molecular orientation meter (MOA-6004 type molecular orientation meter manufactured by Oji Instruments Co., Ltd.). Details regarding the measurement of the degree of orientation will be described later in Examples.
さらに、前記ポリエチレンテレフタレート系樹脂フィルムは、Ｘ線回折で遅相軸方向に測定した結晶の（－１０５）面の結晶サイズが３６Å（オングストローム）以上であることが好ましい。前記結晶の（－１０５面）の結晶サイズは、３６Å以上が好ましく、より好ましくは３８Å以上であり、さらに好ましくは３９Å以上である。上限は６０Åが好ましいが、４５Å程度で十分である Further, the polyethylene terephthalate-based resin film preferably has a crystal size of 36 angstroms or more on the (-105) plane of crystals measured in the slow axis direction by X-ray diffraction. The crystal size of (−105 plane) of the crystal is preferably 36 Å or more, more preferably 38 Å or more, and still more preferably 39 Å or more. The upper limit is preferably 60 Å, but about 45 Å is sufficient.
ポリエチレンテレフタレート系樹脂フィルムの結晶の分子鎖方向（ｃ軸方向）がフィルムの遅相軸方向に配向し、結晶の分子鎖方向（ｃ軸方向）の結晶サイズが特定の値より大きく、結晶の分子鎖方向軸（ｃ軸）まわりの配向を低くすることで、より虹状の色斑が発生しにくくなると考えられる。結晶の分子鎖軸方向の結晶サイズは、下記のとおり結晶の（－１０５）面の見かけの結晶サイズとして測定することができる。 The molecular chain direction (c-axis direction) of the crystals of the polyethylene terephthalate-based resin film is oriented in the slow axis direction of the film, the crystal size in the molecular chain direction (c-axis direction) of the crystals is larger than a specific value, and the crystal molecules By lowering the orientation around the chain direction axis (c-axis), it is believed that rainbow-like color spots are less likely to occur. The crystal size in the molecular chain axis direction of the crystal can be measured as the apparent crystal size of the (−105) plane of the crystal as described below.
遅相軸方向に測定した結晶の（－１０５）面の結晶サイズは、Ｘ線回折装置（株式会社リガク社製、ＲＩＮＴ２５００）を用いて遅相軸方向に測定したθ/２θの回折強度プロファイルから、結晶の（－１０５）面の回折位置、実測半値幅（Ｂ）を読み取り、次式（シェラーの式）を用いて見掛けの結晶サイズ（ＡＣＳ）として算出することができる。測定に用いたＸ線は、Ｃｕ－Ｋα線で、波長は１．５４１８Åである。本発明でいう遅相軸方向に測定した結晶の（－１０５）面の結晶サイズとは、見掛けの結晶サイズのことである。（ＡＣＳ＝０．９λ／（βcosθ））。ここで、λはＸ線の波長（１．５４１８Å）、βは読み取った実測半値幅（Ｂ）と補正のための定数（ｂ）から（Ｂ２－ｂ２）１／２で計算される半値幅である。なお、補正のための定数（ｂ）は、シリコン粉末ＮＩＳＴ６４０ｂを同条件で測定したときの半値幅である。β、Ｂ、ｂは、いずれもラジアン単位の値である。 The crystal size of the (−105) plane of the crystal measured in the slow axis direction is obtained from the θ/2θ diffraction intensity profile measured in the slow axis direction using an X-ray diffractometer (RINT2500, manufactured by Rigaku Co., Ltd.). , the diffraction position of the (−105) plane of the crystal, and the measured half-value width (B) are read, and the apparent crystal size (ACS) can be calculated using the following formula (Scherrer's formula). The X-rays used for the measurement were Cu-Kα rays with a wavelength of 1.5418 Å. The crystal size of the (−105) plane of the crystal measured in the direction of the slow axis referred to in the present invention is the apparent crystal size. (ACS=0.9λ/(β cos θ)). where λ is the wavelength of the X-ray (1.5418 Å), β is the half width calculated by (B 2 −b 2 ) 1/2 from the measured half width (B) and the constant (b) for correction. price range. The constant (b) for correction is the half width when the silicon powder NIST640b is measured under the same conditions. β, B, and b are all values in radians.
結晶の（－１０５）面の面内配向度は、０．６以上が好ましく、より好ましくは０．７以上、さらに好ましくは０．８以上である。結晶の（－１０５）面の面内配向度は、Ｘ線回折装置（株式会社リガク社製、ＲＩＮＴ２５００）を用いて測定することができる。測定は、θ/2θを固定して方位角測定用サンプルホルダーを用いてサンプルを３６０°回転させることにより結晶の（－１０５）面の回折強度の円周方向の分布を得る。得られた分布の半値幅から、（１８０－半値幅）／１８０で定義されるパラメーターを面内配向度とする。ここでいう半値幅の単位は度である。 The degree of in-plane orientation of the (−105) plane of the crystal is preferably 0.6 or more, more preferably 0.7 or more, and still more preferably 0.8 or more. The in-plane orientation degree of the (−105) plane of the crystal can be measured using an X-ray diffractometer (RINT2500, manufactured by Rigaku Corporation). The measurement is carried out by fixing θ/2θ and rotating the sample by 360° using a sample holder for azimuth angle measurement to obtain the distribution of the diffraction intensity of the (−105) plane of the crystal in the circumferential direction. A parameter defined by (180-half width)/180 is taken as the in-plane orientation degree from the half width of the obtained distribution. The unit of the half width here is degrees.
結晶の分子鎖軸方向を一軸に配向させるためには、フィルムを一方向に延伸することが好ましい。一般に延伸方向への配向度を高めるためには、延伸倍率を高くする、または、延伸温度を低くする方法がある。また、フィルム状物を一軸延伸する際、延伸方向、フィルム平面内で延伸方向に垂直な方向、厚み方向で内部に発生する応力は異なることがある。一般的には、自由端一軸延伸、固定端一軸延伸と呼ばれるように、延伸方向に垂直な方向の寸法を自由にする場合と固定する場合で内部の応力は大きく異なることが知られている。これは、延伸時に発生するポアソン収縮を延伸方向に垂直な方向に自由にするか、抑制するかの違いによるものである。通常のテンター横延伸の場合、端部をクリップで把持しているため、横延伸時にフィルム流れ方向（ＭＤ）のポアソン収縮が制限される。したがって、横延伸方向（ＴＤ）はもちろん、流れ方向への応力も発生する。厚み方向については制限されないため、応力も発生していないと考えられる。すなわち、延伸方向に配向した分子鎖軸周りの応力分布が、流れ方向と厚み方向で異なることにより、結晶のベンゼン環面の配向が進むと考えられる。よって、結晶の分子鎖方向軸（ｃ軸）まわりの配向を低くするためには、延伸方向への応力とひずみを保ちつつ、配向軸まわりの応力を均等にすることが好ましい。実質的に、厚み方向には応力は働かないので、延伸方向に垂直な方向（流れ方向）への応力を下げることが好ましい。 In order to uniaxially orient the molecular chain axes of crystals, it is preferable to stretch the film in one direction. Generally, in order to increase the degree of orientation in the drawing direction, there is a method of increasing the draw ratio or lowering the drawing temperature. Further, when a film-like material is uniaxially stretched, the stress generated inside may differ in the stretching direction, the direction perpendicular to the stretching direction in the plane of the film, and the thickness direction. Generally, it is known that the internal stress differs greatly depending on whether the dimension in the direction perpendicular to the drawing direction is free or fixed, as is called free-end uniaxial stretching and fixed-end uniaxial stretching. This is due to the difference in whether the Poisson contraction that occurs during stretching is freed in the direction perpendicular to the stretching direction or suppressed. In the case of normal transverse stretching of the tenter, since the ends are gripped with clips, Poisson shrinkage in the machine direction (MD) of the film is restricted during transverse stretching. Therefore, not only the transverse stretching direction (TD) but also the machine direction stress is generated. Since there is no restriction in the thickness direction, it is considered that no stress is generated. That is, it is thought that the orientation of the benzene ring planes of the crystal progresses because the stress distribution around the molecular chain axis oriented in the stretching direction differs between the flow direction and the thickness direction. Therefore, in order to lower the orientation around the molecular chain direction axis (c-axis) of the crystal, it is preferable to equalize the stress around the orientation axis while maintaining the stress and strain in the drawing direction. Since substantially no stress acts in the thickness direction, it is preferable to reduce the stress in the direction perpendicular to the stretching direction (machine direction).
本発明の保護フィルムであるポリエチレンテレフタレート系樹脂フィルムは、一般的なポリエステルフィルムの製造方法に従って製造することができる。例えば、ポリエチレンテレフタレート系樹脂を溶融し、シート状に押出し成形された無配向ポリエチレンテレフタレート系樹脂をガラス転移温度以上の温度において、ロールの速度差を利用して縦方向に延伸した後、テンターにより横方向に延伸し、熱処理を施す方法が挙げられる。 The polyethylene terephthalate-based resin film, which is the protective film of the present invention, can be produced according to a general polyester film production method. For example, a non-oriented polyethylene terephthalate resin melted and extruded into a sheet is stretched in the longitudinal direction using the speed difference between the rolls at a temperature above the glass transition temperature, and then stretched horizontally by a tenter. A method in which the film is stretched in the direction and subjected to heat treatment can be mentioned.
ポリエチレンテレフタレート系樹脂フィルムの製膜条件を具体的に説明すると、縦延伸温度、横延伸温度は１００～１３０℃が好ましく、特に好ましくは１１０～１２５℃である。 Specifically, the film-forming conditions for the polyethylene terephthalate-based resin film are as follows: longitudinal stretching temperature and transverse stretching temperature are preferably 100 to 130°C, particularly preferably 110 to 125°C.
フィルム幅方向（ＴＤ方向）に遅相軸を有するフィルムを製造する場合、縦延伸倍率は０．７～１．０倍が好ましい。また、横延伸倍率は４．０～６．０倍が好ましく、より好ましくは４．０～５．５倍、最も好ましくは４．５～５．５倍である。 When producing a film having a slow axis in the film width direction (TD direction), the longitudinal draw ratio is preferably 0.7 to 1.0 times. The transverse draw ratio is preferably 4.0 to 6.0 times, more preferably 4.0 to 5.5 times, and most preferably 4.5 to 5.5 times.
一方、フィルム縦方向（ＭＤ方向）に遅相軸を有するフィルムを製造する場合、横延伸倍率は１．０～３．０倍が好ましく、より好ましくは１．５～３．０倍、さらに好ましくは２．０～３．０倍である。縦延伸倍率は４．０～６．５倍が好ましく、より好ましくは５．０～６．０倍である。なお、フィルム縦方向に遅相軸を有するフィルムを製造する場合、結晶の（１００）面のフィルム面に対する配向度を下げる観点から、横延伸した後、縦延伸することが好ましい。 On the other hand, when producing a film having a slow axis in the longitudinal direction (MD direction) of the film, the transverse draw ratio is preferably 1.0 to 3.0 times, more preferably 1.5 to 3.0 times, and still more preferably. is 2.0 to 3.0 times. The longitudinal draw ratio is preferably 4.0 to 6.5 times, more preferably 5.0 to 6.0 times. When producing a film having a slow axis in the longitudinal direction of the film, it is preferable to longitudinally stretch the film after transversely stretching it, from the viewpoint of lowering the degree of orientation of the crystal (100) plane with respect to the film plane.
リタデーションを上記範囲に制御するためには、縦延伸倍率と横延伸倍率の比率や、延伸温度、フィルムの厚みを制御することが好ましい。縦横の延伸倍率の差が小さすぎるとリタデーションを高くすることが難しくなり好ましくない。 In order to control the retardation within the above range, it is preferable to control the ratio of the longitudinal draw ratio to the transverse draw ratio, the drawing temperature, and the thickness of the film. If the difference in stretch ratio in the vertical and horizontal directions is too small, it is difficult to increase the retardation, which is not preferable.
結晶の（－１０５）面の結晶サイズを大きくし、結晶の（１００）面のフィルム面に対する配向度を下げるためには、一方向に対する延伸倍率を大きくすること、延伸温度を高く設定すること、その際、フィルムに十分な熱量が加わるように熱風の風速を適切に調整することが好ましい。熱風の風速は、好ましくは６ｍ／秒～１５ｍ／秒であり、より好ましくは８ｍ／秒～１２ｍ／秒である。フィルムに十分な熱量を加えながら高倍率で一方向に延伸することで、延伸方向への応力とひずみを保ちつつ、配向軸まわりの応力を均等にでき、結晶の（－１０５）面の結晶サイズを大きくし、結晶の（１００）面のフィルム面に対する配向度を下げることができる。 In order to increase the crystal size of the (-105) plane of the crystal and lower the degree of orientation of the (100) plane of the crystal with respect to the film plane, the stretching ratio in one direction should be increased, the stretching temperature should be set high, At that time, it is preferable to appropriately adjust the wind speed of the hot air so that a sufficient amount of heat is applied to the film. The wind speed of the hot air is preferably 6 m/sec to 15 m/sec, more preferably 8 m/sec to 12 m/sec. By applying a sufficient amount of heat to the film and stretching it in one direction at a high magnification, the stress and strain in the stretching direction can be maintained, and the stress around the orientation axis can be made uniform. can be increased to decrease the degree of orientation of the (100) plane of the crystal with respect to the film plane.
続く熱処理においては、処理温度は１５０～２５０℃が好ましく、特に好ましくは１８０～２２０℃である。結晶の（１００）面のフィルム面に対する配向度を下げる観点からは、熱処理の処理温度は低いほうが好ましい。一方、結晶の（－１０５）面の結晶サイズを大きくする観点からは、熱処理の処理温度は高いほうが好ましいため、両者のバランスを考慮して調整することが好ましい。 In the subsequent heat treatment, the treatment temperature is preferably 150-250°C, particularly preferably 180-220°C. From the viewpoint of lowering the degree of orientation of the (100) plane of the crystal with respect to the film plane, the heat treatment temperature is preferably low. On the other hand, from the viewpoint of enlarging the crystal size of the (−105) plane of the crystal, the treatment temperature of the heat treatment is preferably high, so it is preferable to make adjustments in consideration of the balance between the two.
ポリエチレンテレフタレート系樹脂フィルムを構成するポリエチレンテレフタレート系樹脂は、モノマーユニットの８５モル％以上がエチレンテレフタレートであることが好ましい。エチレンテレフタレート単位は９０モル％以上が好ましく、より好ましくは９５モル％以上である。なお、共重合成分としては、公知の酸成分、グリコール成分を含んでもよい。ポリエチレンテレフタレート系樹脂として、特に好ましいものは、ホモポリマーであるポリエチレンテレフタレートである。モノマーユニットの割合は、１Ｈ－NMR測定により確認することができる。 In the polyethylene terephthalate-based resin constituting the polyethylene terephthalate-based resin film, 85 mol % or more of the monomer units is preferably ethylene terephthalate. The ethylene terephthalate unit is preferably at least 90 mol %, more preferably at least 95 mol %. In addition, as a copolymerization component, a well-known acid component and a glycol component may be included. A particularly preferred polyethylene terephthalate-based resin is polyethylene terephthalate, which is a homopolymer. The ratio of monomer units can be confirmed by 1 H-NMR measurement.
これらの樹脂は透明性に優れるとともに、熱的、機械的特性にも優れており、延伸加工によって容易にリタデーションを制御することができる。ポリエチレンテレフタレートは、固有複屈折が大きく、フィルムの厚みが薄くても比較的容易に大きなリタデーションが得ることができ、最も好適な素材である。 These resins are excellent in transparency as well as in thermal and mechanical properties, and their retardation can be easily controlled by stretching. Polyethylene terephthalate has a large intrinsic birefringence and can relatively easily obtain a large retardation even if the film is thin, and is the most suitable material.
また、ヨウ素色素などの光学機能性色素の劣化を抑制することを目的として、本発明の保護フィルムは、波長３８０ｎｍの光線透過率が２０％以下であることが望ましい。３８０ｎｍの光線透過率は１５％以下がより好ましく、１０％以下がさらに好ましく、５％以下が特に好ましい。前記光線透過率が２０％以下であれば、光学機能性色素の紫外線による変質を抑制することができる。なお、本発明における光線透過率は、フィルムの平面に対して垂直方向に測定したものであり、分光光度計（例えば、日立Ｕ－３５００型）を用いて測定することができる。 For the purpose of suppressing deterioration of optically functional dyes such as iodine dyes, the protective film of the present invention preferably has a light transmittance of 20% or less at a wavelength of 380 nm. The light transmittance at 380 nm is more preferably 15% or less, even more preferably 10% or less, and particularly preferably 5% or less. If the light transmittance is 20% or less, deterioration of the optical functional dye due to ultraviolet rays can be suppressed. The light transmittance in the present invention is measured in the direction perpendicular to the plane of the film, and can be measured using a spectrophotometer (for example, Hitachi U-3500).
本発明の保護フィルムの波長３８０ｎｍの光線透過率を２０％以下にするためには、紫外線吸収剤の種類、濃度、及びフィルムの厚みを適宜調節することが望ましい。本発明で使用される紫外線吸収剤は公知の物質である。紫外線吸収剤としては、有機系紫外線吸収剤と無機系紫外線吸収剤が挙げられるが、透明性の観点から有機系紫外線吸収剤が好ましい。有機系紫外線吸収剤としては、ベンゾトリアゾール系、ベンゾフェノン系、環状イミノエステル系等、及びその組み合わせが挙げられるが本発明の規定する吸光度の範囲であれば特に限定されない。しかし、耐久性の観点からはベンゾトリアゾール系、環状イミノエステル系が特に好ましい。２種以上の紫外線吸収剤を併用した場合には、別々の波長の紫外線を同時に吸収させることができるので、より紫外線吸収効果を改善することができる。 In order to make the light transmittance of the protective film of the present invention 20% or less at a wavelength of 380 nm, it is desirable to appropriately adjust the type and concentration of the ultraviolet absorbent and the thickness of the film. The ultraviolet absorbers used in the present invention are known substances. Examples of the UV absorber include organic UV absorbers and inorganic UV absorbers, but organic UV absorbers are preferred from the viewpoint of transparency. Examples of organic UV absorbers include benzotriazole-based, benzophenone-based, cyclic iminoester-based, and combinations thereof, but are not particularly limited as long as the absorbance is within the range defined by the present invention. However, from the viewpoint of durability, benzotriazole-based and cyclic iminoester-based are particularly preferred. When two or more ultraviolet absorbers are used in combination, ultraviolet rays of different wavelengths can be absorbed at the same time, so that the ultraviolet absorption effect can be further improved.
ベンゾフェノン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤、アクリロニトリル系紫外線吸収剤としては例えば２－［２'－ヒドロキシ－５' －（メタクリロイルオキシメチル）フェニル］－２Ｈ－ベンゾトリアゾール、２－［２' －ヒドロキシ－５' －（メタクリロイルオキシエチル）フェニル］－２Ｈ－ベンゾトリアゾール、２－［２' －ヒドロキシ－５' －（メタクリロイルオキシプロピル）フェニル］－２Ｈ－ベンゾトリアゾール、２，２'－ジヒドロキシ－４，４'－ジメトキシベンゾフェノン、２，２'，４，４'－テトラヒドロキシベンゾフェノン、２，４－ジ－ｔｅｒｔ－ブチル－６－（５－クロロベンゾトリアゾール－２－イル）フェノール、２－（２'－ヒドロキシ－３'－ｔｅｒｔ－ブチル－５'－メチルフェニル）－５－クロロベンゾトリアゾール、２－（５－クロロ（２Ｈ）－ベンゾトリアゾール－２－イル）－４－メチル－６－（ｔｅｒｔ－ブチル）フェノール、２，２'－メチレンビス（４－（１，１，３，３－テトラメチルブチル）－６－（２Ｈ－ベンゾトリアゾール－２－イル）フェノールなどが挙げられる。環状イミノエステル系紫外線吸収剤としては例えば２，２’－（１，４－フェニレン）ビス（４Ｈ－３，１－ベンズオキサジン－４－オン）、２－メチル－３，１－ベンゾオキサジン－４－オン、２－ブチル－３，１－ベンゾオキサジン－４－オン、２－フェニル－３，１－ベンゾオキサジン－４－オンなどが挙げられる。しかし特にこれらに限定されるものではない。 Examples of benzophenone UV absorbers, benzotriazole UV absorbers, and acrylonitrile UV absorbers include 2-[2'-hydroxy-5'-(methacryloyloxymethyl)phenyl]-2H-benzotriazole, 2-[2' -hydroxy-5'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxypropyl)phenyl]-2H-benzotriazole, 2,2'-dihydroxy- 4,4′-dimethoxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol, 2-( 2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole, 2-(5-chloro(2H)-benzotriazol-2-yl)-4-methyl-6-( tert-butyl)phenol, 2,2′-methylenebis(4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol, etc. Cyclic iminoesters Examples of UV absorbers include 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one), 2-methyl-3,1-benzoxazin-4-one, Examples include 2-butyl-3,1-benzoxazin-4-one, 2-phenyl-3,1-benzoxazin-4-one, etc. However, it is not particularly limited to these.
紫外線吸収剤以外に、本発明の効果を妨げない範囲で、触媒以外の各種の添加剤を含有させることも好ましい様態である。添加剤として、例えば、無機粒子、耐熱性高分子粒子、アルカリ金属化合物、アルカリ土類金属化合物、リン化合物、帯電防止剤、耐光剤、難燃剤、熱安定剤、酸化防止剤、ゲル化防止剤、界面活性剤等が挙げられる。また、高い透明性を奏するためにはポリエチレンテレフタレート系樹脂フィルムに実質的に粒子を含有しないことも好ましい。「粒子を実質的に含有させない」とは、例えば無機粒子の場合、ケイ光Ｘ線分析で無機元素を定量した場合に５０ｐｐｍ以下、好ましくは１０ｐｐｍ以下、特に好ましくは検出限界以下となる含有量を意味する。 In addition to the ultraviolet absorber, it is also a preferred embodiment to contain various additives other than the catalyst within a range that does not impair the effects of the present invention. Examples of additives include inorganic particles, heat-resistant polymer particles, alkali metal compounds, alkaline earth metal compounds, phosphorus compounds, antistatic agents, light stabilizers, flame retardants, heat stabilizers, antioxidants, and anti-gelling agents. , surfactants, and the like. Moreover, in order to exhibit high transparency, it is also preferable that the polyethylene terephthalate-based resin film contains substantially no particles. The term "substantially contains no particles" means, for example, in the case of inorganic particles, a content of 50 ppm or less, preferably 10 ppm or less, particularly preferably a detection limit or less when an inorganic element is quantified by fluorescence X-ray analysis. means.
本発明におけるポリエチレンテレフタレート系樹脂フィルムに紫外線吸収剤を配合する方法としては、公知の方法を組み合わせて採用し得るが、例えば予め混練押出機を用い、乾燥させた紫外線吸収剤とポリマー原料とをブレンドしマスターバッチを作製しておき、フィルム製膜時に所定の該マスターバッチとポリマー原料を混合する方法などによって配合することができる。 As a method for blending the ultraviolet absorber with the polyethylene terephthalate resin film in the present invention, a combination of known methods can be employed. Alternatively, a masterbatch may be prepared in advance, and the predetermined masterbatch and the polymer raw material may be mixed at the time of film formation.
この時マスターバッチの紫外線吸収剤濃度は紫外線吸収剤を均一に分散させ、且つ経済的に配合するために５～３０質量％の濃度にするのが好ましい。マスターバッチを作製する条件としては混練押出機を用い、押し出し温度はポリエチレンテレフタレート系樹脂原料の融点以上、２９０℃以下の温度で１～１５分間で押し出すのが好ましい。２９０℃以上では紫外線吸収剤の減量が大きく、また、マスターバッチの粘度低下が大きくなる。押し出し時間１分以下では紫外線吸収剤の均一な混合が困難となる。この時、必要に応じて安定剤、色調調整剤、帯電防止剤を添加しても良い。 At this time, the concentration of the UV absorber in the masterbatch is preferably 5 to 30% by weight in order to uniformly disperse the UV absorber and to blend it economically. As conditions for preparing the masterbatch, a kneading extruder is preferably used, and the extrusion temperature is preferably the melting point of the polyethylene terephthalate-based resin raw material or higher and 290° C. or lower for 1 to 15 minutes. At 290° C. or higher, the weight loss of the ultraviolet absorber is large, and the viscosity of the masterbatch is greatly lowered. If the extrusion time is less than 1 minute, it becomes difficult to uniformly mix the ultraviolet absorber. At this time, a stabilizer, a color tone adjusting agent, and an antistatic agent may be added as necessary.
本発明ではフィルムを少なくとも３層以上の多層構造とし、フィルムの中間層に紫外線吸収剤を添加することが好ましい。中間層に紫外線吸収剤を含む３層構造のフィルムは、具体的には次のように作製することができる。外層用としてポリエチレンテレフタレート系樹脂のペレット単独、中間層用として紫外線吸収剤を含有したマスターバッチとポリエチレンテレフタレート系樹脂のペレットを所定の割合で混合し、乾燥したのち、公知の溶融積層用押出機に供給し、スリット状のダイからシート状に押出し、キャスティングロール上で冷却固化せしめて未延伸フィルムを作る。すなわち、２台以上の押出機、３層のマニホールドまたは合流ブロック（例えば角型合流部を有する合流ブロック）を用いて、両外層を構成するフィルム層、中間層を構成するフィルム層を積層し、口金から３層のシートを押し出し、キャスティングロールで冷却して未延伸フィルムを作る。なお、発明では、光学欠点の原因となる、原料のポリエチレンテレフタレート系樹中に含まれている異物を除去するため、溶融押し出しの際に高精度濾過を行うことが好ましい。溶融樹脂の高精度濾過に用いる濾材の濾過粒子サイズ（初期濾過効率９５％）は、１５μｍ以下が好ましい。濾材の濾過粒子サイズが１５μｍを超えると、２０μｍ以上の異物の除去が不十分となりやすい。 In the present invention, it is preferred that the film has a multi-layered structure of at least three layers and that an ultraviolet absorber is added to an intermediate layer of the film. Specifically, a three-layer film containing an ultraviolet absorber in the intermediate layer can be produced as follows. Polyethylene terephthalate-based resin pellets alone for the outer layer, and a masterbatch containing an ultraviolet absorber and polyethylene terephthalate-based resin pellets for the intermediate layer are mixed in a predetermined ratio, dried, and then extruded into a known melt lamination extruder. It is supplied, extruded into a sheet form through a slit-shaped die, and cooled and solidified on a casting roll to produce an unstretched film. That is, using two or more extruders, a three-layer manifold or a confluence block (for example, a confluence block having a square confluence portion), the film layers constituting both outer layers and the film layers constituting the intermediate layer are laminated, A three-layer sheet is extruded through a die and cooled on casting rolls to form an unstretched film. In addition, in the present invention, in order to remove foreign substances contained in the raw material polyethylene terephthalate-based tree, which causes optical defects, it is preferable to perform high-precision filtration at the time of melt extrusion. The filtration particle size (initial filtration efficiency of 95%) of the filter medium used for high-precision filtration of molten resin is preferably 15 μm or less. If the filtration particle size of the filter medium exceeds 15 μm, the removal of foreign matter with a size of 20 μm or more tends to be insufficient.
さらに、本発明のポリエチレンテレフタレート系樹脂フィルムには、偏光子との接着性を良好にするためにコロナ処理、コーティング処理や火炎処理等を施したりすることも可能である。 Furthermore, the polyethylene terephthalate-based resin film of the present invention may be subjected to corona treatment, coating treatment, flame treatment, or the like in order to improve adhesion to the polarizer.
本発明においては、偏光子との接着性を改良のために、本発明のフィルムの少なくとも片面（好ましくは、偏光子と接する面）に、ポリエステル樹脂、ポリウレタン樹脂またはポリアクリル樹脂の少なくとも１種類を主成分とする易接着層を有することが好ましい。ここで、「主成分」とは易接着層を構成する固形成分のうち５０質量％以上である成分をいう。本発明の易接着層の形成に用いる塗布液は、水溶性又は水分散性の共重合ポリエステル樹脂、アクリル樹脂及びポリウレタン樹脂の内、少なくとも１種を含む水性塗布液が好ましい。これらの塗布液としては、例えば、特許第３５６７９２７号公報、特許第３５８９２３２号公報、特許第３５８９２３３号公報、特許第３９００１９１号公報、特許第４１５０９８２号公報等に開示された水溶性又は水分散性共重合ポリエステル樹脂溶液、アクリル樹脂溶液、ポリウレタン樹脂溶液等が挙げられる。 In the present invention, at least one surface of the film of the present invention (preferably, the surface in contact with the polarizer) is coated with at least one of polyester resin, polyurethane resin and polyacrylic resin in order to improve adhesion to the polarizer. It is preferable to have an easy-adhesion layer as a main component. Here, the "main component" refers to a component that accounts for 50% by mass or more of the solid components that constitute the easy-adhesion layer. The coating liquid used for forming the easy-adhesion layer of the present invention is preferably an aqueous coating liquid containing at least one of water-soluble or water-dispersible copolyester resins, acrylic resins and polyurethane resins. Examples of these coating liquids include water-soluble or water-dispersible coating liquids disclosed in Japanese Patent No. 3567927, Japanese Patent No. 3589232, Japanese Patent No. 3589233, Japanese Patent No. 3900191 and Japanese Patent No. 4150982. A polymerized polyester resin solution, an acrylic resin solution, a polyurethane resin solution and the like can be used.
易接着層は、前記塗布液を未延伸フィルム又は縦方向の１軸延伸フィルムの片面または両面に塗布した後、１００～１５０℃で乾燥し、さらに横方向に延伸して得ることができる。最終的な易接着層の塗布量は、０．０５～０．２０ｇ／ｍ２に管理することが好ましい。塗布量が０．０５ｇ／ｍ２未満であると、得られる偏光子との接着性が不十分となる場合がある。一方、塗布量が０．２０ｇ／ｍ２を超えると、耐ブロッキング性が低下する場合がある。ポリエチレンテレフタレート系樹脂フィルムの両面に易接着層を設ける場合は、両面の易接着層の塗布量は、同じであっても異なっていてもよく、それぞれ独立して上記範囲内で設定することができる。 The easy-adhesion layer can be obtained by applying the above-described coating liquid to one or both sides of an unstretched film or a uniaxially stretched film in the longitudinal direction, drying at 100 to 150° C., and stretching in the transverse direction. It is preferable to control the final coating amount of the easy-adhesion layer to 0.05 to 0.20 g/m 2 . If the coating amount is less than 0.05 g/m 2 , the adhesion to the resulting polarizer may be insufficient. On the other hand, if the coating amount exceeds 0.20 g/m 2 , blocking resistance may deteriorate. When the easy-adhesion layer is provided on both sides of the polyethylene terephthalate-based resin film, the coating amount of the easy-adhesion layer on both sides may be the same or different, and each can be independently set within the above range. .
易接着層には易滑性を付与するために粒子を添加することが好ましい。微粒子の平均粒径は２μｍ以下の粒子を用いることが好ましい。粒子の平均粒径が２μｍを超えると、粒子が被覆層から脱落しやすくなる。易接着層に含有させる粒子としては、例えば、酸化チタン、硫酸バリウム、炭酸カルシウム、硫酸カルシウム、シリカ、アルミナ、タルク、カオリン、クレー、リン酸カルシウム、雲母、ヘクトライト、ジルコニア、酸化タングステン、フッ化リチウム、フッ化カルシウム等の無機粒子や、スチレン系、アクリル系、メラミン系、ベンゾグアナミン系、シリコーン系等の有機ポリマー系粒子等が挙げられる。これらは、単独で易接着層に添加されてもよく、２種以上を組合せて添加することもできる。 Particles are preferably added to the easy-adhesion layer to impart lubricity. It is preferable to use particles having an average particle size of 2 μm or less. When the average particle size of the particles exceeds 2 μm, the particles tend to fall off from the coating layer. Particles contained in the easy-adhesion layer include, for example, titanium oxide, barium sulfate, calcium carbonate, calcium sulfate, silica, alumina, talc, kaolin, clay, calcium phosphate, mica, hectorite, zirconia, tungsten oxide, lithium fluoride, Examples include inorganic particles such as calcium fluoride, and organic polymer particles such as styrene, acrylic, melamine, benzoguanamine, and silicone particles. These may be added to the easy-adhesion layer singly, or two or more of them may be added in combination.
また、塗布液を塗布する方法としては、公知の方法を用いることができる。例えば、リバースロール・コート法、グラビア・コート法、キス・コート法、ロールブラッシュ法、スプレーコート法、エアナイフコート法、ワイヤーバーコート法、パイプドクター法、などが挙げられ、これらの方法を単独であるいは組み合わせて行うことができる。 Moreover, a well-known method can be used as a method of apply|coating a coating liquid. For example, reverse roll coating method, gravure coating method, kiss coating method, roll brush method, spray coating method, air knife coating method, wire bar coating method, pipe doctor method, etc., and these methods can be used alone. Or it can be performed in combination.
なお、上記の粒子の平均粒径の測定は次の方法により行う。粒子を走査型電子顕微鏡（ＳＥＭ）で写真を撮り、最も小さい粒子１個の大きさが２～５ｍｍとなるような倍率で、３００～５００個の粒子の最大径（最も離れた２点間の距離）を測定し、その平均値を平均粒径とする。 The average particle size of the above particles is measured by the following method. The particles are photographed with a scanning electron microscope (SEM) and the largest diameter of 300-500 particles (between the two furthest Distance) is measured, and the average value is taken as the average particle size.
本発明のポリエチレンテレフタレート系樹脂フィルムの厚みは任意であるが、３０～３００μｍの範囲が好ましい。３０μｍを下回る厚みのフィルムでも、原理的には３０００ｎｍ以上のリタデーションを得ることは可能である。しかし、その場合にはフィルムの力学特性の異方性が顕著となり、裂け、破れ等を生じやすくなり、工業材料としての実用性が著しく低下する。好ましい厚みの下限は４０μｍであり、特に好ましい厚みの下限は４５μｍである。一方、偏光子保護フィルムの厚みの上限は、３００μｍを超えると偏光板の厚みが厚くなりすぎてしまい好ましくない。偏光子保護フィルムとしての実用性の観点からは厚みの上限は２００μｍが好ましく、１２０μｍが好ましく、より好ましくは１００μｍ以下、さらにより好ましくは８０μｍ以下、さらにより好ましくは６５μｍ以下、さらにより好ましくは６０μｍ以下、さらにより好ましくは５５μｍ以下である。 Although the thickness of the polyethylene terephthalate-based resin film of the present invention is arbitrary, it is preferably in the range of 30 to 300 μm. In principle, it is possible to obtain a retardation of 3000 nm or more even with a film having a thickness of less than 30 μm. However, in this case, the anisotropy of the mechanical properties of the film becomes conspicuous, and the film is likely to tear, tear, etc., and the practicality as an industrial material is remarkably lowered. A preferable lower limit of the thickness is 40 μm, and a particularly preferable lower limit of the thickness is 45 μm. On the other hand, if the upper limit of the thickness of the polarizer protective film exceeds 300 μm, the thickness of the polarizing plate becomes too thick, which is not preferable. From the viewpoint of practicality as a polarizer protective film, the upper limit of the thickness is preferably 200 μm, preferably 120 μm, more preferably 100 μm or less, even more preferably 80 μm or less, even more preferably 65 μm or less, and even more preferably 60 μm or less. , and more preferably 55 μm or less.
リタデーションの変動を抑制する為には、フィルムの厚み斑が小さいことが好ましい。延伸温度、延伸倍率はフィルムの厚み斑に大きな影響を与えることから、厚み斑の観点からも製膜条件の最適化が好ましい。特にリタデーションを高くするために縦延伸倍率を低くすると、縦厚み斑が悪くなることがある。縦厚み斑は延伸倍率のある特定の範囲で非常に悪くなる領域があることから、この範囲を外したところで製膜条件を設定することが望ましい。 In order to suppress variations in retardation, it is preferable that the thickness unevenness of the film is small. Since the stretching temperature and the stretching ratio have a great effect on the thickness unevenness of the film, it is preferable to optimize the film-forming conditions from the viewpoint of the thickness unevenness. In particular, if the longitudinal draw ratio is lowered in order to increase the retardation, longitudinal thickness unevenness may become worse. Since there is a region in which the longitudinal thickness unevenness becomes extremely poor within a certain range of the draw ratio, it is desirable to set the film-forming conditions outside this range.
本発明のフィルムの厚み斑は５．０％以下であることが好ましく、４．５％以下であることがさらに好ましく、４．０％以下であることがよりさらに好ましく、３．０％以下であることが特に好ましい。 The thickness unevenness of the film of the present invention is preferably 5.0% or less, more preferably 4.5% or less, even more preferably 4.0% or less, and 3.0% or less. It is particularly preferred to have
ポリエチレンテレフタレート系樹脂フィルムは、そのリタデーション（Ｒｅ）と厚さ方向リタデーション（Ｒｔｈ）の比（Ｒｅ／Ｒｔｈ）が、好ましくは０．２以上、より好ましくは０．５以上、さらに好ましくは０．６以上である。斜め方向から見た際の虹斑を抑制する観点から、上記比（Ｒｅ／Ｒｔｈ）が大きいほど好ましい。比（Ｒｅ／Ｒｔｈ）の上限は２．０以下が好ましく、より好ましくは１．８以下である。一方、厚みムラや平面性の観点から上記比（Ｒｅ／Ｒｔｈ）の上限は１．０未満が好ましい。なお、厚さ方向リタデーションとは、フィルム厚さ方向断面から見たときの２つの複屈折△Ｎｘｚ（＝｜ｎｘ－ｎｚ｜）、△Ｎｙｚ（＝｜ｎｙ－ｎｚ｜）にそれぞれフィルム厚さｄを掛けて得られるリタデーションの平均を示すパラメーターである。ｎｘ、ｎｙ、ｎｚとフィルム厚みｄ（ｎｍ）を求め、（△Ｎｘｚ×ｄ）と（△Ｎｙｚ×ｄ）との平均値を算出して厚さ方向リタデーション（Ｒｔｈ）を求めることができる。なお、ｎｘ、ｎｙ、ｎｚは、アッベ屈折率計（アタゴ社製、ＮＡＲ－４Ｔ、測定波長５８９ｎｍ）によって求める。 The polyethylene terephthalate resin film has a retardation (Re) to thickness retardation (Rth) ratio (Re/Rth) of preferably 0.2 or more, more preferably 0.5 or more, and still more preferably 0.6. That's it. From the viewpoint of suppressing iridescence when viewed from an oblique direction, the larger the ratio (Re/Rth), the better. The upper limit of the ratio (Re/Rth) is preferably 2.0 or less, more preferably 1.8 or less. On the other hand, the upper limit of the ratio (Re/Rth) is preferably less than 1.0 from the viewpoint of thickness unevenness and flatness. The retardation in the thickness direction refers to the two birefringences ΔNxz (=|nx-nz|) and ΔNyz (=|ny-nz|) when viewed from the cross section in the film thickness direction, and the film thickness d is a parameter indicating the average retardation obtained by multiplying by . nx, ny, nz and film thickness d (nm) are obtained, and the average value of (ΔNxz×d) and (ΔNyz×d) is calculated to obtain thickness direction retardation (Rth). Note that nx, ny, and nz are determined by an Abbe refractometer (NAR-4T manufactured by Atago Co., Ltd., measuring wavelength 589 nm).
２．偏光板
本発明の偏光板は、ポリビニルアルコール（ＰＶＡ）などにヨウ素を染着させた偏光子の少なくとも一方の面に偏光子保護フィルムを貼り合わせた構造を有し、いずれかの偏光子保護フィルムが前述した本発明の偏光子保護フィルムであることが好ましい。他方の偏光子保護フィルムには、ＴＡＣフィルムやアクリルフィルム、ノルボルネン系フィルムに代表されるような複屈折が無いフィルムを用いることが好ましい。もしくは他方には偏光子保護フィルムが存在しなくてもよい。本発明に用いられる偏光板には、写り込み防止やギラツキ抑制、キズ抑制などを目的として、種々のハードコートを表面に塗布することも好ましい様態である。
2. Polarizing Plate The polarizing plate of the present invention has a structure in which a polarizer protective film is attached to at least one surface of a polarizer made by dyeing polyvinyl alcohol (PVA) or the like with iodine. is preferably the polarizer protective film of the present invention described above. As the other polarizer protective film, it is preferable to use a non-birefringent film such as a TAC film, an acrylic film, or a norbornene film. Alternatively, there may be no polarizer protective film on the other. It is also preferable to apply various hard coats on the surface of the polarizing plate used in the present invention for the purpose of preventing reflection, suppressing glare, and suppressing scratches.
３．液晶表示装置
一般に、液晶パネルは、バックライト光源に対向する側から画像を表示する側（視認側）に向かう順に、後面モジュール、液晶セルおよび前面モジュールから構成されている。後面モジュールおよび前面モジュールは、一般に、透明基板と、その液晶セル側表面に形成された透明導電膜と、その反対側に配置された偏光板とから構成されている。ここで、偏光板は、後面モジュールでは、バックライト光源に対向する側に配置され、前面モジュールでは、画像を表示する側（視認側）に配置されている。
3. Liquid Crystal Display Device In general, a liquid crystal panel is composed of a rear module, a liquid crystal cell, and a front module in order from the side facing the backlight source toward the image display side (viewing side). The rear module and the front module are generally composed of a transparent substrate, a transparent conductive film formed on the liquid crystal cell side surface of the substrate, and a polarizing plate disposed on the opposite side. Here, the polarizing plate is arranged on the side facing the backlight light source in the rear module, and is arranged on the image display side (viewing side) in the front module.
本発明の液晶表示装置は少なくとも、バックライト光源と、２つの偏光板の間に配された液晶セルとを構成部材とする。また、これら以外の他の構成、例えばカラーフィルター、レンズフィルム、拡散シート、反射防止フィルムなどを適宜有しても構わない。前記２つの偏光板のうち、少なくとも一方の偏光板が前述した本発明の偏光板であることが好ましい。 The liquid crystal display device of the present invention includes at least a backlight source and a liquid crystal cell disposed between two polarizing plates as constituent members. In addition, other structures other than these, such as a color filter, a lens film, a diffusion sheet, an antireflection film, and the like, may be provided as appropriate. At least one of the two polarizing plates is preferably the polarizing plate of the present invention described above.
バックライトの構成としては、導光板や反射板などを構成部材とするエッジライト方式であっても、直下型方式であっても構わない。 The configuration of the backlight may be an edge-light type in which a light guide plate, a reflector, or the like is used as constituent members, or a direct type.
液晶表示装置のバックライト光源としては、特に限定されない。例えば、バックライト光源は、蛍光体方式の白色ＬＥＤ（すなわち化合物半導体を使用した青色光、もしくは紫外光を発する発光ダイオードと蛍光体を組み合わせることにより白色を発する素子）であってもよい。蛍光体としては、イットリウム・アルミニウム・ガーネット系の黄色蛍光体やテルビウム・アルミニウム・ガーネット系の黄色蛍光体等がある。 The backlight source of the liquid crystal display device is not particularly limited. For example, the backlight source may be a phosphor type white LED (that is, an element that emits white light by combining a light emitting diode that emits blue light or ultraviolet light using a compound semiconductor with a phosphor). Examples of phosphors include yttrium-aluminum-garnet-based yellow phosphors and terbium-aluminum-garnet-based yellow phosphors.
一実施形態において、バックライト光源は、４００ｎｍ以上４９５ｎｍ未満、４９５ｎｍ以上６００ｎｍ未満、及び６００ｎｍ以上７８０ｎｍ以下の各波長領域にそれぞれ発光スペクトルのピークトップを有する白色光源が好ましい。例えば、量子ドット技術を利用した白色光源、励起光によりＲ（赤）、Ｇ（緑）の領域にそれぞれ発光ピークを有する蛍光体と青色ＬＥＤを用いた蛍光体方式の白色ＬＥＤ光源、３波長方式の白色ＬＥＤ光源、赤色レーザーを組み合わせた白色ＬＥＤ光源、その他、例えば組成式がＫ２ＳｉＦ６：Ｍｎ４＋であるフッ化物蛍光体（「ＫＳＦ」ともいう）等と青色ＬＥＤを用いた白色ＬＥＤ光源等が挙げられる。これらは、広色域対応の液晶表示装置のバックライト光源として注目されているものである。 In one embodiment, the backlight source is preferably a white light source having an emission spectrum peak top in each wavelength region of 400 nm or more and less than 495 nm, 495 nm or more and less than 600 nm, and 600 nm or more and 780 nm or less. For example, a white light source using quantum dot technology, a phosphor-type white LED light source using a blue LED and a phosphor having emission peaks in the R (red) and G (green) regions of excitation light, and a three-wavelength method. white LED light sources, white LED light sources combined with red lasers, and other white LED light sources using, for example, a fluoride phosphor (also referred to as “KSF”) having a composition formula of K 2 SiF 6 : Mn 4+ and blue LEDs etc. These are attracting attention as backlight sources for liquid crystal display devices compatible with a wide color gamut.
当該特定のリタデーションを有する本発明の偏光子保護フィルムの液晶表示装置内における配置は特に限定されないが、入射光側（光源側）に配される偏光板と、液晶セルと、出射光側（視認側）に配される偏光板とを配された液晶表示装置の場合、入射光側に配される偏光板の入射光側の偏光子保護フィルム、及び/又は出射光側に配される偏光板の射出光側の偏光子保護フィルムが当該特定のリタデーションを有するポリエチレンテレフタレート系樹脂フィルムからなる偏光子保護フィルムであることが好ましい。特に好ましい態様は、出射光側に配される偏光板の射出光側の偏光子保護フィルムを当該特定のリタデーションを有するポリエチレンテレフタレート系樹脂フィルムとする態様である。上記以外の位置にポリエチレンテレフタレート系樹脂フィルムを配する場合は、液晶セルの偏光特性を変化させてしまう場合がある。偏光特性が必要とされる箇所には本発明の高分子フィルムを用いることは好ましくない為、このような特定の位置の偏光板の保護フィルムとして使用されることが好ましい。 The arrangement of the polarizer protective film of the present invention having the specific retardation in the liquid crystal display device is not particularly limited. side), the polarizer protective film on the incident light side of the polarizing plate arranged on the incident light side, and / or the polarizing plate arranged on the outgoing light side It is preferable that the polarizer protective film on the exiting light side is a polarizer protective film made of a polyethylene terephthalate-based resin film having the specific retardation. A particularly preferred embodiment is one in which the polyethylene terephthalate-based resin film having the specific retardation is used as the polarizer protective film on the exit light side of the polarizing plate arranged on the exit light side. If the polyethylene terephthalate-based resin film is arranged at a position other than the above, the polarization characteristics of the liquid crystal cell may be changed. Since it is not preferable to use the polymer film of the present invention where polarizing properties are required, it is preferably used as a protective film for the polarizing plate at such a specific position.
以下、実施例を挙げて本発明をより具体的に説明するが、本発明は、下記実施例によって制限を受けるものではなく、本発明の趣旨に適合し得る範囲で適宜変更を加えて実施することも可能であり、それらは、いずれも本発明の技術的範囲に含まれる。なお、以下の実施例における物性の評価方法は以下の通りである。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples, and can be carried out with appropriate modifications within the scope of the gist of the present invention. It is also possible, and all of them are included in the technical scope of the present invention. Methods for evaluating physical properties in the following examples are as follows.
（１）リタデーション（Ｒｅ）
リタデーションとは、フィルム上の直交する二軸の屈折率の異方性（△Ｎｘｙ＝｜ｎｘ－ｎｙ｜）とフィルム厚みｄ（ｎｍ）との積（△Ｎｘｙ×ｄ）と定義されるパラメーターであり、光学的等方性又は異方性を示す尺度である。二軸の屈折率の異方性（△Ｎｘｙ）は、以下の方法により求めた。分子配向計（王子計測器株式会社製、ＭＯＡ－６００４型分子配向計）を用いて、フィルムの遅相軸方向を求め、遅相軸方向が測定用サンプル長辺と平行になるように、４ｃｍ×２ｃｍの長方形を切り出し、測定用サンプルとした。このサンプルについて、直交する二軸の屈折率（遅相軸方向の屈折率：ｎｙ，遅相軸方向と直交する方向の屈折率：ｎｘ）、及び厚さ方向の屈折率（ｎｚ）をアッベ屈折率計（アタゴ社製、ＮＡＲ－４Ｔ、測定波長５８９ｎｍ）によって求め、前記二軸の屈折率差の絶対値（｜ｎｘ－ｎｙ｜）を屈折率の異方性（△Ｎｘｙ）とした。フィルムの厚みｄ（ｎｍ）は電気マイクロメータ（ファインリューフ社製、ミリトロン１２４５Ｄ）を用いて測定し、単位をｎｍに換算した。屈折率の異方性（△Ｎｘｙ）とフィルムの厚みｄ（ｎｍ）の積（△Ｎｘｙ×ｄ）より、リタデーション（Ｒｅ）を求めた。
(1) Retardation (Re)
Retardation is a parameter defined as the product (ΔNxy×d) of the refractive index anisotropy (ΔNxy=|nx−ny|) of the film and the thickness d (nm) of the biaxial orthogonal to each other on the film. , which is a measure of optical isotropy or anisotropy. The biaxial refractive index anisotropy (ΔNxy) was obtained by the following method. Using a molecular orientation meter (MOA-6004 type molecular orientation meter manufactured by Oji Keisoku Co., Ltd.), the slow axis direction of the film was determined, and the slow axis direction was 4 cm so that it was parallel to the long side of the sample for measurement. A 2 cm x 2 cm rectangle was cut out and used as a measurement sample. For this sample, the refractive index in the biaxial direction perpendicular to each other (refractive index in the slow axis direction: ny, refractive index in the direction perpendicular to the slow axis direction: nx) and the refractive index in the thickness direction (nz) were measured by Abbe refracting The absolute value of the biaxial refractive index difference (|nx−ny|) was defined as the anisotropy of the refractive index (ΔNxy) by using an index meter (NAR-4T manufactured by Atago Co., measuring wavelength 589 nm). The thickness d (nm) of the film was measured using an electric micrometer (Millitron 1245D, manufactured by Finereuf Co.) and converted into nm. The retardation (Re) was obtained from the product (ΔNxy×d) of the refractive index anisotropy (ΔNxy) and the film thickness d (nm).
（２）厚さ方向リタデーション（Ｒｔｈ）
厚さ方向リタデーションとは、フィルム厚さ方向断面から見たときの２つの複屈折△Ｎｘｚ（＝｜ｎｘ－ｎｚ｜）、△Ｎｙｚ（＝｜ｎｙ－ｎｚ｜）にそれぞれフィルム厚さｄを掛けて得られるリタデーションの平均を示すパラメーターである。リタデーションの測定と同様の方法でｎｘ、ｎｙ、ｎｚとフィルム厚みｄ（ｎｍ）を求め、（△Ｎｘｚ×ｄ）と（△Ｎｙｚ×ｄ）との平均値を算出して厚さ方向リタデーション（Ｒｔｈ）を求めた。
(2) Retardation in thickness direction (Rth)
The retardation in the thickness direction is obtained by multiplying the two birefringences ΔNxz (=|nx-nz|) and ΔNyz (=|ny-nz|) when viewed from the cross section in the thickness direction of the film by the film thickness d. is a parameter that indicates the average retardation obtained by Obtain nx, ny, nz and film thickness d (nm) in the same manner as for measuring retardation, and calculate the average value of (ΔNxz × d) and (ΔNyz × d) to obtain thickness direction retardation (Rth ).
（３）結晶の（１００）面のフィルム面に対する配向度
結晶の（１００）面のフィルム面に対する配向度は、Ｘ線回折装置（株式会社リガク社製、ＲＩＮＴ２１００ＰＣ）を用いて、極点測定により得られた回折強度の遅相軸方向を軸とした半値幅から、（１８０－半値幅）／１８０で定義されるパラメーターである。測定に用いたＸ線は、Ｃｕ－Ｋα線で、波長は１．５４１８Åである。極点測定はＲＩＮＴ２１００ＰＣに装着できるＲＩＮＴ２０００ゴニオメータと極点用多目的試料台を取り付け、シュルツ反射法にて行った。サンプルは直径５ｃｍの円状に切り出し、遅相軸方向がβ＝９０度および２７０度方向と一致するよう試料台に取り付けた。なお、サンプルの遅相軸方向は、分子配向計（王子計測器株式会社製、ＭＯＡ－６００４型分子配向計）を用いて求めた。測定条件の詳細は、管電圧を４０ｋＶ、管電流を４０ｍＡ、２θ固定角度を２５．８３０度、発散縦制限を１．２ｍｍ、発散スリットを１度、散乱スリットを７ｍｍ、受光スリットを７ｍｍとした。透過測定ではα開始角度＝０度、α終了角度＝３５度、αステップ角度＝５度とした。反射測定ではα開始角度＝２５度、α終了角度＝９０度、αステップ角度＝５度とした。走査方法は同心円にβ開始角度＝０度、β終了角度＝３６０度、βステップ角度＝５度である。
以下、結晶の（１００）面のフィルム面に対する配向度の計算方法を示す。測定で得られたβ＝０度およびβ＝１８０度における反射回折強度プロファイルをI（α）（２５≦α≦９０）とする。横軸をα’（β＝０度のときα’＝α、β＝１８０度のときα’＝１８０－α）、縦軸を各α’における回折強度とすることで、β＝０度および１８０度における回折強度プロファイルを接続し、回折強度プロファイルI（α’）（２５≦α’≦１５５）が得られる。このとき、α’＝９０度における回折強度は、β＝０度とβ＝１８０度の平均値を用いた。α’＝２５度および１５５度での回折強度を結ぶ直線をベースラインとして差し引き、得られた回折強度プロファイルから半値幅を用いて、（１８０－半値幅）／１８０により、結晶の（１００）面のフィルム面に対する配向度を算出した。半値幅の単位は度である。
(3) Orientation of the (100) plane of the crystal with respect to the film plane The orientation of the (100) plane of the crystal with respect to the film plane is obtained by pole point measurement using an X-ray diffractometer (manufactured by Rigaku Co., Ltd., RINT2100PC). It is a parameter defined by (180-half width)/180 from the half width of the diffraction intensity measured along the slow axis direction. The X-rays used for the measurement were Cu-Kα rays with a wavelength of 1.5418 Å. Pole measurement was carried out by the Schulz reflection method with a RINT2000 goniometer that can be attached to the RINT2100PC and a multi-purpose sample stand for poles. A circular sample with a diameter of 5 cm was cut out and mounted on a sample stage so that the slow axis direction coincided with the direction of β=90 degrees and 270 degrees. The slow axis direction of the sample was determined using a molecular orientation meter (MOA-6004 type molecular orientation meter manufactured by Oji Instruments Co., Ltd.). The details of the measurement conditions were as follows: tube voltage: 40 kV, tube current: 40 mA, 2θ fixed angle: 25.830 degrees, vertical divergence limit: 1.2 mm, divergence slit: 1 degree, scattering slit: 7 mm, light receiving slit: 7 mm . In the transmission measurement, α start angle=0 degrees, α end angle=35 degrees, and α step angle=5 degrees. For reflection measurements, α start angle = 25 degrees, α end angle = 90 degrees, and α step angle = 5 degrees. The scanning method is concentric with β start angle=0 degrees, β end angle=360 degrees, and β step angle=5 degrees.
A method for calculating the degree of orientation of the (100) plane of the crystal with respect to the film plane will be described below. Let I(α) (25≦α≦90) be the reflection diffraction intensity profile at β=0 degree and β=180 degree obtained by the measurement. By taking the horizontal axis as α'(α' = α when β = 0 degrees, α' = 180-α when β = 180 degrees) and the vertical axis as the diffraction intensity at each α', β = 0 degrees and By connecting the diffraction intensity profiles at 180 degrees, the diffraction intensity profile I(α') (25≤α'≤155) is obtained. At this time, the average value of β=0 degrees and β=180 degrees was used for the diffraction intensity at α′=90 degrees. A straight line connecting the diffraction intensities at α′=25 degrees and 155 degrees is subtracted as a baseline, and using the half-value width from the obtained diffraction intensity profile, (180−half-value width)/180, the (100) plane of the crystal The degree of orientation with respect to the film surface was calculated. The unit of half width is degree.
（４）結晶の（－１０５）面の結晶サイズ
フィルムの遅相軸方向における結晶の（－１０５）面の結晶サイズは、Ｘ線回折装置（株式会社リガク社製、ＲＩＮＴ２５００）を用いて遅相軸方向に測定したθ／２θの回折強度プロファイルから、結晶の（－１０５）面の回折位置（２θ＝４２．７度）における回折ピークの実測半値幅（Ｂ）を読み取り、次式（シェラーの式）を用いて見掛けの結晶サイズ（ＡＣＳ）として算出した。測定に用いたＸ線は、Ｃｕ－Ｋα線で、波長は１．５４１８Åである。なお、ベースラインは、２θが３０度から４２．７度の間で最も回折強度が小さい点と、４２．７度から５０度の間で最も回折強度の小さい点の２点を直線で繋いだ線とした。（ＡＣＳ＝０．９λ／（βcosθ））。ここで、λはＸ線の波長（１．５４１８Å）、βは読み取った実測半値幅（Ｂ）と補正のための定数（ｂ）から（Ｂ２－ｂ２）１／２で計算される半値幅である。なお、補正のための定数（ｂ）は、シリコン粉末ＮＩＳＴ６４０ｂを同条件で測定したときの半値幅である。ここで、β、Ｂ、ｂはいずれもラジアン単位の値である。なお、サンプルの遅相軸方向は、分子配向計（王子計測器株式会社製、ＭＯＡ－６００４型分子配向計）を用いて求めた。
(4) Crystal size of crystal (-105) plane The crystal size of the crystal (-105) plane in the slow axis direction of the film was measured using an X-ray diffractometer (manufactured by Rigaku Co., Ltd., RINT2500). From the diffraction intensity profile of θ/2θ measured in the axial direction, the measured half-value width (B) of the diffraction peak at the diffraction position (2θ=42.7 degrees) of the (−105) plane of the crystal is read, and the following formula (Scherrer's Formula) was used to calculate the apparent crystal size (ACS). The X-rays used for the measurement were Cu-Kα rays with a wavelength of 1.5418 Å. The baseline is a point where the diffraction intensity is the lowest between 30 degrees and 42.7 degrees 2θ, and a point where the diffraction intensity is the lowest between 42.7 degrees and 50 degrees. line. (ACS=0.9λ/(β cos θ)). where λ is the wavelength of the X-ray (1.5418 Å), β is the half width calculated by (B 2 −b 2 ) 1/2 from the measured half width (B) and the constant (b) for correction. price range. The constant (b) for correction is the half width when the silicon powder NIST640b is measured under the same conditions. Here, β, B, and b are all values in radians. The slow axis direction of the sample was determined using a molecular orientation meter (MOA-6004 type molecular orientation meter manufactured by Oji Instruments Co., Ltd.).
（５）虹斑観察
ＰＶＡとヨウ素からなる偏光子の片側に後述する方法で作成したポリエチレンテレフタレートフィルムを偏光子の吸収軸とフィルムの配向主軸が垂直になるように貼り付け、その反対の面に市販のＴＡＣフィルムを貼り付けて、ポリエチレンテレフタレートフィルム/偏光子/ＴＡＣフィルムからなる偏光板を作成した。得られた偏光板を、市販の液晶表示装置（ＳＯＮＹ社製のＢＲＡＶＩＡ ＫＤＬ－４０Ｗ９２０Ａ）に元々存在した出射光側の偏光板と置き換えた。なお、偏光板の吸収軸が、元々液晶表示装置に貼付されていた偏光板の吸収軸方向と一致するように、ポリエチレンテレフタレートフィルムが視認側になるよう偏光板を置き換えた。前記液晶表示装置は、励起光を出射する光源と量子ドットを含むバックライト光源を有する。この液晶表示装置のバックライト光源の発光スペクトルを、浜松ホトニクス製 マルチチャンネル分光器 ＰＭＡ－１２を用いて測定したところ、４５０ｎｍ、５２８ｎｍ、６３０ｎｍ付近にピークトップを有する発光スペクトルが観察され、各ピークトップの半値幅は１６ｎｍ～３４ｎｍであった。なお、スペクトル測定の際の露光時間は２０ｍｓｅｃとした。
このようにして作製した液晶表示装置に白画像を表示させ、ディスプレイの正面、および、斜め方向から目視観察を行って、虹ムラの発生について、以下の基準に従って判定した。なお、観察角度は、ディスプレイの画面の中心から法線方向（垂直）に引いた線と、ディスプレイ中心と観察時の眼の位置とを結ぶ直線とのなす角とした。
◎： 観察角度０～６５度の範囲で、虹ムラは観察されなかった。
○： 観察角度０～６５度の範囲で、わずかに虹ムラは観察された。
×： 観察角度０～６５度の範囲で虹ムラが観察された。
(5) Observation of iridescence A polyethylene terephthalate film prepared by the method described later is attached to one side of a polarizer made of PVA and iodine so that the absorption axis of the polarizer and the main orientation axis of the film are perpendicular, and A commercially available TAC film was adhered to prepare a polarizing plate composed of polyethylene terephthalate film/polarizer/TAC film. The resulting polarizing plate was used to replace the polarizing plate on the outgoing light side originally present in a commercially available liquid crystal display (BRAVIA KDL-40W920A manufactured by SONY). The polarizing plate was replaced so that the polyethylene terephthalate film was on the viewing side so that the absorption axis of the polarizing plate coincided with the direction of the absorption axis of the polarizing plate originally attached to the liquid crystal display device. The liquid crystal display device has a light source for emitting excitation light and a backlight source including quantum dots. When the emission spectrum of the backlight light source of this liquid crystal display device was measured using a multichannel spectrometer PMA-12 manufactured by Hamamatsu Photonics, an emission spectrum having peak tops near 450 nm, 528 nm, and 630 nm was observed, and each peak top was 16 nm to 34 nm. The exposure time for spectrum measurement was 20 msec.
A white image was displayed on the thus manufactured liquid crystal display device, and visual observation was performed from the front and oblique directions of the display to determine the occurrence of rainbow unevenness according to the following criteria. The viewing angle was the angle between a line drawn in the normal direction (perpendicular) from the center of the screen of the display and a straight line connecting the center of the display and the eye position during viewing.
A: Rainbow unevenness was not observed within the observation angle range of 0 to 65 degrees.
◯: Slight iridescent unevenness was observed in the observation angle range of 0 to 65 degrees.
x: Rainbow unevenness was observed in the range of observation angles from 0 to 65 degrees.
（製造例１－ポリエステルＡ）
エステル化反応缶を昇温し２００℃に到達した時点で、テレフタル酸を８６．４質量部およびエチレングリコール６４．６質量部を仕込み、撹拌しながら触媒として三酸化アンチモンを０．０１７質量部、酢酸マグネシウム４水和物を０．０６４質量部、トリエチルアミン０．１６質量部を仕込んだ。ついで、加圧昇温を行いゲージ圧０．３４ＭＰａ、２４０℃の条件で加圧エステル化反応を行った後、エステル化反応缶を常圧に戻し、リン酸０.０１４質量部を添加した。さらに、１５分かけて２６０℃に昇温し、リン酸トリメチル０．０１２質量部を添加した。次いで１５分後に、高圧分散機で分散処理を行い、１５分後、得られたエステル化反応生成物を重縮合反応缶に移送し、２８０℃で減圧下重縮合反応を行った。
(Production Example 1-Polyester A)
When the temperature of the esterification reactor was raised to 200° C., 86.4 parts by mass of terephthalic acid and 64.6 parts by mass of ethylene glycol were charged, and 0.017 parts by mass of antimony trioxide as a catalyst was added while stirring. 0.064 parts by mass of magnesium acetate tetrahydrate and 0.16 parts by mass of triethylamine were charged. Then, the temperature was increased under pressure to carry out a pressure esterification reaction under conditions of a gauge pressure of 0.34 MPa and 240° C., after which the pressure in the esterification reactor was returned to normal pressure, and 0.014 parts by mass of phosphoric acid was added. Furthermore, the temperature was raised to 260° C. over 15 minutes, and 0.012 parts by mass of trimethyl phosphate was added. After 15 minutes, dispersion treatment was performed with a high-pressure disperser. After 15 minutes, the obtained esterification reaction product was transferred to a polycondensation reactor, and polycondensation reaction was performed at 280°C under reduced pressure.
重縮合反応終了後、９５％カット径が５μｍのナスロン製フィルターで濾過処理を行い、ノズルからストランド状に押出し、予め濾過処理（孔径：１μｍ以下）を行った冷却水を用いて冷却、固化させ、ペレット状にカットした。得られたポリエチレンテレフタレート樹脂（Ａ）の固有粘度は０．６２ｄｌ／ｇであり、不活性粒子及び内部析出粒子は実質上含有していなかった。（以後、ＰＥＴ（Ａ）と略す。） After the completion of the polycondensation reaction, it is filtered through a NASLON filter with a 95% cut diameter of 5 μm, extruded from a nozzle in the form of a strand, and cooled and solidified using cooling water that has been previously filtered (pore size: 1 μm or less). , cut into pellets. The resulting polyethylene terephthalate resin (A) had an intrinsic viscosity of 0.62 dl/g and contained substantially no inert particles or internal precipitated particles. (Hereinafter abbreviated as PET (A).)
（製造例２－ポリエステルＢ）
乾燥させた紫外線吸収剤（２，２’－（１，４－フェニレン）ビス（４Ｈ－３，１－ベンズオキサジン－４－オン）１０質量部、粒子を実質上含有しないＰＥＴ（Ａ）（固有粘度が０．６２ｄｌ／ｇ）９０質量部を混合し、混練押出機を用い、紫外線吸収剤含有するポリエチレンテレフタレート樹脂（Ｂ）を得た。（以後、ＰＥＴ（Ｂ）と略す。）
(Production Example 2-Polyester B)
10 parts by mass of dried UV absorber (2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one), PET (A) (inherent (Viscosity: 0.62 dl/g) was mixed with 90 parts by mass, and a kneading extruder was used to obtain a polyethylene terephthalate resin (B) containing an ultraviolet absorber (hereinafter abbreviated as PET (B)).
（製造例３－接着性改質塗布液の調整）
常法によりエステル交換反応および重縮合反応を行って、ジカルボン酸成分として（ジカルボン酸成分全体に対して）テレフタル酸４６モル％、イソフタル酸４６モル％および５－スルホナトイソフタル酸ナトリウム８モル％、グリコール成分として（グリコール成分全体に対して）エチレングリコール５０モル％およびネオペンチルグリコール５０モル％の組成の水分散性スルホン酸金属塩基含有共重合ポリエステル樹脂を調製した。次いで、水５１．４質量部、イソプロピルアルコール３８質量部、ｎ－ブチルセルソルブ５質量部、ノニオン系界面活性剤０．０６質量部を混合した後、加熱撹拌し、７７℃に達したら、上記水分散性スルホン酸金属塩基含有共重合ポリエステル樹脂５質量部を加え、樹脂の固まりが無くなるまで撹拌し続けた後、樹脂水分散液を常温まで冷却して、固形分濃度５．０質量％の均一な水分散性共重合ポリエステル樹脂液を得た。さらに、凝集体シリカ粒子（富士シリシア（株）社製、サイリシア３１０）３質量部を水５０質量部に分散させた後、上記水分散性共重合ポリエステル樹脂液９９．４６質量部にサイリシア３１０の水分散液０．５４質量部を加えて、撹拌しながら水２０質量部を加えて、接着性改質塗布液を得た。
(Production Example 3-Adhesion-improving coating liquid preparation)
A transesterification reaction and a polycondensation reaction were carried out by a conventional method to obtain 46 mol % of terephthalic acid, 46 mol % of isophthalic acid and 8 mol % of sodium 5-sulfonatoisophthalate as dicarboxylic acid components (relative to the total dicarboxylic acid components). A water-dispersible sulfonic acid metal group-containing copolymer polyester resin was prepared having a composition of 50 mol % ethylene glycol and 50 mol % neopentyl glycol as the glycol component (relative to the total glycol component). Next, 51.4 parts by mass of water, 38 parts by mass of isopropyl alcohol, 5 parts by mass of n-butyl cellosolve, and 0.06 parts by mass of a nonionic surfactant are mixed and then heated and stirred. After adding 5 parts by mass of a water-dispersible sulfonic acid metal group-containing copolymerized polyester resin and continuing to stir until the lumps of the resin disappear, the resin aqueous dispersion was cooled to room temperature to obtain a solid content concentration of 5.0% by mass. A homogeneous water-dispersible copolyester resin liquid was obtained. Furthermore, after dispersing 3 parts by mass of aggregated silica particles (manufactured by Fuji Silysia Co., Ltd., Silysia 310) in 50 parts by mass of water, Silysia 310 was added to 99.46 parts by mass of the water-dispersible copolymer polyester resin liquid. 0.54 parts by mass of the aqueous dispersion was added, and 20 parts by mass of water was added while stirring to obtain an adhesion-improving coating liquid.
（実施例１）
基材フィルム中間層用原料として粒子を含有しないＰＥＴ（Ａ）樹脂ペレット９０質量部と紫外線吸収剤を含有したＰＥＴ（Ｂ）樹脂ペレット１０質量部を１３５℃で６時間減圧乾燥（１Ｔｏｒｒ）した後、押出機２（中間層ＩＩ層用）に供給し、また、ＰＥＴ（Ａ）を常法により乾燥して押出機１（外層Ｉ層および外層ＩＩＩ用）にそれぞれ供給し、２８５℃で溶解した。この２種のポリマーを、それぞれステンレス焼結体の濾材（公称濾過精度１０μｍ粒子９５％カット）で濾過し、２種３層合流ブロックにて、積層し、口金よりシート状にして押し出した後、静電印加キャスト法を用いて表面温度３０℃のキャスティングドラムに巻きつけて冷却固化し、未延伸フィルムを作った。この時、Ｉ層、ＩＩ層、ＩＩＩ層の厚さの比は１０：８０：１０となるように各押し出し機の吐出量を調整した。
(Example 1)
After drying under reduced pressure (1 Torr) at 135° C. for 6 hours, 90 parts by mass of PET (A) resin pellets containing no particles and 10 parts by mass of PET (B) resin pellets containing an ultraviolet absorber as raw materials for the base film intermediate layer. , supplied to extruder 2 (for intermediate layer II layer), and PET (A) was dried by a conventional method, supplied to extruder 1 (for outer layer I layer and outer layer III), and melted at 285 ° C. . These two types of polymers are each filtered with a stainless sintered filter material (nominal filtration accuracy: 10 μm, 95% cut of particles), laminated in a two-type, three-layer confluence block, extruded in a sheet form from a nozzle, An unstretched film was produced by winding the film around a casting drum having a surface temperature of 30° C. and solidifying it by cooling using an electrostatic casting method. At this time, the discharge rate of each extruder was adjusted so that the thickness ratio of the I layer, the II layer, and the III layer was 10:80:10.
次いで、リバースロール法によりこの未延伸ＰＥＴフィルムの両面に乾燥後の塗布量が０．０８ｇ／ｍ２になるように、上記接着性改質塗布液を塗布した後、８０℃で２０秒間乾燥した。 Next, the adhesion-improving coating solution was applied to both sides of the unstretched PET film by a reverse roll method so that the coating amount after drying was 0.08 g/m 2 , and then dried at 80°C for 20 seconds. .
この塗布層を形成した未延伸フィルムをテンター延伸機に導き、フィルムの端部をクリップで把持しながら、温度１１０℃で熱風吹き出し口の風速が１２ｍ／秒の熱風ゾーンに導き、幅方向（ＴＤ）に４．０倍、フィルム流れ方向（ＭＤ）に０．７倍となるよう延伸した。次に、幅方向に延伸された幅を保ったまま、温度２００℃で熱風吹き出し口の風速が１０ｍ／秒の熱風ゾーンで熱処理し、さらに幅方向に３％の緩和処理を行い、フィルム厚み約５０μｍの一軸配向ＰＥＴフィルムを得た。 The unstretched film with the coating layer formed thereon is guided to a tenter stretching machine, and while holding the ends of the film with clips, it is guided to a hot air zone at a temperature of 110 ° C. and a hot air outlet with a wind speed of 12 m / sec, and the width direction (TD ) and 0.7 times in the machine direction (MD). Next, while maintaining the stretched width in the width direction, heat treatment is performed in a hot air zone at a temperature of 200 ° C. and a hot air outlet with a wind speed of 10 m / sec. A uniaxially oriented PET film of 50 μm was obtained.
（実施例２）
実施例１と同じ方法で作製された未延伸フィルムをテンター延伸機に導き、フィルムの端部をクリップで把持しながら、温度１２５℃で熱風吹き出し口の風速が１０ｍ／秒の熱風ゾーンに導き、幅方向に４．５倍となるよう延伸した。次に、幅方向に延伸された幅を保ったまま、温度２００℃で熱風吹き出し口の風速が１０ｍ／秒の熱風ゾーンで熱処理し、さらに幅方向に３％の緩和処理を行い、フィルム厚み約８０μmの一軸配向ＰＥＴフィルムを得た。
(Example 2)
An unstretched film produced in the same manner as in Example 1 is guided to a tenter stretching machine, and while gripping the ends of the film with clips, the film is guided to a hot air zone at a temperature of 125 ° C. and a hot air outlet with a wind speed of 10 m / sec, The film was stretched 4.5 times in the width direction. Next, while maintaining the stretched width in the width direction, heat treatment is performed in a hot air zone at a temperature of 200 ° C. and a hot air outlet with a wind speed of 10 m / sec. A uniaxially oriented PET film of 80 μm was obtained.
（実施例３）
実施例１と同じ方法で作製された未延伸フィルムをテンター延伸機に導き、フィルムの端部をクリップで把持しながら、温度１２０℃で熱風吹き出し口の風速が１２ｍ／秒の熱風ゾーンに導き、幅方向に４．５倍となるよう延伸した。次に、幅方向に延伸された幅を保ったまま、温度２００℃で熱風吹き出し口の風速が１０ｍ／秒の熱風ゾーンで熱処理し、さらに幅方向に３％の緩和処理を行い、フィルム厚み約１００μmの一軸配向ＰＥＴフィルムを得た。
(Example 3)
An unstretched film prepared in the same manner as in Example 1 is guided to a tenter stretching machine, and while holding the ends of the film with clips, the film is guided to a hot air zone at a temperature of 120 ° C. and a hot air outlet with a wind speed of 12 m / sec, The film was stretched 4.5 times in the width direction. Next, while maintaining the stretched width in the width direction, heat treatment is performed in a hot air zone at a temperature of 200 ° C. and a hot air outlet with a wind speed of 10 m / sec. A uniaxially oriented PET film of 100 μm was obtained.
（実施例４）
実施例１と同じ方法で作製された未延伸フィルムをテンター延伸機に導き、フィルムの端部をクリップで把持しながら、温度１３０℃で熱風吹き出し口の風速が９ｍ／秒の熱風ゾーンに導き、幅方向に５．５倍となるよう延伸した。次に、幅方向に延伸された幅を保ったまま、温度２００℃で熱風吹き出し口の風速が１０ｍ／秒の熱風ゾーンで熱処理し、さらに幅方向に３％の緩和処理を行い、フィルム厚み約６０μmの一軸配向ＰＥＴフィルムを得た。
(Example 4)
An unstretched film produced in the same manner as in Example 1 is guided to a tenter stretching machine, and while gripping the ends of the film with clips, the film is guided to a hot air zone at a temperature of 130 ° C. and a hot air outlet with a wind speed of 9 m / sec, The film was stretched 5.5 times in the width direction. Next, while maintaining the stretched width in the width direction, heat treatment is performed in a hot air zone at a temperature of 200 ° C. and a hot air outlet with a wind speed of 10 m / sec. A uniaxially oriented PET film of 60 μm was obtained.
（実施例５）
実施例１と同じ方法で作製された未延伸フィルムをテンター延伸機に導き、フィルムの端部をクリップで把持しながら、温度１２５℃で熱風吹き出し口の風速が１０ｍ／秒の熱風ゾーンに導き、幅方向に５．０倍、流れ方向に０．９倍となるよう延伸した。次に、幅方向に延伸された幅を保ったまま、温度２００℃で熱風吹き出し口の風速が１０ｍ／秒の熱風ゾーンで熱処理し、さらに幅方向に３％の緩和処理を行い、フィルム厚み約６０μmの一軸配向ＰＥＴフィルムを得た。
(Example 5)
An unstretched film produced in the same manner as in Example 1 is guided to a tenter stretching machine, and while gripping the ends of the film with clips, the film is guided to a hot air zone at a temperature of 125 ° C. and a hot air outlet with a wind speed of 10 m / sec, It was stretched 5.0 times in the width direction and 0.9 times in the machine direction. Next, while maintaining the stretched width in the width direction, heat treatment is performed in a hot air zone at a temperature of 200 ° C. and a hot air outlet with a wind speed of 10 m / sec. A uniaxially oriented PET film of 60 μm was obtained.
（実施例６）
実施例１と同じ方法で作製された未延伸フィルムをテンター延伸機に導き、フィルムの端部をクリップで把持しながら、温度１２０℃で熱風吹き出し口の風速が１０ｍ／秒の熱風ゾーンに導き、幅方向に５．０倍となるよう延伸した。次に、幅方向に延伸された幅を保ったまま、温度２００℃で熱風吹き出し口の風速が１０ｍ／秒の熱風ゾーンで熱処理し、さらに幅方向に３％の緩和処理を行い、フィルム厚み約４０μmの一軸配向ＰＥＴフィルムを得た。
(Example 6)
An unstretched film produced by the same method as in Example 1 is guided to a tenter stretching machine, and while holding the ends of the film with clips, the film is guided to a hot air zone at a temperature of 120 ° C. and a hot air outlet with a wind speed of 10 m / sec, The film was stretched 5.0 times in the width direction. Next, while maintaining the stretched width in the width direction, heat treatment is performed in a hot air zone at a temperature of 200 ° C. and a hot air outlet with a wind speed of 10 m / sec. A 40 μm uniaxially oriented PET film was obtained.
（実施例７）
実施例１と同じ方法で作製された未延伸フィルムをテンター延伸機に導き、フィルムの端部をクリップで把持しながら、温度１１０℃で熱風吹き出し口の風速が１２ｍ／秒の熱風ゾーンに導き、幅方向に４．５倍となるよう延伸した。次に、幅方向に延伸された幅を保ったまま、温度２００℃で熱風吹き出し口の風速が１０ｍ／秒の熱風ゾーンで熱処理し、さらに幅方向に３％の緩和処理を行い、フィルム厚み約１２５μmの一軸配向ＰＥＴフィルムを得た。
(Example 7)
An unstretched film prepared by the same method as in Example 1 is guided to a tenter stretching machine, and while holding the ends of the film with clips, the film is guided to a hot air zone at a temperature of 110 ° C. and a hot air outlet with a wind speed of 12 m / sec, The film was stretched 4.5 times in the width direction. Next, while maintaining the stretched width in the width direction, heat treatment is performed in a hot air zone at a temperature of 200 ° C. and a hot air outlet with a wind speed of 10 m / sec. A uniaxially oriented PET film of 125 μm was obtained.
（実施例８）
実施例１と同じ方法で作製された未延伸フィルムをテンター延伸機に導き、フィルムの端部をクリップで把持しながら、温度１１５℃で熱風吹き出し口の風速が１０ｍ／秒の熱風ゾーンに導き、幅方向に４．５倍となるよう延伸した。次に、幅方向に延伸された幅を保ったまま、温度２００℃で熱風吹き出し口の風速が１０ｍ／秒の熱風ゾーンで熱処理し、さらに幅方向に３％の緩和処理を行い、フィルム厚み約６０μmの一軸配向ＰＥＴフィルムを得た。
(Example 8)
An unstretched film produced by the same method as in Example 1 is guided to a tenter stretching machine, and while holding the ends of the film with clips, the film is guided to a hot air zone at a temperature of 115 ° C. and a hot air outlet with a wind speed of 10 m / sec, The film was stretched 4.5 times in the width direction. Next, while maintaining the stretched width in the width direction, heat treatment is performed in a hot air zone at a temperature of 200 ° C. and a hot air outlet with a wind speed of 10 m / sec. A uniaxially oriented PET film of 60 μm was obtained.
（実施例９）
実施例１と同じ方法で作製された未延伸フィルムをテンター延伸機に導き、フィルムの端部をクリップで把持しながら、温度１２０℃で熱風吹き出し口の風速が１２ｍ／秒の熱風ゾーンに導き、幅方向に５．０倍となるよう延伸した。次に、幅方向に延伸された幅を保ったまま、温度１３０℃で熱風吹き出し口の風速が１０ｍ／秒の熱風ゾーンで熱処理し、さらに幅方向に３％の緩和処理を行い、フィルム厚み約５０μmの一軸配向ＰＥＴフィルムを得た。
(Example 9)
An unstretched film prepared in the same manner as in Example 1 is guided to a tenter stretching machine, and while holding the ends of the film with clips, the film is guided to a hot air zone at a temperature of 120 ° C. and a hot air outlet with a wind speed of 12 m / sec, The film was stretched 5.0 times in the width direction. Next, while maintaining the stretched width in the width direction, heat treatment is performed in a hot air zone at a temperature of 130 ° C. and a hot air outlet with a wind speed of 10 m / sec. A uniaxially oriented PET film of 50 μm was obtained.
（比較例１）
実施例１と同じ方法で作製された未延伸フィルムをテンター延伸機に導き、フィルムの端部をクリップで把持しながら、温度１２５℃で熱風吹き出し口の風速が５ｍ／秒の熱風ゾーンに導き、幅方向に４．０倍となるよう延伸した。次に、幅方向に延伸された幅を保ったまま、温度２２５℃で熱風吹き出し口の風速が５ｍ／秒の熱風ゾーンで熱処理し、さらに幅方向に３％の緩和処理を行い、フィルム厚み約５０μmの一軸配向ＰＥＴフィルムを得た。
(Comparative example 1)
An unstretched film produced by the same method as in Example 1 is guided to a tenter stretching machine, and while holding the ends of the film with clips, the film is guided to a hot air zone at a temperature of 125 ° C. and a hot air outlet with a wind speed of 5 m / sec, The film was stretched 4.0 times in the width direction. Next, while maintaining the stretched width in the width direction, heat treatment is performed in a hot air zone at a temperature of 225 ° C. and a hot air outlet with a wind speed of 5 m / sec. A uniaxially oriented PET film of 50 μm was obtained.
（比較例２）
実施例１と同じ方法で作製された未延伸フィルムをテンター延伸機に導き、フィルムの端部をクリップで把持しながら、温度９５℃で熱風吹き出し口の風速が１０ｍ／秒の熱風ゾーンに導き、幅方向に４．０倍となるよう延伸した。次に、幅方向に延伸された幅を保ったまま、温度１５０℃で熱風吹き出し口の風速が１０ｍ／秒の熱風ゾーンで熱処理し、さらに幅方向に３％の緩和処理を行い、フィルム厚み約６０μmの一軸配向ＰＥＴフィルムを得た。
(Comparative example 2)
An unstretched film prepared by the same method as in Example 1 is guided to a tenter stretching machine, and while holding the ends of the film with clips, the film is guided to a hot air zone at a temperature of 95 ° C. and a hot air outlet with a wind speed of 10 m / sec, The film was stretched 4.0 times in the width direction. Next, while maintaining the stretched width in the width direction, heat treatment is performed in a hot air zone at a temperature of 150 ° C. and a hot air outlet with a wind speed of 10 m / sec. A uniaxially oriented PET film of 60 μm was obtained.
（比較例３）
実施例１と同じ方法で作製された未延伸フィルムを、加熱されたロール群および赤外線ヒーターを用いて１０５℃に加熱し、その後周速差のあるロール群で走行方向に１．５倍延伸した後、温度１００℃で熱風吹き出し口の風速が１０ｍ／秒の熱風ゾーンに導き、幅方向に４．０倍となるよう延伸した。次に、幅方向に延伸された幅を保ったまま、温度２００℃で熱風吹き出し口の風速が１０ｍ／秒の熱風ゾーンで熱処理し、さらに幅方向に３％の緩和処理を行い、フィルム厚み約５０μmの二軸配向ＰＥＴフィルムを得た。
(Comparative Example 3)
An unstretched film prepared in the same manner as in Example 1 was heated to 105° C. using a heated roll group and an infrared heater, and then stretched 1.5 times in the running direction with a roll group having a peripheral speed difference. After that, the film was led to a hot air zone having a temperature of 100° C. and a hot air outlet with a wind velocity of 10 m/sec, and was stretched 4.0 times in the width direction. Next, while maintaining the stretched width in the width direction, heat treatment is performed in a hot air zone at a temperature of 200 ° C. and a hot air outlet with a wind speed of 10 m / sec. A 50 μm biaxially oriented PET film was obtained.
（比較例４）
実施例１と同じ方法で作製された未延伸フィルムをテンター延伸機に導き、フィルムの端部をクリップで把持しながら、温度９０℃で熱風吹き出し口の風速が１０ｍ／秒の熱風ゾーンに導き、幅方向に４．０倍となるよう延伸した。次に、幅方向に延伸された幅を保ったまま、温度２００℃で熱風吹き出し口の風速が１０ｍ／秒の熱風ゾーンで熱処理し、さらに幅方向に３％の緩和処理を行い、フィルム厚み約５０μmの一軸配向ＰＥＴフィルムを得た。
(Comparative Example 4)
An unstretched film prepared by the same method as in Example 1 is guided to a tenter stretching machine, and while holding the ends of the film with clips, the film is guided to a hot air zone at a temperature of 90 ° C. and a hot air outlet with a wind speed of 10 m / sec, The film was stretched 4.0 times in the width direction. Next, while maintaining the stretched width in the width direction, heat treatment is performed in a hot air zone at a temperature of 200 ° C. and a hot air outlet with a wind speed of 10 m / sec. A uniaxially oriented PET film of 50 μm was obtained.
（比較例５）
実施例１と同じ方法で作製された未延伸フィルムを、加熱されたロール群および赤外線ヒーターを用いて１０５℃に加熱し、その後周速差のあるロール群で走行方向に３．５倍延伸した後、テンター延伸機に導き、フィルムの端部をクリップで把持しながら、温度１３０℃で熱風吹き出し口の風速が１０ｍ／秒の熱風ゾーンに導き、幅方向に４．０倍となるよう延伸した。次に、幅方向に延伸された幅を保ったまま、温度２２０℃で熱風吹き出し口の風速が１０ｍ／秒の熱風ゾーンで熱処理し、さらに幅方向に３％の緩和処理を行い、フィルム厚み約１００μmの二軸配向ＰＥＴフィルムを得た。
(Comparative Example 5)
An unstretched film produced by the same method as in Example 1 was heated to 105° C. using a heated roll group and an infrared heater, and then stretched 3.5 times in the running direction with a roll group having a peripheral speed difference. After that, the film was led to a tenter stretching machine, and while holding the ends of the film with a clip, was led to a hot air zone at a temperature of 130 ° C. and a hot air outlet with a wind speed of 10 m / sec, and stretched to 4.0 times in the width direction. . Next, while maintaining the stretched width in the width direction, heat treatment is performed in a hot air zone at a temperature of 220 ° C. and a hot air outlet with a wind speed of 10 m / sec. A 100 μm biaxially oriented PET film was obtained.
実施例１～９、比較例１～５のＰＥＴフィルムについて、各物性、Ｘ線構造解析、虹斑観察をした結果を以下の表１に示す。なお、実施例２～４、６～９で得られたＰＥＴフィルムは、Ｒｅ/Ｒｔｈが１未満でありフィルムの平面性に優れていた。 Table 1 below shows the results of physical properties, X-ray structural analysis, and rainbow spot observation of the PET films of Examples 1 to 9 and Comparative Examples 1 to 5. The PET films obtained in Examples 2 to 4 and 6 to 9 had a Re/Rth of less than 1 and were excellent in film flatness.
本発明の液晶表示装置、偏光板および偏光子保護フィルムであれば、偏光子保護フィルムとしてのポリエチレンテレフタレート系樹脂フィルムを、広色域化対応の液晶表示装置に使用した場合や、薄膜化した場合にも、表示画面に観察される虹斑の発生を抑制することができる。 If the liquid crystal display device, the polarizing plate and the polarizer protective film of the present invention, the polyethylene terephthalate-based resin film as the polarizer protective film is used in a liquid crystal display device compatible with widening the color gamut, or when it is thinned. Also, it is possible to suppress the occurrence of iridescence observed on the display screen.
Claims (4)
前記ポリエチレンテレフタレート系樹脂フィルムは下記の（１）及び（２）を満たすことを特徴とする偏光子保護フィルム。
（１）ポリエチレンテレフタレート系樹脂フィルムが３０００ｎｍ以上３００００ｎｍ以下のリタデーションを有する
（２）Ｘ線回折で測定した結晶の（１００）面のフィルム面に対する配向度が０．７０以下である A polarizer protective film made of a polyethylene terephthalate-based resin film,
A polarizer protective film, wherein the polyethylene terephthalate-based resin film satisfies the following (1) and (2).
(1) The polyethylene terephthalate-based resin film has a retardation of 3000 nm or more and 30000 nm or less. (2) The degree of orientation of the crystal (100) plane with respect to the film surface measured by X-ray diffraction is 0.70 or less.
前記２つの偏光板のうち、少なくとも一方が請求項３に記載の偏光板である、液晶表示装置。 A liquid crystal display device comprising a backlight source, two polarizing plates, and a liquid crystal cell arranged between the two polarizing plates,
A liquid crystal display device, wherein at least one of the two polarizing plates is the polarizing plate according to claim 3 .
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| PCT/JP2017/044827 WO2018110625A1 (en) | 2016-12-14 | 2017-12-14 | Liquid crystal display device, polarizing plate, and polarizer protective film |
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| CN111566523A (en) * | 2018-10-17 | 2020-08-21 | 株式会社Lg化学 | Antireflection film, polarizing plate and display device |
| KR102581428B1 (en) * | 2019-05-28 | 2023-09-21 | 주식회사 엘지화학 | Anti-reflective film, polarizing plate, and display apparatus |
| KR102514152B1 (en) * | 2019-11-06 | 2023-03-24 | 삼성에스디아이 주식회사 | Protective film for polarizer, polarizing plate comprising the same and optical display apparatus comprising the same |
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| JP2011053271A (en) * | 2009-08-31 | 2011-03-17 | Teijin Dupont Films Japan Ltd | Film for polarizer supporting base material |
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| CN110050208A (en) | 2019-07-23 |
| JP7156034B2 (en) | 2022-10-19 |
| JP7396402B2 (en) | 2023-12-12 |
| KR20190087619A (en) | 2019-07-24 |
| TWI795086B (en) | 2023-03-01 |
| CN110050208B (en) | 2021-09-28 |
| JPWO2018110625A1 (en) | 2019-10-24 |
| WO2018110625A1 (en) | 2018-06-21 |
| TWI750280B (en) | 2021-12-21 |
| CN113912994A (en) | 2022-01-11 |
| KR102216520B1 (en) | 2021-02-17 |
| TW201831554A (en) | 2018-09-01 |
| TW202208525A (en) | 2022-03-01 |
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