WO2020100861A1 - Polarizing membrane, polarizing film, laminated polarizing film, image display panel, and image display device - Google Patents
Polarizing membrane, polarizing film, laminated polarizing film, image display panel, and image display device Download PDFInfo
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- WO2020100861A1 WO2020100861A1 PCT/JP2019/044266 JP2019044266W WO2020100861A1 WO 2020100861 A1 WO2020100861 A1 WO 2020100861A1 JP 2019044266 W JP2019044266 W JP 2019044266W WO 2020100861 A1 WO2020100861 A1 WO 2020100861A1
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- Prior art keywords
- polarizing film
- film
- weight
- image display
- stretching
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- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
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- IPZIVCLZBFDXTA-UHFFFAOYSA-N ethyl n-prop-2-enoylcarbamate Chemical compound CCOC(=O)NC(=O)C=C IPZIVCLZBFDXTA-UHFFFAOYSA-N 0.000 description 1
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- 238000009832 plasma treatment Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
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- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 239000011112 polyethylene naphthalate Substances 0.000 description 1
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- 229920005862 polyol Polymers 0.000 description 1
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- 239000001103 potassium chloride Substances 0.000 description 1
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- 239000004323 potassium nitrate Substances 0.000 description 1
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- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
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- 235000011151 potassium sulphates Nutrition 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
-
- 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
- B32B7/023—Optical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R11/00—Arrangements for holding or mounting articles, not otherwise provided for
- B60R11/02—Arrangements for holding or mounting articles, not otherwise provided for for radio sets, television sets, telephones, or the like; Arrangement of controls thereof
- B60R11/0229—Arrangements for holding or mounting articles, not otherwise provided for for radio sets, television sets, telephones, or the like; Arrangement of controls thereof for displays, e.g. cathodic tubes
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/50—OLEDs integrated with light modulating elements, e.g. with electrochromic elements, photochromic elements or liquid crystal elements
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
Definitions
- a polarizing film used for various image display devices such as liquid crystal display devices and organic EL display devices
- dyed such as iodine and dichroic dyes
- Polyvinyl alcohol-based films (containing dichroic substances) have been used.
- the polarizing film is produced by subjecting a polyvinyl alcohol-based film to various treatments such as swelling, dyeing, crosslinking and stretching in a bath, followed by washing treatment and drying.
- the polarizing film is usually used as a polarizing film (polarizing plate) in which a protective film such as triacetyl cellulose is attached to one surface or both surfaces thereof with an adhesive.
- the above-mentioned iodine concentration (content) of the polarizing film is 6% by weight or more from the viewpoint of improving the initial degree of polarization of the polarizing film.
- the iodine concentration (content) of the polarizing film is preferably 7% by weight or more, more preferably 8% by weight or more, and From the viewpoint of controlling the peak temperature of the maximum strength of water detected by the evolved gas analysis method to 200 ° C. or higher, it is preferably 12% by weight or less, and more preferably 10% by weight or less.
- R 2 to R 5 are preferably an alkyl group having 1 to 6 carbon atoms, and having 1 to 3 carbon atoms, from the viewpoint of easy availability. More preferably, it is an alkyl group.
- R 6 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom.
- R 7 and R 8 are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a hydrogen atom. Is more preferable.
- the thermoplastic resin base material has a glass transition temperature (Tg) of about 120 ° C. or lower from the viewpoint of being able to sufficiently secure the stretchability of the laminate while suppressing the crystallization of the PVA-based resin layer. Is preferred. Further, in consideration of the plasticization of the thermoplastic resin substrate with water and the favorable underwater drawing, the glass transition temperature (Tg) is more preferably about 100 ° C. or lower, and about 90 ° C. or lower. Is more preferable. On the other hand, the glass transition temperature of the thermoplastic resin base material is such that when the coating liquid is applied and dried, problems such as deformation of the thermoplastic resin base material can be prevented and a good laminate can be produced. Therefore, the temperature is preferably about 60 ° C. or higher. The glass transition temperature can be adjusted, for example, by introducing a modifying group into the constituent material of the thermoplastic resin substrate or by heating with a crystallization material. The glass transition temperature (Tg) is a value determined according to JIS K7121.
- the content of the compound having a function is usually preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and 0.1% by weight or more. More preferably, it is preferably 30% by weight or less, more preferably 25% by weight or less, still more preferably 20% by weight or less.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
Abstract
A polarizing membrane formed having iodine adsorbed and oriented on a polyvinyl alcohol film. The iodine concentration is at least 6 wt% and the peak temperature at maximum intensity for detected water is at least 200°C, in a generated gas analysis method in the presence of inert gas and under conditions of a temperature increase speed of 10°C/min and a temperature increase range of 40–350°C. This polarizing membrane has good initial polarization and, in a high-temperature environment, has an excellent suppression effect on reduction in single transmittance caused by polarizing membrane coloring.
Description
本発明は、偏光膜、偏光フィルム、積層偏光フィルム、画像表示パネル、および画像表示装置に関する。
The present invention relates to a polarizing film, a polarizing film, a laminated polarizing film, an image display panel, and an image display device.
従来、液晶表示装置や有機ＥＬ表示装置等の各種画像表示装置に用いる偏光膜としては、高透過率と高偏光度を兼ね備えていることから、染色処理された（ヨウ素や二色性染料等の二色性物質を含有する）ポリビニルアルコール系フィルムが用いられている。当該偏光膜は、ポリビニルアルコール系フィルムに、浴中にて、例えば、膨潤、染色、架橋、延伸等の各処理を施した後に、洗浄処理を施してから、乾燥することにより製造される。また前記偏光膜は、通常、その片面または両面にトリアセチルセルロース等の保護フィルムが接着剤を用いて貼合された偏光フィルム（偏光板）として用いられている。
Conventionally, as a polarizing film used for various image display devices such as liquid crystal display devices and organic EL display devices, since it has both high transmittance and high polarization degree, it has been dyed (such as iodine and dichroic dyes). Polyvinyl alcohol-based films (containing dichroic substances) have been used. The polarizing film is produced by subjecting a polyvinyl alcohol-based film to various treatments such as swelling, dyeing, crosslinking and stretching in a bath, followed by washing treatment and drying. The polarizing film is usually used as a polarizing film (polarizing plate) in which a protective film such as triacetyl cellulose is attached to one surface or both surfaces thereof with an adhesive.
前記偏光フィルムは、必要に応じ、他の光学層を積層して積層偏光フィルム（光学積層体）として用いられ、前記偏光フィルムあるいは前記積層偏光フィルム（光学積層体）は、液晶セルや有機ＥＬ素子等の画像表示セルと、視認側における前面透明板（ウインドウ層）やタッチパネル等の前面透明部材との間に粘着剤層や接着剤層を介して貼合されて、上記の各種画像表示装置として用いられる（特許文献１）。
The polarizing film is used as a laminated polarizing film (optical laminated body) by laminating other optical layers as necessary, and the polarizing film or the laminated polarizing film (optical laminated body) is a liquid crystal cell or an organic EL element. And the like, and the front transparent plate (window layer) on the viewing side and the front transparent member such as a touch panel, which are bonded together via a pressure-sensitive adhesive layer or an adhesive layer. It is used (Patent Document 1).
近年、このような各種画像表示装置は、携帯電話やタブレット端末等のモバイル機器に加えて、カーナビゲーション装置やバックモニター等の車載用の画像表示装置としても使用される等、その用途は広がっている。これに伴い、前記画像表示装置には、従来要求されてきたよりも、より過酷な環境下（例えば、高温環境下）における高い耐久性が求められており、そのような耐久性を確保することを目的とした画像表示装置が提案されている（特許文献２）。
In recent years, such various image display devices have been widely used, such as being used as in-vehicle image display devices such as car navigation devices and back monitors in addition to mobile devices such as mobile phones and tablet terminals. There is. Along with this, the image display device is required to have higher durability in a more severe environment (for example, in a high temperature environment) than has been conventionally required, and it is necessary to secure such durability. A target image display device has been proposed (Patent Document 2).
ヨウ素系偏光膜を用いた偏光フィルムや積層偏光フィルムは、高温環境下に曝された場合に、偏光膜を構成するポリビニルアルコールが脱水反応によってポリエン化されることにより、偏光膜に着色が生じ、その単体透過率が低下する問題があった。
A polarizing film or a laminated polarizing film using an iodine-based polarizing film, when exposed to a high-temperature environment, the polyvinyl alcohol constituting the polarizing film is polyeneized by a dehydration reaction, whereby the polarizing film is colored, There was a problem that the single-body transmittance was lowered.
本発明者らが、鋭意検討したところ、ヨウ素系偏光膜中に含まれるヨウ素が高温環境下でポリエン化を促進させることを見出した。よって、高温環境下における、偏光膜の着色による単体透過率の低下を抑制するためには、偏光膜中のヨウ素濃度（含有量）を減少させることは有効である。一方で、良好な偏光度を有するヨウ素が濃い偏光膜を得ることが困難であった。
The inventors of the present invention have made extensive studies and found that iodine contained in the iodine-based polarizing film promotes polyene formation in a high temperature environment. Therefore, it is effective to reduce the iodine concentration (content) in the polarizing film in order to suppress the decrease in the single-body transmittance due to the coloring of the polarizing film in a high temperature environment. On the other hand, it was difficult to obtain a polarizing film having a high iodine concentration and having a high degree of polarization.
以上のような事情に鑑み、本発明は、ヨウ素濃度が濃い偏光膜において、初期の偏光度が良好であり、高温環境下において、偏光膜の着色による単体透過率の低下の抑制効果に優れる偏光膜を提供することを目的とする。
In view of the above circumstances, the present invention, in the polarizing film having a high iodine concentration, the initial degree of polarization is good, and in a high temperature environment, the polarization effect is excellent in suppressing the decrease in the single transmittance due to the coloring of the polarizing film. The purpose is to provide a membrane.
また、本発明は、上記の偏光膜を用いた偏光フィルム、積層偏光フィルム、画像表示パネル、および画像表示装置を提供することを目的とする。
Another object of the present invention is to provide a polarizing film using the above polarizing film, a laminated polarizing film, an image display panel, and an image display device.
すなわち、本発明は、ポリビニルアルコール系フィルムにヨウ素が吸着配向して形成される偏光膜であって、ヨウ素濃度が６重量％以上であり、かつ、発生ガス分析法において、不活性ガスの存在下、昇温速度が１０℃／分で、昇温範囲が４０℃から３５０℃までの条件にて、検出される水の最大強度のピーク温度が２００℃以上である偏光膜に関する。
That is, the present invention is a polarizing film formed by adsorbing and orienting iodine on a polyvinyl alcohol-based film, having an iodine concentration of 6% by weight or more, and in an evolved gas analysis method in the presence of an inert gas. The present invention relates to a polarizing film having a temperature rising rate of 10 ° C./minute and a temperature rising range of 40 ° C. to 350 ° C., and a peak temperature of maximum intensity of water detected is 200 ° C. or higher.
また、本発明は、前記偏光膜の少なくとも一方の面に透明保護フィルムが貼り合わされている偏光フィルムに関する。
The present invention also relates to a polarizing film having a transparent protective film attached to at least one surface of the polarizing film.
また、本発明は、前記偏光フィルムが光学層に貼り合わされている積層偏光フィルムに関する。
The present invention also relates to a laminated polarizing film in which the polarizing film is attached to an optical layer.
また、本発明は、画像表示セルに、前記偏光フィルム、または前記積層偏光フィルムが貼り合わされている画像表示パネルに関する。
The present invention also relates to an image display panel in which the polarizing film or the laminated polarizing film is attached to an image display cell.
また、本発明は、前記画像表示パネルの偏光フィルムまたは積層偏光フィルム側に、前面透明部材を備える画像表示装置に関する。
The present invention also relates to an image display device comprising a front transparent member on the polarizing film or laminated polarizing film side of the image display panel.
本発明の偏光膜における効果の作用メカニズムの詳細は不明な部分があるが、以下のように推定される。ただし、本発明は、この作用メカニズムに限定して解釈されなくてもよい。
The details of the mechanism of action of the effect of the polarizing film of the present invention are unknown, but it is presumed as follows. However, the present invention may not be construed as being limited to this mechanism of action.
本発明の偏光膜は、ポリビニルアルコール系フィルムにヨウ素が吸着配向して形成されるヨウ素系偏光膜であり、ヨウ素濃度が６重量％以上であり、かつ、発生ガス分析法において、不活性ガスの存在下、昇温速度が１０℃／分で、昇温範囲が４０℃から３５０℃までの条件にて、検出される水の最大強度のピーク温度が２００℃以上である。上述のとおり、ヨウ素系偏光膜は、高温環境下でポリビニルアルコールの脱水反応によりポリエン化が生じるが、本発明の偏光膜は、この脱水反応が起こる温度を高温側、すなわち、発生ガス分析法にて検出（観測）される水の最大強度のピーク温度を２００℃以上、に設定することにより、高温環境下において、偏光膜の着色による単体透過率の低下を抑制できるものである。さらには、本発明の偏光膜は、偏光膜中のヨウ素濃度を一定範囲以上に設定することにより、発生ガス分析法にて検出（観測）される水の最大強度のピーク温度を２００℃以上に制御できながらも、初期の偏光度が良好になる。
The polarizing film of the present invention is an iodine-based polarizing film formed by adsorbing and orienting iodine on a polyvinyl alcohol-based film, and has an iodine concentration of 6% by weight or more, and an inert gas of In the presence, the temperature rise rate is 10 ° C./min, the temperature rise range is 40 ° C. to 350 ° C., and the peak temperature of the maximum strength of water detected is 200 ° C. or higher. As described above, the iodine-based polarizing film undergoes polyeneization due to the dehydration reaction of polyvinyl alcohol in a high temperature environment, but the polarizing film of the present invention has a temperature at which this dehydration reaction occurs on the high temperature side, that is, in the evolved gas analysis method. By setting the peak temperature of the maximum intensity of water detected (observed) to 200 ° C. or higher, it is possible to suppress a decrease in the single transmittance due to coloring of the polarizing film in a high temperature environment. Further, in the polarizing film of the present invention, the peak temperature of the maximum intensity of water detected (observed) by the evolved gas analysis method is set to 200 ° C. or more by setting the iodine concentration in the polarizing film to a certain range or more. Although it can be controlled, the initial degree of polarization becomes good.
一方、本発明者らは、ヨウ素含有のポリビニルアルコール系フィルムにヨウ素が吸着配向して形成された偏光膜を、一定時間高温環境下に曝したところ、偏光膜からラジカルの発生を観測した。偏光膜がポリエン化によって着色するタイミングと、このラジカルが生成するタイミングとが酷似していたことから、偏光膜のポリエン化の進行によりラジカルが発生する現象が示唆された。したがって、偏光膜において、上述した脱水反応が起こる温度を高温側、すなわち、発生ガス分析法にて検出（観測）される水の最大強度のピーク温度を２００℃以上、に設定するには、偏光膜にラジカル捕捉機能を有する化合物を含有させることが好ましい。
On the other hand, the present inventors observed the generation of radicals from the polarizing film when the polarizing film formed by iodine adsorption and orientation on the iodine-containing polyvinyl alcohol film was exposed to a high temperature environment for a certain period of time. Since the timing at which the polarizing film was colored by polyene formation was very similar to the timing at which the radicals were generated, it was suggested that radicals are generated by the progress of polyeneization of the polarizing film. Therefore, in order to set the temperature at which the above-mentioned dehydration reaction occurs in the polarizing film on the high temperature side, that is, the peak temperature of the maximum intensity of water detected (observed) by the evolved gas analysis method is 200 ° C. or higher, It is preferable that the film contains a compound having a radical scavenging function.
また、本発明の偏光膜は、画像表示装置のパネルの薄型化に伴い、偏光フィルムや積層偏光フィルムの加熱時のパネル反りを防止する観点から、薄型の偏光膜として有用である。
Further, the polarizing film of the present invention is useful as a thin polarizing film from the viewpoint of preventing panel warpage during heating of the polarizing film or the laminated polarizing film as the panel of the image display device becomes thinner.
＜偏光膜＞
本発明の偏光膜は、ポリビニルアルコール系フィルムにヨウ素が吸着配向して形成されるヨウ素系偏光膜であり、ヨウ素濃度が６重量％以上であり、かつ、発生ガス分析法において、不活性ガスの存在下、昇温速度が１０℃／分で、昇温範囲が４０℃から３５０℃までの条件にて、検出される水の最大強度のピーク温度が２００℃以上である。 <Polarizing film>
The polarizing film of the present invention is an iodine-based polarizing film formed by adsorbing and orienting iodine on a polyvinyl alcohol-based film, and has an iodine concentration of 6% by weight or more, and an inert gas of In the presence, the temperature rise rate is 10 ° C./min, the temperature rise range is 40 ° C. to 350 ° C., and the peak temperature of the maximum strength of water detected is 200 ° C. or higher.
本発明の偏光膜は、ポリビニルアルコール系フィルムにヨウ素が吸着配向して形成されるヨウ素系偏光膜であり、ヨウ素濃度が６重量％以上であり、かつ、発生ガス分析法において、不活性ガスの存在下、昇温速度が１０℃／分で、昇温範囲が４０℃から３５０℃までの条件にて、検出される水の最大強度のピーク温度が２００℃以上である。 <Polarizing film>
The polarizing film of the present invention is an iodine-based polarizing film formed by adsorbing and orienting iodine on a polyvinyl alcohol-based film, and has an iodine concentration of 6% by weight or more, and an inert gas of In the presence, the temperature rise rate is 10 ° C./min, the temperature rise range is 40 ° C. to 350 ° C., and the peak temperature of the maximum strength of water detected is 200 ° C. or higher.
前記ポリビニルアルコール（ＰＶＡ）系フィルムは、可視光領域において透光性を有し、ヨウ素を分散吸着するものを特に制限なく使用できる。また、通常、原反として用いる、ＰＶＡ系フィルムは、厚さが１～１００μｍ程度であることが好ましく、１～５０μｍ程度であることがより好ましく、幅が１００～５０００ｍｍ程度であることが好ましい。
As the polyvinyl alcohol (PVA) film, a film having a light-transmitting property in a visible light region and capable of dispersing and adsorbing iodine can be used without particular limitation. Further, the PVA-based film, which is usually used as a raw fabric, preferably has a thickness of about 1 to 100 μm, more preferably about 1 to 50 μm, and a width of about 100 to 5000 mm.
前記ポリビニルアルコール系フィルムの材料としては、ポリビニルアルコールまたはその誘導体が挙げられる。前記ポリビニルアルコールの誘導体としては、例えば、ポリビニルホルマール、ポリビニルアセタール；エチレン、プロピレン等のオレフィン；アクリル酸、メタクリル酸、クロトン酸等の不飽和カルボン酸、およびそのアルキルエステル、アクリルアミド等で変性したもの等が挙げられる。前記ポリビニルアルコールは、平均重合度が１００～１０，０００程度であることが好ましく、１，０００～１０，０００程度であることがより好ましく、１，５００～４，５００程度であることがさらに好ましい。また、前記ポリビニルアルコールは、ケン化度が８０～１００モル％程度であることが好ましく、９５モル％～９９．９５モル程度であることがより好ましい。なお、前記平均重合度および前記ケン化度は、ＪＩＳ Ｋ ６７２６に準じて求めることができる。
As the material of the polyvinyl alcohol film, polyvinyl alcohol or its derivative can be mentioned. Examples of the polyvinyl alcohol derivative include polyvinyl formal, polyvinyl acetal, olefins such as ethylene and propylene, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and their modified alkyl esters, acrylamides, and the like. Is mentioned. The polyvinyl alcohol preferably has an average degree of polymerization of about 100 to 10,000, more preferably about 1,000 to 10,000, and even more preferably about 1,500 to 4,500. .. The saponification degree of the polyvinyl alcohol is preferably about 80 to 100 mol%, more preferably about 95 mol% to 99.95 mol. The average degree of polymerization and the degree of saponification can be determined according to JIS K 6726.
前記ポリビニルアルコール系フィルムには、可塑剤や界面活性剤等の添加剤を含有していてもよい。前記可塑剤としては、例えば、グリセリン、ジグリセリン、トリグリセリン、エチレングリコール、プロピレングリコール、ポリエチレングリコール等の、ポリオールおよびその縮合物等が挙げられる。前記添加剤の使用量は、特に制限はないが、例えば、ポリビニルアルコール系フィルム中、２０重量％以下程度が好適である。
The polyvinyl alcohol film may contain additives such as a plasticizer and a surfactant. Examples of the plasticizer include polyols such as glycerin, diglycerin, triglycerin, ethylene glycol, propylene glycol, and polyethylene glycol, and condensates thereof. The amount of the additive used is not particularly limited, but is preferably about 20% by weight or less in the polyvinyl alcohol film.
前記偏光膜は、偏光膜の初期の偏光度を良好にする観点から、前記ヨウ素濃度（含有量）が６重量％以上である。前記偏光膜は、偏光膜の初期の偏光度を向上させる観点から、前記ヨウ素濃度（含有量）が、７重量％以上であることが好ましく、８重量％以上であることがより好ましく、そして、発生ガス分析法にて検出される水の最大強度のピーク温度を２００℃以上に制御する観点から、１２重量％以下であることが好ましく、１０重量％以下であることがより好ましい。
The above-mentioned iodine concentration (content) of the polarizing film is 6% by weight or more from the viewpoint of improving the initial degree of polarization of the polarizing film. From the viewpoint of improving the initial degree of polarization of the polarizing film, the iodine concentration (content) of the polarizing film is preferably 7% by weight or more, more preferably 8% by weight or more, and From the viewpoint of controlling the peak temperature of the maximum strength of water detected by the evolved gas analysis method to 200 ° C. or higher, it is preferably 12% by weight or less, and more preferably 10% by weight or less.
前記偏光膜は、発生ガス分析法において、不活性ガスの存在下、昇温速度が１０℃／分で、昇温範囲が４０℃から３５０℃までの条件にて、検出される水の最大強度のピーク温度が２００℃以上を示す。前記偏光膜は、ポリビニルアルコールの脱水反応が起こる温度を高温側、すなわち、発生ガス分析法にて検出される水の最大強度のピーク温度を２００℃以上、に設定することにより、高温環境下において、偏光膜の着色による単体透過率の低下を抑制できる。一方、上記の水の最大強度のピーク温度が２００℃以上よりも低い場合、ローエンドの車載ディスプレイに求められる高温耐久性の指標とされる加熱耐久性試験（９５℃×７５０時間）前後における偏光膜の単体透過率の変化量を０％以上５％以下に制御することが困難となる。
In the evolved gas analysis method, the polarizing film has a maximum strength of water detected in the presence of an inert gas at a temperature rising rate of 10 ° C./min and a temperature rising range of 40 ° C. to 350 ° C. Shows a peak temperature of 200 ° C. or higher. The polarizing film is set in a high temperature environment by setting the temperature at which the dehydration reaction of polyvinyl alcohol occurs on the high temperature side, that is, the peak temperature of the maximum strength of water detected by the evolved gas analysis method to 200 ° C. or higher. In addition, it is possible to suppress a decrease in the single transmittance due to the coloring of the polarizing film. On the other hand, when the peak temperature of the maximum strength of water is lower than 200 ° C. or higher, the polarizing film before and after the heating durability test (95 ° C. × 750 hours), which is an index of high temperature durability required for low-end in-vehicle displays. It becomes difficult to control the change amount of the simple substance transmittance of 0% to 5%.
図１は、上記の発生ガス分析法にて、検出される水のピークを示すチャートの一例であり、検出される水の最大強度のピーク温度が２００℃以上である。
FIG. 1 is an example of a chart showing peaks of water detected by the above-described evolved gas analysis method, and the peak temperature of the maximum intensity of water detected is 200 ° C. or higher.
また、上記の発生ガス分析法は、ガスクロマトグラフィ装置と質量分析装置を不活性の金属キャピラリーなどで直結し、試料を昇温加熱した時に発生するガスをリアルタイムでモニターする分析方法であり、一般的に、ＥＧＡ／ＭＳ法、ＥＧＡ／ＴＯＦＭＳ法などと呼ばれる。
In addition, the above-mentioned generated gas analysis method is an analysis method in which a gas chromatography device and a mass spectrometry device are directly connected by an inert metal capillary or the like, and a gas generated when a sample is heated and heated is monitored in real time. In addition, it is called an EGA / MS method, an EGA / TOFMS method, or the like.
前記偏光膜は、ラジカル捕捉機能を有する化合物を含むことが好ましい。前記ラジカル捕捉機能を有する化合物は、偏光膜のポリビニルアルコールが加熱にて生じるラジカルを捕捉して、ポリエン化の脱水反応が起こる温度を高温側に設定することができると推定される。前記ラジカル捕捉機能を有する化合物としては、例えば、ヒンダードフェノール系、ヒンダードアミン系、リン系、イオウ系、ベンゾトリアゾール系、ベンゾフェノン系、ヒドロキシルアミン系、サルチル酸エステル系、トリアジン系の化合物などのラジカル捕捉機能を有する化合物（例えば、酸化防止剤など）が挙げられる。前記ラジカル捕捉機能を有する化合物としては、ポリエン化の脱水反応が起こる温度を高温側に容易に設定することができる観点から、例えば、ニトロキシラジカル、またはニトロキシド基を有する化合物であることが好ましい。
The polarizing film preferably contains a compound having a radical scavenging function. It is presumed that the compound having a radical scavenging function can set the temperature at which the polyvinyl alcohol of the polarizing film traps radicals generated by heating to cause the dehydration reaction of polyene conversion to a high temperature side. Examples of the compound having a radical scavenging function include radical scavenging compounds such as hindered phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, benzotriazole compounds, benzophenone compounds, hydroxylamine compounds, salicylate compounds, and triazine compounds. Examples thereof include compounds having a function (for example, antioxidants and the like). The compound having a radical scavenging function is preferably, for example, a compound having a nitroxy radical or a nitroxide group, from the viewpoint that the temperature at which the dehydration reaction of polyene conversion occurs can be easily set to a high temperature side.
前記ニトロキシラジカル、またはニトロキシド基を有する化合物としては、室温、空気中で比較的に安定なラジカルを有する観点から、Ｎ－オキシル化合物（官能基として、Ｃ－Ｎ（－Ｃ）－Ｏ・を有する化合物（Ｏ・はオキシラジカルを示す））が挙げられ、公知のものが使用できる。Ｎ－オキシル化合物としては、例えば、以下の構造の有機基を有する化合物などが挙げられる。
（一般式（１）中、Ｒ１は、オキシラジカルを表し、Ｒ２からＲ５は、独立して、水素原子、または炭素原子数が１～１０のアルキル基を表し、ｎは０または１を表す。）なお、一般式（１）中の、点線部の左は任意の有機基を示す。
Examples of the compound having a nitroxyl radical or a nitroxide group, at room temperature, from the viewpoint of having a relatively stable radical in air, as N- oxyl compound (functional group, the C-N (-C) -O · compounds having (O · is an oxy radical)) can be mentioned, known materials can be used. Examples of the N-oxyl compound include compounds having an organic group having the following structure.
(In the general formula (1), R 1 represents an oxy radical, R 2 to R 5 independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is 0 or 1 It should be noted that the left side of the dotted line portion in the general formula (1) represents an arbitrary organic group.
上記の有機基を有する化合物としては、例えば、以下の一般式（２）～（５）で表される化合物などが挙げられる。
（一般式（２）中、Ｒ１～Ｒ５、およびｎは、上記と同様であり、Ｒ６は水素原子、または炭素原子数が１～１０のアルキル基、アシル基、もしくはアリール基を表し、ｎは０または１を表す。）
（一般式（３）中、Ｒ１からＲ５、およびｎは、上記と同様であり、Ｒ７およびＲ８は、独立して、水素原子、または炭素原子数が１～１０のアルキル基、アシル基、もしくはアリール基を表す。）
（一般式（４）中、Ｒ１からＲ５、およびｎは、上記と同様であり、Ｒ９からＲ１１は、独立して、水素原子、または炭素原子数が１～１０のアルキル基、アシル基、アミノ基、アルコキシ基、ヒドロキシ基、もしくはアリール基を表す。）
（一般式（５）中、Ｒ１からＲ５、およびｎは、上記と同様であり、Ｒ１２は、水素原子、または炭素原子数が１～１０のアルキル基、アミノ基、アルコキシ基、ヒドロキシ基、もしくはアリール基を表す。）
Examples of the compound having an organic group include compounds represented by the following general formulas (2) to (5).
(In the general formula (2), R 1 to R 5 and n are the same as above, and R 6 represents a hydrogen atom or an alkyl group, an acyl group, or an aryl group having 1 to 10 carbon atoms. , N represents 0 or 1.)
(In the general formula (3), R 1 to R 5 and n are the same as above, and R 7 and R 8 are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Represents an acyl group or an aryl group.)
(In the general formula (4), R 1 to R 5 and n are the same as above, and R 9 to R 11 are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Represents an acyl group, an amino group, an alkoxy group, a hydroxy group, or an aryl group.)
(In the general formula (5), R 1 to R 5 and n are the same as above, and R 12 is a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an amino group, an alkoxy group, a hydroxy group. Represents a group or an aryl group.)
前記一般式（１）～（５）中、Ｒ２からＲ５は、入手容易性の観点から、炭素原子数が１～６のアルキル基であることが好ましく、炭素原子数が１～３のアルキル基であることがより好ましい。また、前記一般式（２）中、入手容易性の観点から、Ｒ６は水素原子、または炭素原子数が１～１０のアルキル基であることが好ましく、水素原子であることがより好ましい。また、前記一般式（３）中、入手容易性の観点から、Ｒ７およびＲ８は独立して水素原子、または炭素原子数が１～１０のアルキル基であることが好ましく、水素原子であることがより好ましい。また、前記一般式（４）中、入手容易性の観点から、Ｒ９からＲ１１は、水素原子、または炭素原子数が１～１０のアルキル基であることが好ましい。また、前記一般式（５）中、入手容易性の観点から、Ｒ１２は、ヒドロキシ基、アミノ基、またはアルコキシ基であることが好ましい。前記一般式（１）～（５）中、ｎは、入手容易性の観点から、１であることが好ましい。
In the general formulas (1) to (5), R 2 to R 5 are preferably an alkyl group having 1 to 6 carbon atoms, and having 1 to 3 carbon atoms, from the viewpoint of easy availability. More preferably, it is an alkyl group. Further, in the general formula (2), from the viewpoint of easy availability, R 6 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom. Further, in the general formula (3), from the viewpoint of easy availability, it is preferable that R 7 and R 8 are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a hydrogen atom. Is more preferable. In the general formula (4), R 9 to R 11 are preferably hydrogen atoms or alkyl groups having 1 to 10 carbon atoms from the viewpoint of easy availability. In addition, in the general formula (5), R 12 is preferably a hydroxy group, an amino group, or an alkoxy group from the viewpoint of easy availability. In the general formulas (1) to (5), n is preferably 1 from the viewpoint of easy availability.
また、前記Ｎ－オキシル化合物としては、例えば、特開２００３－６４０２２号公報、特開平１１－２２２４６２号公報、特開２００２－２８４７３７号公報、国際公開第２０１６／０４７６５５号などに記載されたＮ－オキシル化合物が挙げられる。
The N-oxyl compound is described in, for example, JP-A-2003-64022, JP-A-11-222462, JP-A-2002-284737, and WO-A-2016 / 047655. An oxyl compound is mentioned.
また、前記ラジカル捕捉機能を有する化合物は、ポリエン化反応において発生するラジカルを効率よく捕捉できる観点から、分子量が、１０００以下であることが好ましく、５００以下であることがより好ましく、３００以下であることがさらに好ましい。
Further, the compound having a radical scavenging function has a molecular weight of preferably 1,000 or less, more preferably 500 or less, and further preferably 300 or less, from the viewpoint of efficiently trapping radicals generated in the polyene conversion reaction. Is more preferable.
前記ラジカル捕捉機能を有する化合物は、偏光膜の製造の際に水と共に効率よく偏光膜に染み込むことができる観点、偏光膜に高濃度に含侵できる観点、厚みが厚いポリビニルアルコール系フィルムを使用した場合でも短時間で含侵できるため、偏光膜の生産性を高くできる観点から、２５℃の水１００重量部に対して１重量部以上溶解できることが好ましく、２５℃の水１００重量部に対して２重量部以上溶解できることがより好ましく、２５℃の水１００重量部に対して５重量部以上溶解できることがさらに好ましい。
The compound having a radical scavenging function uses a thick polyvinyl alcohol-based film from the viewpoint that the polarizing film can be efficiently impregnated with water during the production of the polarizing film, the polarizing film can be impregnated at a high concentration, and the like. Even if it is impregnated in a short time, it is preferable that it can be dissolved in 1 part by weight or more with respect to 100 parts by weight of water at 25 ° C. from the viewpoint of increasing productivity of the polarizing film. It is more preferable that 2 parts by weight or more can be dissolved, and even more preferably 5 parts by weight or more can be dissolved in 100 parts by weight of water at 25 ° C.
また、前記ニトロキシラジカル、またはニトロキシド基を有する化合物としては、例えば、以下の化合物などが挙げられる。
（一般式（６）中、Ｒは、水素原子、または炭素原子数が１～１０のアルキル基、アシル基、もしくはアリール基を表す。）
Examples of the compound having a nitroxy radical or a nitroxide group include the following compounds.
(In the general formula (6), R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an acyl group, or an aryl group.)
前記偏光膜が、前記ラジカル捕捉機能を有する化合物を含む場合、前記ラジカル捕捉機能を有する化合物の含有量は、高温環境下における偏光膜の着色による単体透過率の低下を抑制する観点から、前記偏光膜中、０．００５重量％以上であることが好ましく、０．０１重量％以上であることがより好ましく、０．０２重量％以上であることがさらに好ましく、そして、外観の観点から、１５重量％以下であることが好ましく、１２重量％以下であることがより好ましく、１０重量％以下であることがさらに好ましい。
When the polarizing film contains the compound having the radical scavenging function, the content of the compound having the radical scavenging function is from the viewpoint of suppressing a decrease in single transmittance due to coloring of the polarizing film under a high temperature environment. In the film, it is preferably 0.005% by weight or more, more preferably 0.01% by weight or more, further preferably 0.02% by weight or more, and 15% by weight from the viewpoint of appearance. % Or less, more preferably 12% by weight or less, and further preferably 10% by weight or less.
＜偏光膜の製造方法＞
前記偏光膜の製造方法は、前記ポリビニルアルコール系フィルムに、任意の膨潤工程および洗浄工程と、少なくとも、染色工程、架橋工程、および延伸工程を施して得られる。前記偏光膜中に含まれる前記ヨウ素の含有量は、膨潤工程、染色工程、架橋工程、延伸工程および洗浄工程における各処理浴のいずれかに含まれる前記ヨウ素ならびにヨウ化カリウム等のヨウ化物等の濃度、上記の各処理浴による処理温度および処理時間によって制御できる。 <Method of manufacturing polarizing film>
The method for producing the polarizing film can be obtained by subjecting the polyvinyl alcohol-based film to an arbitrary swelling step and a washing step, and at least a dyeing step, a crosslinking step, and a stretching step. The content of the iodine contained in the polarizing film is such that the iodine and iodide such as potassium iodide contained in any of the treatment baths in the swelling step, the dyeing step, the crosslinking step, the stretching step and the washing step. It can be controlled by the concentration, the treatment temperature and the treatment time of each treatment bath described above.
前記偏光膜の製造方法は、前記ポリビニルアルコール系フィルムに、任意の膨潤工程および洗浄工程と、少なくとも、染色工程、架橋工程、および延伸工程を施して得られる。前記偏光膜中に含まれる前記ヨウ素の含有量は、膨潤工程、染色工程、架橋工程、延伸工程および洗浄工程における各処理浴のいずれかに含まれる前記ヨウ素ならびにヨウ化カリウム等のヨウ化物等の濃度、上記の各処理浴による処理温度および処理時間によって制御できる。 <Method of manufacturing polarizing film>
The method for producing the polarizing film can be obtained by subjecting the polyvinyl alcohol-based film to an arbitrary swelling step and a washing step, and at least a dyeing step, a crosslinking step, and a stretching step. The content of the iodine contained in the polarizing film is such that the iodine and iodide such as potassium iodide contained in any of the treatment baths in the swelling step, the dyeing step, the crosslinking step, the stretching step and the washing step. It can be controlled by the concentration, the treatment temperature and the treatment time of each treatment bath described above.
また、前記ラジカル捕捉機能を有する化合物を含む偏光膜を製造する場合、前記膨潤工程、前記洗浄工程、前記染色工程、前記架橋工程、および前記延伸工程のいずれか１つ以上の処理浴には、前記ラジカル捕捉機能を有する化合物を含有すればよい。前記各処理浴のいずれかに含まれる前記ラジカル捕捉機能を有する化合物の濃度は、各処理の処理回数、処理時間、処理温度等の影響を受けるため一概に決定できないが、偏光膜中のラジカル捕捉機能を有する化合物の含有量を効率よく制御できる観点から、通常、０．０１重量％以上であることが好ましく、０．０５重量％以上であることがより好ましく、０．１重量％以上であることがさらに好ましく、そして、３０重量％以下であることが好ましく、２５重量％以下であることがより好ましく、２０重量％以下であることがさらに好ましい。
Further, in the case of producing a polarizing film containing a compound having a radical scavenging function, in any one or more treatment baths of the swelling step, the washing step, the dyeing step, the crosslinking step, and the stretching step, It suffices to contain the compound having the radical scavenging function. The concentration of the compound having the radical scavenging function contained in any of the treatment baths cannot be unconditionally determined because it is affected by the number of treatments, the treatment time, the treatment temperature, etc. of each treatment, but the radical scavenger in the polarizing film is trapped. From the viewpoint of efficiently controlling the content of the compound having a function, it is usually preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and 0.1% by weight or more. More preferably, it is preferably 30% by weight or less, more preferably 25% by weight or less, still more preferably 20% by weight or less.
とくに、染色工程、架橋工程、および延伸工程を施した後に、洗浄工程を施す場合、洗浄工程は、染色工程、架橋工程、および延伸工程等での処理条件を考慮したうえで、ヨウ素や前記ラジカル捕捉機能を有する化合物等の成分をポリビニルアルコール系フィルムから溶出、あるいはポリビニルアルコール系フィルムに吸着させることができる観点から、前記ヨウ素や、前記ラジカル捕捉機能を有する化合物の含有量を所望の範囲に調整し易い。
In particular, when the washing step is performed after the dyeing step, the cross-linking step, and the stretching step, the washing step should be performed in consideration of the treatment conditions in the dyeing step, the cross-linking step, the stretching step, and the like. From the viewpoint that components such as compounds having a scavenging function can be eluted from the polyvinyl alcohol-based film or adsorbed to the polyvinyl alcohol-based film, the content of the iodine or the compound having a radical scavenging function is adjusted to a desired range. Easy to do.
さらに、前記膨潤工程、前記染色工程、前記架橋工程、前記延伸工程および前記洗浄工程における各処理浴には、亜鉛塩、ｐＨ調整剤、ｐＨ緩衝剤、その他塩類のような添加剤を含有していてもよい。前記亜鉛塩としては、例えば、塩化亜鉛、ヨウ化亜鉛等のハロゲン化亜鉛；硫酸亜鉛、酢酸亜鉛等の無機亜鉛塩等が挙げられる。前記ｐＨ調整剤としては、例えば、塩酸、硫酸、硝酸等の強酸や、水酸化ナトリウム、水酸化カリウム等の強塩基が挙げられる。前記ｐＨ緩衝剤としては、例えば、酢酸、シュウ酸、クエン酸等のカルボン酸およびその塩や、リン酸、炭酸のような無機弱酸およびその塩が挙げられる。前記その他塩類としては、例えば、塩化ナトリウム、塩化カリウム、塩化バリウム等の塩化物、硝酸ナトリウム、硝酸カリウムのような硝酸塩、硫酸ナトリウム、硫酸カリウムのような硫酸塩、およびアルカリ金属、アルカリ土類金属の塩等が挙げられる。
Further, each treatment bath in the swelling step, the dyeing step, the crosslinking step, the stretching step and the washing step contains an additive such as a zinc salt, a pH adjusting agent, a pH buffering agent and other salts. May be. Examples of the zinc salt include zinc halides such as zinc chloride and zinc iodide; inorganic zinc salts such as zinc sulfate and zinc acetate. Examples of the pH adjuster include strong acids such as hydrochloric acid, sulfuric acid and nitric acid, and strong bases such as sodium hydroxide and potassium hydroxide. Examples of the pH buffer include carboxylic acids such as acetic acid, oxalic acid and citric acid and salts thereof, and weak inorganic acids such as phosphoric acid and carbonic acid and salts thereof. Examples of the other salts include chlorides such as sodium chloride, potassium chloride and barium chloride, nitrates such as sodium nitrate and potassium nitrate, sulfates such as sodium sulfate and potassium sulfate, and alkali metals and alkaline earth metals. Salt etc. are mentioned.
前記膨潤工程は、ポリビニルアルコール系フィルムを、膨潤浴中に浸漬する処理工程であり、ポリビニルアルコール系フィルムの表面の汚れやブロッキング剤等を除去でき、また、ポリビニルアルコール系フィルムを膨潤させることで染色ムラを抑制できる。前記膨潤浴は、通常、水、蒸留水、純水等の水を主成分とする媒体が用いられる。前記膨潤浴は、常法に従って、界面活性剤、アルコール等が適宜に添加されていてもよい。
The swelling step is a treatment step of immersing the polyvinyl alcohol-based film in a swelling bath, which can remove stains and blocking agents on the surface of the polyvinyl alcohol-based film, and can also be dyed by swelling the polyvinyl alcohol-based film. Unevenness can be suppressed. For the swelling bath, a medium containing water as a main component, such as water, distilled water, or pure water, is usually used. To the swelling bath, a surfactant, alcohol, etc. may be appropriately added according to a conventional method.
前記膨潤浴の温度は、１０～６０℃程度であることが好ましく、１５～４５℃程度であることがより好ましく、１８～３０℃程度であることがさらに好ましい。また、前記膨潤浴への浸漬時間は、ポリビニルアルコール系フィルムの膨潤の程度が膨潤浴の温度の影響を受けるため一概に決定できないが、５～３００秒間程度であることが好ましく、１０～２００秒間程度であることがより好ましく、２０～１００秒間程度であることがさらに好ましい。前記膨潤工程は１回だけ実施されてもよく、必要に応じて複数回実施されてもよい。
The temperature of the swelling bath is preferably about 10 to 60 ° C, more preferably about 15 to 45 ° C, and even more preferably about 18 to 30 ° C. The dipping time in the swelling bath cannot be unconditionally determined because the degree of swelling of the polyvinyl alcohol film is affected by the temperature of the swelling bath, but is preferably about 5 to 300 seconds, and preferably 10 to 200 seconds. It is more preferably about 10 to 100 seconds, still more preferably about 20 to 100 seconds. The swelling step may be performed only once, or may be performed multiple times as necessary.
前記染色工程は、ポリビニルアルコール系フィルムを、染色浴（ヨウ素溶液）に浸漬する処理工程であり、ポリビニルアルコール系フィルムに、ヨウ素を吸着・配向させることができる。前記ヨウ素溶液は、通常、ヨウ素水溶液であることが好ましく、ヨウ素および溶解助剤としてヨウ化物を含有する。なお、前記ヨウ化物としては、ヨウ化カリウム、ヨウ化リチウム、ヨウ化ナトリウム、ヨウ化亜鉛、ヨウ化アルミニウム、ヨウ化鉛、ヨウ化銅、ヨウ化バリウム、ヨウ化カルシウム、ヨウ化錫、ヨウ化チタン等が挙げられる。これらの中でも、前記偏光膜中のカリウムの含有量を制御する観点から、ヨウ化カリウムが好適である。
The dyeing step is a step of immersing the polyvinyl alcohol film in a dyeing bath (iodine solution), and iodine can be adsorbed and oriented on the polyvinyl alcohol film. Usually, the iodine solution is preferably an aqueous iodine solution and contains iodine and iodide as a dissolution aid. Examples of the iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and iodide. Examples include titanium. Among these, potassium iodide is preferable from the viewpoint of controlling the content of potassium in the polarizing film.
前記染色浴中、ヨウ素の濃度は、０．０１～１重量％程度であることが好ましく、０．０２～０．５重量％程度であることがより好ましい。前記染色浴中、前記ヨウ化物の濃度は、０．０１～２０重量％程度であることが好ましく、０．０５～１０重量％程度であることがより好ましく、０．１～５重量％程度であることがさらに好ましい。
The iodine concentration in the dyeing bath is preferably about 0.01 to 1% by weight, more preferably about 0.02 to 0.5% by weight. In the dyeing bath, the iodide concentration is preferably about 0.01 to 20% by weight, more preferably about 0.05 to 10% by weight, and about 0.1 to 5% by weight. It is more preferable that there is.
前記染色浴の温度は、１０～５０℃程度であることが好ましく、１５～４５℃程度であることがより好ましく、１８～３０℃程度であることがさらに好ましい。また、前記染色浴への浸漬時間は、ポリビニルアルコール系フィルムの染色の程度が染色浴の温度の影響を受けるため一概に決定できないが、１０～３００秒間程度であることが好ましく、２０～２４０秒間程度であることがより好ましい。前記染色工程は１回だけ実施されてもよく、必要に応じて複数回実施されてもよい。
The temperature of the dyeing bath is preferably about 10 to 50 ° C., more preferably about 15 to 45 ° C., and further preferably about 18 to 30 ° C. The immersion time in the dyeing bath cannot be unconditionally determined because the degree of dyeing of the polyvinyl alcohol film is affected by the temperature of the dyeing bath, but it is preferably about 10 to 300 seconds, and 20 to 240 seconds. It is more preferable that the degree is approximately. The dyeing step may be performed only once, or may be performed multiple times as necessary.
前記架橋工程は、ポリビニルアルコール系フィルムを、ホウ素化合物を含む処理浴（架橋浴）中に浸漬する処理工程であり、ホウ素化合物によりポリビニルアルコール系フィルムが架橋して、ヨウ素分子または染料分子が当該架橋構造に吸着できる。前記ホウ素化合物としては、例えば、ホウ酸、ホウ酸塩、ホウ砂等が挙げられる。前記架橋浴は、水溶液が一般的であるが、例えば、水との混和性のある有機溶媒および水の混合溶液であってもよい。また、前記架橋浴は、前記偏光膜中のカリウムの含有量を制御する観点から、ヨウ化カリウムを含んでいてもよい。
The cross-linking step is a step of immersing the polyvinyl alcohol-based film in a treatment bath containing a boron compound (cross-linking bath), and the polyvinyl alcohol-based film is cross-linked by the boron compound, and the iodine molecule or the dye molecule is cross-linked. Can be adsorbed on the structure. Examples of the boron compound include boric acid, borate, and borax. The cross-linking bath is generally an aqueous solution, but may be, for example, a mixed solution of an organic solvent miscible with water and water. Further, the crosslinking bath may contain potassium iodide from the viewpoint of controlling the content of potassium in the polarizing film.
前記架橋浴中、前記ホウ素化合物の濃度は、１～１５重量％程度であることが好ましく、１．５～１０重量％程度であることがより好ましく、２～５重量％程度であることがより好ましい。また、前記架橋浴にヨウ化カリウムを使用する場合、前記架橋浴中、ヨウ化カリウムの濃度は、１～１５重量％程度であることが好ましく、１．５～１０重量％程度であることがより好ましく、２～５重量％程度であることがより好ましい。
The concentration of the boron compound in the crosslinking bath is preferably about 1 to 15% by weight, more preferably about 1.5 to 10% by weight, and even more preferably about 2 to 5% by weight. preferable. When potassium iodide is used in the crosslinking bath, the concentration of potassium iodide in the crosslinking bath is preferably about 1 to 15% by weight, more preferably about 1.5 to 10% by weight. More preferably, it is more preferably about 2 to 5% by weight.
前記架橋浴の温度は、２０～７０℃程度であることが好ましく、３０～６０℃程度であることがより好ましい。また、前記架橋浴への浸漬時間は、ポリビニルアルコール系フィルムの架橋の程度が架橋浴の温度の影響を受けるため一概に決定できないが、５～３００秒間程度であることが好ましく、１０～２００秒間程度であることがより好ましい。前記架橋工程は１回だけ実施されてもよく、必要に応じて複数回実施されてもよい。
The temperature of the crosslinking bath is preferably about 20 to 70 ° C, more preferably about 30 to 60 ° C. The immersion time in the crosslinking bath cannot be unconditionally determined because the degree of crosslinking of the polyvinyl alcohol film is affected by the temperature of the crosslinking bath, but it is preferably about 5 to 300 seconds, preferably 10 to 200 seconds. It is more preferable that the degree is approximately. The cross-linking step may be performed only once, or may be performed multiple times as necessary.
前記延伸工程は、ポリビニルアルコール系フィルムを、少なくとも一方向に所定の倍率に延伸する処理工程である。一般には、ポリビニルアルコール系フィルムを、搬送方向（長手方向）に１軸延伸する。前記延伸の方法は特に制限されず、湿潤延伸法と乾式延伸法のいずれも採用できる。前記延伸工程は１回だけ実施されてもよく、必要に応じて複数回実施されてもよい。前記延伸工程は、偏光膜の製造において、いずれの段階で行われてもよい。
The stretching step is a treatment step of stretching the polyvinyl alcohol film in at least one direction at a predetermined ratio. Generally, a polyvinyl alcohol film is uniaxially stretched in the transport direction (longitudinal direction). The stretching method is not particularly limited, and either a wet stretching method or a dry stretching method can be adopted. The stretching step may be performed only once, or may be performed multiple times as necessary. The stretching process may be performed at any stage in manufacturing the polarizing film.
前記湿潤延伸法における処理浴（延伸浴）は、通常、水、または水との混和性のある有機溶媒および水の混合溶液等の溶媒を用いることができる。前記延伸浴は、前記偏光膜中の前記カリウムの含有量を制御する観点から、ヨウ化カリウムを含んでいてもよい。前記延伸浴にヨウ化カリウムを使用する場合、当該延伸浴中、ヨウ化カリウムの濃度は、１～１５重量％程度であることが好ましく、２～１０重量％程度であることがより好ましく、３～６重量％程度であることがより好ましい。また、前記処理浴（延伸浴）には、延伸中のフィルム破断を抑制する観点から、前記ホウ素化合物を含むことができ、この場合、当該延伸浴中、前記ホウ素化合物の濃度は、１～１５重量％程度であることが好ましく、１．５～１０重量％程度であることがより好ましく、２～５重量％程度であることがより好ましい。
As the treatment bath (stretching bath) in the wet stretching method, usually, water or a solvent such as a mixed solution of an organic solvent miscible with water and water can be used. The stretching bath may contain potassium iodide from the viewpoint of controlling the content of the potassium in the polarizing film. When potassium iodide is used in the stretching bath, the concentration of potassium iodide in the stretching bath is preferably about 1 to 15% by weight, more preferably about 2 to 10% by weight, and 3 It is more preferably about 6 to 6% by weight. Further, the treatment bath (stretching bath) may contain the boron compound from the viewpoint of suppressing film breakage during stretching, and in this case, the concentration of the boron compound in the stretching bath is 1 to 15. It is preferably about wt%, more preferably about 1.5 to 10 wt%, and even more preferably about 2 to 5 wt%.
前記延伸浴の温度は、２５～８０℃程度であることが好ましく、４０～７５℃程度であることがより好ましく、５０～７０℃程度であることがさらに好ましい。また、前記延伸浴への浸漬時間は、ポリビニルアルコール系フィルムの延伸の程度が延伸浴の温度の影響を受けるため一概に決定できないが、１０～８００秒間程度であることが好ましく、３０～５００秒間程度であることがより好ましい。なお、前記湿潤延伸法における延伸処理は、前記膨潤工程、前記染色工程、前記架橋工程、および前記洗浄工程のいずれか１つ以上の処理工程とともに施してもよい。
The temperature of the stretching bath is preferably about 25 to 80 ° C, more preferably about 40 to 75 ° C, and further preferably about 50 to 70 ° C. The dipping time in the stretching bath cannot be unconditionally determined because the extent of stretching of the polyvinyl alcohol film is affected by the temperature of the stretching bath, but is preferably about 10 to 800 seconds, and preferably 30 to 500 seconds. It is more preferable that the degree is approximately. The stretching treatment in the wet stretching method may be performed together with one or more treatment steps of the swelling step, the dyeing step, the crosslinking step, and the washing step.
前記乾式延伸法としては、例えば、ロール間延伸方法、加熱ロール延伸方法、圧縮延伸方法等が挙げられる。なお、前記乾式延伸法は、前記乾燥工程とともに施してもよい。
Examples of the dry stretching method include a roll stretching method, a heated roll stretching method, and a compression stretching method. The dry stretching method may be performed together with the drying step.
前記ポリビニルアルコール系フィルムに施される総延伸倍率（累積の延伸倍率）は、目的に応じ適宜設定できるが、２～７倍程度であることが好ましく、３～６．８倍程度であることがより好ましく、３．５～６．５倍程度であることがさらに好ましい。
The total draw ratio (cumulative draw ratio) applied to the polyvinyl alcohol film can be appropriately set according to the purpose, but it is preferably about 2 to 7 times, and preferably about 3 to 6.8 times. More preferably, it is more preferably about 3.5 to 6.5 times.
前記洗浄工程は、ポリビニルアルコール系フィルムを、洗浄浴中に浸漬する処理工程であり、ポリビニルアルコール系フィルムの表面等に残存する異物を除去できる。前記洗浄浴は、通常、水、蒸留水、純水等の水を主成分とする媒体が用いられる。また、前記偏光膜中のカリウムの含有量を制御する観点から、前記洗浄浴にヨウ化カリウムを含んでいてもよく、この場合、前記洗浄浴中、ヨウ化カリウムの濃度は、１～１０重量％程度であることが好ましく、１．５～４重量％程度であることがより好ましく、１．８～３．８重量％程度であることがさらに好ましい。
The cleaning step is a treatment step of immersing the polyvinyl alcohol-based film in a cleaning bath, and foreign substances remaining on the surface of the polyvinyl alcohol-based film can be removed. For the cleaning bath, a medium containing water as a main component, such as water, distilled water, or pure water, is usually used. Further, from the viewpoint of controlling the content of potassium in the polarizing film, the cleaning bath may contain potassium iodide. In this case, the concentration of potassium iodide in the cleaning bath is 1 to 10% by weight. %, Preferably about 1.5 to 4% by weight, more preferably about 1.8 to 3.8% by weight.
前記洗浄浴の温度は、５～５０℃程度であることが好ましく、１０～４０℃程度であることがより好ましく、１５～３５℃程度であることがさらに好ましい。また、前記洗浄浴への浸漬時間は、ポリビニルアルコール系フィルムの洗浄の程度が洗浄浴の温度の影響を受けるため一概に決定できないが、１～１００秒間程度であることが好ましく、２～５０秒間程度であることがより好ましく、３～２０秒間程度であることがさらに好ましい。前記膨潤工程は１回だけ実施されてもよく、必要に応じて複数回実施されてもよい。
The temperature of the washing bath is preferably about 5 to 50 ° C, more preferably about 10 to 40 ° C, and further preferably about 15 to 35 ° C. The dipping time in the washing bath cannot be unconditionally determined because the washing degree of the polyvinyl alcohol film is affected by the temperature of the washing bath, but it is preferably about 1 to 100 seconds, and preferably 2 to 50 seconds. It is more preferably about 3 to 20 seconds. The swelling step may be performed only once, or may be performed multiple times as necessary.
本発明の偏光膜の製造方法は、乾燥工程を設けてもよい。前記乾燥工程は、前記洗浄工程にて洗浄されたポリビニルアルコール系フィルムを、乾燥して偏光膜を得る工程であり、乾燥により所望の水分率を有する偏光膜が得られる。前記乾燥は、任意の適切な方法で行われ、例えば、自然乾燥、送風乾燥、加熱乾燥が挙げられる。
The method for producing a polarizing film of the present invention may include a drying step. The drying step is a step of drying the polyvinyl alcohol film washed in the washing step to obtain a polarizing film, and by drying, a polarizing film having a desired moisture content is obtained. The drying is performed by any appropriate method, and examples thereof include natural drying, blast drying, and heat drying.
前記乾燥の温度は、２０～１５０℃程度であることが好ましく、２５～１００℃程度であることがより好ましい。また、前記乾燥の時間は、偏光膜の乾燥の程度が乾燥の温度の影響を受けるため一概に決定できないが、１０～６００秒間程度であることが好ましく、３０～３００秒間程度であることがより好ましい。前記乾燥工程は１回だけ実施されてもよく、必要に応じて複数回実施されてもよい。
The drying temperature is preferably about 20 to 150 ° C, more preferably about 25 to 100 ° C. The drying time cannot be unconditionally determined because the drying degree of the polarizing film is affected by the drying temperature, but is preferably about 10 to 600 seconds, more preferably about 30 to 300 seconds. preferable. The drying step may be performed only once, or may be performed multiple times as necessary.
前記偏光膜は、偏光膜の初期の偏光度を向上させる観点から、厚みが１μｍ以上であることが好ましく、２μｍ以上であることがより好ましく、そして、パネルの反りを防止する観点から、１５μｍ以下であることが好ましく、１０μｍ以下であることがより好ましく、８μｍ以下であることがさらに好ましい。とくに、厚みが８μｍ程度以下の偏光膜を得るためには、前記ポリビニルアルコール系フィルムとして、熱可塑性樹脂基材上に製膜されたポリビニルアルコール系樹脂層を含む積層体を用いる、以下の薄型の偏光膜の製造方法が適用できる。
The polarizing film preferably has a thickness of 1 μm or more, more preferably 2 μm or more, from the viewpoint of improving the initial degree of polarization of the polarizing film, and 15 μm or less from the viewpoint of preventing panel warpage. Is preferable, 10 μm or less is more preferable, and 8 μm or less is further preferable. In particular, in order to obtain a polarizing film having a thickness of about 8 μm or less, a laminated body including a polyvinyl alcohol-based resin layer formed on a thermoplastic resin substrate is used as the polyvinyl alcohol-based film. A method of manufacturing a polarizing film can be applied.
＜薄型の偏光膜の製造方法＞
薄型の偏光膜の製造方法は、長尺状の熱可塑性樹脂基材の片側に、ポリビニルアルコール系樹脂（ＰＶＡ系樹脂）を含むポリビニルアルコール系樹脂層（ＰＶＡ系樹脂層）を形成して積層体とすること、および、積層体に、空中補助延伸処理と、染色処理と、水中延伸処理と、乾燥収縮処理と、をこの順に施すことを含む。とくに、高い光学特性を有する偏光膜を得るためには、空中補助延伸処理（乾式延伸）と、ホウ酸水溶液中での水中延伸処理を組み合わせる、２段延伸の方法が選択される。 <Method for manufacturing thin polarizing film>
A method of manufacturing a thin polarizing film is a laminate in which a polyvinyl alcohol resin layer (PVA resin layer) containing a polyvinyl alcohol resin (PVA resin) is formed on one side of a long thermoplastic resin substrate. And that the laminated body is subjected to an in-air auxiliary stretching treatment, a dyeing treatment, an underwater stretching treatment, and a drying shrinkage treatment in this order. In particular, in order to obtain a polarizing film having high optical properties, a two-stage stretching method is selected in which the auxiliary stretching treatment in air (dry stretching) and the stretching treatment in water in an aqueous boric acid solution are combined.
薄型の偏光膜の製造方法は、長尺状の熱可塑性樹脂基材の片側に、ポリビニルアルコール系樹脂（ＰＶＡ系樹脂）を含むポリビニルアルコール系樹脂層（ＰＶＡ系樹脂層）を形成して積層体とすること、および、積層体に、空中補助延伸処理と、染色処理と、水中延伸処理と、乾燥収縮処理と、をこの順に施すことを含む。とくに、高い光学特性を有する偏光膜を得るためには、空中補助延伸処理（乾式延伸）と、ホウ酸水溶液中での水中延伸処理を組み合わせる、２段延伸の方法が選択される。 <Method for manufacturing thin polarizing film>
A method of manufacturing a thin polarizing film is a laminate in which a polyvinyl alcohol resin layer (PVA resin layer) containing a polyvinyl alcohol resin (PVA resin) is formed on one side of a long thermoplastic resin substrate. And that the laminated body is subjected to an in-air auxiliary stretching treatment, a dyeing treatment, an underwater stretching treatment, and a drying shrinkage treatment in this order. In particular, in order to obtain a polarizing film having high optical properties, a two-stage stretching method is selected in which the auxiliary stretching treatment in air (dry stretching) and the stretching treatment in water in an aqueous boric acid solution are combined.
前記積層体を作製する方法としては、任意の適切な方法が採用され、例えば、前記熱可塑性樹脂基材の表面に、前記ＰＶＡ系樹脂を含む塗布液を塗布し、乾燥することに方法が挙げられる。前記熱可塑性樹脂基材の厚みは、２０～３００μｍ程度であることが好ましく、５０～２００μｍ程度であることがより好ましい。前記ＰＶＡ系樹脂層の厚みは、３～４０μｍ程度であることが好ましく、３～２０μｍ程度であることがより好ましい。
As a method for producing the laminate, any suitable method is adopted, and for example, a method of applying a coating solution containing the PVA-based resin on the surface of the thermoplastic resin substrate and drying the coating solution is mentioned. Be done. The thickness of the thermoplastic resin substrate is preferably about 20 to 300 μm, more preferably about 50 to 200 μm. The thickness of the PVA-based resin layer is preferably about 3 to 40 μm, more preferably about 3 to 20 μm.
前記熱可塑性樹脂基材は、水を吸収して延伸応力を大幅に低下させ、高倍率に延伸することができる観点から、吸水率が０．２％程度以上であることが好ましく、０．３％程度以上であることがより好ましい。一方、前記熱可塑性樹脂基材は、熱可塑性樹脂基材の寸法安定性が著しく低下して、得られる偏光膜の外観が悪化するなどの不具合を防止することができる観点から、吸水率が３％程度以下であることが好ましく、１％程度以下であることがより好ましい。なお、前記吸水率は、例えば、前記熱可塑性樹脂基材の構成材料に変性基を導入することにより調整することができる。前記吸水率は、ＪＩＳ Ｋ ７２０９に準じて求められる値である。
The thermoplastic resin base material preferably has a water absorption rate of about 0.2% or more, from the viewpoint of absorbing water to significantly reduce the stretching stress and allowing stretching to a high ratio, and 0.3. % Or more is more preferable. On the other hand, the thermoplastic resin base material has a water absorption of 3 from the viewpoint that the dimensional stability of the thermoplastic resin base material is remarkably lowered and the appearance of the polarizing film obtained is deteriorated. % Or less, and more preferably about 1% or less. The water absorption can be adjusted, for example, by introducing a modifying group into the constituent material of the thermoplastic resin substrate. The water absorption rate is a value obtained according to JIS K7209.
前記熱可塑性樹脂基材は、ＰＶＡ系樹脂層の結晶化を抑制しながら、積層体の延伸性を十分に確保することができる観点から、ガラス転移温度（Ｔｇ）が１２０℃程度以下であることが好ましい。さらに、水による熱可塑性樹脂基材の可塑化と、水中延伸を良好に行うことを考慮すると、前記ガラス転移温度（Ｔｇ）が１００℃程度以下であることがより好ましく、９０℃程度以下であることがさらに好ましい。一方、熱可塑性樹脂基材のガラス転移温度は、塗布液を塗布・乾燥する際に、熱可塑性樹脂基材が変形するなどの不具合を防止して、良好な積層体を作製することができる観点から、６０℃程度以上であることが好ましい。なお、前記ガラス転移温度は、例えば、前記熱可塑性樹脂基材の構成材料に変性基を導入する、結晶化材料を用いて加熱する、ことにより調整することができる。前記ガラス転移温度（Ｔｇ）は、ＪＩＳ Ｋ ７１２１に準じて求められる値である。
The thermoplastic resin base material has a glass transition temperature (Tg) of about 120 ° C. or lower from the viewpoint of being able to sufficiently secure the stretchability of the laminate while suppressing the crystallization of the PVA-based resin layer. Is preferred. Further, in consideration of the plasticization of the thermoplastic resin substrate with water and the favorable underwater drawing, the glass transition temperature (Tg) is more preferably about 100 ° C. or lower, and about 90 ° C. or lower. Is more preferable. On the other hand, the glass transition temperature of the thermoplastic resin base material is such that when the coating liquid is applied and dried, problems such as deformation of the thermoplastic resin base material can be prevented and a good laminate can be produced. Therefore, the temperature is preferably about 60 ° C. or higher. The glass transition temperature can be adjusted, for example, by introducing a modifying group into the constituent material of the thermoplastic resin substrate or by heating with a crystallization material. The glass transition temperature (Tg) is a value determined according to JIS K7121.
前記熱可塑性樹脂基材の構成材料としては、任意の適切な熱可塑性樹脂が採用され得る。前記熱可塑性樹脂としては、例えば、ポリエチレンテレフタレート系樹脂等のエステル系樹脂、ノルボルネン系樹脂等のシクロオレフィン系樹脂、ポリプロピレン等のオレフィン系樹脂、ポリアミド系樹脂、ポリカーボネート系樹脂、これらの共重合体樹脂等が挙げられる。これらの中でも、ノルボルネン系樹脂、非晶質（非晶性）のポリエチレンテレフタレート系樹脂が好ましく、さらに、熱可塑性樹脂基材は延伸性に極めて優れるとともに、延伸時の結晶化が抑制され得る観点から、非晶質（非晶性）ポリエチレンテレフタレート系樹脂が好ましく用いられる。非晶質（非晶性）のポリエチレンテレフタレート系樹脂としては、ジカルボン酸としてイソフタル酸および／またはシクロヘキサンジカルボン酸を含む共重合体や、グリコールとしてシクロヘキサンジメタノールやジエチレングリコールを含む共重合体が挙げられる。
Any appropriate thermoplastic resin can be adopted as the constituent material of the thermoplastic resin base material. Examples of the thermoplastic resin include ester resins such as polyethylene terephthalate resins, cycloolefin resins such as norbornene resins, olefin resins such as polypropylene, polyamide resins, polycarbonate resins, and copolymer resins thereof. Etc. Among these, norbornene-based resins and amorphous (amorphous) polyethylene terephthalate-based resins are preferable. Further, the thermoplastic resin base material has extremely excellent stretchability, and from the viewpoint that crystallization during stretching can be suppressed. Amorphous (non-crystalline) polyethylene terephthalate resin is preferably used. Examples of the amorphous (amorphous) polyethylene terephthalate-based resin include a copolymer containing isophthalic acid and / or cyclohexanedicarboxylic acid as a dicarboxylic acid, and a copolymer containing cyclohexanedimethanol or diethylene glycol as a glycol.
前記熱可塑性樹脂基材は、ＰＶＡ系樹脂層を形成する前に、表面処理（例えば、コロナ処理等）を施してもよいし、熱可塑性樹脂基材上に易接着層を形成してもよい。このような処理を行うことにより、熱可塑性樹脂基材とＰＶＡ系樹脂層との密着性を向上させることができる。また、前記熱可塑性樹脂基材は、ＰＶＡ系樹脂層を形成する前に、延伸されていてもよい。
The thermoplastic resin substrate may be subjected to a surface treatment (for example, corona treatment) before forming the PVA-based resin layer, or an easy adhesion layer may be formed on the thermoplastic resin substrate. . By performing such a treatment, it is possible to improve the adhesion between the thermoplastic resin substrate and the PVA-based resin layer. The thermoplastic resin substrate may be stretched before forming the PVA-based resin layer.
前記塗布液は、ＰＶＡ系樹脂を溶媒に溶解させた溶液である。前記溶媒としては、例えば、水、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ－メチルピロリドン、各種グリコール類、トリメチロールプロパン等の多価アルコール類、エチレンジアミン、ジエチレントリアミン等のアミン類が挙げられ、水が好ましい。これらは単独で、または、二種以上組み合わせて用いることができる。前記塗布液のＰＶＡ系樹脂濃度は、熱可塑性樹脂基材に密着した均一な塗布膜を形成することができる観点から、溶媒１００重量部に対して、３～２０重量部程度であることが好ましい。
The above coating solution is a solution of PVA resin dissolved in a solvent. Examples of the solvent include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various glycols, polyhydric alcohols such as trimethylolpropane, amines such as ethylenediamine and diethylenetriamine, and water. preferable. These can be used alone or in combination of two or more. The concentration of the PVA-based resin in the coating liquid is preferably about 3 to 20 parts by weight based on 100 parts by weight of the solvent, from the viewpoint of forming a uniform coating film in close contact with the thermoplastic resin substrate. ..
前記塗布液には、延伸によるポリビニルアルコール分子の配向性を向上させる観点から、ハロゲン化物が配合されていることが好ましい。前記ハロゲン化物としては、任意の適切なハロゲン化物が採用でき、例えば、ヨウ化物および塩化ナトリウム等が挙げられる。前記ヨウ化物としては、例えば、ヨウ化カリウム、ヨウ化ナトリウム、ヨウ化リチウム等が挙げられ、ヨウ化カリウムが好ましい。前記塗布液中の前記ハロゲン化物の濃度は、ＰＶＡ系樹脂１００重量部に対して、５～２０重量部程度であることが好ましく、１０～１５重量部程度であることがより好ましい。
From the viewpoint of improving the orientation of polyvinyl alcohol molecules by stretching, it is preferable that the coating liquid contains a halide. Any appropriate halide can be adopted as the halide, and examples thereof include iodide and sodium chloride. Examples of the iodide include potassium iodide, sodium iodide, lithium iodide and the like, and potassium iodide is preferable. The concentration of the halide in the coating liquid is preferably about 5 to 20 parts by weight, more preferably about 10 to 15 parts by weight, based on 100 parts by weight of the PVA-based resin.
また、前記塗布液には、添加剤を配合してもよい。前記添加剤としては、例えば、エチレングリコールやグリセリン等の可塑剤；非イオン界面活性剤等の界面活性剤等が挙げられる。
Also, additives may be added to the coating liquid. Examples of the additives include plasticizers such as ethylene glycol and glycerin; surfactants such as nonionic surfactants.
前記塗布液の塗布方法としては、任意の適切な方法を採用することができ、例えば、ロールコート法、スピンコート法、ワイヤーバーコート法、ディップコート法、ダイコート法、カーテンコート法、スプレーコート法、ナイフコート法（コンマコート法等）等が挙げられる。また、前記塗布液の乾燥温度は、５０℃程度以上であることが好ましい。
Any appropriate method can be adopted as a method for applying the coating solution, and examples thereof include a roll coating method, a spin coating method, a wire bar coating method, a dip coating method, a die coating method, a curtain coating method, and a spray coating method. , Knife coating method (comma coating method, etc.) and the like. The drying temperature of the coating liquid is preferably about 50 ° C or higher.
前記空中補助延伸処理は、熱可塑性樹脂基材の結晶化を抑制しながら延伸することができるため、積層体を高倍率に延伸することができる。前記空中補助延伸処理の延伸方法は、固定端延伸（例えば、テンター延伸機を用いて延伸する方法）でもよいし、自由端延伸（例えば、周速の異なるロール間に積層体を通して一軸延伸する方法）でもよいが、高い光学特性を得る観点から、自由端延伸が好ましい。
The above-mentioned in-air auxiliary stretching treatment enables stretching while suppressing crystallization of the thermoplastic resin substrate, so that the laminate can be stretched at a high ratio. The stretching method of the in-air auxiliary stretching treatment may be fixed-end stretching (for example, a stretching method using a tenter stretching machine) or free-end stretching (for example, a uniaxial stretching method in which a laminate is passed between rolls having different peripheral speeds). ) May be used, but free-end stretching is preferable from the viewpoint of obtaining high optical characteristics.
前記空中補助延伸における延伸倍率は、２～３．５倍程度であることが好ましい。前記空中補助延伸は、一段階で行ってもよいし、多段階で行ってもよい。多段階で行う場合、延伸倍率は、各段階の延伸倍率の積である。
The draw ratio in the in-air auxiliary drawing is preferably about 2 to 3.5 times. The in-air auxiliary stretching may be performed in one step or in multiple steps. When performing in multiple stages, the draw ratio is the product of the draw ratios of the respective stages.
前記空中補助延伸における延伸温度は、熱可塑性樹脂基材の形成材料、延伸方式等に応じて、任意の適切な値に設定することができ、例えば、熱可塑性樹脂基材のガラス転移温度（Ｔｇ）以上であることが好ましく、前記ガラス転移温度（Ｔｇ）＋１０℃以上であることがより好ましく、前記ガラス転移温度（Ｔｇ）＋１５℃以上であることがさらに好ましい。一方、延伸温度の上限は、ＰＶＡ系樹脂の結晶化が急速に進むのを抑制して、結晶化による不具合（例えば、延伸によるＰＶＡ系樹脂層の配向を妨げる）を抑制することができる観点から、１７０℃程度であることが好ましい。
The stretching temperature in the in-air auxiliary stretching can be set to any appropriate value depending on the forming material of the thermoplastic resin substrate, the stretching method, and the like. For example, the glass transition temperature (Tg of the thermoplastic resin substrate). ) Or more, more preferably the glass transition temperature (Tg) + 10 ° C. or more, still more preferably the glass transition temperature (Tg) + 15 ° C. or more. On the other hand, the upper limit of the stretching temperature is from the viewpoint that the crystallization of the PVA-based resin can be prevented from rapidly progressing and defects due to crystallization (for example, hindering the orientation of the PVA-based resin layer due to the stretching) can be suppressed. It is preferably about 170 ° C.
必要に応じて、前記空中補助延伸処理の後、染色処理や水中延伸処理の前に、不溶化処理を施してもよい。前記不溶化処理は、代表的には、ホウ酸水溶液にＰＶＡ系樹脂層を浸漬することにより行う。不溶化処理を施すことにより、ＰＶＡ系樹脂層に耐水性を付与し、水に浸漬した時のＰＶＡの配向低下を防止することができる。当該ホウ酸水溶液の濃度は、水１００重量部に対して、１～５重量部程度であることが好ましい。不溶化処理浴の液温は、２０～５０℃程度であることが好ましい。
If necessary, an insolubilization treatment may be performed after the aerial auxiliary stretching treatment and before the dyeing treatment or the underwater stretching treatment. The insolubilization treatment is typically performed by immersing the PVA-based resin layer in an aqueous boric acid solution. By performing the insolubilization treatment, it is possible to impart water resistance to the PVA-based resin layer and prevent the orientation of PVA from being lowered when immersed in water. The concentration of the boric acid aqueous solution is preferably about 1 to 5 parts by weight with respect to 100 parts by weight of water. The solution temperature of the insolubilization bath is preferably about 20 to 50 ° C.
前記染色処理は、ＰＶＡ系樹脂層をヨウ素で染色することにより行う。当該吸着方法としては、例えば、ヨウ素を含む染色液にＰＶＡ系樹脂層（積層体）を浸漬させる方法、ＰＶＡ系樹脂層に当該染色液を塗工する方法、当該染色液をＰＶＡ系樹脂層に噴霧する方法等が挙げられ、ヨウ素を含む染色液にＰＶＡ系樹脂層（積層体）を浸漬させる方法が好ましい。
The dyeing process is performed by dyeing the PVA resin layer with iodine. Examples of the adsorption method include a method of immersing the PVA-based resin layer (laminate) in a dyeing solution containing iodine, a method of applying the dyeing solution to the PVA-based resin layer, and a method of applying the dyeing solution to the PVA-based resin layer. Examples thereof include a method of spraying, and a method of immersing the PVA-based resin layer (laminate) in a dyeing solution containing iodine is preferable.
前記染色浴におけるヨウ素の配合量は、水１００重量部に対して、０．０５～０．５重量部程度であることが好ましい。ヨウ素の水に対する溶解度を高めるため、ヨウ素水溶液に前記ヨウ化物を配合することが好ましい。前記ヨウ化物の配合量は、水１００重量部に対して、０．１～１０重量部程度であることが好ましく、０．３～５重量部程度であることがより好ましい。染色浴の液温は、ＰＶＡ系樹脂の溶解を抑制するため、２０～５０℃程度であることが好ましい。また、浸漬時間は、ＰＶＡ系樹脂層の透過率を確保する観点から、５秒～５分程度であることが好ましく、３０秒～９０秒程度であることがより好ましい。良好な光学特性を有する偏光膜を得る観点から、ヨウ素水溶液におけるヨウ素およびヨウ化物の含有量の比が、１：５～１：２０程度であることが好ましく、１：５～１：１０程度であることがより好ましい。
The blending amount of iodine in the dyeing bath is preferably about 0.05 to 0.5 parts by weight with respect to 100 parts by weight of water. In order to increase the solubility of iodine in water, it is preferable to add the iodide to the aqueous iodine solution. The iodide content is preferably about 0.1 to 10 parts by weight, and more preferably about 0.3 to 5 parts by weight, based on 100 parts by weight of water. The liquid temperature of the dyeing bath is preferably about 20 to 50 ° C. in order to suppress dissolution of the PVA-based resin. Further, the immersion time is preferably about 5 seconds to 5 minutes, and more preferably about 30 seconds to 90 seconds, from the viewpoint of ensuring the transmittance of the PVA-based resin layer. From the viewpoint of obtaining a polarizing film having good optical properties, the ratio of the iodine and iodide contents in the iodine aqueous solution is preferably about 1: 5 to 1:20, and about 1: 5 to 1:10. More preferably.
必要に応じて、染色処理の後、水中延伸処理の前に、架橋処理を施してもよい。前記架橋処理は、代表的には、ホウ酸水溶液にＰＶＡ系樹脂層を浸漬させることにより行う。架橋処理を施すことにより、ＰＶＡ系樹脂層に耐水性を付与し、後の水中延伸で、高温の水中へ浸漬した際のＰＶＡの配向低下を防止することができる。当該ホウ酸水溶液のホウ酸濃度は、水１００重量部に対して、１～５重量部程度であることが好ましい。また、架橋処理を行う場合、さらに、架橋処理のおける架橋浴には前記ヨウ化物を配合することが好ましい。前記ヨウ化物を配合することにより、ＰＶＡ系樹脂層に吸着させたヨウ素の溶出を抑制することができる。前記ヨウ化物の配合量は、水１００重量部に対して、１～５重量部程度であることが好ましい。架橋浴（ホウ酸水溶液）の液温は、２０～５０℃程度であることが好ましい。
If necessary, a crosslinking treatment may be applied after the dyeing treatment and before the underwater stretching treatment. The cross-linking treatment is typically performed by immersing the PVA-based resin layer in an aqueous boric acid solution. By performing the cross-linking treatment, it is possible to impart water resistance to the PVA-based resin layer and prevent the PVA from lowering in orientation when it is immersed in high-temperature water in the subsequent underwater stretching. The boric acid concentration of the aqueous boric acid solution is preferably about 1 to 5 parts by weight with respect to 100 parts by weight of water. When the crosslinking treatment is carried out, it is preferable that the above-mentioned iodide is further added to the crosslinking bath for the crosslinking treatment. By blending the iodide, the elution of iodine adsorbed on the PVA-based resin layer can be suppressed. The iodide content is preferably about 1 to 5 parts by weight with respect to 100 parts by weight of water. The liquid temperature of the crosslinking bath (boric acid aqueous solution) is preferably about 20 to 50 ° C.
前記水中延伸処理は、積層体を延伸浴に浸漬させて行う。水中延伸処理によれば、上記熱可塑性樹脂基材やＰＶＡ系樹脂層のガラス転移温度（代表的には、８０℃程度）よりも低い温度で延伸でき、ＰＶＡ系樹脂層を、その結晶化を抑えながら、高倍率に延伸することができる。前記水中延伸処理の延伸方法は、固定端延伸（たとえば、テンター延伸機を用いて延伸する方法）でもよいし、自由端延伸（たとえば、周速の異なるロール間に積層体を通して一軸延伸する方法）でもよいが、高い光学特性を得る観点から、自由端延伸が好ましい。
The above-mentioned underwater stretching treatment is performed by immersing the laminate in a stretching bath. By the underwater stretching treatment, it is possible to stretch at a temperature lower than the glass transition temperature (typically about 80 ° C.) of the thermoplastic resin substrate or the PVA type resin layer, and the PVA type resin layer is crystallized. It can be stretched to a high magnification while suppressing it. The stretching method of the underwater stretching treatment may be fixed-end stretching (for example, stretching with a tenter stretching machine) or free-end stretching (for example, uniaxial stretching through a laminate between rolls having different peripheral speeds). However, free-end stretching is preferable from the viewpoint of obtaining high optical characteristics.
前記水中延伸処理は、ホウ酸水溶液中に積層体を浸漬させて行うこと（ホウ酸水中延伸）が好ましい。延伸浴としてホウ酸水溶液を用いることで、ＰＶＡ系樹脂層に、延伸時にかかる張力に耐える剛性と、水に溶解しない耐水性とを付与することができる。ホウ酸水溶液のホウ酸濃度は、水１００重量部に対して、１～１０重量部であることが好ましく、２．５～６重量部であることがより好ましい。また、前記延伸浴（ホウ酸水溶液）には、ヨウ化物を配合してもよい。延伸浴の液温は、４０～８５℃程度であることが好ましく、６０℃～７５℃程度であることがより好ましい。積層体の延伸浴への浸漬時間は、１５秒～５分程度であることが好ましい。
The above-mentioned underwater stretching treatment is preferably performed by immersing the laminate in a boric acid aqueous solution (boric acid underwater stretching). By using an aqueous boric acid solution as the stretching bath, the PVA-based resin layer can be provided with rigidity that can withstand the tension applied during stretching and water resistance that does not dissolve in water. The boric acid concentration of the boric acid aqueous solution is preferably 1 to 10 parts by weight, and more preferably 2.5 to 6 parts by weight with respect to 100 parts by weight of water. Moreover, you may mix | blend an iodide with the said drawing bath (boric-acid aqueous solution). The liquid temperature of the stretching bath is preferably about 40 to 85 ° C, more preferably about 60 to 75 ° C. The immersion time of the laminate in the stretching bath is preferably about 15 seconds to 5 minutes.
前記水中延伸における延伸倍率は、１．５倍程度以上であることが好ましく、３倍程度以上であることがより好ましい。
The draw ratio in the underwater stretching is preferably about 1.5 times or more, more preferably about 3 times or more.
なお、積層体の総延伸倍率は、積層体の元長に対して、５倍程度以上であることが好ましく、５．５倍程度以上であることがより好ましい。
Note that the total draw ratio of the laminate is preferably about 5 times or more, more preferably about 5.5 times or more of the original length of the laminate.
前記乾燥収縮処理は、ゾーン全体を加熱して行うゾーン加熱により行ってもよく、搬送ロールを加熱する（いわゆる加熱ロールを用いる）ことにより行ってもよいが。好ましくは、その両方を用いる。加熱ロールを用いて乾燥させることにより、効率的に積層体の加熱カールを抑制して、外観に優れた偏光膜を製造することができ、また、積層体を平らな状態に維持しながら乾燥できるので、カールだけでなくシワの発生も抑制することができる。また、乾燥収縮処理の際、幅方向に収縮させることにより、得られる偏光膜の光学特性を向上させることができる観点から、乾燥収縮処理による積層体の幅方向の収縮率は、１～１０％程度であることが好ましく、２～８％程度であることがより好ましい。
The drying shrinkage treatment may be performed by zone heating performed by heating the entire zone, or by heating the transport roll (using a so-called heating roll). Both are preferably used. By drying using a heating roll, it is possible to efficiently suppress the heating curl of the laminate to produce a polarizing film having an excellent appearance, and it is possible to dry while maintaining the laminate in a flat state. Therefore, not only curling but also generation of wrinkles can be suppressed. Further, in the drying shrinkage treatment, the shrinkage in the width direction of the laminate due to the drying shrinkage treatment is 1 to 10% from the viewpoint that the optical properties of the obtained polarizing film can be improved by shrinking in the width direction. The degree is preferably about 2 to 8%, and more preferably about 2 to 8%.
搬送ロールの加熱温度（加熱ロールの温度）、加熱ロールの数、加熱ロールとの接触時間等を調整することにより、乾燥条件を制御することができる。加熱ロールの温度は、６０～１２０℃程度であることが好ましく、６５～１００℃程度であることがより好ましく、７０～８０℃であることがさらに好ましい。熱可塑性樹脂の結晶化度を良好に増加させて、カールを良好に抑制することができる観点から、搬送ロールは、通常２個～４０個程度、好ましくは４個～３０個程度設けられる。積層体と加熱ロールとの接触時間（総接触時間）は、１～３００秒程度であることが好ましく、１～２０秒であることがより好ましく、１～１０秒であることがさらに好ましい。
The drying conditions can be controlled by adjusting the heating temperature of the transfer rolls (heating roll temperature), the number of heating rolls, the contact time with the heating rolls, and the like. The temperature of the heating roll is preferably about 60 to 120 ° C, more preferably about 65 to 100 ° C, and further preferably 70 to 80 ° C. From the viewpoint that the crystallinity of the thermoplastic resin can be increased satisfactorily and curling can be suppressed satisfactorily, the number of transport rolls is usually about 2 to 40, preferably about 4 to 30. The contact time (total contact time) between the laminate and the heating roll is preferably about 1 to 300 seconds, more preferably 1 to 20 seconds, and further preferably 1 to 10 seconds.
加熱ロールは、加熱炉内に設けてもよいし、通常の製造ライン（室温環境下）に設けてもよい。好ましくは、送風手段を備える加熱炉内に設けられる。加熱ロールによる乾燥と熱風乾燥とを併用することにより、加熱ロール間での急峻な温度変化を抑制することができ、幅方向の収縮を容易に制御することができる。熱風乾燥の温度は、３０～１００℃程度であることが好ましい。また、熱風乾燥時間は、１～３００秒程度であることが好ましい。
The heating roll may be installed in the heating furnace or in a normal production line (under room temperature environment). Preferably, it is provided in a heating furnace equipped with a blowing means. By using the drying with the heating roll and the hot air drying together, a sharp temperature change between the heating rolls can be suppressed, and the shrinkage in the width direction can be easily controlled. The hot air drying temperature is preferably about 30 to 100 ° C. The hot air drying time is preferably about 1 to 300 seconds.
水中延伸処理の後、乾燥収縮処理の前に、洗浄処理を施すことが好ましい。前記洗浄処理は、代表的には、ヨウ化カリウム水溶液にＰＶＡ系樹脂層を浸漬させることにより行う。
After the underwater stretching treatment, it is preferable to perform a washing treatment before the drying shrinkage treatment. The cleaning treatment is typically performed by immersing the PVA-based resin layer in an aqueous potassium iodide solution.
また、前記ラジカル捕捉機能を有する化合物を含む薄型の偏光膜を製造する場合、染色処理、水中延伸処理、不溶化処理、架橋処理、および洗浄処理のいずれか１つ以上の処理浴には、前記ラジカル捕捉機能を有する化合物を含有すればよい。前記各処理浴のいずれかに含まれる前記ラジカル捕捉機能を有する化合物の濃度は、各処理の処理回数、処理時間、処理温度等の影響を受けるため一概に決定できないが、偏光膜中のラジカル捕捉機能を有する化合物の含有量を効率よく制御できる観点から、通常、０．０１重量％以上であることが好ましく、０．０５重量％以上であることがより好ましく、０．１重量％以上であることがさらに好ましく、そして、３０重量％以下であることが好ましく、２５重量％以下であることがより好ましく、２０重量％以下であることがさらに好ましい。
Further, in the case of producing a thin polarizing film containing a compound having a radical scavenging function, any one or more treatment baths of dyeing treatment, underwater stretching treatment, insolubilization treatment, crosslinking treatment, and washing treatment may contain the radical A compound having a trapping function may be contained. The concentration of the compound having the radical scavenging function contained in any of the treatment baths cannot be unconditionally determined because it is affected by the number of treatments, the treatment time, the treatment temperature, etc. of each treatment, but the radical scavenger in the polarizing film is trapped. From the viewpoint of efficiently controlling the content of the compound having a function, it is usually preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and 0.1% by weight or more. More preferably, it is preferably 30% by weight or less, more preferably 25% by weight or less, still more preferably 20% by weight or less.
とくに洗浄処理を施す場合、洗浄処理は、染色処理、水中延伸処理等での処理条件を考慮したうえで、ヨウ素や前記ラジカル捕捉機能を有する化合物等の成分をポリビニルアルコール系フィルムから溶出、あるいはポリビニルアルコール系フィルムに吸着させることができる観点から、前記ヨウ素や、前記ラジカル捕捉機能を有する化合物の含有量を所望の範囲に調整し易い。
In particular, when the washing treatment is performed, the washing treatment may be performed by dyeing treatment, underwater stretching treatment, and the like, and then the components such as iodine and the compound having the radical scavenging function are eluted from the polyvinyl alcohol-based film, or polyvinyl. From the viewpoint of being able to be adsorbed on the alcohol-based film, the content of the iodine or the compound having the radical scavenging function can be easily adjusted to a desired range.
＜偏光フィルム＞
本発明の偏光フィルムは、前記偏光膜の少なくとも一方の面に透明保護フィルムが貼り合わされているものである。 <Polarizing film>
In the polarizing film of the present invention, a transparent protective film is attached to at least one surface of the polarizing film.
本発明の偏光フィルムは、前記偏光膜の少なくとも一方の面に透明保護フィルムが貼り合わされているものである。 <Polarizing film>
In the polarizing film of the present invention, a transparent protective film is attached to at least one surface of the polarizing film.
前記透明保護フィルムは、特に制限されず、偏光フィルムに用いられている各種の透明保護フィルムを用いることができる。前記透明保護フィルムを構成する材料としては、例えば、透明性、機械的強度、熱安定性、水分遮断性、等方性等に優れる熱可塑性樹脂が用いられる。前記熱可塑性樹脂としては、例えば、トリアセチルセルロール等のセルロールエステル系樹脂、ポリエチレンテレフタレートやポリエチレンナフタレート等のポリエステル系樹脂、ポリエーテルスルホン系樹脂、ポリスルホン系樹脂、ポリカーボネート系樹脂、ナイロンや芳香族ポリアミド等のポリアミド系樹脂、ポリイミド系樹脂、ポリエチレン、ポリプロピレン、エチレン・プロピレン共重合体の如きポリオレフィン系樹脂、（メタ）アクリル系樹脂、シクロ系ないしはノルボルネン構造を有する環状ポリオレフィン系樹脂（ノルボルネン系樹脂）、ポリアリレート系樹脂、ポリスチレン系樹脂、ポリビニルアルコール系樹脂、およびこれらの混合物があげられる。また、前記透明保護フィルムは、（メタ）アクリル系、ウレタン系、アクリルウレタン系、エポキシ系、シリコーン系等の熱硬化性樹脂または紫外線硬化型樹脂から形成される硬化層を用いることができる。これらの中でも、セルロールエステル系樹脂、ポリカーボネート系樹脂、（メタ）アクリル系樹脂、環状ポリオレフィン系樹脂、ポリエステル系樹脂が好適である。
The transparent protective film is not particularly limited, and various transparent protective films used for polarizing films can be used. As a material forming the transparent protective film, for example, a thermoplastic resin having excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropic property, etc. is used. Examples of the thermoplastic resin include cellulose ester resins such as triacetyl cellulose, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyether sulfone resins, polysulfone resins, polycarbonate resins, nylon and aroma. Polyamide resins such as group polyamides, polyimide resins, polyolefin resins such as polyethylene, polypropylene and ethylene-propylene copolymers, (meth) acrylic resins, cyclo polyolefin resins having a norbornene structure (norbornene resins) ), Polyarylate-based resins, polystyrene-based resins, polyvinyl alcohol-based resins, and mixtures thereof. Further, the transparent protective film may use a cured layer formed of a thermosetting resin such as a (meth) acrylic resin, a urethane resin, an acryl urethane resin, an epoxy resin, a silicone resin or an ultraviolet curable resin. Among these, a cellulose ester resin, a polycarbonate resin, a (meth) acrylic resin, a cyclic polyolefin resin, and a polyester resin are preferable.
前記透明保護フィルムの厚さは、適宜に決定しうるが、一般には強度や取扱性等の作業性、薄層性等の観点から、１～５００μｍ程度であることが好ましく、１～３００μｍ程度あることがより好ましく、５～１００μｍ程度であることがさらに好ましい。
The thickness of the transparent protective film can be appropriately determined, but generally, from the viewpoint of workability such as strength and handleability, thin layer property, etc., it is preferably about 1 to 500 μm, and about 1 to 300 μm. More preferably, it is more preferably about 5 to 100 μm.
前記透明保護フィルムを、前記偏光膜の両面に貼り合わせる場合、その両面の透明保護フィルムは、同じものであってもよく、異なっていてもよい。
When the transparent protective films are attached to both sides of the polarizing film, the transparent protective films on both sides may be the same or different.
前記透明保護フィルムは、正面位相差が４０ｎｍ以上および／または、厚み方向位相差が８０ｎｍ以上の位相差を有する位相差板を用いることができる。正面位相差は、通常、４０～２００ｎｍの範囲に、厚み方向位相差は、通常、８０～３００ｎｍの範囲に制御される。前記透明保護フィルムとして位相差板を用いる場合には、当該位相差板が透明保護フィルムとしても機能するため、薄型化を図ることができる。
As the transparent protective film, a retardation plate having a front surface retardation of 40 nm or more and / or a thickness direction retardation of 80 nm or more can be used. The front retardation is usually controlled in the range of 40 to 200 nm, and the thickness direction retardation is usually controlled in the range of 80 to 300 nm. When a retardation plate is used as the transparent protective film, the retardation plate also functions as a transparent protective film, so that the thickness can be reduced.
前記位相差板としては、例えば、高分子素材を一軸または二軸延伸処理してなる複屈折性フィルム、液晶ポリマーの配向フィルム、液晶ポリマーの配向層をフィルムにて支持したもの等が挙げられる。位相差板の厚さは特に制限されないが、２０～１５０μｍ程度が一般的である。なお、位相差を有しない透明保護フィルムに前記位相板を貼り合わせて使用してもよい。
Examples of the retardation plate include a birefringent film obtained by uniaxially or biaxially stretching a polymer material, a liquid crystal polymer alignment film, and a liquid crystal polymer alignment layer supported by a film. The thickness of the retardation plate is not particularly limited, but is generally about 20 to 150 μm. The phase plate may be attached to a transparent protective film having no retardation.
前記透明保護フィルムには、紫外線吸収剤、酸化防止剤、滑剤、可塑剤、離型剤、着色防止剤、難燃剤、帯電防止剤、顔料、着色剤等の任意の適切な添加剤を含んでいてもよい。とくに、前記透明保護フィルムに紫外線吸収剤を含む場合、偏光フィルムの耐光性を向上できる。
The transparent protective film contains any appropriate additive such as an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a release agent, an anti-coloring agent, a flame retardant, an antistatic agent, a pigment and a colorant. You may stay. In particular, when the transparent protective film contains an ultraviolet absorber, the light resistance of the polarizing film can be improved.
前記透明保護フィルムの偏光膜を貼り合わせない面には、ハードコート層、反射防止層、スティッキング防止層、拡散層やアンチグレア層等の機能層を設けることができる。なお、上記ハードコート層、反射防止層、スティッキング防止層、拡散層やアンチグレア層等の機能層は、保護フィルムそのものに設けることができるほか、別途、保護フィルムとは別体のものとして設けることもできる。
A functional layer such as a hard coat layer, an antireflection layer, an antisticking layer, a diffusion layer or an antiglare layer can be provided on the surface of the transparent protective film on which the polarizing film is not attached. The hard coat layer, the antireflection layer, the antisticking layer, the functional layer such as the diffusion layer and the antiglare layer may be provided on the protective film itself, or may be provided separately from the protective film. it can.
前記偏光膜と前記透明保護フィルム、あるいは前記偏光膜と前記機能層は、通常、粘着剤層または接着剤層を介して貼り合わされる。
The polarizing film and the transparent protective film, or the polarizing film and the functional layer are usually attached via an adhesive layer or an adhesive layer.
前記粘着剤層を形成する粘着剤としては、偏光フィルムに用いられている各種の粘着剤を適用でき、例えば、ゴム系粘着剤、アクリル系粘着剤、シリコーン系粘着剤、ウレタン系粘着剤、ビニルアルキルエーテル系粘着剤、ポリビニルアルコール系粘着剤、ポリビニルポロリドン系粘着剤、ポリアクリルアミド系粘着剤、セルロース系粘着剤等が挙げられる。これらの中でも、アクリル系粘着剤が好適である。
As the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer, various pressure-sensitive adhesives used in polarizing films can be applied, and examples thereof include rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, and vinyl-based pressure-sensitive adhesives. Examples thereof include alkyl ether-based adhesives, polyvinyl alcohol-based adhesives, polyvinylporolidone-based adhesives, polyacrylamide-based adhesives, and cellulose-based adhesives. Among these, acrylic adhesives are suitable.
粘着剤層を形成する方法としては、例えば、前記粘着剤を剥離処理したセパレータ等に塗布し、乾燥して粘着剤層を形成した後に、偏光膜等に転写する方法、または前記粘着剤を偏光膜等に塗布し、乾燥して粘着剤層を形成する方法等が例示できる。前記粘着剤層の厚さは、特に制限されず、例えば、１～１００μｍ程度であり、２～５０μｍ程度であることが好ましい。
As a method of forming the pressure-sensitive adhesive layer, for example, a method of applying the pressure-sensitive adhesive to a release-treated separator or the like, forming a pressure-sensitive adhesive layer by drying, and then transferring to a polarizing film, or the pressure-sensitive adhesive is polarized. Examples thereof include a method of forming a pressure-sensitive adhesive layer by applying it on a film or the like and drying it. The thickness of the pressure-sensitive adhesive layer is not particularly limited and is, for example, about 1 to 100 μm, preferably about 2 to 50 μm.
前記接着剤層を形成する接着剤としては、偏光フィルムに用いられている各種の接着剤を適用でき、例えば、イソシアネート系接着剤、ポリビニルアルコール系接着剤、ゼラチン系接着剤、ビニル系ラテックス系、水系ポリエステル等が挙げられる。これら接着剤は、通常、水溶液からなる接着剤（水系接着剤）として用いられ、０．５～６０重量％の固形分を含有してなる。
As the adhesive forming the adhesive layer, various adhesives used in polarizing films can be applied, for example, isocyanate adhesives, polyvinyl alcohol adhesives, gelatin adhesives, vinyl latex adhesives, Examples include water-based polyester. These adhesives are usually used as an adhesive composed of an aqueous solution (water-based adhesive) and contain a solid content of 0.5 to 60% by weight.
前記水系接着剤は、架橋剤を含んでいてもよい。前記架橋剤としては、通常、接着剤を構成するポリマー等の成分と反応性を有する官能基を１分子中に少なくとも２つ有する化合物が用いられ、例えば、アルキレンジアミン類；イソシアネート類；エポキシ類；アルデヒド類；メチロール尿素、メチロールメラミン等のアミノ－ホルムアルデヒド等が挙げられる。接着剤中の架橋剤の配合量は、接着剤を構成するポリマー等の成分１００重量部に対して、通常、１０～６０重量部程度である。
The water-based adhesive may contain a crosslinking agent. As the cross-linking agent, a compound having at least two functional groups reactive with a component such as a polymer constituting an adhesive in one molecule is usually used, and examples thereof include alkylenediamines; isocyanates; epoxies; Aldehydes; amino-formaldehyde and the like such as methylol urea and methylol melamine. The compounding amount of the crosslinking agent in the adhesive is usually about 10 to 60 parts by weight with respect to 100 parts by weight of the components such as the polymer constituting the adhesive.
前記接着剤としては、上記の他、紫外線硬化型接着剤、電子線硬化型接着剤等の活性エネルギー線硬化型接着剤が挙げられる。前記活性エネルギー線硬化型接着剤としては、例えば、（メタ）アクリレート系接着剤が挙げられる。前記（メタ）アクリレート系接着剤における硬化性成分としては、例えば、（メタ）アクリロイル基を有する化合物、ビニル基を有する化合物が挙げられる。（メタ）アクリロイル基を有する化合物としては、例えば、炭素数が１～２０の鎖状アルキル（メタ）アクリレート、脂環式アルキル（メタ）アクリレート、多環式アルキル（メタ）アクリレート等のアルキル（メタ）アクリレート；ヒドロキシル基含有（メタ）アクリレート；グリシジル（メタ）アクリレート等のエポキシ基含有（メタ）アクリレート等が挙げられる。（メタ）アクリレート系接着剤は、ヒドロキシエチル（メタ）アクリルアミド、Ｎ‐メチロール（メタ）アクリルアミド、Ｎ‐メトキシメチル（メタ）アクリルアミド、Ｎ‐エトキシメチル（メタ）アクリルアミド、（メタ）アクリルアミド、（メタ）アクリロイルモルホリン等の窒素含有モノマーを含んでいてもよい。（メタ）アクリレート系接着剤は、架橋成分として、トリプロピレングリコールジアクリレート、１，９－ノナンジオールジアクリレート、トリシクロデカンジメタノールジアクリレート、環状トリメチロールプロパンフォルマルアクリレート、ジオキサングリコールジアクリレート、ＥＯ変性ジグリセリンテトラアクリレート等の多官能モノマーを含んでいてもよい。また、カチオン重合硬化型接着剤としてエポキシ基やオキセタニル基を有する化合物も使用することができる。エポキシ基を有する化合物は、分子内に少なくとも２個のエポキシ基を有するものであれば特に限定されず、一般に知られている各種の硬化性エポキシ化合物を用いることができる。
In addition to the above, examples of the adhesive include active energy ray curable adhesives such as ultraviolet curable adhesives and electron beam curable adhesives. Examples of the active energy ray-curable adhesive include (meth) acrylate adhesives. Examples of the curable component in the (meth) acrylate-based adhesive include compounds having a (meth) acryloyl group and compounds having a vinyl group. Examples of the compound having a (meth) acryloyl group include alkyl (meth) acrylates such as a chain alkyl (meth) acrylate having 1 to 20 carbon atoms, an alicyclic alkyl (meth) acrylate, and a polycyclic alkyl (meth) acrylate. ) Acrylate; hydroxyl group-containing (meth) acrylate; epoxy group-containing (meth) acrylate such as glycidyl (meth) acrylate. (Meth) acrylate adhesives include hydroxyethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, (meth) acrylamide, (meth) It may contain a nitrogen-containing monomer such as acryloylmorpholine. The (meth) acrylate-based adhesive includes tripropylene glycol diacrylate, 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, cyclic trimethylolpropane formal acrylate, dioxane glycol diacrylate, and EO as cross-linking components. It may contain a polyfunctional monomer such as modified diglycerin tetraacrylate. Further, a compound having an epoxy group or an oxetanyl group can also be used as the cationic polymerization curable adhesive. The compound having an epoxy group is not particularly limited as long as it has at least two epoxy groups in the molecule, and various commonly known curable epoxy compounds can be used.
前記接着剤は、必要に応じて適宜の添加剤を含んでいてもよい。前記添加剤としては、例えば、シランカップリング剤、チタンカップリング剤等のカップリング剤、エチレンオキシド等の接着促進剤、紫外線吸収剤、劣化防止剤、染料、加工助剤、イオントラップ剤、酸化防止剤、粘着付与剤、充填剤、可塑剤、レベリング剤、発泡抑制剤、帯電防止剤、耐熱安定剤、耐加水分解安定剤等が挙げられる。
The adhesive may contain an appropriate additive as needed. Examples of the additives include silane coupling agents, coupling agents such as titanium coupling agents, adhesion promoters such as ethylene oxide, ultraviolet absorbers, deterioration inhibitors, dyes, processing aids, ion trap agents, and antioxidants. Agents, tackifiers, fillers, plasticizers, leveling agents, foaming inhibitors, antistatic agents, heat resistance stabilizers, hydrolysis resistance stabilizers and the like.
前記接着剤の塗布は、前記透明保護フィルム側（または前記機能層側）、前記偏光膜側のいずれに行ってもよく、両者に行ってもよい。貼り合わせ後には、乾燥工程を施し、塗布乾燥層からなる接着剤層を形成する。前記乾燥工程の後には、必要に応じ、紫外線や電子線を照射することができる。前記接着剤層の厚さは、特に制限されず、水系接着剤等を用いる場合には、３０～５０００ｎｍ程度であることが好ましく、１００～１０００ｎｍ程度であることがより好ましく、紫外線硬化型接着剤、電子線硬化型接着剤等を用いる場合には、０．１～１００μｍ程度であることが好ましく、０．５～１０μｍ程度であることがより好ましい。
The application of the adhesive may be performed on either the transparent protective film side (or the functional layer side), the polarizing film side, or both. After the bonding, a drying process is performed to form an adhesive layer composed of a coating and drying layer. After the drying step, ultraviolet rays or an electron beam can be irradiated if necessary. The thickness of the adhesive layer is not particularly limited, and when an aqueous adhesive or the like is used, it is preferably about 30 to 5000 nm, more preferably about 100 to 1000 nm, and an ultraviolet curable adhesive. When using an electron beam curable adhesive or the like, the thickness is preferably about 0.1 to 100 μm, more preferably about 0.5 to 10 μm.
前記透明保護フィルムと前記偏光膜、あるいは前記偏光膜と前記機能層は、表面改質処理層、易接着剤層、ブロック層、屈折率調整層等の介在層を介して積層されていてもよい。
The transparent protective film and the polarizing film, or the polarizing film and the functional layer may be laminated via an intervening layer such as a surface modification treatment layer, an easy-adhesive layer, a block layer, and a refractive index adjusting layer. ..
前記表面改質層を形成する表面改質処理としては、例えば、コロナ処理、プラズマ処理、プライマー処理、ケン化処理等が挙げられる。
Examples of the surface modification treatment for forming the surface modification layer include corona treatment, plasma treatment, primer treatment, saponification treatment and the like.
前記易接着層を形成する易接着剤としては、例えば、ポリエステル骨格、ポリエーテル骨格、ポリカーボネート骨格、ポリウレタン骨格、シリコーン系、ポリアミド骨格、ポリイミド骨格、ポリビニルアルコール骨格等を有する各種樹脂を含む形成材が挙げられる。前記易接着層は、通常、保護フィルムに予め設けておき、当該保護フィルムの易接着層側と偏光膜とを、前記粘着剤層または前記接着剤層により積層する。
Examples of the easy-adhesive agent for forming the easy-adhesion layer include a forming material containing various resins having a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, a silicone-based, a polyamide skeleton, a polyimide skeleton, a polyvinyl alcohol skeleton, or the like. Can be mentioned. The easy-adhesion layer is usually provided in advance on the protective film, and the easy-adhesion layer side of the protective film and the polarizing film are laminated with the pressure-sensitive adhesive layer or the adhesive layer.
前記ブロック層は、透明保護フィルム等から溶出されるオリゴマーやイオン等の不純物が偏光膜中に移行（侵入）することを防止するため機能を有する層である。前記ブロック層は、透明性を有し、かつ透明保護フィルム等から溶出される不純物が防止できる層であればよく、ブロック層を形成する材としては、例えば、ウレタンプレポリマー系形成材、シアノアクリレート系形成材、エポキシ系形成材等が挙げられる。
The blocking layer is a layer that has a function of preventing impurities (such as oligomers and ions) eluted from the transparent protective film and the like from moving (entering) into the polarizing film. The block layer may be any layer as long as it has transparency and can prevent impurities eluted from the transparent protective film and the like, and examples of the material for forming the block layer include urethane prepolymer-based forming material and cyanoacrylate. Examples include a system forming material and an epoxy forming material.
前記屈折率調整層は、前記透明保護フィルムと偏光膜等屈折率の異なる層間での反射に伴う透過率の低下を抑制するために設けられる層である。前記屈折率調整層を形成する屈折率調整材としては、例えば、シリカ系、アクリル系、アクリル－スチレン系、メラミン系等を有する各種樹脂及び添加剤を含む形成剤が挙げられる。
The refractive index adjusting layer is a layer provided for suppressing a decrease in transmittance due to reflection between the transparent protective film and a layer such as a polarizing film having a different refractive index. Examples of the refractive index adjusting material for forming the refractive index adjusting layer include various resins having a silica type, an acrylic type, an acryl-styrene type, a melamine type, etc., and a forming agent containing an additive.
前記偏光フィルムは、偏光度が９９．９８％以上であることが好ましく、偏光度が９９．９９％以上であることがより好ましい。
The polarization degree of the polarizing film is preferably 99.98% or more, and more preferably 99.99% or more.
＜積層偏光フィルム＞
本発明の積層偏光フィルム（光学積層体）は、前記偏光フィルムが光学層に貼り合わされているものである。前記光学層は特に限定はないが、例えば、反射板や半透過板、位相差板（１／２や１／４等の波長板を含む）、視角補償フィルム等の液晶表示装置等の形成に用いられることのある光学層を１層または２層以上用いることができる。前記積層偏光フィルムとしては、特に、前記偏光フィルムに更に反射板または半透過反射板が積層されてなる反射型偏光フィルムまたは半透過型偏光フィルム、前記偏光フィルムに更に位相差板が積層されてなる楕円偏光フィルムまたは円偏光フィルム、前記偏光フィルムに更に視角補償フィルムが積層されてなる広視野角偏光フィルム、あるいは前記偏光フィルムに更に輝度向上フィルムが積層されてなる偏光フィルムが挙げられる。 <Laminated polarizing film>
The laminated polarizing film (optical laminate) of the present invention is one in which the polarizing film is attached to an optical layer. The optical layer is not particularly limited, but for example, for forming a liquid crystal display device such as a reflection plate, a semi-transmission plate, a retardation plate (including a wavelength plate such as 1/2 or 1/4), and a viewing angle compensation film. One or two or more optical layers that may be used can be used. As the laminated polarizing film, in particular, a reflective polarizing film or a semi-transmissive polarizing film obtained by further laminating a reflecting plate or a semi-transmissive reflecting plate on the polarizing film, and further comprising a retardation plate laminated on the polarizing film. Examples thereof include an elliptically polarizing film or a circularly polarizing film, a wide viewing angle polarizing film obtained by further laminating a viewing angle compensation film on the polarizing film, or a polarizing film obtained by further laminating a brightness improving film on the polarizing film.
本発明の積層偏光フィルム（光学積層体）は、前記偏光フィルムが光学層に貼り合わされているものである。前記光学層は特に限定はないが、例えば、反射板や半透過板、位相差板（１／２や１／４等の波長板を含む）、視角補償フィルム等の液晶表示装置等の形成に用いられることのある光学層を１層または２層以上用いることができる。前記積層偏光フィルムとしては、特に、前記偏光フィルムに更に反射板または半透過反射板が積層されてなる反射型偏光フィルムまたは半透過型偏光フィルム、前記偏光フィルムに更に位相差板が積層されてなる楕円偏光フィルムまたは円偏光フィルム、前記偏光フィルムに更に視角補償フィルムが積層されてなる広視野角偏光フィルム、あるいは前記偏光フィルムに更に輝度向上フィルムが積層されてなる偏光フィルムが挙げられる。 <Laminated polarizing film>
The laminated polarizing film (optical laminate) of the present invention is one in which the polarizing film is attached to an optical layer. The optical layer is not particularly limited, but for example, for forming a liquid crystal display device such as a reflection plate, a semi-transmission plate, a retardation plate (including a wavelength plate such as 1/2 or 1/4), and a viewing angle compensation film. One or two or more optical layers that may be used can be used. As the laminated polarizing film, in particular, a reflective polarizing film or a semi-transmissive polarizing film obtained by further laminating a reflecting plate or a semi-transmissive reflecting plate on the polarizing film, and further comprising a retardation plate laminated on the polarizing film. Examples thereof include an elliptically polarizing film or a circularly polarizing film, a wide viewing angle polarizing film obtained by further laminating a viewing angle compensation film on the polarizing film, or a polarizing film obtained by further laminating a brightness improving film on the polarizing film.
前記偏光フィルム、あるいは前記積層偏光フィルムの一方の面あるいは両方の面には、液晶セルや有機ＥＬ素子等の画像表示セルと、視認側における前面透明板やタッチパネル等の前面透明部材等の他の部材を貼り合わせるための接着剤層が付設されてもよい。当該接着剤層としては、粘着剤層が好適である。前記粘着剤層を形成する粘着剤は特に制限されないが、例えば、アクリル系重合体、シリコーン系ポリマー、ポリエステル、ポリウレタン、ポリアミド、ポリエーテル、フッ素系やゴム系等のポリマーをベースポリマーとするものを適宜に選択して用いることができる。特に、アクリル系重合体を含む粘着剤のように、光学的透明性に優れ、適度な濡れ性と凝集性と接着性を示し、耐候性や耐熱性等に優れるものが好ましく用いられる。
On one surface or both surfaces of the polarizing film or the laminated polarizing film, an image display cell such as a liquid crystal cell or an organic EL element, and another front transparent member such as a front transparent plate or a touch panel on the viewing side are provided. An adhesive layer for attaching the members may be additionally provided. A pressure-sensitive adhesive layer is suitable as the adhesive layer. The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited, but for example, an acrylic polymer, a silicone-based polymer, polyester, polyurethane, polyamide, polyether, or a polymer having a fluorine-based or rubber-based polymer as a base polymer It can be appropriately selected and used. In particular, a pressure-sensitive adhesive containing an acrylic polymer, which has excellent optical transparency, shows appropriate wettability, cohesiveness and adhesiveness, and has excellent weather resistance and heat resistance, is preferably used.
前記偏光フィルムや前記積層偏光フィルムの片面または両面への粘着剤層の付設は、適宜な方式で行いうる。粘着剤層の付設としては、例えば、粘着剤溶液を調製し、それを流延方式や塗布方式等の適宜な展開方式で前記偏光フィルムや前記積層偏光フィルム上に直接付設する方式、あるいは、セパレータ上に粘着剤層を形成して、それを前記偏光フィルムや前記積層偏光フィルム上に移着する方式等が挙げられる。前記粘着剤層の厚さは、使用目的や接着力等に応じて適宜に決定でき、一般には１～５００μｍであり、５～２００μｍであることが好ましく、１０～１００μｍであることがより好ましい。このように、前記偏光フィルムや前記積層偏光フィルムの少なくとも一方の面に粘着剤層が設けられたものを、粘着剤層付き偏光フィルム、または粘着剤層付き積層偏光フィルムという。
The adhesive layer may be attached to one side or both sides of the polarizing film or the laminated polarizing film by an appropriate method. As the attachment of the pressure-sensitive adhesive layer, for example, a method of preparing a pressure-sensitive adhesive solution and directly attaching it to the polarizing film or the laminated polarizing film by an appropriate developing method such as a casting method or a coating method, or a separator Examples include a method in which an adhesive layer is formed on the adhesive layer and transferred onto the polarizing film or the laminated polarizing film. The thickness of the pressure-sensitive adhesive layer can be appropriately determined depending on the purpose of use, adhesive strength, etc., and is generally 1 to 500 μm, preferably 5 to 200 μm, and more preferably 10 to 100 μm. Thus, the polarizing film or the laminated polarizing film provided with the adhesive layer on at least one surface thereof is referred to as an adhesive layer-attached polarizing film or an adhesive layer-attached laminated polarizing film.
前記粘着剤層の露出面に対しては、実用に供するまでの間、その汚染防止等を目的にセパレータが仮着されてカバーされることが好ましい。これにより、通例の取扱状態で粘着剤層の汚染等が防止できる。前記セパレータとしては、例えば、プラスチックフィルム、ゴムシート、紙、布、不織布、ネット、発泡シートや金属箔、それらのラミネート体等の適宜な薄葉体を、必要に応じシリコーン系や長鎖アルキル系、フッ素系や硫化モリブデン等の適宜な剥離剤でコート処理したもの等が用いられる。
It is preferable that the exposed surface of the pressure-sensitive adhesive layer is temporarily attached and covered with a separator for practical use until it is put to practical use. As a result, it is possible to prevent the pressure-sensitive adhesive layer from being contaminated in the usual handling state. As the separator, for example, a plastic film, a rubber sheet, a paper, a cloth, a non-woven fabric, a net, a foam sheet or a metal foil, an appropriate thin sheet such as a laminate thereof, a silicone-based or long-chain alkyl-based, if necessary, Those coated with an appropriate release agent such as fluorine-based or molybdenum sulfide are used.
＜画像表示パネルおよび画像表示装置＞
本発明の画像表示パネルは、画像表示セルに、前記偏光フィルム、または前記積層偏光フィルムが貼り合わされているものである。また、本発明の画像表示装置は、前記画像表示パネルの偏光フィルムまたは積層偏光フィルム側（視認側）に、前面透明部材を備えるものである。 <Image display panel and image display device>
The image display panel of the present invention is one in which the polarizing film or the laminated polarizing film is attached to an image display cell. The image display device of the present invention includes a front transparent member on the polarizing film or laminated polarizing film side (viewing side) of the image display panel.
本発明の画像表示パネルは、画像表示セルに、前記偏光フィルム、または前記積層偏光フィルムが貼り合わされているものである。また、本発明の画像表示装置は、前記画像表示パネルの偏光フィルムまたは積層偏光フィルム側（視認側）に、前面透明部材を備えるものである。 <Image display panel and image display device>
The image display panel of the present invention is one in which the polarizing film or the laminated polarizing film is attached to an image display cell. The image display device of the present invention includes a front transparent member on the polarizing film or laminated polarizing film side (viewing side) of the image display panel.
前記画像表示セルとしては、例えば、液晶セルや有機ＥＬセル等が挙げられる。前記液晶セルとしては、例えば、外光を利用する反射型液晶セル、バックライト等の光源からの光を利用する透過型液晶セル、外部からの光と光源からの光の両者を利用する半透過半反射型液晶セルのいずれを用いてもよい。前記液晶セルが光源からの光を利用するものである場合、画像表示装置（液晶表示装置）は、画像表示セル（液晶セル）の視認側と反対側にも偏光フィルムが配置され、さらに光源が配置される。当該光源側の偏光フィルムと液晶セルとは、適宜の接着剤層を介して貼り合せられていることが好ましい。前記液晶セルの駆動方式としては、例えば、ＶＡモード、ＩＰＳモード、ＴＮモード、ＳＴＮモードやベンド配向（π型）等の任意なタイプのものを用いうる。
Examples of the image display cell include a liquid crystal cell and an organic EL cell. Examples of the liquid crystal cell include a reflective liquid crystal cell that uses external light, a transmissive liquid crystal cell that uses light from a light source such as a backlight, and a semi-transmissive liquid crystal cell that uses both external light and light from a light source. Any of the semi-reflective liquid crystal cells may be used. When the liquid crystal cell utilizes light from a light source, the image display device (liquid crystal display device) has a polarizing film arranged on the side opposite to the viewing side of the image display cell (liquid crystal cell). Will be placed. It is preferable that the polarizing film on the light source side and the liquid crystal cell are bonded together via an appropriate adhesive layer. As a driving method of the liquid crystal cell, for example, any type such as a VA mode, an IPS mode, a TN mode, an STN mode, a bend alignment (π type), or the like can be used.
前記有機ＥＬセルとしては、例えば、透明基板上に透明電極と有機発光層と金属電極とを順に積層して発光体（有機エレクトロルミネセンス発光体）を形成したもの等が好適に用いられる。前記有機発光層は、種々の有機薄膜の積層体であり、例えば、トリフェニルアミン誘導体等からなる正孔注入層と、アントラセン等の蛍光性の有機固体からなる発光層との積層体や、これらの発光層とペリレン誘導体等からなる電子注入層の積層体、あるいは正孔注入層、発光層、および電子注入層の積層体等、種々層構成が採用され得る。
As the organic EL cell, for example, one in which a transparent electrode, an organic light emitting layer, and a metal electrode are laminated in this order on a transparent substrate to form a light emitting body (organic electroluminescent light emitting body) is preferably used. The organic light emitting layer is a laminate of various organic thin films, for example, a laminate of a hole injection layer made of a triphenylamine derivative or the like and a light emitting layer made of a fluorescent organic solid such as anthracene, or the like. Various layer configurations such as a laminated body of the above-mentioned light emitting layer and an electron injection layer composed of a perylene derivative or a laminated body of a hole injection layer, a light emitting layer, and an electron injection layer can be adopted.
前記画像表示セルの視認側に配置される前面透明部材としては、例えば、前面透明板（ウインドウ層）やタッチパネル等が挙げられる。前記前面透明板としては、適宜の機械強度および厚みを有する透明板が用いられる。このような透明板としては、例えば、アクリル系樹脂やポリカーボネート系樹脂のような透明樹脂板、あるいはガラス板等が用いられる。前記タッチパネルとしては、例えば、抵抗膜方式、静電容量方式、光学方式、超音波方式等の各種タッチパネルや、タッチセンサー機能を備えるガラス板や透明樹脂板等が用いられる。前記前面透明部材として静電容量方式のタッチパネルが用いられる場合、タッチパネルよりもさらに視認側に、ガラスや透明樹脂板からなる前面透明板が設けられることが好ましい。
The front transparent member arranged on the viewing side of the image display cell includes, for example, a front transparent plate (window layer) and a touch panel. As the front transparent plate, a transparent plate having appropriate mechanical strength and thickness is used. As such a transparent plate, for example, a transparent resin plate such as an acrylic resin or a polycarbonate resin, or a glass plate is used. As the touch panel, for example, various touch panels such as a resistive film type, an electrostatic capacitance type, an optical type, an ultrasonic type, and a glass plate or a transparent resin plate having a touch sensor function are used. When a capacitive touch panel is used as the front transparent member, it is preferable that a front transparent plate made of glass or a transparent resin plate is provided on the side closer to the viewer than the touch panel.
本発明の偏光膜は、初期の偏光度が良好であり、高温環境下において、偏光膜の着色による単体透過率の低下の抑制効果に優れるため、本発明の偏光膜、ならびに当該偏光膜を用いた偏光フィルム、積層偏光フィルム、画像表示パネル、および画像表示装置は、カーナビゲーション装置やバックモニター等の車載用の画像表示装置の用途に好適である。
The polarizing film of the present invention has a good initial degree of polarization and, under a high temperature environment, has an excellent effect of suppressing a decrease in the single transmittance due to the coloring of the polarizing film. Therefore, the polarizing film of the present invention and the polarizing film are used. The polarizing film, the laminated polarizing film, the image display panel, and the image display device are suitable for use in vehicle-mounted image display devices such as car navigation devices and back monitors.
以下に実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
＜実施例１＞
＜偏光膜の作製＞
熱可塑性樹脂基材として、長尺状で、吸水率０．７５％、Ｔｇ約７５℃である、非晶質のイソフタル共重合ポリエチレンテレフタレートフィルム（厚み：１００μｍ）を用いた。樹脂基材の片面に、コロナ処理を施した。ポリビニルアルコール（重合度４２００、ケン化度９９．２モル％）およびアセトアセチル変性ＰＶＡ（日本合成化学工業社製、商品名「ゴーセファイマーＺ４１０」）を９：１で混合したＰＶＡ系樹脂１００重量部に、ヨウ化カリウム１３重量部を添加し、ＰＶＡ水溶液（塗布液）を調製した。樹脂基材のコロナ処理面に、上記ＰＶＡ水溶液を塗布して６０℃で乾燥することにより、厚み１３μｍのＰＶＡ系樹脂層を形成し、積層体を作製した。得られた積層体を、１３０℃のオーブン内で周速の異なるロール間で縦方向（長手方向）に２．４倍に自由端一軸延伸した（空中補助延伸処理）。次いで、積層体を、液温４０℃の不溶化浴（ホウ酸濃度４.０重量％である水溶液）に３０秒間浸漬させた（不溶化処理）。次いで、液温３０℃の染色浴（水１００重量部に対して、ヨウ素とヨウ化カリウムを１：７の重量比で配合して得られたヨウ素水溶液）に、最終的に得られる偏光膜のヨウ素濃度が９．３％となるように濃度を調整しながら６０秒間浸漬させた（染色処理）。次いで、液温４０℃の架橋浴（ヨウ化カリウム濃度３．０重量％、ホウ酸濃度５．０重量％である水溶液）に３０秒間浸漬させた（架橋処理）。その後、積層体を、液温７０℃のホウ酸水溶液（ホウ酸濃度４．０重量％）に浸漬させながら、周速の異なるロール間で縦方向（長手方向）に総延伸倍率が５．５倍となるように一軸延伸を行った（水中延伸処理）。その後、積層体を液温２０℃の洗浄浴（ヨウ化カリウム濃度３重量％、ラジカル捕捉機能を有する化合物として、下記一般式（９）で表される化合物濃度が１．０重量％である水溶液）に浸漬させた（洗浄処理）。その後、９０℃に保たれたオーブン中で乾燥しながら、表面温度が７５℃に保たれたＳＵＳ製の加熱ロールに約２秒接触させた（乾燥収縮処理）。このようにして、樹脂基材上に厚み５μｍの偏光膜を形成した。また、得られた偏光膜は、発生ガス分析法にて検出される水の最大強度のピーク温度が２０４℃であり、偏光膜中の下記一般式（９）で表される化合物の含有量が０．３重量％であった。
<Example 1>
<Production of polarizing film>
As the thermoplastic resin base material, an amorphous isophthalic copolymer polyethylene terephthalate film (thickness: 100 μm) having a long shape, a water absorption rate of 0.75% and a Tg of about 75 ° C. was used. Corona treatment was applied to one surface of the resin substrate. Polyvinyl alcohol (polymerization degree: 4200, saponification degree: 99.2 mol%) and acetoacetyl-modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "Gosephimmer Z410") in a ratio of 9: 1 100 weight of PVA-based resin To 13 parts by weight, 13 parts by weight of potassium iodide was added to prepare a PVA aqueous solution (coating solution). The PVA aqueous solution was applied to the corona-treated surface of the resin substrate and dried at 60 ° C. to form a PVA-based resin layer having a thickness of 13 μm, and a laminate was prepared. The obtained laminate was uniaxially stretched 2.4 times in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds in an oven at 130 ° C. (in-air auxiliary stretching treatment). Next, the laminate was immersed in an insolubilization bath (solution of boric acid having a concentration of 4.0% by weight) having a liquid temperature of 40 ° C. for 30 seconds (insolubilization treatment). Then, a dyeing bath having a liquid temperature of 30 ° C. (an iodine aqueous solution obtained by mixing iodine and potassium iodide in a weight ratio of 1: 7 with respect to 100 parts by weight of water) was added to the finally obtained polarizing film. Immersion was carried out for 60 seconds while adjusting the iodine concentration to 9.3% (dyeing treatment). Next, it was immersed for 30 seconds in a crosslinking bath (aqueous solution having a potassium iodide concentration of 3.0% by weight and a boric acid concentration of 5.0% by weight) at a liquid temperature of 40 ° C. (crosslinking treatment). Then, while the laminate was immersed in a boric acid aqueous solution (boric acid concentration 4.0% by weight) having a liquid temperature of 70 ° C., the total draw ratio was 5.5 in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds. Uniaxial stretching was performed so as to double the length (underwater stretching treatment). Then, the laminated body was washed with a washing bath having a liquid temperature of 20 ° C. (potassium iodide concentration 3% by weight, an aqueous solution having a compound concentration represented by the following general formula (9) as a compound having a radical scavenging function of 1.0% by weight). )) (Washing process). Then, while being dried in an oven kept at 90 ° C., it was brought into contact with a SUS heating roll whose surface temperature was kept at 75 ° C. for about 2 seconds (dry shrinkage treatment). In this way, a polarizing film having a thickness of 5 μm was formed on the resin substrate. Further, the obtained polarizing film has a peak temperature of the maximum intensity of water detected by the evolved gas analysis method of 204 ° C., and the content of the compound represented by the following general formula (9) in the polarizing film is It was 0.3% by weight.
＜偏光膜の作製＞
熱可塑性樹脂基材として、長尺状で、吸水率０．７５％、Ｔｇ約７５℃である、非晶質のイソフタル共重合ポリエチレンテレフタレートフィルム（厚み：１００μｍ）を用いた。樹脂基材の片面に、コロナ処理を施した。ポリビニルアルコール（重合度４２００、ケン化度９９．２モル％）およびアセトアセチル変性ＰＶＡ（日本合成化学工業社製、商品名「ゴーセファイマーＺ４１０」）を９：１で混合したＰＶＡ系樹脂１００重量部に、ヨウ化カリウム１３重量部を添加し、ＰＶＡ水溶液（塗布液）を調製した。樹脂基材のコロナ処理面に、上記ＰＶＡ水溶液を塗布して６０℃で乾燥することにより、厚み１３μｍのＰＶＡ系樹脂層を形成し、積層体を作製した。得られた積層体を、１３０℃のオーブン内で周速の異なるロール間で縦方向（長手方向）に２．４倍に自由端一軸延伸した（空中補助延伸処理）。次いで、積層体を、液温４０℃の不溶化浴（ホウ酸濃度４.０重量％である水溶液）に３０秒間浸漬させた（不溶化処理）。次いで、液温３０℃の染色浴（水１００重量部に対して、ヨウ素とヨウ化カリウムを１：７の重量比で配合して得られたヨウ素水溶液）に、最終的に得られる偏光膜のヨウ素濃度が９．３％となるように濃度を調整しながら６０秒間浸漬させた（染色処理）。次いで、液温４０℃の架橋浴（ヨウ化カリウム濃度３．０重量％、ホウ酸濃度５．０重量％である水溶液）に３０秒間浸漬させた（架橋処理）。その後、積層体を、液温７０℃のホウ酸水溶液（ホウ酸濃度４．０重量％）に浸漬させながら、周速の異なるロール間で縦方向（長手方向）に総延伸倍率が５．５倍となるように一軸延伸を行った（水中延伸処理）。その後、積層体を液温２０℃の洗浄浴（ヨウ化カリウム濃度３重量％、ラジカル捕捉機能を有する化合物として、下記一般式（９）で表される化合物濃度が１．０重量％である水溶液）に浸漬させた（洗浄処理）。その後、９０℃に保たれたオーブン中で乾燥しながら、表面温度が７５℃に保たれたＳＵＳ製の加熱ロールに約２秒接触させた（乾燥収縮処理）。このようにして、樹脂基材上に厚み５μｍの偏光膜を形成した。また、得られた偏光膜は、発生ガス分析法にて検出される水の最大強度のピーク温度が２０４℃であり、偏光膜中の下記一般式（９）で表される化合物の含有量が０．３重量％であった。
<Production of polarizing film>
As the thermoplastic resin base material, an amorphous isophthalic copolymer polyethylene terephthalate film (thickness: 100 μm) having a long shape, a water absorption rate of 0.75% and a Tg of about 75 ° C. was used. Corona treatment was applied to one surface of the resin substrate. Polyvinyl alcohol (polymerization degree: 4200, saponification degree: 99.2 mol%) and acetoacetyl-modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "Gosephimmer Z410") in a ratio of 9: 1 100 weight of PVA-based resin To 13 parts by weight, 13 parts by weight of potassium iodide was added to prepare a PVA aqueous solution (coating solution). The PVA aqueous solution was applied to the corona-treated surface of the resin substrate and dried at 60 ° C. to form a PVA-based resin layer having a thickness of 13 μm, and a laminate was prepared. The obtained laminate was uniaxially stretched 2.4 times in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds in an oven at 130 ° C. (in-air auxiliary stretching treatment). Next, the laminate was immersed in an insolubilization bath (solution of boric acid having a concentration of 4.0% by weight) having a liquid temperature of 40 ° C. for 30 seconds (insolubilization treatment). Then, a dyeing bath having a liquid temperature of 30 ° C. (an iodine aqueous solution obtained by mixing iodine and potassium iodide in a weight ratio of 1: 7 with respect to 100 parts by weight of water) was added to the finally obtained polarizing film. Immersion was carried out for 60 seconds while adjusting the iodine concentration to 9.3% (dyeing treatment). Next, it was immersed for 30 seconds in a crosslinking bath (aqueous solution having a potassium iodide concentration of 3.0% by weight and a boric acid concentration of 5.0% by weight) at a liquid temperature of 40 ° C. (crosslinking treatment). Then, while the laminate was immersed in a boric acid aqueous solution (boric acid concentration 4.0% by weight) having a liquid temperature of 70 ° C., the total draw ratio was 5.5 in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds. Uniaxial stretching was performed so as to double the length (underwater stretching treatment). Then, the laminated body was washed with a washing bath having a liquid temperature of 20 ° C. (potassium iodide concentration 3% by weight, an aqueous solution having a compound concentration represented by the following general formula (9) as a compound having a radical scavenging function of 1.0% by weight). )) (Washing process). Then, while being dried in an oven kept at 90 ° C., it was brought into contact with a SUS heating roll whose surface temperature was kept at 75 ° C. for about 2 seconds (dry shrinkage treatment). In this way, a polarizing film having a thickness of 5 μm was formed on the resin substrate. Further, the obtained polarizing film has a peak temperature of the maximum intensity of water detected by the evolved gas analysis method of 204 ° C., and the content of the compound represented by the following general formula (9) in the polarizing film is It was 0.3% by weight.
［偏光膜中のヨウ素濃度（重量％）の測定方法］
偏光膜について、蛍光Ｘ線分析装置（リガク社製、商品名「ＺＳＸ－ＰＲＩＭＵＳ ＩＶ」、測定径：ψ２０ｍｍ）を用いて、下記式を用いてヨウ素濃度（重量％）を求めた。
ヨウ素濃度（ｗｔ％）＝１４．４７４×（蛍光Ｘ線強度）／（フィルム厚み）（ｋｃｐｓ／μｍ）なお、濃度を算出する際の係数は測定装置によって異なるが、当該係数は適切な検量線を用いて求めることができる。 [Method of measuring iodine concentration (% by weight) in polarizing film]
With respect to the polarizing film, the iodine concentration (% by weight) was determined using the following formula using a fluorescent X-ray analyzer (Rigaku Corporation, trade name “ZSX-PRIMUS IV”, measurement diameter: ψ20 mm).
Iodine concentration (wt%) = 14.474 x (fluorescent X-ray intensity) / (film thickness) (kcps / μm) Although the coefficient for calculating the concentration differs depending on the measuring device, the coefficient is an appropriate calibration curve. Can be obtained using.
偏光膜について、蛍光Ｘ線分析装置（リガク社製、商品名「ＺＳＸ－ＰＲＩＭＵＳ ＩＶ」、測定径：ψ２０ｍｍ）を用いて、下記式を用いてヨウ素濃度（重量％）を求めた。
ヨウ素濃度（ｗｔ％）＝１４．４７４×（蛍光Ｘ線強度）／（フィルム厚み）（ｋｃｐｓ／μｍ）なお、濃度を算出する際の係数は測定装置によって異なるが、当該係数は適切な検量線を用いて求めることができる。 [Method of measuring iodine concentration (% by weight) in polarizing film]
With respect to the polarizing film, the iodine concentration (% by weight) was determined using the following formula using a fluorescent X-ray analyzer (Rigaku Corporation, trade name “ZSX-PRIMUS IV”, measurement diameter: ψ20 mm).
Iodine concentration (wt%) = 14.474 x (fluorescent X-ray intensity) / (film thickness) (kcps / μm) Although the coefficient for calculating the concentration differs depending on the measuring device, the coefficient is an appropriate calibration curve. Can be obtained using.
［発生ガス分析法］
偏光膜を加熱炉型パイロライザー（フロンティアラボ製、ＰＹ－２０２０ｉＤ）に導入し、発生したガスを直接ＴＯＦＭＳ（ＪＥＯＬ製、ＪＭＳ－Ｔ１００ＧＣＶ）に導入して発生ガス分析（ＥＧＡ／ＴＯＦＭＳ）法を行った。
［測定条件］
昇温条件：４０℃→＋１０℃/ｍｉｎ→３５０℃
インターフェイス：不活性フューズドシリカチューブ、２．５ｍ×０．１５ｍｍ ｉｄ
キャリアーガス：Ｈｅ（１．０ｍＬ/ｍｉｎ）
注入口温度：３００℃
注入口：スプリット比 ２０：１
インターフェイス温度：３００℃
質量分析計：ＴＯＦＭＳ
イオン化法：ＥＩ法
質量範囲：ｍ／ｚ＝１８ [Generated gas analysis method]
The polarizing film was introduced into a heating furnace type pyrolyzer (PY-2020iD, manufactured by Frontier Lab), and the generated gas was directly introduced into TOFMS (JEOL, JMS-T100GCV) to analyze the generated gas (EGA / TOFMS). It was
[Measurement condition]
Temperature rising condition: 40 ° C → + 10 ° C / min → 350 ° C
Interface: Inert fused silica tube, 2.5m x 0.15mm id
Carrier gas: He (1.0 mL / min)
Inlet temperature: 300 ℃
Inlet: Split ratio 20: 1
Interface temperature: 300 ℃
Mass spectrometer: TOFMS
Ionization method: EI method Mass range: m / z = 18
偏光膜を加熱炉型パイロライザー（フロンティアラボ製、ＰＹ－２０２０ｉＤ）に導入し、発生したガスを直接ＴＯＦＭＳ（ＪＥＯＬ製、ＪＭＳ－Ｔ１００ＧＣＶ）に導入して発生ガス分析（ＥＧＡ／ＴＯＦＭＳ）法を行った。
［測定条件］
昇温条件：４０℃→＋１０℃/ｍｉｎ→３５０℃
インターフェイス：不活性フューズドシリカチューブ、２．５ｍ×０．１５ｍｍ ｉｄ
キャリアーガス：Ｈｅ（１．０ｍＬ/ｍｉｎ）
注入口温度：３００℃
注入口：スプリット比 ２０：１
インターフェイス温度：３００℃
質量分析計：ＴＯＦＭＳ
イオン化法：ＥＩ法
質量範囲：ｍ／ｚ＝１８ [Generated gas analysis method]
The polarizing film was introduced into a heating furnace type pyrolyzer (PY-2020iD, manufactured by Frontier Lab), and the generated gas was directly introduced into TOFMS (JEOL, JMS-T100GCV) to analyze the generated gas (EGA / TOFMS). It was
[Measurement condition]
Temperature rising condition: 40 ° C → + 10 ° C / min → 350 ° C
Interface: Inert fused silica tube, 2.5m x 0.15mm id
Carrier gas: He (1.0 mL / min)
Inlet temperature: 300 ℃
Inlet: Split ratio 20: 1
Interface temperature: 300 ℃
Mass spectrometer: TOFMS
Ionization method: EI method Mass range: m / z = 18
［偏光膜中のラジカル捕捉機能を有する化合物の含有量（重量％）の測定方法］
偏光膜約２０ｍｇを採取、定量し、水１ｍＬ中で加熱溶解させた後、メタノール４．５ｍＬで希釈し、得られた抽出液をメンブレンフィルターでろ過し、ろ液をＨＰＬＣ（Ｗａｔｅｒｓ社製 ＡＣＱＵＩＴＹ ＵＰＬＣ Ｈ－ｃｌａｓｓ Ｂｉｏ）を用いてラジカル捕捉機能を有する化合物の濃度を測定した。 [Method of measuring content (% by weight) of compound having radical scavenging function in polarizing film]
About 20 mg of the polarizing film was sampled, quantified, dissolved by heating in 1 mL of water, diluted with 4.5 mL of methanol, the obtained extract was filtered through a membrane filter, and the filtrate was analyzed by HPLC (ACQUITY UPLC manufactured by Waters) The concentration of the compound having a radical scavenging function was measured using H-class Bio).
偏光膜約２０ｍｇを採取、定量し、水１ｍＬ中で加熱溶解させた後、メタノール４．５ｍＬで希釈し、得られた抽出液をメンブレンフィルターでろ過し、ろ液をＨＰＬＣ（Ｗａｔｅｒｓ社製 ＡＣＱＵＩＴＹ ＵＰＬＣ Ｈ－ｃｌａｓｓ Ｂｉｏ）を用いてラジカル捕捉機能を有する化合物の濃度を測定した。 [Method of measuring content (% by weight) of compound having radical scavenging function in polarizing film]
About 20 mg of the polarizing film was sampled, quantified, dissolved by heating in 1 mL of water, diluted with 4.5 mL of methanol, the obtained extract was filtered through a membrane filter, and the filtrate was analyzed by HPLC (ACQUITY UPLC manufactured by Waters) The concentration of the compound having a radical scavenging function was measured using H-class Bio).
＜偏光フィルムの作製＞
接着剤として、アセトアセチル基を含有するポリビニルアルコール樹脂（平均重合度が１，２００、ケン化度が９８．５モル％、アセトアセチル化度が５モル％）とメチロールメラミンとを重量比３：１で含有する水溶液を用いた。この接着剤を用いて、上記で得られた偏光膜の樹脂基材とは反対面の表面（画像表示セル側）に（メタ）アクリル系樹脂（ラクトン環構造を有する変性アクリル系ポリマー）からなる厚み３０μｍの透明保護フィルム（日本触媒製、透湿度が１２５ｇ／（ｍ２・２４ｈ））をロール貼り合わせ機を使用して貼り合わせた。次いで、樹脂基材を剥離し、剥離した面（視認側）に透明保護フィルムとして、トリアセチルセルロースフィルム（富士フィルム製、商品名「ＴＪ４０ＵＬ」）にＨＣを形成した厚み４７μｍの透明保護フィルム（透湿度は３８０ｇ／（ｍ２・２４ｈ））を紫外線硬化型接着剤を介してロール貼り合わせ機で貼り合わせ、その後、透明保護フィルム面からＵＶ光線を照射して接着剤を硬化させ、偏光フィルムを作製した。 <Production of polarizing film>
As an adhesive, polyvinyl alcohol resin containing acetoacetyl group (average polymerization degree: 1,200, saponification degree: 98.5 mol%, acetoacetylation degree: 5 mol%) and methylolmelamine in a weight ratio of 3: The aqueous solution contained in 1 was used. Using this adhesive, the polarizing film obtained above is made of a (meth) acrylic resin (modified acrylic polymer having a lactone ring structure) on the surface (image display cell side) opposite to the resin substrate. A transparent protective film having a thickness of 30 μm (manufactured by Nippon Shokubai Co., Ltd., moisture permeability of 125 g / (m 2 · 24 h)) was laminated using a roll laminating machine. Then, the resin base material was peeled off, and as a transparent protective film on the peeled surface (viewing side), a triacetyl cellulose film (manufactured by Fuji Film Co., Ltd., trade name "TJ40UL") was coated with HC to form a transparent protective film with a thickness of 47 μm (transparent film). Humidity of 380 g / (m 2 · 24 h) is bonded with a roll bonding machine via an ultraviolet curable adhesive, and then UV light is irradiated from the surface of the transparent protective film to cure the adhesive and the polarizing film It was made.
接着剤として、アセトアセチル基を含有するポリビニルアルコール樹脂（平均重合度が１，２００、ケン化度が９８．５モル％、アセトアセチル化度が５モル％）とメチロールメラミンとを重量比３：１で含有する水溶液を用いた。この接着剤を用いて、上記で得られた偏光膜の樹脂基材とは反対面の表面（画像表示セル側）に（メタ）アクリル系樹脂（ラクトン環構造を有する変性アクリル系ポリマー）からなる厚み３０μｍの透明保護フィルム（日本触媒製、透湿度が１２５ｇ／（ｍ２・２４ｈ））をロール貼り合わせ機を使用して貼り合わせた。次いで、樹脂基材を剥離し、剥離した面（視認側）に透明保護フィルムとして、トリアセチルセルロースフィルム（富士フィルム製、商品名「ＴＪ４０ＵＬ」）にＨＣを形成した厚み４７μｍの透明保護フィルム（透湿度は３８０ｇ／（ｍ２・２４ｈ））を紫外線硬化型接着剤を介してロール貼り合わせ機で貼り合わせ、その後、透明保護フィルム面からＵＶ光線を照射して接着剤を硬化させ、偏光フィルムを作製した。 <Production of polarizing film>
As an adhesive, polyvinyl alcohol resin containing acetoacetyl group (average polymerization degree: 1,200, saponification degree: 98.5 mol%, acetoacetylation degree: 5 mol%) and methylolmelamine in a weight ratio of 3: The aqueous solution contained in 1 was used. Using this adhesive, the polarizing film obtained above is made of a (meth) acrylic resin (modified acrylic polymer having a lactone ring structure) on the surface (image display cell side) opposite to the resin substrate. A transparent protective film having a thickness of 30 μm (manufactured by Nippon Shokubai Co., Ltd., moisture permeability of 125 g / (m 2 · 24 h)) was laminated using a roll laminating machine. Then, the resin base material was peeled off, and as a transparent protective film on the peeled surface (viewing side), a triacetyl cellulose film (manufactured by Fuji Film Co., Ltd., trade name "TJ40UL") was coated with HC to form a transparent protective film with a thickness of 47 μm (transparent film). Humidity of 380 g / (m 2 · 24 h) is bonded with a roll bonding machine via an ultraviolet curable adhesive, and then UV light is irradiated from the surface of the transparent protective film to cure the adhesive and the polarizing film It was made.
［偏光度の評価］
偏光フィルムの偏光度は、分光光度計（日本分光製、製品名「Ｖ７１００」）を用いて測定することができる。偏光度の具体的な測定方法としては、偏光膜の平行透過率（Ｈ０）及び直交透過率（Ｈ９０）を測定し、式：偏光度（％）＝｛（Ｈ０－Ｈ９０）／（Ｈ０＋Ｈ９０）｝１／２×１００より求めることができる。平行透過率（Ｈ０）は、同じ偏光膜２枚を互いの吸収軸が平行となるように重ね合わせて作製した平行型積層偏光膜の透過率の値である。また、直交透過率（Ｈ９０）は、同じ偏光膜２枚を互いの吸収軸が直交するように重ね合わせて作製した直交型積層偏光膜の透過率の値である。なお、これらの透過率は、ＪｌＳ Ｚ ８７０１－１９８２の２度視野（Ｃ光源）により、視感度補正を行ったＹ値である。結果を表１に示す。 [Evaluation of degree of polarization]
The polarization degree of the polarizing film can be measured using a spectrophotometer (manufactured by JASCO Corporation, product name “V7100”). As a specific measuring method of the polarization degree, the parallel transmittance (H0) and the orthogonal transmittance (H90) of the polarizing film are measured, and the formula: polarization degree (%) = {(H0-H90) / (H0 + H90)} It can be calculated from 1/2 × 100. The parallel transmittance (H0) is a value of the transmittance of a parallel type laminated polarizing film produced by stacking two identical polarizing films so that their absorption axes are parallel to each other. The orthogonal transmittance (H90) is the value of the transmittance of an orthogonal laminated polarizing film produced by stacking two identical polarizing films so that their absorption axes are orthogonal to each other. Note that these transmittances are Y values that have been subjected to luminosity correction by the 2-degree visual field (C light source) of JLS Z 8701-1982. The results are shown in Table 1.
偏光フィルムの偏光度は、分光光度計（日本分光製、製品名「Ｖ７１００」）を用いて測定することができる。偏光度の具体的な測定方法としては、偏光膜の平行透過率（Ｈ０）及び直交透過率（Ｈ９０）を測定し、式：偏光度（％）＝｛（Ｈ０－Ｈ９０）／（Ｈ０＋Ｈ９０）｝１／２×１００より求めることができる。平行透過率（Ｈ０）は、同じ偏光膜２枚を互いの吸収軸が平行となるように重ね合わせて作製した平行型積層偏光膜の透過率の値である。また、直交透過率（Ｈ９０）は、同じ偏光膜２枚を互いの吸収軸が直交するように重ね合わせて作製した直交型積層偏光膜の透過率の値である。なお、これらの透過率は、ＪｌＳ Ｚ ８７０１－１９８２の２度視野（Ｃ光源）により、視感度補正を行ったＹ値である。結果を表１に示す。 [Evaluation of degree of polarization]
The polarization degree of the polarizing film can be measured using a spectrophotometer (manufactured by JASCO Corporation, product name “V7100”). As a specific measuring method of the polarization degree, the parallel transmittance (H0) and the orthogonal transmittance (H90) of the polarizing film are measured, and the formula: polarization degree (%) = {(H0-H90) / (H0 + H90)} It can be calculated from 1/2 × 100. The parallel transmittance (H0) is a value of the transmittance of a parallel type laminated polarizing film produced by stacking two identical polarizing films so that their absorption axes are parallel to each other. The orthogonal transmittance (H90) is the value of the transmittance of an orthogonal laminated polarizing film produced by stacking two identical polarizing films so that their absorption axes are orthogonal to each other. Note that these transmittances are Y values that have been subjected to luminosity correction by the 2-degree visual field (C light source) of JLS Z 8701-1982. The results are shown in Table 1.
［高温環境下における単体透過率の評価］
上記で得られた偏光フィルムを、偏光膜の吸収軸が長辺と平行になるように５．０×４．５ｃｍのサイズに切断し、偏光フィルムの画像表示セル側の保護フィルム面に、厚み２０μｍのアクリル系粘着剤層を介してガラス板（疑似画像表示セル）を貼り合わせ、５０℃、０．５ＭＰａで１５分間オートクレーブ処理して、積層体を作製した。得られた積層体を、温度９５℃の熱風オーブン内に７５０時間静置し、投入（加熱）前後の単体透過率（ΔＴｓ）を測定した。単体透過率は、分光光度計（日本分光製、製品名「Ｖ７１００」）を用いて測定し、以下の基準で評価した。なお、測定波長は、３８０～７００ｎｍ（５ｎｍ毎）である。結果を表１に示す。
ΔＴｓ（％）＝Ｔｓ７５０－Ｔｓ０
ここで、Ｔｓ０は加熱前の積層体の単体透過率であり、Ｔｓ７５０は７５０時間加熱後の積層体の単体透過率である。前記ΔＴｓ（％）は、５≧ΔＴｓ（％）≧０であることが好ましく、３≧ΔＴｓ（％）≧０であることがより好ましい。 [Evaluation of single transmittance in high temperature environment]
The polarizing film obtained above was cut into a size of 5.0 × 4.5 cm so that the absorption axis of the polarizing film was parallel to the long side, and the protective film surface on the image display cell side of the polarizing film had a thickness of A glass plate (pseudo image display cell) was attached via an acrylic adhesive layer of 20 μm, and autoclaved at 50 ° C. and 0.5 MPa for 15 minutes to prepare a laminate. The obtained laminated body was allowed to stand in a hot air oven at a temperature of 95 ° C. for 750 hours, and the single-body transmittance (ΔTs) before and after charging (heating) was measured. The simple substance transmittance was measured using a spectrophotometer (manufactured by JASCO Corporation, product name "V7100"), and evaluated according to the following criteria. The measurement wavelength is 380 to 700 nm (every 5 nm). The results are shown in Table 1.
ΔTs (%) = Ts 750 −Ts 0
Here, Ts 0 is the simple substance transmittance of the laminate before heating, and Ts 750 is the simple substance transmittance of the laminate after heating for 750 hours. The ΔTs (%) is preferably 5 ≧ ΔTs (%) ≧ 0, and more preferably 3 ≧ ΔTs (%) ≧ 0.
上記で得られた偏光フィルムを、偏光膜の吸収軸が長辺と平行になるように５．０×４．５ｃｍのサイズに切断し、偏光フィルムの画像表示セル側の保護フィルム面に、厚み２０μｍのアクリル系粘着剤層を介してガラス板（疑似画像表示セル）を貼り合わせ、５０℃、０．５ＭＰａで１５分間オートクレーブ処理して、積層体を作製した。得られた積層体を、温度９５℃の熱風オーブン内に７５０時間静置し、投入（加熱）前後の単体透過率（ΔＴｓ）を測定した。単体透過率は、分光光度計（日本分光製、製品名「Ｖ７１００」）を用いて測定し、以下の基準で評価した。なお、測定波長は、３８０～７００ｎｍ（５ｎｍ毎）である。結果を表１に示す。
ΔＴｓ（％）＝Ｔｓ７５０－Ｔｓ０
ここで、Ｔｓ０は加熱前の積層体の単体透過率であり、Ｔｓ７５０は７５０時間加熱後の積層体の単体透過率である。前記ΔＴｓ（％）は、５≧ΔＴｓ（％）≧０であることが好ましく、３≧ΔＴｓ（％）≧０であることがより好ましい。 [Evaluation of single transmittance in high temperature environment]
The polarizing film obtained above was cut into a size of 5.0 × 4.5 cm so that the absorption axis of the polarizing film was parallel to the long side, and the protective film surface on the image display cell side of the polarizing film had a thickness of A glass plate (pseudo image display cell) was attached via an acrylic adhesive layer of 20 μm, and autoclaved at 50 ° C. and 0.5 MPa for 15 minutes to prepare a laminate. The obtained laminated body was allowed to stand in a hot air oven at a temperature of 95 ° C. for 750 hours, and the single-body transmittance (ΔTs) before and after charging (heating) was measured. The simple substance transmittance was measured using a spectrophotometer (manufactured by JASCO Corporation, product name "V7100"), and evaluated according to the following criteria. The measurement wavelength is 380 to 700 nm (every 5 nm). The results are shown in Table 1.
ΔTs (%) = Ts 750 −Ts 0
Here, Ts 0 is the simple substance transmittance of the laminate before heating, and Ts 750 is the simple substance transmittance of the laminate after heating for 750 hours. The ΔTs (%) is preferably 5 ≧ ΔTs (%) ≧ 0, and more preferably 3 ≧ ΔTs (%) ≧ 0.
［パネルの反りの評価］
偏光フィルムの吸収軸が長辺と平行になるように、１４５×１０５ｍｍのサイズに切断し、偏光フィルムの画像表示セル側の保護フィルム面に厚みが２０μｍのアクリル系粘着剤層を介して、厚みが０．４ｍｍでサイズ１５５×１１５ｍｍのガラス板を貼り合わせした。得られた偏光フィルム付きガラス（疑似パネル）サンプルを８５℃の熱風オーブン内に５時間静置した後、常温常湿環境下に１時間静置した後のガラスの反り量を評価した。反りとはガラスおよび偏光板が下側に凸状となる反り量をいう。結果を表１に示す。
〇：反り量１．０ｍｍ未満
×：反り量１．０ｍｍ以上 [Evaluation of panel warpage]
The polarizing film was cut into a size of 145 × 105 mm so that the absorption axis was parallel to the long side, and the protective film surface of the polarizing film on the image display cell side was covered with an acrylic pressure-sensitive adhesive layer having a thickness of 20 μm. A glass plate having a size of 0.4 mm and a size of 155 × 115 mm was attached. The obtained glass (pseudo panel) with a polarizing film sample was allowed to stand in a hot air oven at 85 ° C. for 5 hours, and then allowed to stand in a normal temperature and normal humidity environment for 1 hour, and the amount of warpage of the glass was evaluated. The warpage refers to the amount of warpage in which the glass and the polarizing plate are convex downward. The results are shown in Table 1.
◯: Warp amount less than 1.0 mm ×: Warp amount 1.0 mm or more
偏光フィルムの吸収軸が長辺と平行になるように、１４５×１０５ｍｍのサイズに切断し、偏光フィルムの画像表示セル側の保護フィルム面に厚みが２０μｍのアクリル系粘着剤層を介して、厚みが０．４ｍｍでサイズ１５５×１１５ｍｍのガラス板を貼り合わせした。得られた偏光フィルム付きガラス（疑似パネル）サンプルを８５℃の熱風オーブン内に５時間静置した後、常温常湿環境下に１時間静置した後のガラスの反り量を評価した。反りとはガラスおよび偏光板が下側に凸状となる反り量をいう。結果を表１に示す。
〇：反り量１．０ｍｍ未満
×：反り量１．０ｍｍ以上 [Evaluation of panel warpage]
The polarizing film was cut into a size of 145 × 105 mm so that the absorption axis was parallel to the long side, and the protective film surface of the polarizing film on the image display cell side was covered with an acrylic pressure-sensitive adhesive layer having a thickness of 20 μm. A glass plate having a size of 0.4 mm and a size of 155 × 115 mm was attached. The obtained glass (pseudo panel) with a polarizing film sample was allowed to stand in a hot air oven at 85 ° C. for 5 hours, and then allowed to stand in a normal temperature and normal humidity environment for 1 hour, and the amount of warpage of the glass was evaluated. The warpage refers to the amount of warpage in which the glass and the polarizing plate are convex downward. The results are shown in Table 1.
◯: Warp amount less than 1.0 mm ×: Warp amount 1.0 mm or more
＜実施例２＞
＜偏光膜、偏光フィルムの作製＞
偏光膜の作製において、最終的に得られる偏光膜のヨウ素濃度が６．３重量％となるように染色浴のヨウ素濃度を調整したこと以外は、実施例１と同様の操作にて、偏光膜および偏光フィルムを作製した。得られた偏光膜は、発生ガス分析法にて検出される水の最大強度のピーク温度が２０７℃であり、偏光膜中の上記一般式（９）で表される化合物の含有量が０．３重量％であり、偏光膜の厚みが５μｍであった。 <Example 2>
<Production of polarizing film and polarizing film>
In the production of the polarizing film, the polarizing film was prepared in the same manner as in Example 1 except that the iodine concentration of the dyeing bath was adjusted so that the iodine concentration of the finally obtained polarizing film was 6.3% by weight. And the polarizing film was produced. In the obtained polarizing film, the peak temperature of the maximum intensity of water detected by the evolved gas analysis method is 207 ° C., and the content of the compound represented by the general formula (9) in the polarizing film is 0. It was 3% by weight, and the thickness of the polarizing film was 5 μm.
＜偏光膜、偏光フィルムの作製＞
偏光膜の作製において、最終的に得られる偏光膜のヨウ素濃度が６．３重量％となるように染色浴のヨウ素濃度を調整したこと以外は、実施例１と同様の操作にて、偏光膜および偏光フィルムを作製した。得られた偏光膜は、発生ガス分析法にて検出される水の最大強度のピーク温度が２０７℃であり、偏光膜中の上記一般式（９）で表される化合物の含有量が０．３重量％であり、偏光膜の厚みが５μｍであった。 <Example 2>
<Production of polarizing film and polarizing film>
In the production of the polarizing film, the polarizing film was prepared in the same manner as in Example 1 except that the iodine concentration of the dyeing bath was adjusted so that the iodine concentration of the finally obtained polarizing film was 6.3% by weight. And the polarizing film was produced. In the obtained polarizing film, the peak temperature of the maximum intensity of water detected by the evolved gas analysis method is 207 ° C., and the content of the compound represented by the general formula (9) in the polarizing film is 0. It was 3% by weight, and the thickness of the polarizing film was 5 μm.
＜実施例３＞
＜偏光膜、偏光フィルムの作製＞
平均重合度が２，４００、ケン化度が９９．９モル％、厚みが３０μｍであるポリビニルアルコールフィルムを用意した。ポリビニルアルコールフィルムを、周速比の異なるロール間で、２０℃の膨潤浴（水浴）中に３０秒間浸漬して膨潤しながら搬送方向に２．２倍に延伸し（膨潤工程）、続いて、３０℃の染色浴（水１００重量部に対して、ヨウ素とヨウ化カリウムを１：７の重量比で配合して得られたヨウ素水溶液）中で、最終的に得られる偏光膜のヨウ素濃度が６．１重量％となるように濃度を調整しながら３０秒間浸漬して染色しながら元のポリビニルアルコールフィルム（搬送方向に全く延伸していないポリビニルアルコールフィルム）を基準にして搬送方向に３．３倍に延伸した（染色工程）。次いで、染色したポリビニルアルコールフィルムを、４０℃の架橋浴（ホウ酸濃度が３．５重量％、ヨウ化カリウム濃度が３．０重量％、硫酸亜鉛濃度が３．６重量％である水溶液）中で２８秒間浸漬して元のポリビニルアルコールフィルムを基準にして搬送方向に３．６倍まで延伸した（架橋工程）。さらに、得られたポリビニルアルコールフィルムを、６４℃の延伸浴（ホウ酸濃度が４．５重量％、ヨウ化カリウム濃度が５．０重量％、硫酸亜鉛濃度５．０重量％である水溶液）中で６０秒間浸漬して元のポリビニルアルコールフィルムを基準にして搬送方向に６．０倍まで延伸した（延伸工程）後、２７℃の洗浄浴（ヨウ化カリウム濃度が２．３重量％、ラジカル捕捉機能を有する化合物として、下記一般式（６）で示される化合物濃度が１．０重量％である水溶液）中で１０秒間浸漬した（洗浄工程）。洗浄したポリビニルアルコールフィルムを、４０℃で３０秒間乾燥して偏光膜を作製した。得られた偏光膜は、発生ガス分析法にて検出される水の最大強度のピーク温度が２０９℃であり、偏光膜中の上記一般式（９）で表される化合物の含有量が０．２重量％であり、偏光膜の厚みが１２μｍであった。 <Example 3>
<Production of polarizing film and polarizing film>
A polyvinyl alcohol film having an average degree of polymerization of 2,400, a degree of saponification of 99.9 mol% and a thickness of 30 μm was prepared. The polyvinyl alcohol film was dipped in a swelling bath (water bath) at 20 ° C. for 30 seconds between rolls having different peripheral speed ratios and stretched to 2.2 times in the transport direction while swelling (swelling step). In a dyeing bath at 30 ° C. (an iodine aqueous solution obtained by mixing iodine and potassium iodide in a weight ratio of 1: 7 to 100 parts by weight of water), the iodine concentration of the finally obtained polarizing film is While adjusting the concentration so as to be 6.1% by weight, while soaking for 30 seconds while dyeing, 3.3 in the transport direction based on the original polyvinyl alcohol film (polyvinyl alcohol film that has not been stretched in the transport direction at all). It was stretched twice (dyeing step). Then, the dyed polyvinyl alcohol film is placed in a crosslinking bath at 40 ° C. (an aqueous solution having a boric acid concentration of 3.5% by weight, a potassium iodide concentration of 3.0% by weight, and a zinc sulfate concentration of 3.6% by weight). For 28 seconds, and stretched up to 3.6 times in the transport direction based on the original polyvinyl alcohol film (crosslinking step). Furthermore, the obtained polyvinyl alcohol film was placed in a stretching bath at 64 ° C. (an aqueous solution having a boric acid concentration of 4.5% by weight, a potassium iodide concentration of 5.0% by weight, and a zinc sulfate concentration of 5.0% by weight). After being soaked for 60 seconds, and stretched to 6.0 times in the transport direction based on the original polyvinyl alcohol film (stretching step), a washing bath at 27 ° C. (potassium iodide concentration: 2.3 wt%, radical scavenging) As a compound having a function, it was immersed for 10 seconds in an aqueous solution in which the compound represented by the following general formula (6) had a concentration of 1.0% by weight (washing step). The washed polyvinyl alcohol film was dried at 40 ° C. for 30 seconds to prepare a polarizing film. In the obtained polarizing film, the peak temperature of the maximum intensity of water detected by the evolved gas analysis method is 209 ° C., and the content of the compound represented by the general formula (9) in the polarizing film is 0. It was 2% by weight, and the thickness of the polarizing film was 12 μm.
＜偏光膜、偏光フィルムの作製＞
平均重合度が２，４００、ケン化度が９９．９モル％、厚みが３０μｍであるポリビニルアルコールフィルムを用意した。ポリビニルアルコールフィルムを、周速比の異なるロール間で、２０℃の膨潤浴（水浴）中に３０秒間浸漬して膨潤しながら搬送方向に２．２倍に延伸し（膨潤工程）、続いて、３０℃の染色浴（水１００重量部に対して、ヨウ素とヨウ化カリウムを１：７の重量比で配合して得られたヨウ素水溶液）中で、最終的に得られる偏光膜のヨウ素濃度が６．１重量％となるように濃度を調整しながら３０秒間浸漬して染色しながら元のポリビニルアルコールフィルム（搬送方向に全く延伸していないポリビニルアルコールフィルム）を基準にして搬送方向に３．３倍に延伸した（染色工程）。次いで、染色したポリビニルアルコールフィルムを、４０℃の架橋浴（ホウ酸濃度が３．５重量％、ヨウ化カリウム濃度が３．０重量％、硫酸亜鉛濃度が３．６重量％である水溶液）中で２８秒間浸漬して元のポリビニルアルコールフィルムを基準にして搬送方向に３．６倍まで延伸した（架橋工程）。さらに、得られたポリビニルアルコールフィルムを、６４℃の延伸浴（ホウ酸濃度が４．５重量％、ヨウ化カリウム濃度が５．０重量％、硫酸亜鉛濃度５．０重量％である水溶液）中で６０秒間浸漬して元のポリビニルアルコールフィルムを基準にして搬送方向に６．０倍まで延伸した（延伸工程）後、２７℃の洗浄浴（ヨウ化カリウム濃度が２．３重量％、ラジカル捕捉機能を有する化合物として、下記一般式（６）で示される化合物濃度が１．０重量％である水溶液）中で１０秒間浸漬した（洗浄工程）。洗浄したポリビニルアルコールフィルムを、４０℃で３０秒間乾燥して偏光膜を作製した。得られた偏光膜は、発生ガス分析法にて検出される水の最大強度のピーク温度が２０９℃であり、偏光膜中の上記一般式（９）で表される化合物の含有量が０．２重量％であり、偏光膜の厚みが１２μｍであった。 <Example 3>
<Production of polarizing film and polarizing film>
A polyvinyl alcohol film having an average degree of polymerization of 2,400, a degree of saponification of 99.9 mol% and a thickness of 30 μm was prepared. The polyvinyl alcohol film was dipped in a swelling bath (water bath) at 20 ° C. for 30 seconds between rolls having different peripheral speed ratios and stretched to 2.2 times in the transport direction while swelling (swelling step). In a dyeing bath at 30 ° C. (an iodine aqueous solution obtained by mixing iodine and potassium iodide in a weight ratio of 1: 7 to 100 parts by weight of water), the iodine concentration of the finally obtained polarizing film is While adjusting the concentration so as to be 6.1% by weight, while soaking for 30 seconds while dyeing, 3.3 in the transport direction based on the original polyvinyl alcohol film (polyvinyl alcohol film that has not been stretched in the transport direction at all). It was stretched twice (dyeing step). Then, the dyed polyvinyl alcohol film is placed in a crosslinking bath at 40 ° C. (an aqueous solution having a boric acid concentration of 3.5% by weight, a potassium iodide concentration of 3.0% by weight, and a zinc sulfate concentration of 3.6% by weight). For 28 seconds, and stretched up to 3.6 times in the transport direction based on the original polyvinyl alcohol film (crosslinking step). Furthermore, the obtained polyvinyl alcohol film was placed in a stretching bath at 64 ° C. (an aqueous solution having a boric acid concentration of 4.5% by weight, a potassium iodide concentration of 5.0% by weight, and a zinc sulfate concentration of 5.0% by weight). After being soaked for 60 seconds, and stretched to 6.0 times in the transport direction based on the original polyvinyl alcohol film (stretching step), a washing bath at 27 ° C. (potassium iodide concentration: 2.3 wt%, radical scavenging) As a compound having a function, it was immersed for 10 seconds in an aqueous solution in which the compound represented by the following general formula (6) had a concentration of 1.0% by weight (washing step). The washed polyvinyl alcohol film was dried at 40 ° C. for 30 seconds to prepare a polarizing film. In the obtained polarizing film, the peak temperature of the maximum intensity of water detected by the evolved gas analysis method is 209 ° C., and the content of the compound represented by the general formula (9) in the polarizing film is 0. It was 2% by weight, and the thickness of the polarizing film was 12 μm.
続いて、接着剤として、アセトアセチル基を含有するポリビニルアルコール樹脂（平均重合度が１，２００、ケン化度が９８．５モル％、アセトアセチル化度が５モル％）とメチロールメラミンとを重量比３：１で含有する水溶液を用いた。この接着剤を用いて、上記で得られた偏光膜の一方の面（画像表示装置セル側）に、（メタ）アクリル系樹脂（ラクトン環構造を有する変性アクリル系ポリマー）からなる厚み３０μｍの透明保護フィルム（日本触媒製、透湿度は１２５ｇ／（ｍ２・２４ｈ））を、また、他方の面（視認側）に、トリアセチルセルロースフィルム（富士フィルム製、商品名「ＴＪ４０ＵＬ」）にＨＣを形成した厚み４７μｍの透明保護フィルム（透湿度は３８０ｇ／（ｍ２・２４ｈ））をロール貼合機で貼り合わせた後、引き続きオーブン内で加熱乾燥（温度が９０℃、時間が１０分間）させて、偏光膜の両面に透明保護フィルムが貼り合わせられた偏光フィルムを作製した。
Subsequently, as an adhesive, a polyvinyl alcohol resin containing an acetoacetyl group (average polymerization degree: 1,200, saponification degree: 98.5 mol%, acetoacetylation degree: 5 mol%) and methylolmelamine were weighed. An aqueous solution containing a ratio of 3: 1 was used. Using this adhesive, a 30 μm-thick transparent film made of a (meth) acrylic resin (modified acrylic polymer having a lactone ring structure) on one surface (image display device cell side) of the polarizing film obtained above Protective film (manufactured by Nippon Shokubai, water vapor transmission rate is 125 g / (m 2 · 24 h)), and on the other surface (viewing side), triacetyl cellulose film (manufactured by Fuji Film, trade name “TJ40UL”) is charged with HC. The formed transparent protective film with a thickness of 47 μm (moisture permeability is 380 g / (m 2 · 24 h)) was pasted with a roll laminating machine, and then dried by heating in an oven (temperature 90 ° C., time 10 minutes). Thus, a polarizing film having transparent protective films attached to both surfaces of the polarizing film was produced.
＜実施例４＞
＜偏光膜、偏光フィルムの作製＞
偏光膜の作製において、最終的に得られる偏光膜のヨウ素濃度が７．９重量％となるように染色浴のヨウ素濃度を調整したこと、また、洗浄工程の浴にラジカル捕捉機能を有する化合物として、上記一般式（９）の代わりに、上記一般式（８）で表される化合物を濃度が１．０重量％添加したこと以外は、実施例１と同様の操作にて、偏光膜および偏光フィルムを作製した。得られた偏光膜は、発生ガス分析法にて検出される水の最大強度のピーク温度が２０６℃であり、偏光膜中の上記一般式（８）で表される化合物の含有量が０．３重量％であり、偏光膜の厚みが５μｍであった。 <Example 4>
<Production of polarizing film and polarizing film>
In the production of the polarizing film, the iodine concentration of the dyeing bath was adjusted so that the iodine concentration of the finally obtained polarizing film was 7.9% by weight, and a compound having a radical scavenging function was added to the bath in the washing step. In the same manner as in Example 1, except that the compound represented by the general formula (8) was added in a concentration of 1.0 wt% instead of the general formula (9), a polarizing film and a polarizing film were obtained. A film was made. In the obtained polarizing film, the peak temperature of the maximum intensity of water detected by the evolved gas analysis method is 206 ° C., and the content of the compound represented by the general formula (8) in the polarizing film is 0. It was 3% by weight, and the thickness of the polarizing film was 5 μm.
＜偏光膜、偏光フィルムの作製＞
偏光膜の作製において、最終的に得られる偏光膜のヨウ素濃度が７．９重量％となるように染色浴のヨウ素濃度を調整したこと、また、洗浄工程の浴にラジカル捕捉機能を有する化合物として、上記一般式（９）の代わりに、上記一般式（８）で表される化合物を濃度が１．０重量％添加したこと以外は、実施例１と同様の操作にて、偏光膜および偏光フィルムを作製した。得られた偏光膜は、発生ガス分析法にて検出される水の最大強度のピーク温度が２０６℃であり、偏光膜中の上記一般式（８）で表される化合物の含有量が０．３重量％であり、偏光膜の厚みが５μｍであった。 <Example 4>
<Production of polarizing film and polarizing film>
In the production of the polarizing film, the iodine concentration of the dyeing bath was adjusted so that the iodine concentration of the finally obtained polarizing film was 7.9% by weight, and a compound having a radical scavenging function was added to the bath in the washing step. In the same manner as in Example 1, except that the compound represented by the general formula (8) was added in a concentration of 1.0 wt% instead of the general formula (9), a polarizing film and a polarizing film were obtained. A film was made. In the obtained polarizing film, the peak temperature of the maximum intensity of water detected by the evolved gas analysis method is 206 ° C., and the content of the compound represented by the general formula (8) in the polarizing film is 0. It was 3% by weight, and the thickness of the polarizing film was 5 μm.
＜比較例１＞
＜偏光膜、偏光フィルムの作製＞
偏光膜の作製において、最終的に得られる偏光膜のヨウ素濃度が８．５重量％となるように染色浴のヨウ素濃度を調整し、また、洗浄浴にラジカル捕捉機能を有する化合物として、上記一般式（９）で表される化合物を添加しなかったこと以外は、実施例１と同様の操作にて、偏光膜および偏光フィルムを作製した。得られた偏光膜は、発生ガス分析法にて検出される水の最大強度のピーク温度が１９３℃であり、偏光膜中の上記一般式（９）で表される化合物の含有量が０重量％であり、偏光膜の厚みが５μｍであった。 <Comparative Example 1>
<Production of polarizing film and polarizing film>
In the production of the polarizing film, the iodine concentration of the dyeing bath is adjusted so that the iodine concentration of the finally obtained polarizing film will be 8.5% by weight, and the washing bath may be a compound having a radical scavenging function as described above. A polarizing film and a polarizing film were produced in the same manner as in Example 1, except that the compound represented by the formula (9) was not added. In the obtained polarizing film, the peak temperature of the maximum intensity of water detected by the evolved gas analysis method is 193 ° C., and the content of the compound represented by the general formula (9) in the polarizing film is 0% by weight. %, And the thickness of the polarizing film was 5 μm.
＜偏光膜、偏光フィルムの作製＞
偏光膜の作製において、最終的に得られる偏光膜のヨウ素濃度が８．５重量％となるように染色浴のヨウ素濃度を調整し、また、洗浄浴にラジカル捕捉機能を有する化合物として、上記一般式（９）で表される化合物を添加しなかったこと以外は、実施例１と同様の操作にて、偏光膜および偏光フィルムを作製した。得られた偏光膜は、発生ガス分析法にて検出される水の最大強度のピーク温度が１９３℃であり、偏光膜中の上記一般式（９）で表される化合物の含有量が０重量％であり、偏光膜の厚みが５μｍであった。 <Comparative Example 1>
<Production of polarizing film and polarizing film>
In the production of the polarizing film, the iodine concentration of the dyeing bath is adjusted so that the iodine concentration of the finally obtained polarizing film will be 8.5% by weight, and the washing bath may be a compound having a radical scavenging function as described above. A polarizing film and a polarizing film were produced in the same manner as in Example 1, except that the compound represented by the formula (9) was not added. In the obtained polarizing film, the peak temperature of the maximum intensity of water detected by the evolved gas analysis method is 193 ° C., and the content of the compound represented by the general formula (9) in the polarizing film is 0% by weight. %, And the thickness of the polarizing film was 5 μm.
＜比較例２＞
＜偏光膜、偏光フィルムの作製＞
偏光膜の作製において、最終的に得られる偏光膜のヨウ素濃度が５．６重量％となるように染色浴のヨウ素濃度を調整し、また、洗浄浴にラジカル捕捉機能を有する化合物として、上記一般式（９）で表される化合物を添加しなかったこと以外は、実施例１と同様の操作にて、偏光膜および偏光フィルムを作製した。得られた偏光膜は、発生ガス分析法にて検出される水の最大強度のピーク温度が２０３℃であり、偏光膜中の上記一般式（９）で表される化合物の含有量が０重量％であり、偏光膜の厚みが５μｍであった。 <Comparative example 2>
<Production of polarizing film and polarizing film>
In the production of the polarizing film, the iodine concentration of the dyeing bath is adjusted so that the iodine concentration of the finally obtained polarizing film is 5.6% by weight, and the washing bath is a compound having a radical scavenging function. A polarizing film and a polarizing film were produced in the same manner as in Example 1 except that the compound represented by the formula (9) was not added. In the obtained polarizing film, the peak temperature of the maximum intensity of water detected by the evolved gas analysis method is 203 ° C., and the content of the compound represented by the general formula (9) in the polarizing film is 0% by weight. %, And the thickness of the polarizing film was 5 μm.
＜偏光膜、偏光フィルムの作製＞
偏光膜の作製において、最終的に得られる偏光膜のヨウ素濃度が５．６重量％となるように染色浴のヨウ素濃度を調整し、また、洗浄浴にラジカル捕捉機能を有する化合物として、上記一般式（９）で表される化合物を添加しなかったこと以外は、実施例１と同様の操作にて、偏光膜および偏光フィルムを作製した。得られた偏光膜は、発生ガス分析法にて検出される水の最大強度のピーク温度が２０３℃であり、偏光膜中の上記一般式（９）で表される化合物の含有量が０重量％であり、偏光膜の厚みが５μｍであった。 <Comparative example 2>
<Production of polarizing film and polarizing film>
In the production of the polarizing film, the iodine concentration of the dyeing bath is adjusted so that the iodine concentration of the finally obtained polarizing film is 5.6% by weight, and the washing bath is a compound having a radical scavenging function. A polarizing film and a polarizing film were produced in the same manner as in Example 1 except that the compound represented by the formula (9) was not added. In the obtained polarizing film, the peak temperature of the maximum intensity of water detected by the evolved gas analysis method is 203 ° C., and the content of the compound represented by the general formula (9) in the polarizing film is 0% by weight. %, And the thickness of the polarizing film was 5 μm.
上記で得られた実施例および比較例の偏光フィルムを用い、上記の［偏光度の評価］、［高温環境下における単体透過率の評価］、および［パネルの反りの評価］を行った。結果を表１に示す。
Using the polarizing films of Examples and Comparative Examples obtained above, the above [evaluation of polarization degree], [evaluation of single transmittance under high temperature environment], and [evaluation of warp of panel] were performed. The results are shown in Table 1.
Claims (10)
- ポリビニルアルコール系フィルムにヨウ素が吸着配向して形成される偏光膜であって、
ヨウ素濃度が６重量％以上であり、かつ、
発生ガス分析において、不活性ガスの存在下、昇温速度が１０℃／分で、昇温範囲が４０℃から３５０℃までの条件にて、検出される水の最大強度のピーク温度が２００℃以上であることを特徴とする偏光膜。 A polarizing film formed by adsorbing and orienting iodine on a polyvinyl alcohol film,
The iodine concentration is 6% by weight or more, and
In the generated gas analysis, in the presence of an inert gas, the temperature rise rate was 10 ° C / min, and the temperature rise range was 40 ° C to 350 ° C. A polarizing film having the above. - 厚みが１５μｍ以下であることを特徴とする請求項１記載の偏光膜。 The polarizing film according to claim 1, which has a thickness of 15 μm or less.
- ラジカル捕捉機能を有する化合物を含むことを特徴とする請求項１または請求項２記載の偏光膜。 The polarizing film according to claim 1 or 2, which comprises a compound having a radical scavenging function.
- 前記ラジカル捕捉機能を有する化合物が、ニトロキシラジカル、またはニトロキシド基を有する化合物であることを特徴とする請求項３記載の偏光膜。 The polarizing film according to claim 3, wherein the compound having a radical scavenging function is a compound having a nitroxy radical or a nitroxide group.
- 請求項１～４のいずれかに記載の偏光膜の少なくとも一方の面に透明保護フィルムが貼り合わされていることを特徴とする偏光フィルム。 A polarizing film, characterized in that a transparent protective film is attached to at least one surface of the polarizing film according to any one of claims 1 to 4.
- 偏光度が９９．９８％以上であることを特徴とする請求項５記載の偏光フィルム。 The polarizing film according to claim 5, wherein the degree of polarization is 99.98% or more.
- 請求項５または６記載の偏光フィルムが光学層に貼り合わされていることを特徴とする積層偏光フィルム。 A laminated polarizing film comprising the polarizing film according to claim 5 or 6 bonded to an optical layer.
- 画像表示セルに、請求項５または６記載の偏光フィルム、または請求項７記載の積層偏光フィルムが貼り合わされていることを特徴とする画像表示パネル。 An image display panel, characterized in that the polarizing film according to claim 5 or 6 or the laminated polarizing film according to claim 7 is attached to the image display cell.
- 請求項８記載の画像表示パネルの偏光フィルムまたは積層偏光フィルム側に、前面透明部材を備えることを特徴とする画像表示装置。 An image display device comprising a front transparent member on the polarizing film or laminated polarizing film side of the image display panel according to claim 8.
- 車載用であることを特徴とする請求項９記載の画像表示装置。 The image display device according to claim 9, which is for use in a vehicle.
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| CN202211392485.4A CN115685435A (en) | 2018-11-12 | 2019-11-12 | Polarizing film, laminated polarizing film, image display panel, and image display device |
| CN201980063377.2A CN112840241B (en) | 2018-11-12 | 2019-11-12 | Polarizing film, laminated polarizing film, image display panel, and image display device |
| JP2020555702A JP6964798B2 (en) | 2018-11-12 | 2019-11-12 | Polarizing film, polarizing film, laminated polarizing film, image display panel, and image display device |
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| JPWO2020100889A1 (en) * | 2018-11-12 | 2021-04-01 | 日東電工株式会社 | Polarizing film, polarizing film, laminated polarizing film, image display panel, and image display device |
| JPWO2020100871A1 (en) * | 2018-11-12 | 2021-04-08 | 日東電工株式会社 | Polarizing film, polarizing film, laminated polarizing film, image display panel, and image display device |
| WO2021206073A1 (en) * | 2020-04-08 | 2021-10-14 | 日東電工株式会社 | Polarizing film |
| WO2021210342A1 (en) * | 2020-04-14 | 2021-10-21 | 日東電工株式会社 | Polarizing membrane and polarizing film |
| WO2021225114A1 (en) * | 2020-05-08 | 2021-11-11 | 日東電工株式会社 | Image display device |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN112840241A (en) | 2021-05-25 |
| JP6964798B2 (en) | 2021-11-10 |
| JP2022009239A (en) | 2022-01-14 |
| KR20210089630A (en) | 2021-07-16 |
| JP7212123B2 (en) | 2023-01-24 |
| JPWO2020100861A1 (en) | 2021-03-25 |
| CN115685435A (en) | 2023-02-03 |
| TW202024689A (en) | 2020-07-01 |
| CN112840241B (en) | 2023-05-12 |
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