CN112771419B - Polarizing film, laminated polarizing film, image display panel, and image display device - Google Patents
Polarizing film, laminated polarizing film, image display panel, and image display device Download PDFInfo
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- CN112771419B CN112771419B CN201980063373.4A CN201980063373A CN112771419B CN 112771419 B CN112771419 B CN 112771419B CN 201980063373 A CN201980063373 A CN 201980063373A CN 112771419 B CN112771419 B CN 112771419B
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- polarizing film
- image display
- film
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Classifications
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- 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
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Chemical & Material Sciences (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Theoretical Computer Science (AREA)
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
- Electroluminescent Light Sources (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
The present invention provides a polarizing film formed by adsorbing and orienting iodine to a polyvinyl alcohol film, wherein the iodine concentration is 3 wt% or more and 10 wt% or less, and wherein the peak temperature of the maximum intensity of water detected by the polarizing film in the presence of an inert gas in the temperature rising rate of 10 ℃/min and the temperature rising range of 40 ℃ to 350 ℃ is 205 ℃ or more in the generated gas analysis method. The polarizing film has excellent initial polarization degree and excellent effect of suppressing the decrease of the monomer transmittance caused by the coloring of the polarizing film in a high temperature environment.
Description
Technical Field
The invention relates to a polarizing film, a laminated polarizing film, an image display panel and an image display device.
Background
Conventionally, as a polarizing film used for various image display devices such as a liquid crystal display device and an organic EL display device, a polyvinyl alcohol film (containing a dichroic substance such as iodine or a dichroic dye) which has been subjected to a dyeing treatment has been used in view of having both a high transmittance and a high polarization degree. The polarizing film was produced as follows: the polyvinyl alcohol film is subjected to various treatments such as swelling, dyeing, crosslinking, stretching, etc. in a bath, then subjected to a cleaning treatment, and then dried. The polarizing film is generally used in the form of a polarizing film (polarizing plate) having a protective film such as cellulose triacetate attached to one or both surfaces thereof by an adhesive.
The polarizing film is used in the form of a laminated polarizing film (optical laminate) in which other optical layers are laminated as necessary, and the polarizing film or the laminated polarizing film (optical laminate) is laminated between an image display unit such as a liquid crystal cell or an organic EL element and a front surface transparent plate (window layer) on the visible side or a front surface transparent member such as a touch panel via an adhesive layer or an adhesive layer to manufacture the various image display devices (patent document 1).
In recent years, such various image display devices are used as image display devices for vehicles such as car navigation devices and rear view monitors, in addition to mobile devices such as mobile phones and tablet terminals, and their uses are expanding. Accordingly, there has been proposed an image display device which is required to have high durability in a severe environment (for example, a high-temperature environment) as compared with conventional requirements, and which is aimed at securing such durability (patent document 2).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2014-102353
Patent document 2: japanese patent application laid-open No. 2018-101117
Disclosure of Invention
Problems to be solved by the invention
When a polarizing film or a laminated polarizing film using an iodine-based polarizing film is exposed to a high-temperature environment, polyvinyl alcohol constituting the polarizing film becomes multi-functionalized by a dehydration reaction, and thus the polarizing film is colored, which has a problem that the transmittance of a monomer thereof is lowered.
As a result of intensive studies, the present inventors have found that iodine contained in an iodine-based polarizing film promotes multiolefination in a high-temperature environment. Thus, in order to suppress the decrease in the transmittance of the monomer due to the coloration of the polarizing film in a high-temperature environment, it is effective to reduce the iodine concentration (content) in the polarizing film. On the other hand, although a polarizing film having a good degree of polarization can be obtained with a small iodine concentration by thickening the polarizing film, when such a polarizing film is used, there is a tendency that peeling is easily generated when the polarizing film or the laminated polarizing film is heated, along with an increase in the size of a panel of an image display device.
In view of the above, an object of the present invention is to provide a polarizing film which has a good initial polarization degree and is excellent in an effect of suppressing a decrease in the transmittance of a monomer due to coloring of the polarizing film in a high-temperature environment.
Another object of the present invention is to provide a polarizing film, a laminated polarizing film, an image display panel, and an image display device using the polarizing film.
Means for solving the problems
Specifically, the present invention relates to a polarizing film formed by adsorbing and orienting iodine to a polyvinyl alcohol film, wherein the iodine concentration is 3 to 10 wt%, and wherein the peak temperature of the maximum intensity of water detected in the presence of an inert gas in a temperature rise rate of 10 ℃/min and a temperature rise range of 40 to 350 ℃ in a generated gas analysis method is 205 ℃ or higher.
The present invention also relates to a polarizing film having a transparent protective film bonded to at least one surface of the polarizing film.
The present invention also relates to a laminated polarizing film, wherein the polarizing film is bonded to an optical layer.
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 unit.
The present invention also relates to an image display device including a front surface transparent member on the polarizing film or laminated polarizing film side of the image display panel.
ADVANTAGEOUS EFFECTS OF INVENTION
The details of the mechanism of action of the effect of the polarizing film of the present invention are not clear, but are estimated as follows. However, the present invention may be interpreted not to be limited to this mechanism of action.
The polarizing film of the present invention is an iodine-based polarizing film in which iodine is adsorbed on a polyvinyl alcohol film and oriented, and has an iodine concentration of 3 to 10 wt% inclusive, and in a generated gas analysis method, the polarizing film has a peak temperature of 205 ℃ or higher at a maximum intensity of water detected under conditions of a temperature rise rate of 10 ℃/min and a temperature rise range of 40 to 350 ℃ in the presence of an inert gas. As described above, the iodine-based polarizing film is subjected to a multi-olefination by the dehydration reaction of polyvinyl alcohol in a high-temperature environment, but in the polarizing film of the present invention, the decrease in the transmittance of the monomer due to the coloration of the polarizing film in a high-temperature environment can be suppressed by setting the temperature at which the dehydration reaction occurs to the high-temperature side, that is, setting the peak temperature of the maximum intensity of water detected (observed) by the generated gas analysis method to 205 ℃. In the polarizing film of the present invention, by setting the iodine concentration in the polarizing film to a constant range, the peak temperature of the maximum intensity of water detected (observed) by the generated gas analysis method can be controlled to 205 ℃.
On the other hand, the present inventors have observed that radicals are generated in a polarizing film formed by adsorbing and aligning iodine to an iodine-containing polyvinyl alcohol film, as a result of exposing the polarizing film to a high-temperature environment for a certain period of time. Since the time for coloring the polarizing film by multi-olefination is very similar to the time for generating the radicals, it is suggested that the phenomenon of generating the radicals occurs due to the multi-olefination of the polarizing film. Therefore, in order to set the temperature at which the dehydration reaction described above occurs in the polarizing film to a high temperature side, that is, to set the peak temperature of the maximum intensity of water detected (observed) by the generated gas analysis method to 205 ℃.
Drawings
Fig. 1 is an example of a graph showing peaks of water detected in a generated gas analysis method using an iodine-based polarizing film as a sample.
Detailed Description
< polarizing film >
The polarizing film of the present invention is an iodine-based polarizing film in which iodine is adsorbed to a polyvinyl alcohol film and oriented, and the iodine concentration is 3 to 10 wt% inclusive, and in the presence of an inert gas in a generated gas analysis method, the peak temperature of the maximum intensity of water detected by the polarizing film under conditions of a temperature rise rate of 10 ℃/min and a temperature rise range of 40 to 350 ℃ is 205 ℃ or higher.
The polyvinyl alcohol (PVA) based film may be a polyvinyl alcohol (PVA) based film having transparency in the visible light range and obtained by dispersing and adsorbing iodine, without particular limitation. The thickness of the PVA film used in the film roll is usually about 1 to 100. Mu.m, more preferably about 1 to 50. Mu.m, and the width is preferably about 100 to 5000 mm.
As the material of the polyvinyl alcohol film, polyvinyl alcohol or a derivative thereof is exemplified. Examples of the derivative of the polyvinyl alcohol include: polyvinyl formal and polyvinyl acetal; olefins such as ethylene and propylene; and derivatives obtained by modification with unsaturated carboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, alkyl esters thereof, acrylamide and the like. The average polymerization degree of the polyvinyl alcohol is preferably about 100 to 10000, more preferably about 1000 to 10000, and even more preferably about 1500 to 4500. The saponification degree of the polyvinyl alcohol is preferably about 80 to 100 mol%, and more preferably about 95 to 99.95 mol%. The average polymerization degree and the saponification degree can be obtained based on JIS K6726.
Additives such as plasticizers and surfactants may be contained in the polyvinyl alcohol film. Examples of the plasticizer include: polyhydric alcohols such as glycerin, diglycerin, triglycerin, ethylene glycol, propylene glycol, and polyethylene glycol, and condensates thereof. The amount of the above-mentioned additive is not particularly limited, and for example, it is preferably 20% by weight or less in a polyvinyl alcohol film.
The iodine concentration (content) of the polarizing film is 3 wt% or more and 10 wt% or less from the viewpoint of improving the initial polarization degree of the polarizing film and controlling the peak temperature of the maximum intensity of water detected by the generated gas analysis method to 205 ℃ or more. The iodine concentration (content) of the polarizing film is preferably 3.5 wt% or more, more preferably 4 wt% or more, from the viewpoint of improving the initial polarization degree of the polarizing film, and is preferably 9 wt% or less, more preferably 7 wt% or less, from the viewpoint of controlling the peak temperature of the maximum intensity of water detected by the generated gas analysis method to 205 ℃.
In the generated gas analysis method, the polarizing film exhibits a peak temperature of 205 ℃ or higher at a maximum intensity of water detected under conditions of a temperature rising rate of 10 ℃/min and a temperature rising range of 40 ℃ to 350 ℃ in the presence of an inert gas. In the polarizing film, the decrease in the transmittance of the monomer due to the coloration of the polarizing film in a high-temperature environment can be suppressed by setting the temperature at which the dehydration reaction of polyvinyl alcohol occurs to the high-temperature side, that is, setting the peak temperature of the maximum intensity of water detected by the generated gas analysis method to 205 ℃. On the other hand, when the peak temperature of the maximum intensity of water is lower than 205 ℃, it is difficult to control the amount of change in the monomer transmittance of the polarizing film before and after the heating durability test (105 ℃ C.×750 hours) which is an index of high temperature durability required in a high-end in-vehicle display to 0% or more and 5% or less.
Fig. 1 is an example of a graph showing peaks of water detected by the generated gas analysis method, and the peak temperature of the maximum intensity of the detected water is 205 ℃.
The generated gas analysis method is an analysis method in which a gas chromatograph apparatus and a mass spectrometer apparatus are directly connected by an inert metal capillary or the like, and gas generated when a sample is heated by heating is monitored in real time, and is generally called an EGA/MS method, an EGA/TOFMS method, or the like.
The polarizing film preferably contains a compound having a radical trapping function. It is estimated that the compound having a radical trapping function can trap radicals generated by heating polyvinyl alcohol of a polarizing film, and the temperature at which a multi-olefination dehydration reaction occurs is set to a high temperature side. Examples of the compound having a radical trapping function include: compounds having a radical trapping function (e.g., antioxidants) such as hindered phenols, hindered amines, phosphorus compounds, sulfur compounds, benzotriazole compounds, benzophenone compounds, hydroxylamine compounds, salicylate compounds, and triazine compounds. The compound having a radical trapping function is preferably a compound having a nitroxyl radical or a nitroxyl group, for example, from the viewpoint that the temperature at which the dehydration reaction of the polyalkylene is caused can be easily set to the high temperature side.
The nitroxyl radical or nitroxyl radical-containing compound may be an N-oxyl compound (a compound having C-N (-C) -O.as a functional group (O.represents an oxygen radical)), or a known compound from the viewpoint of having a relatively stable radical at room temperature in air. Examples of the N-oxyl compound include compounds having an organic group having the following structure.
[ chemical formula 1]
(in the general formula (1), R 1 Represents oxygen radicals, R 2 ~R 5 Independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n represents 0 or 1), and the left side of the dotted line portion in the general formula (1) represents an arbitrary organic group.
Examples of the compound having an organic group include compounds represented by the following general formulae (2) to (5).
[ chemical formula 2]
(in the general formula (2), R 1 ~R 5 And n is as defined above, R 6 Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group, or an aryl group, and n represents 0 or 1. )
[ chemical formula 3]
(in the general formula (3), R 1 ~R 5 And n is as defined above, R 7 R is R 8 Independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group, or an aryl group. )
[ chemical formula 4]
(in the general formula (4), R 1 ~R 5 And n is as defined above, R 9 ~R 11 Independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group, an amino group, an alkoxy group, a hydroxyl group, or an aryl group. )
[ chemical formula 5]
(in the general formula (5), R 1 ~R 5 And n is as defined above, R 12 Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an amino group, an alkoxy group, a hydroxyl group, or an aryl group. )
In the general formulae (1) to (5), R is from the viewpoint of easiness of acquisition 2 ~R 5 The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. In the general formula (2), the compound is obtained fromFrom the viewpoint of easiness, R 6 Preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom. In the general formula (3), R is preferable from the viewpoint of easy availability 7 R is R 8 Independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom. In the general formula (4), R is from the viewpoint of easy availability 9 ~R 11 Preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. In the general formula (5), R is from the viewpoint of easiness of acquisition 12 Preferably hydroxy, amino or alkoxy. In the general formulae (1) to (5), n is preferably 1 from the viewpoint of ease of acquisition.
Examples of the N-oxyl compound include: an N-oxyl compound described in Japanese patent application laid-open No. 2003-64022, japanese patent application laid-open No. 11-222462, japanese patent application laid-open No. 2002-284737, international publication No. 2016/047655, and the like.
In addition, the molecular weight of the compound having a radical capturing function is preferably 1000 or less, more preferably 500 or less, and further preferably 300 or less, from the viewpoint of being able to efficiently capture radicals generated in the polyethylenic reaction.
The compound having a radical trapping function is preferably soluble in 100 parts by weight of 25 ℃ water in an amount of 1 part by weight or more, more preferably soluble in 100 parts by weight of 25 ℃ water in an amount of 2 parts by weight or more, and even more preferably soluble in 100 parts by weight of 25 ℃ water in an amount of 5 parts by weight or more, from the viewpoint of allowing efficient permeation of water into the polarizing film at the time of producing the polarizing film, impregnating the polarizing film at a high concentration, and allowing impregnation in a short time even in the case of using a polyvinyl alcohol film having a thick thickness, thereby improving productivity of the polarizing film.
Examples of the compound having a nitroxyl radical or a nitroxyl group include the following compounds.
[ chemical formula 6]
(in the general formula (6), R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group, or an aryl group.)
[ chemical formula 7]
[ chemical formula 8]
In the case where the polarizing film contains the compound having a radical trapping function, the content of the compound having a radical trapping function in the polarizing film is preferably 0.005 wt% or more, more preferably 0.01 wt% or more, still more preferably 0.02 wt% or more, from the viewpoint of suppressing a decrease in the transmittance of the monomer due to the coloring of the polarizing film in a high-temperature environment, and is preferably 15 wt% or less, more preferably 12 wt% or less, still more preferably 10 wt% or less, from the viewpoint of appearance.
Method for producing polarizing film
The method for manufacturing the polarizing film comprises the following steps: the polarizing film is obtained by performing an optional swelling step and a washing step, and at least a dyeing step, a crosslinking step, and a stretching step on the polyvinyl alcohol film. The iodine content in the polarizing film can be controlled by the concentration of iodine, potassium iodide, and other iodides contained in any of the treatment baths in the swelling step, dyeing step, crosslinking step, stretching step, and cleaning step, and the treatment temperature and treatment time in the treatment baths.
In the case of producing a polarizing film containing the compound having a radical trapping function, the compound having a radical trapping function may be contained in a treatment bath in any one or more of the swelling step, the cleaning step, the dyeing step, the crosslinking step, and the stretching step. The concentration of the compound having a radical trapping function contained in any of the treatment baths is affected by the number of treatments, the treatment time, the treatment temperature, and the like of each treatment, and therefore cannot be determined in general, and is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, still more preferably 0.1% by weight or more, and is preferably 30% by weight or less, more preferably 25% by weight or less, still more preferably 20% by weight or less, from the viewpoint of being able to efficiently control the content of the compound having a radical trapping function in the polarizing film.
In particular, in the case where the cleaning step is performed after the dyeing step, the crosslinking step, and the stretching step, the content of iodine or the compound having a radical trapping function is easily adjusted to a desired range from the viewpoint of allowing the component such as iodine or the compound having a radical trapping function to be eluted from or adsorbed to the polyvinyl alcohol film in consideration of the treatment conditions in the dyeing step, the crosslinking step, the stretching step, and the like.
In addition, additives such as zinc salts, pH adjusters, pH buffers, and other salts may be contained in each treatment bath in the swelling step, the dyeing step, the crosslinking step, the stretching step, and the washing step. 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, salts thereof, inorganic weak 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, salts of alkali metals and alkaline earth metals, and the like.
The swelling step is a treatment step of immersing the polyvinyl alcohol film in a swelling bath, and can remove dirt, an anti-blocking agent, and the like on the surface of the polyvinyl alcohol film, and can suppress uneven dyeing by swelling the polyvinyl alcohol film. The swelling bath generally uses a medium containing water as a main component, such as water, distilled water, and pure water. The swelling bath may be appropriately added with a surfactant, alcohol, or the like according to a usual method.
The temperature of the swelling bath is preferably about 10 to 60 ℃, more preferably about 15 to 45 ℃, and still more preferably about 18 to 30 ℃. Further, since the swelling degree of the polyvinyl alcohol film is affected by the temperature of the swelling bath, the immersion time in the swelling bath cannot be determined in a simple manner, and is preferably about 5 to 300 seconds, more preferably about 10 to 200 seconds, and further preferably about 20 to 100 seconds. The swelling step may be performed only 1 time, or may be performed as many times as necessary.
The dyeing step is a treatment step of immersing the polyvinyl alcohol film in a dyeing bath (iodine solution), and iodine can be adsorbed to the polyvinyl alcohol film and oriented. The iodine solution is usually preferably an aqueous iodine solution, and more preferably contains iodine and an 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 titanium iodide. Among these, potassium iodide is preferable from the viewpoint of controlling the potassium content in the polarizing film.
In the dyeing bath, the concentration of iodine is preferably about 0.01 to 1% by weight, more preferably about 0.02 to 0.5% by weight. In the dyeing bath, the concentration of the iodide is preferably about 0.01 to 20% by weight, more preferably about 0.05 to 10% by weight, and still more preferably about 0.1 to 5% by weight.
The temperature of the dyeing bath is preferably about 10 to 50 ℃, more preferably about 15 to 45 ℃, and still more preferably about 18 to 30 ℃. Further, since the dyeing degree of the polyvinyl alcohol film is affected by the temperature of the dyeing bath, the immersion time in the dyeing bath cannot be determined in a simple manner, and is preferably about 10 to 300 seconds, more preferably about 20 to 240 seconds. The dyeing step may be performed only 1 time, or may be performed as many times as necessary.
The crosslinking step is a treatment step of immersing the polyvinyl alcohol film in a treatment bath (crosslinking bath) containing a boron compound, and the polyvinyl alcohol film can be crosslinked with the boron compound to adsorb iodine molecules or dye molecules to the crosslinked structure. Examples of the boron compound include: boric acid, borates, borax, and the like. The crosslinking bath is generally an aqueous solution, and may be a mixed solution of an organic solvent having miscibility with water and water, for example. In addition, from the viewpoint of controlling the potassium content in the polarizing film, the crosslinking bath may contain potassium iodide.
In the crosslinking bath, the concentration of the boron compound is preferably about 1 to 15% by weight, more preferably about 1.5 to 10% by weight, and still more preferably about 2 to 5% by weight. In the case where 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, and still more preferably about 2 to 5% by weight.
The temperature of the crosslinking bath is preferably about 20 to 70 ℃, more preferably about 30 to 60 ℃. Further, since the degree of crosslinking of the polyvinyl alcohol film is affected by the temperature of the crosslinking bath, the immersion time in the crosslinking bath cannot be determined in a simple manner, and is preferably about 5 to 300 seconds, more preferably about 10 to 200 seconds. The crosslinking step may be performed only 1 time, or may be performed as many times as necessary.
The stretching step is a treatment step of stretching the polyvinyl alcohol film in at least one direction at a predetermined magnification. In general, a polyvinyl alcohol film is uniaxially stretched in a transport direction (longitudinal direction). The stretching method is not particularly limited, and any of wet stretching and dry stretching may be used. The stretching step may be performed only 1 time, or may be performed as many times as necessary. The stretching step may be performed at any stage in the production of the polarizing film.
The treatment bath (stretching bath) in the wet stretching method may be water, or a solvent such as an organic solvent having a miscibility with water or a mixed solution of water. The stretching bath may contain potassium iodide from the viewpoint of controlling the content of 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 still more preferably about 3 to 6% by weight. In addition, from the viewpoint of suppressing film breakage during stretching, the boron compound may be contained in the treatment bath (stretching bath), and in this case, the concentration of the boron compound in the stretching bath is preferably about 1 to 15% by weight, more preferably about 1.5 to 10% by weight, and still more preferably about 2 to 5% by weight.
The temperature of the stretching bath is preferably about 25 to 80 ℃, more preferably about 40 to 75 ℃, and still more preferably about 50 to 70 ℃. Further, since the degree of stretching of the polyvinyl alcohol film is affected by the temperature of the stretching bath, the immersion time in the stretching bath cannot be determined in a simple manner, and is preferably about 10 to 800 seconds, more preferably about 30 to 500 seconds. The stretching treatment in the wet stretching method may be performed together with any one or more of the swelling step, the dyeing step, the crosslinking step, and the cleaning step.
Examples of the dry stretching method include: an inter-roll stretching method, a heated roll stretching method, a compression stretching method, and the like. The dry stretching method may be performed together with the drying step.
The total stretching ratio (cumulative stretching ratio) of the polyvinyl alcohol film can be set as appropriate according to the purpose, and is preferably about 2 to 7 times, more preferably about 3 to 6.8 times, and even more preferably about 3.5 to 6.5 times.
The cleaning step is a treatment step of immersing the polyvinyl alcohol film in a cleaning bath, and can remove foreign matters remaining on the surface of the polyvinyl alcohol film. The above-mentioned washing bath generally uses a medium containing water as a main component, such as water, distilled water, and pure water. In addition, from the viewpoint of controlling the potassium content in the polarizing film, potassium iodide may be contained in the cleaning bath, and in this case, the concentration of potassium iodide in the cleaning bath is preferably about 1 to 10% by weight, more preferably about 1.5 to 4% by weight, and still more preferably about 1.8 to 3.8% by weight.
The temperature of the cleaning bath is preferably about 5 to 50 ℃, more preferably about 10 to 40 ℃, and still more preferably about 15 to 35 ℃. Further, the degree of cleaning of the polyvinyl alcohol film in the above-mentioned cleaning bath is affected by the temperature of the cleaning bath, and thus cannot be determined in general, but is preferably about 1 to 100 seconds, more preferably about 2 to 50 seconds, and still more preferably about 3 to 20 seconds. The swelling step may be performed only 1 time, or may be performed as many times as necessary.
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 by the washing step to obtain a polarizing film, and the polarizing film having a desired moisture content can be obtained by drying. The drying is performed by any suitable method, and examples thereof include: natural drying, air drying and heating drying.
The drying temperature is preferably about 20 to 150 ℃, more preferably about 25 to 100 ℃. Further, since the drying time is affected by the drying temperature, the drying degree of the polarizing film cannot be determined in a lump, and is preferably about 10 to 600 seconds, more preferably about 30 to 300 seconds. The drying step may be performed only 1 time, or may be performed as many times as necessary.
The thickness of the polarizing film is preferably 1 μm or more, more preferably 2 μm or more from the viewpoint of improving the initial polarization degree of the polarizing film, and is preferably 20 μm or less, more preferably 18 μm or less, more preferably 15 μm or less from the viewpoint of preventing heat peeling. In particular, in order to obtain a polarizing film having a thickness of about 8 μm or less, a method for producing a thin polarizing film may be applied, in which a laminate including a thermoplastic resin substrate and a polyvinyl alcohol resin layer formed on the thermoplastic resin substrate is used as the polyvinyl alcohol film.
Method for producing thin polarizing film
The method for manufacturing the thin polarizing film comprises the following steps: forming a polyvinyl alcohol resin layer (PVA-based resin layer) containing a polyvinyl alcohol resin (PVA-based resin) on one side of a long thermoplastic resin substrate to form a laminate; and sequentially performing auxiliary stretching treatment, dyeing treatment, stretching treatment in aqueous solution and drying shrinkage treatment on the laminated body in a gas atmosphere. In particular, in order to obtain a polarizing film having high optical characteristics, a method of two-stage stretching in which an auxiliary stretching treatment in a gas atmosphere (dry stretching) and an aqueous stretching treatment in an aqueous boric acid solution are combined is selected.
As a method for producing the laminate, any suitable method can be used, and examples thereof include: and a method of applying a coating liquid containing the PVA-based resin to a surface of the thermoplastic resin substrate and drying the coating liquid. The thickness of the thermoplastic resin base material is preferably about 20 to 300. Mu.m, more preferably about 50 to 200. Mu.m. The thickness of the PVA-based resin layer is preferably about 3 to 40 μm, more preferably about 3 to 20 μm.
The thermoplastic resin base material absorbs water and greatly reduces the tensile stress, and from the viewpoint of being capable of being stretched at a high rate, the water absorption rate is preferably about 0.2% or more, more preferably about 0.3% or more. On the other hand, the water absorption rate of the thermoplastic resin substrate is preferably about 3% or less, more preferably about 1% or less, from the viewpoint that the thermoplastic resin substrate can be prevented from being significantly reduced in dimensional stability and the appearance of the obtained polarizing film is deteriorated. The water absorption rate can be adjusted by introducing a modifying group into the constituent material of the thermoplastic resin base material, for example. The water absorption is a value obtained based on JIS K7209.
The thermoplastic resin substrate preferably has a glass transition temperature (Tg) of about 120 ℃ or less, from the viewpoint of being able to suppress crystallization of the PVA-based resin layer and sufficiently secure stretchability of the laminate. In view of plasticization of the thermoplastic resin substrate with water and good stretching in an aqueous solution, the glass transition temperature (Tg) is preferably about 100 ℃ or less, more preferably about 90 ℃ or less. On the other hand, from the viewpoint that the thermoplastic resin substrate can be prevented from being deformed or the like when the coating liquid is applied and dried, and a good laminate can be produced, the glass transition temperature of the thermoplastic resin substrate is preferably about 60 ℃ or higher. The glass transition temperature can be adjusted by introducing a modifying group into the constituent material of the thermoplastic resin base material and heating the constituent material with a crystallizing material, for example. The glass transition temperature (Tg) is a value obtained based on JIS K7121.
As a constituent material of the thermoplastic resin base material, any suitable thermoplastic resin may be used. 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, copolymer resins thereof, and the like. Among these, norbornene-based resins and amorphous (noncrystalline) polyethylene terephthalate-based resins are preferable, and further, from the viewpoint that the stretchability of the thermoplastic resin base material is extremely excellent and crystallization at the time of stretching can be suppressed, amorphous (noncrystalline) polyethylene terephthalate-based resins are preferable. Examples of the amorphous (noncrystalline) polyethylene terephthalate resin include copolymers containing isophthalic acid and/or cyclohexanedicarboxylic acid as dicarboxylic acid and copolymers containing cyclohexanedimethanol and diethylene glycol as diol.
The surface treatment (for example, corona treatment) may be applied to the thermoplastic resin substrate before the PVA-based resin layer is formed, or an easy-to-adhere layer may be formed on the thermoplastic resin substrate. By performing such a treatment, the adhesion between the thermoplastic resin base material and the PVA-based resin layer can be improved. The thermoplastic resin base material may be stretched before the PVA-based resin layer is formed.
The coating liquid is a solution obtained by dissolving a PVA-based resin in a solvent. Examples of the solvent include: water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various glycols, polyols such as trimethylolpropane, and amines such as ethylenediamine and diethylenetriamine, and water is preferable. These solvents may be used alone, or two or more kinds may be used in combination. The PVA-based resin concentration of the coating liquid is preferably about 3 to 20 parts by weight per 100 parts by weight of the solvent, from the viewpoint of forming a uniform coating film adhered to the thermoplastic resin substrate.
From the viewpoint of improving the orientation of the polyvinyl alcohol molecules by stretching, it is preferable to blend a halide in the coating liquid. Any suitable halide may be used as the halide, and examples thereof include iodide and sodium chloride. Examples of the iodide include: potassium iodide, sodium iodide, lithium iodide, etc., potassium iodide is preferred. 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.
In addition, an additive may be blended in the coating liquid. Examples of the additive include: plasticizers such as ethylene glycol and glycerin; surfactants such as nonionic surfactants, and the like.
As a coating method of the coating liquid, any suitable method can be used, and examples thereof include: roll coating, spin coating, bar coating, dip coating, die coating, curtain coating, spray coating, knife coating (comma coating, etc.), and the like. The drying temperature of the coating liquid is preferably about 50 ℃ or higher.
In the auxiliary stretching treatment in the gas atmosphere, the laminate may be stretched at a high rate so that the stretching may be performed while suppressing crystallization of the thermoplastic resin substrate. The stretching method of the auxiliary stretching treatment in the gas atmosphere may be fixed-end stretching (for example, stretching by a tenter), or free-end stretching (for example, stretching the laminate in one direction by passing it between rolls having different circumferential speeds), and from the viewpoint of obtaining high optical characteristics, free-end stretching is preferable.
The stretching ratio in the auxiliary stretching in the gas atmosphere is preferably about 2 to 3.5 times. The auxiliary stretching in the gas atmosphere may be performed in one stage or may be performed in multiple stages. In the case of multi-stage stretching, the stretching ratio is the product of stretching ratios in the respective stages.
The stretching temperature in the auxiliary stretching in the gas atmosphere may be set to any appropriate value depending on the material for forming the thermoplastic resin substrate, the stretching method, and the like, and is preferably not less than the glass transition temperature (Tg), more preferably not less than the glass transition temperature (Tg) +10 ℃, and still more preferably not less than the glass transition temperature (Tg) +15 ℃. On the other hand, the upper limit of the stretching temperature is preferably about 170 ℃.
The insolubilization treatment may be performed after the auxiliary stretching treatment in the above-mentioned gas atmosphere and before the dyeing treatment and the stretching treatment in the aqueous solution, if necessary. The insolubilization treatment is typically performed by immersing the PVA-based resin layer in an aqueous boric acid solution. By performing the insolubilization treatment, water resistance can be imparted to the PVA-based resin layer, and the decrease in orientation of PVA when immersed in water can be prevented. The concentration of the aqueous boric acid solution is preferably about 1 to 5 parts by weight per 100 parts by weight of water. The temperature of the insolubilization treatment bath is preferably about 20 to 50 ℃.
The dyeing treatment is performed by dyeing the PVA-based resin layer with iodine. Examples of the adsorption method include: a method of impregnating a PVA-based resin layer (laminate) in a staining solution containing iodine; a method of applying the dyeing liquid on the PVA resin layer; for example, a method of spraying the dyeing liquid onto the PVA-based resin layer is preferable, and a method of immersing the PVA-based resin layer (laminate) in the iodine-containing dyeing liquid is preferable.
The amount of iodine in the dyeing bath is preferably about 0.05 to 0.5 parts by weight per 100 parts by weight of water. In order to increase the solubility of iodine in water, the iodine is preferably mixed with an aqueous iodine solution. The amount of the iodide to be blended is preferably about 0.1 to 10 parts by weight, more preferably about 0.3 to 5 parts by weight, based on 100 parts by weight of water. In order to suppress dissolution of the PVA-based resin, the liquid temperature of the dyeing bath is preferably about 20 to 50 ℃. In order to ensure the transmittance of the PVA-based resin layer, the immersion time is preferably about 5 seconds to 5 minutes, more preferably about 30 seconds to 90 seconds. From the viewpoint of obtaining a polarizing film having good optical characteristics, the ratio of iodine to iodide in the aqueous iodine solution is preferably about 1:5 to 1:20, more preferably about 1:5 to 1:10.
If necessary, the crosslinking treatment may be performed after the dyeing treatment and before the stretching treatment in the aqueous solution. The crosslinking treatment is typically performed by immersing the PVA-based resin layer in an aqueous boric acid solution. By performing the crosslinking treatment, water resistance can be imparted to the PVA-based resin layer, and in the subsequent stretching in an aqueous solution, the decrease in the orientation of PVA when immersed in high-temperature water can be prevented. The boric acid concentration of the aqueous boric acid solution is preferably about 1 to 5 parts by weight per 100 parts by weight of water. In the case of performing the crosslinking treatment, the iodide is preferably further mixed in a crosslinking bath during the crosslinking treatment. By adding the iodide, elution of iodine adsorbed to the PVA-based resin layer can be suppressed. The amount of the iodide to be blended is preferably about 1 to 5 parts by weight per 100 parts by weight of water. The crosslinking bath (boric acid aqueous solution) preferably has a liquid temperature of about 20 to 50 ℃.
The stretching treatment in the aqueous solution is performed by immersing the laminate in a stretching bath. According to the stretching treatment in an aqueous solution, stretching can be performed at a temperature lower than the glass transition temperature (typically about 80 ℃) of the thermoplastic resin base material and the PVA-based resin layer, and stretching can be performed at a high magnification while suppressing crystallization of the PVA-based resin layer. The stretching method of the stretching treatment in the aqueous solution may be fixed-end stretching (for example, stretching by a tenter), or free-end stretching (for example, stretching the laminate in one direction by passing it between rolls having different circumferential speeds), and from the viewpoint of obtaining high optical characteristics, free-end stretching is preferable.
The stretching treatment in the aqueous solution is preferably performed by immersing the laminate in an aqueous boric acid solution (stretching in an aqueous boric acid solution). By using an aqueous boric acid solution as the stretching bath, rigidity that can withstand tension applied at the time of stretching and water resistance that is insoluble in water can be imparted to the PVA-based resin layer. The boric acid concentration of the aqueous boric acid solution is preferably 1 to 10 parts by weight, more preferably 2.5 to 6 parts by weight, relative to 100 parts by weight of water. Further, iodide may be blended in the stretching bath (boric acid aqueous solution). The liquid temperature of the stretching bath is preferably about 40 to 85 ℃, more preferably about 60 to 75 ℃. The immersion time of the laminate in the stretching bath is preferably about 15 seconds to 5 minutes.
The stretching ratio in the stretching in the aqueous solution is preferably about 1.5 times or more, more preferably about 3 times or more.
The total stretch ratio of the laminate is preferably about 5 times or more, more preferably about 5.5 times or more, relative to the original length of the laminate.
The drying shrinkage treatment may be performed by zone heating in which the entire zone is heated, or by heating a conveying roller (using a so-called heating roller), and it is preferable to use both of them. By drying with the heating roller, the laminate can be efficiently suppressed from being heated to curl, and a polarizing film excellent in appearance can be produced, and the laminate can be dried while being kept flat, so that not only curling but also occurrence of wrinkles can be suppressed. Further, from the viewpoint of improving the optical characteristics of the obtained polarizing film by shrinking the polarizing film in the width direction during the drying shrinkage treatment, the shrinkage ratio in the width direction of the laminate by the drying shrinkage treatment is preferably about 1 to 10%, more preferably about 2 to 8%.
The drying condition can be controlled by adjusting the heating temperature of the conveying roller (temperature of the heating roller), the number of heating rollers, the contact time with the heating roller, and the like. The temperature of the heating roller is preferably about 60 to 120 ℃, more preferably about 65 to 100 ℃, and still more preferably 70 to 80 ℃. The number of the conveying rollers is usually about 2 to 40, preferably about 4 to 30, from the viewpoint of favorably increasing the crystallinity of the thermoplastic resin and favorably suppressing curling. The contact time (total contact time) between the laminate and the heating roller is preferably about 1 to 300 seconds, more preferably 1 to 20 seconds, and still more preferably 1 to 10 seconds.
The heating roller may be provided in the heating furnace or in a normal manufacturing line (in a room temperature environment), and is preferably provided in the heating furnace provided with the blower mechanism. By using drying by the heating roller and hot air drying in combination, abrupt temperature change between the heating rollers can be suppressed, and shrinkage in the width direction can be easily controlled. The temperature of the hot air drying is preferably about 30 to 100 ℃. The hot air drying time is preferably about 1 to 300 seconds.
The washing treatment is preferably performed after the stretching treatment in the aqueous solution and before the drying shrinkage treatment. The above-mentioned washing treatment is typically performed by immersing the PVA-based resin layer in an aqueous potassium iodide solution.
In the case of producing a thin polarizing film containing the compound having a radical trapping function, the compound having a radical trapping function may be contained in any one or more of a dyeing treatment, an aqueous solution stretching treatment, an insolubilizing treatment, a crosslinking treatment, and a cleaning treatment. The concentration of the compound having a radical trapping function contained in any of the treatment baths is affected by the number of treatments, the treatment time, the treatment temperature, and the like of each treatment, and therefore cannot be determined in general, and is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, still more preferably 0.1% by weight or more, and is preferably 30% by weight or less, more preferably 25% by weight or less, still more preferably 20% by weight or less, from the viewpoint of being able to efficiently control the content of the compound having a radical trapping function in the polarizing film.
In particular, when the cleaning treatment is performed, the content of iodine or the compound having a radical trapping function can be easily adjusted to a desired range from the viewpoint of allowing the component such as iodine or the compound having a radical trapping function to be eluted from or adsorbed to the polyvinyl alcohol film, taking into consideration the treatment conditions in the dyeing treatment, the stretching treatment in an aqueous solution, and the like.
< polarizing film >
The polarizing film of the present invention is formed by laminating a transparent protective film on at least one surface of the polarizing film.
The transparent protective film is not particularly limited, and various transparent protective films used in the polarizing film can be used. As a material constituting the transparent protective film, for example, it is possible to use: thermoplastic resins excellent in transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy and the like. Examples of the thermoplastic resin include: cellulose ester resins such as cellulose triacetate, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyether sulfone resins, polysulfone resins, polycarbonate resins, polyamide resins such as nylon and aromatic polyamide resins, polyimide resins, polyolefin resins such as polyethylene, polypropylene and ethylene-propylene copolymer, (meth) acrylic resins, cyclic polyolefin resins (norbornene resins) having a cyclic or norbornene structure, polyacrylic resins, polystyrene resins, polyvinyl alcohol resins and mixtures thereof. The transparent protective film may be a cured layer formed of a thermosetting resin such as (meth) acrylic, urethane, acrylic urethane, epoxy, or silicone, or an ultraviolet curable resin. Among these, cellulose ester resins, polycarbonate resins, (meth) acrylic resins, cyclic polyolefin resins, and polyester resins are preferable.
The thickness of the transparent protective film can be appropriately determined, and in general, it is preferably about 1 to 500 μm, more preferably about 1 to 300 μm, and even more preferably about 5 to 100 μm from the viewpoints of handleability such as strength and handleability, and thin layer property.
When the transparent protective films are bonded to both surfaces of the polarizing film, the transparent protective films may be the same or different from each other.
The transparent protective film may be a retardation plate having a retardation in the front direction of 40nm or more and/or a retardation in the thickness direction of 80nm or more. The front phase difference is usually controlled to a range of 40 to 200nm, and the thickness direction phase difference is usually controlled to a range of 80 to 300 nm. When a retardation plate is used as the transparent protective film, the retardation plate also functions as the transparent protective film, and thus can be thinned.
Examples of the retardation plate include: a birefringent film obtained by subjecting a polymer material to unidirectional or bidirectional stretching treatment, an alignment film of a liquid crystal polymer, a retardation plate obtained by supporting an alignment layer of a liquid crystal polymer with a film, and the like. The thickness of the retardation plate is not particularly limited, but is usually about 20 to 150. Mu.m. The retardation plate may be bonded to a transparent protective film having no retardation.
Any suitable additive such as an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a mold release agent, an anti-coloring agent, a flame retardant, an antistatic agent, a pigment, a coloring agent, and the like may be contained in the transparent protective film. In particular, when the ultraviolet absorber is contained in the transparent protective film, the light resistance of the polarizing film can be improved.
The transparent protective film may be provided with a functional layer such as a hard coat layer, an antireflection layer, an anti-sticking layer, a diffusion layer, an antiglare layer, etc. on one surface thereof which is not bonded to the polarizing film. The functional layers such as the hard coat layer, the antireflection layer, the adhesion preventing layer, the diffusion layer, and the antiglare layer may be provided as a layer different from the protective film itself.
The polarizing film and the transparent protective film, or the polarizing film and the functional layer are usually bonded together with an adhesive layer or an adhesive layer interposed therebetween.
As the adhesive for forming the adhesive layer, various adhesives used for the polarizing film can be applied, and examples thereof include: rubber-based adhesives, acrylic adhesives, silicone-based adhesives, urethane-based adhesives, vinyl alkyl ether-based adhesives, polyvinyl alcohol-based adhesives, polyvinyl pyrrolidone-based adhesives, polyacrylamide-based adhesives, cellulose-based adhesives, and the like. Among these, acrylic adhesives are preferable.
As a method of forming the adhesive layer, for example, there can be exemplified: a method in which the adhesive is applied to a separator or the like after the peeling treatment, and dried to form an adhesive layer, and then transferred to a polarizing film or the like; or a method of forming an adhesive layer by applying the adhesive to a polarizing film or the like and drying the same. The thickness of the pressure-sensitive adhesive layer is not particularly limited, and is, for example, about 1 to 100. Mu.m, preferably about 2 to 50. Mu.m.
As the adhesive for forming the adhesive layer, various adhesives used for polarizing films can be applied, and examples thereof include: isocyanate adhesives, polyvinyl alcohol adhesives, gelatin adhesives, vinyl latex, aqueous polyester, and the like. These adhesives are usually used in the form of an adhesive formed from an aqueous solution (aqueous adhesive), and contain 0.5 to 60% by weight of a solid content.
The aqueous adhesive may contain a crosslinking agent. As the crosslinking agent, a compound having at least 2 functional groups in 1 molecule which are reactive with components such as a polymer constituting the adhesive can be generally used, and examples thereof include: alkylene diamines; isocyanates; epoxy; aldehydes; amino-formaldehyde such as methylol urea and methylol melamine. The amount of the crosslinking agent blended in the adhesive is usually about 10 to 60 parts by weight per 100 parts by weight of the components such as the polymer constituting the adhesive.
The adhesive may be an active energy ray-curable adhesive such as an ultraviolet-curable adhesive or an electron beam-curable adhesive, in addition to the above. The active energy ray-curable adhesive may be, for example, a (meth) acrylate adhesive. Examples of the curable component in the (meth) acrylate adhesive include: a compound having a (meth) acryloyl group, and a compound having a vinyl group. As a resin having (meth) acryloyl groupsExamples of the radical compound include: alkyl (meth) acrylates such as alkyl (meth) acrylate having 1 to 20 carbon atoms, alicyclic alkyl (meth) acrylate, and polycyclic alkyl (meth) acrylate; hydroxyl group-containing (meth) acrylates; epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate, and the like. The (meth) acrylate adhesive may contain a nitrogen-containing monomer such as hydroxyethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, or (meth) acryloylmorpholine. The (meth) acrylic acid ester adhesive may contain tripropylene glycol diacrylate, 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, cyclic trimethylolpropane methylacrylate, and di-methyl alcohol diacrylate As the crosslinking component, a polyfunctional monomer such as alkylene glycol diacrylate or EO-modified diglycerol tetraacrylate is used. In addition, as the cationic polymerization curable adhesive, a compound having an epoxy group or an oxetanyl group may be used. The compound having an epoxy group is not particularly limited as long as it has at least 2 epoxy groups in the molecule, and various conventionally known curable epoxy compounds can be used.
The adhesive may contain a suitable additive as required. Examples of the additive 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 capturing agents, antioxidants, tackifiers, fillers, plasticizers, leveling agents, foaming inhibitors, antistatic agents, heat-resistant stabilizers, hydrolysis-resistant stabilizers, and the like.
The adhesive may be applied on either one of the transparent protective film side (or the functional layer side) and the polarizing film side, or on both sides. After bonding, a drying step is performed to form an adhesive layer made of a coated and dried layer. After the drying step, ultraviolet rays and electron beams may be irradiated as necessary. The thickness of the adhesive layer is not particularly limited, but is preferably about 30 to 5000nm, more preferably about 100 to 1000nm in the case of using an aqueous adhesive or the like, and is preferably about 0.1 to 100 μm, more preferably about 0.5 to 10 μm in the case of using an ultraviolet-curable adhesive, an electron beam-curable adhesive or the like.
The transparent protective film and the polarizing film, or the polarizing film and the functional layer may be laminated with a surface modifying treatment layer, an easy-to-adhere layer, a barrier layer, a refractive index adjusting layer, or other interlayer.
Examples of the surface modification treatment for forming the surface modification layer include: corona treatment, plasma treatment, primer treatment, saponification treatment, and the like.
Examples of the easy-adhesive agent for forming the easy-adhesive layer include: including various resin forming materials including polyester skeletons, polyether skeletons, polycarbonate skeletons, polyurethane skeletons, organosilicon skeletons, polyamide skeletons, polyimide skeletons, and polyvinyl alcohol skeletons. The pressure sensitive adhesive layer may be provided in advance in a protective film, and the pressure sensitive adhesive layer side of the protective film and the polarizing film may be laminated with the pressure sensitive adhesive layer or the pressure sensitive adhesive layer interposed therebetween.
The barrier layer is a layer having a function of preventing an oligomer eluted from the transparent protective film or the like, and impurities such as ions from moving (penetrating) into the polarizing film. The barrier layer may be any layer that has transparency and can prevent impurities eluted from the transparent protective film or the like, and examples of the material forming the barrier layer include: urethane prepolymer-forming materials, cyanoacrylate-forming materials, epoxy-forming materials, and the like.
The refractive index adjustment layer is provided to suppress a decrease in transmittance due to reflection between layers having different refractive indexes such as the transparent protective film and the polarizing film. Examples of the refractive index adjusting material for forming the refractive index adjusting layer include: including forming agents having various resins and additives such as silica, acrylic-styrene, melamine, and the like.
The polarization degree of the polarizing film is preferably 99.98% or more, and more preferably 99.99% or more.
< laminated polarizing film >)
In the laminated polarizing film (optical laminate) of the present invention, the polarizing film is bonded to an optical layer. The optical layer is not particularly limited, and for example, 1 or 2 or more layers of reflective plates, semi-transmissive plates, phase difference plates (including 1/2, 1/4, etc. wave plates), vision compensation films, etc. may be used in the formation of liquid crystal display devices, etc. Examples of the laminated polarizing film include a reflective polarizing film or a semi-transmissive polarizing film in which a reflective plate or a semi-transmissive reflective plate is further laminated on the polarizing film, an elliptical polarizing film or a circular polarizing film in which a phase difference plate is further laminated on the polarizing film, a wide viewing angle polarizing film in which a viewing angle compensation film is further laminated on the polarizing film, and a polarizing film in which a brightness enhancement film is further laminated on the polarizing film.
An adhesive layer for bonding an image display unit such as a liquid crystal cell or an organic EL element to other members such as a front transparent plate on the visible side and a front transparent member of a touch panel may be provided on one or both surfaces of the polarizing film or the laminated polarizing film. As the adhesive layer, an adhesive layer is preferable. The pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer is not particularly limited, and a pressure-sensitive adhesive containing, as a base polymer, a polymer such as an acrylic polymer, a silicone polymer, a polyester, a polyurethane, a polyamide, a polyether, a fluorine-based polymer, or a rubber-based polymer can be suitably selected and used. Particularly, an adhesive having excellent optical transparency, moderate wettability, aggregation and adhesion, weather resistance, heat resistance, and the like, such as an adhesive containing an acrylic polymer, can be preferably used.
The adhesive layer may be provided on one or both surfaces of the polarizing film and the laminated polarizing film by a suitable method. Examples of the arrangement of the adhesive layer include: a method of preparing a binder solution and directly disposing the binder solution on the polarizing film and the laminated polarizing film by a proper development method such as a casting method and a coating method; or a method of forming an adhesive layer on a separator and transferring the adhesive layer to the polarizing film or the laminated polarizing film. The thickness of the pressure-sensitive adhesive layer may be appropriately determined depending on the purpose of use, the adhesive strength, etc., and is generally 1 to 500. Mu.m, preferably 5 to 200. Mu.m, more preferably 10 to 100. Mu.m. The material having the adhesive layer provided on at least one surface of the polarizing film, the laminated polarizing film, or the laminated polarizing film with the adhesive layer in this manner is referred to as an adhesive layer-attached polarizing film.
The exposed surface of the pressure-sensitive adhesive layer is preferably covered with a temporary pressure-sensitive adhesive film for the purpose of preventing contamination or the like until the pressure-sensitive adhesive layer is put to practical use. This can prevent contamination of the adhesive layer in a normal processing state. As the separator, a separator obtained by coating a suitable thin layer such as a plastic film, a rubber sheet, paper, cloth, nonwoven fabric, a net, a foam sheet, a metal foil, or a laminate thereof with a suitable release agent such as silicone, long-chain alkyl, fluorine, or molybdenum sulfide, as necessary, can be used.
Image display panel and image display device
The image display panel of the present invention is formed by laminating the polarizing film or the laminated polarizing film on an image display unit. The image display device of the present invention includes a front surface transparent member on the polarizing film or laminated polarizing film side (visible side) of the image display panel.
Examples of the image display means include: a liquid crystal cell, an organic EL cell, and the like. As the liquid crystal cell, for example, any one of a reflective liquid crystal cell using external light, a transmissive liquid crystal cell using light from a light source such as a backlight, and a transflective liquid crystal cell using both light from the outside and light from the light source can be used. In the case where the liquid crystal cell uses light from the light source, the image display device (liquid crystal display device) is also provided with a polarizing film on the side of the image display cell (liquid crystal cell) opposite to the viewing side, and is also provided with the light source. The polarizing film on the light source side and the liquid crystal cell are preferably bonded together with an appropriate adhesive layer interposed therebetween. Examples of the driving method of the liquid crystal cell include: VA mode, IPS mode, TN mode, STN mode, bend (bond) orientation (pi-type), and the like.
As the organic EL unit, for example, an organic EL unit in which a transparent electrode, an organic light-emitting layer, and a metal electrode are sequentially stacked on a transparent substrate to form a light-emitting body (organic electroluminescent light-emitting body) or the like can be suitably used. The organic light-emitting layer is a laminate of various organic thin films, and various layer structures may be employed, including, 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, a laminate of these light-emitting layers and an electron injection layer made of a perylene derivative or the like, or a laminate of a hole injection layer, a light-emitting layer, and an electron injection layer, or the like.
Examples of the front surface transparent member disposed on the visible side of the image display unit include: front surface transparent plate (window layer), touch panel, etc. As the front surface transparent plate, a transparent plate having appropriate mechanical strength and thickness can be used. As such a transparent plate, for example, a transparent resin plate such as an acrylic resin or a polycarbonate resin, a glass plate, or the like can be used. As the touch panel, various touch panels such as a resistive film type, a capacitive type, an optical type, and an ultrasonic type, a glass plate having a touch sensor function, a transparent resin plate, and the like can be used. In the case of using a capacitive touch panel as the front surface transparent member, a front surface transparent plate made of glass or a transparent resin plate is preferably provided on the side closer to the visible side than the touch panel.
The polarizing film of the present invention has excellent initial polarization degree and excellent effect of suppressing a decrease in transmittance of a monomer due to coloring of the polarizing film in a high-temperature environment, and therefore, the polarizing film, and the polarizing film, laminated polarizing film, image display panel, and image display device using the polarizing film of the present invention are suitable for applications of image display devices for vehicles such as car navigation devices and rearview monitors.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Example 1 >
< preparation of polarizing film >)
A polyvinyl alcohol film having an average polymerization degree of 2400, a saponification degree of 99.9 mol% and a thickness of 30 μm was prepared. The polyvinyl alcohol film was immersed in a swelling bath (water bath) at 20℃for 30 seconds between rolls having different circumferential speed ratios to swell the film, and stretched 2.2 times in the transport direction (swelling step), and then, in a dyeing bath at 30℃ (aqueous iodine solution obtained by mixing iodine and potassium iodide at a weight ratio of 1:7 with respect to 100 parts by weight of water), the original polyvinyl alcohol film (completely unstretched polyvinyl alcohol film in the transport direction) was dyed while being stretched 3.3 times in the transport direction with the concentration of iodine of the finally obtained polarizing film adjusted to be 3.8% by weight for 30 seconds (dyeing step). Next, the dyed polyvinyl alcohol film was immersed in a crosslinking bath (aqueous solution having a boric acid concentration of 3.5 wt%, a potassium iodide concentration of 3.0 wt%, and a zinc sulfate concentration of 3.6 wt%) at 40 ℃ for 28 seconds, and the original polyvinyl alcohol film was stretched to 3.6 times in the transport direction with reference to the original polyvinyl alcohol film (crosslinking step). Further, the obtained polyvinyl alcohol film was immersed in a drawing bath (aqueous solution having a boric acid concentration of 4.5 wt%, a potassium iodide concentration of 5.0 wt%, and a zinc sulfate concentration of 5.0 wt%) at 64℃for 60 seconds, and the original polyvinyl alcohol film was drawn to 6.0 times in the transport direction based on the original polyvinyl alcohol film (drawing step), and then immersed in a cleaning bath (aqueous solution having a potassium iodide concentration of 2.3 wt%, and a compound concentration of 1.0 wt% as a compound having a radical trapping function of the following general formula (9)) at 27℃for 10 seconds (cleaning step). The washed polyvinyl alcohol film was dried at 40℃for 30 seconds to prepare a polarizing film. The iodine concentration of the polarizing film was determined by the following measurement method. In addition, the peak temperature of the maximum intensity of water detected by the generated gas analysis method was 210 ℃, the content of the compound represented by the following general formula (9) in the polarizing film was 0.3 wt%, and the thickness of the polarizing film was 12 μm.
[ chemical formula 9]
[ method for measuring iodine concentration (wt%) in polarizing film ]
The polarizing film was subjected to a fluorescent X-ray analysis (trade name "ZSX-PRIMUS IV", manufactured by Kagaku Co., ltd., "measurement diameter: 20 mm) to obtain the iodine concentration (wt%) by the following formula.
Iodine concentration (wt%) = 14.474 × (fluorescence X-ray intensity)/(film thickness) (kcps/. Mu.m)
The coefficient at the time of calculating the concentration varies depending on the measurement apparatus, but the coefficient may be obtained by using an appropriate calibration curve.
[ generated gas analysis method ]
The polarizing film was introduced into a furnace pyrolyzer (manufactured by front Lab, PY-2020 iD), and the generated gas was directly introduced into TOFMS (manufactured by JEOL, JMS-T100 GCV), and then a generated gas analysis (EGA/TOFMS) method was performed.
[ measurement conditions ]
Heating conditions: 40 ℃ -10 ℃/min-350 DEG C
Interface: deactivated fused silica tube, 2.5 m.times.0.15 mm id
Carrier gas: he (1.0 mL/min)
Injection port temperature: 300 DEG C
An injection port: split ratio 20:1
Interface temperature: 300 DEG C
Mass spectrometer: TOFMS
Ionization method: EI method
The mass range is as follows: m/z=18
[ method for measuring content (wt%) of Compound having radical-trapping function in polarizing film ]
The concentration of the compound having a radical trapping function was measured on the filtrate by HPLC (ACQUITYUPLC H-class Bio, manufactured by Waters corporation) by taking about 20mg of a polarizing film, quantifying, heating and dissolving in 1mL of water, diluting with 4.5mL of methanol, filtering the obtained extract with a membrane filter.
< preparation of polarizing film >)
As the adhesive, an aqueous solution containing a polyvinyl alcohol resin having an acetoacetyl group (average degree of polymerization is 1200, degree of saponification is 98.5 mol%, degree of acetoacetylation is 5 mol%) and methylolmelamine in a weight ratio of 3:1 was used. A transparent protective film (manufactured by japan catalyst, moisture permeability of 125 g/(m)) having a thickness of 30 μm and formed of a (meth) acrylic resin (modified acrylic polymer having a lactone ring structure) was laminated on one surface (image display device unit side) of the polarizing film obtained by using the adhesive and using a roll laminator 2 24 h)), and a transparent protective film (having a moisture permeability of 380 g/(m) and having a thickness of 47 μm, in which HC was formed on the other surface (visible side) of a cellulose triacetate film (manufactured by Fuji film, trade name "TJ40 UL") 2 24 h)), followed by drying in an oven (temperature 90 ℃ C. For 10 minutes) to produce a polarizing film having transparent protective films bonded to both surfaces of the polarizing film.
[ evaluation of polarization degree ]
The degree of polarization of the polarizing film can be measured using a spectrophotometer (product name "V7100" of the japanese spectroscopic system). As a specific measurement method of the degree of polarization, the parallel transmittance (H0) and the orthogonal transmittance (H90) of the polarizing film can be measured and expressed according to the formula: the degree of polarization (%) = { (H0-H90)/(h0+h90) }1/2×100 was obtained. The parallel transmittance (H0) is a value of transmittance of a parallel laminated polarizing film produced by laminating 2 identical polarizing films such that absorption axes of the two films are parallel. The orthogonal transmittance (H90) is a value of the transmittance of an orthogonal laminated polarizing film produced by laminating 2 identical polarizing films so that the absorption axes of the two films are orthogonal. These transmittances were Y values obtained by correcting the visibility of a 2-degree field of view (C light source) of JlS Z8701-1982. The results are shown in Table 1.
[ evaluation of transmittance of monomer in high-temperature Environment ]
The polarizing film obtained above was cut into a size of 5.0x4.5 cm so that the absorption axis of the polarizing film was parallel to the long side, and a glass plate (analog image display unit) was bonded to the protective film surface on the image display unit side of the polarizing film via an acrylic pressure-sensitive adhesive layer having a thickness of 20 μm, and autoclave treatment was performed at 50℃and 0.5MPa for 15 minutes to produce a laminate. The obtained laminate was left to stand in a hot air oven at 105℃for 750 hours, and the transmittance (. DELTA.Ts) of the monomer before and after the charging (heating) was measured. The transmittance of the monomer was measured by a spectrophotometer (product name "V7100", manufactured by daily spectrometry) and evaluated based on the following criteria. The measurement wavelength was 380 to 700nm (5 nm interval). The results are shown in Table 1.
ΔTs(%)=Ts 700 -Ts 0
Wherein Ts 0 For the monomer transmittance of the laminate before heating, ts 700 The transmittance of the laminate after 700 hours of heating was measured. The ΔTs (%) is preferably 5 or more and ΔTs (%) or more than 0, and more preferably 3 or more and ΔTs (%) or more than 0.
[ evaluation of heat peeling ]
The polarizing film was cut into 680X 250mm sizes with its absorption axis parallel to the long side. A glass plate (analog image display unit) was produced on the protective film surface on the image display unit side of the polarizing film via an acrylic pressure-sensitive adhesive layer having a thickness of 20 μm. The appearance of the obtained laminate sample after standing in a hot air oven at 105℃for 750 hours was evaluated by visual observation according to the following criteria. The results are shown in Table 1.
O: the end portion was slightly peeled off or foamed, but there was no problem in practical use.
Delta: peeling or foaming is observed at the end portion, but there is no problem in practical use as long as it is not particularly used (for example, a narrow frame display in which the distance from the end portion of the polarizing plate to the Active Area (Active Area) where an image is displayed is short, or the like).
X: there is significant peeling at the ends and there are problems in practical use.
Example 2 >
< polarizing film, production of polarizing film >
A polarizing film and a polarizing film were produced in the same manner as in example 1, except that the iodine concentration in the dye bath was adjusted so that the iodine concentration in the finally obtained polarizing film became 4.3 wt%. The peak temperature of the maximum intensity of water detected by the generated gas analysis method was 208 ℃, the content of the compound represented by the above general formula (9) in the polarizing film was 0.3 wt%, and the thickness of the polarizing film was 12 μm.
Example 3 >
< polarizing film, production of polarizing film >
In the production of the polarizing film, a polarizing film and a polarizing film were produced in the same manner as in example 1, except that the iodine concentration of the dye bath was adjusted so that the iodine concentration of the finally obtained polarizing film became 3.5 wt% with respect to the polyvinyl alcohol film having a thickness of 45 μm. The maximum intensity of water detected by the generated gas analysis method was 210℃at a peak temperature of the obtained polarizing film, the content of the compound represented by the general formula (9) in the polarizing film was 0.2% by weight, and the thickness of the polarizing film was 18. Mu.m.
Example 4 >
< polarizing film, production of polarizing film >
In the production of the polarizing film, a polarizing film and a polarizing film were produced in the same manner as in example 1, except that the iodine concentration of the dye bath was adjusted so that the iodine concentration of the finally obtained polarizing film became 3.7 wt%, and the compound represented by the general formula (8) was added to the bath in the cleaning step in a concentration of 1.0 wt% instead of the compound having the radical trapping function represented by the general formula (9). The peak temperature of the maximum intensity of water detected by the generated gas analysis method was 211 ℃, the content of the compound represented by the above general formula (8) in the polarizing film was 0.3 wt%, and the thickness of the polarizing film was 12 μm.
Comparative example 1 >
< polarizing film, production of polarizing film >
A polarizing film and a polarizing film were produced in the same manner as in example 2, except that the compound represented by the general formula (9) was not added to the cleaning bath as a compound having a radical trapping function in the production of the polarizing film. The peak temperature of the maximum intensity of water detected by the generated gas analysis method was 197℃and the content of the compound represented by the general formula (9) in the polarizing film was 0% by weight, and the thickness of the polarizing film was 12. Mu.m.
Comparative example 2 >
< polarizing film, production of polarizing film >
In the production of the polarizing film, a polarizing film and a polarizing film were produced in the same manner as in example 1, except that the iodine concentration in the dye bath was adjusted so that the iodine concentration in the finally obtained polarizing film became 2.5 wt%, and the compound represented by the above general formula (9) was not added to the cleaning bath as a compound having a radical trapping function. The maximum intensity of water detected by the generated gas analysis method was 206℃at a peak temperature, the content of the compound represented by the above general formula (9) in the polarizing film was 0% by weight, and the thickness of the polarizing film was 12. Mu.m.
The polarizing films of examples and comparative examples obtained above were used to perform the above-described [ evaluation of polarization degree ], [ evaluation of monomer transmittance in high temperature environment ], and [ evaluation of heat peeling ]. The results are shown in Table 1.
TABLE 1
Claims (10)
1. A polarizing film comprising a polyvinyl alcohol film and iodine adsorbed thereon and oriented, wherein,
the iodine concentration is 3 to 10 wt%,
the polarizing film contains 0.02 wt% or more of a compound having a radical trapping function, the compound having a molecular weight of 1000 or less and being capable of dissolving 1 part by weight or more in 100 parts by weight of water at 25 ℃,
In the generated gas analysis, the polarizing film has a peak temperature of 205 ℃ or higher at which the maximum intensity of water is detected under the conditions that the temperature rise rate is 10 ℃/min and the temperature rise range is 40 ℃ to 350 ℃ in the presence of an inert gas.
2. The polarizing film according to claim 1, which has a thickness of 20 μm or less.
3. The polarizing film according to claim 1 or 2, wherein,
the compound with the free radical capturing function is a compound with nitroxyl free radicals.
4. The polarizing film according to claim 1 or 2, wherein,
the compound with the free radical capturing function is a compound with a nitroxyl radical.
5. A polarizing film comprising a transparent protective film bonded to at least one surface of the polarizing film according to any one of claims 1 to 4.
6. The polarizing film according to claim 5, which has a degree of polarization of 99.98% or more.
7. A laminated polarizing film, wherein,
the polarizing film according to claim 5 or 6, which is attached to the optical layer.
8. An image display panel having an image display unit to which the polarizing film according to claim 5 or 6 or the laminated polarizing film according to claim 7 is attached.
9. An image display device comprising a front surface transparent member on the polarizing film or laminated polarizing film side of the image display panel according to claim 8.
10. The image display device according to claim 9, which is an in-vehicle image display device.
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PCT/JP2019/044317 WO2020100889A1 (en) | 2018-11-12 | 2019-11-12 | Polarization membrane, polarization film, layered polarization film, image display panel, and image display device |
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CN202211389860.XA Pending CN115657192A (en) | 2018-11-12 | 2019-11-12 | Polarizing film, laminated polarizing film, image display panel, and image display device |
CN201980063373.4A Active CN112771419B (en) | 2018-11-12 | 2019-11-12 | Polarizing film, laminated polarizing film, image display panel, and image display device |
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KR (1) | KR20210089631A (en) |
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KR20210089632A (en) * | 2018-11-12 | 2021-07-16 | 닛토덴코 가부시키가이샤 | Polarizing film, polarizing film, laminated polarizing film, image display panel, and image display device |
JP6964798B2 (en) * | 2018-11-12 | 2021-11-10 | 日東電工株式会社 | Polarizing film, polarizing film, laminated polarizing film, image display panel, and image display device |
JP2021162858A (en) * | 2020-03-30 | 2021-10-11 | 日東電工株式会社 | Polarization film, laminated polarization film, image display panel and image display unit |
JP2021179604A (en) * | 2020-05-08 | 2021-11-18 | 日東電工株式会社 | Image display device |
JP2022027338A (en) * | 2020-07-31 | 2022-02-10 | 日東電工株式会社 | Polarizing plate and manufacturing method therefor |
WO2022102645A1 (en) * | 2020-11-16 | 2022-05-19 | 日東電工株式会社 | Image display panel |
WO2023112533A1 (en) * | 2021-12-17 | 2023-06-22 | 三菱瓦斯化学株式会社 | Polarizing sheet |
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TW202024690A (en) | 2020-07-01 |
JPWO2020100889A1 (en) | 2021-04-01 |
JP2022009240A (en) | 2022-01-14 |
JP6964800B2 (en) | 2021-11-10 |
TWI832925B (en) | 2024-02-21 |
JP7219799B2 (en) | 2023-02-08 |
CN112771419A (en) | 2021-05-07 |
WO2020100889A1 (en) | 2020-05-22 |
CN115657192A (en) | 2023-01-31 |
KR20210089631A (en) | 2021-07-16 |
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