WO2021039987A1 - Stratifié de film polarisant, panneau d'affichage optique dans lequel ledit stratifié de film polarisant est utilisé, stratifié de film polarisant avec couche adhésive transparente, et ensemble film polarisant - Google Patents

Stratifié de film polarisant, panneau d'affichage optique dans lequel ledit stratifié de film polarisant est utilisé, stratifié de film polarisant avec couche adhésive transparente, et ensemble film polarisant Download PDF

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Publication number
WO2021039987A1
WO2021039987A1 PCT/JP2020/032666 JP2020032666W WO2021039987A1 WO 2021039987 A1 WO2021039987 A1 WO 2021039987A1 JP 2020032666 W JP2020032666 W JP 2020032666W WO 2021039987 A1 WO2021039987 A1 WO 2021039987A1
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WIPO (PCT)
Prior art keywords
polarizing film
coordinate point
water content
iodine concentration
line segment
Prior art date
Application number
PCT/JP2020/032666
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English (en)
Japanese (ja)
Inventor
大祐 大塚
河村　亮
章典 伊▲崎▼
周一 谷
哲郎 竹田
勝則 高田
木村　啓介
山下　智弘
杉野　洋一郎
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2020140953A external-priority patent/JP2021039339A/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN202080060899.XA priority Critical patent/CN114303080A/zh
Priority to KR1020227007841A priority patent/KR20220054320A/ko
Publication of WO2021039987A1 publication Critical patent/WO2021039987A1/fr

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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
    • 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
    • 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
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • 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

Definitions

  • the present invention relates to a polarizing film laminate, an optical display panel in which the polarizing film laminate is used, a polarizing film laminate with a transparent adhesive layer, and a polarizing film assembly.
  • optical display panels such as liquid crystal panels and organic EL panels have been used not only for electronic devices such as smartphones and personal computers, and for electrical appliances such as IoT home appliances, but also for powered vehicles such as automobiles, trains, and airplanes.
  • electrical appliances such as IoT home appliances
  • powered vehicles such as automobiles, trains, and airplanes.
  • various possibilities have been found. For example, it is conceivable to mount an optical display panel on the windshield, dashboard, exterior, and various other vehicle body parts of an automobile to provide various information to the driver and to transmit various information to the outside.
  • polarizing film laminate polarizing plate
  • polarizing film laminate due to a usage environment such as high temperature or high humidity or by irradiation with sunlight.
  • the performance of the polarizing film (polarizer) is deteriorated, and in the worst case, it may become unusable.
  • Patent Document 1 discloses an example of a polarizing element having improved durability in a high temperature or high humidity environment, a polarizing plate using this polarizing element, and a liquid crystal display device using the polarizing plate.
  • red loss polarization loss of long-wavelength light
  • zinc is added.
  • Patent Document 2 relates to a polarizing plate used in an in-vehicle image display device having improved durability in a high temperature or high humidity environment, and here, the water content of the polarizing plate and the protective film.
  • Patent Document 2 describes it. It has been proposed to use a transparent protective film having a saturated water absorption within a predetermined range as a transparent protective film to be bonded to a polarizing element, and to reduce the water content of the polarizing plate.
  • Patent Document 3 also relates to a polarizing plate having improved durability under high temperature or high humidity, and here, attention is paid to the moisture content of the polarizing plate and the moisture permeability of the protective film.
  • the inside of the polarizing plate becomes a high temperature and high humidity state, and as a result, the amount of change in the light transmittance, the degree of polarization, the hue of the image, etc. becomes large, and the reliability of the polarizing plate becomes low. Therefore, it has been proposed to attach a protective film having low moisture permeability in a state where the water content of the polarizer is reduced as much as possible.
  • Patent Document 4 relates to a polarizing plate having improved durability under high temperature or high humidity or low temperature, and here, the polarizer can be deteriorated by ultraviolet rays or infrared rays, and It has been described that the visibility of a liquid crystal display (LCD) may deteriorate due to use at high temperature or under high temperature and high humidity.
  • an ultraviolet absorber or an ultraviolet absorber is applied to the protective film of the polarizing film. It has been proposed to include an infrared absorber to prevent fluctuations in transmittance.
  • Japanese Unexamined Patent Publication No. 2003-29042 Japanese Unexamined Patent Publication No. 2014-102353 JP-A-2002-90546 Japanese Unexamined Patent Publication No. 2006-184883
  • problems that occur in a high temperature or high humidity environment include “polyene formation” and “color loss”. , And “heated reddish” are known.
  • polyenization is a phenomenon in which the single transmittance of a polarizing film laminate is lowered by being placed in a high temperature or high humidity environment, and "color loss” and “heating reddening” are the same.
  • the polarizing film laminate is cross-nicoled and the orthogonal transmittance at a wavelength of 410 nm and a wavelength of 700 nm is measured by being placed in a high temperature or high humidity environment, the orthogonal transmittance is lowered.
  • Color loss is a phenomenon in which the transmittance on the long wavelength side of about 700 nm and the short wavelength side of about 410 nm increases to cause color loss in black display, while “heat red discoloration” is particularly long of about 700 nm. It is known as a phenomenon in which the transmittance on the wavelength side increases and the polarizing film turns red.
  • Patent Document 1 mainly focuses on the problem of "color loss”
  • Patent Document 2 mainly focuses on the problem of "polyenization”
  • Patent Document 3 mainly focuses on the problem of "heating reddening”.
  • the solutions proposed in each document are considered to be effective at least for solving individual problems.
  • the inventions described in each patent document have not always been sufficient to comprehensively solve these problems.
  • the fact that "polyenization”, “color loss”, and “heated reddening” are all interrelated through iodine and moisture, as well as through the temperature and humidity that affect moisture. Based on this, as a result of repeated diligent research, the applicant of the present application has found that these problems can be comprehensively solved by adjusting the iodine concentration of the polarizing film and the water content of the polarizing film laminate. ..
  • the polarizing film film laminate has a polarizing film made of a polyvinyl alcohol-based resin and at least the surface of the polarizing film on the visible side directly or via another optical film.
  • a polarizing film laminate provided with a bonded optically transparent polarizing film protective film, wherein the x-axis is the iodine concentration (wt.%) Of the polarizing film, and the y-axis is the polarizing film laminate.
  • the iodine concentration was 6.0 wt.
  • the polarizing film protective film having an iodine concentration and a water content contained therein is a light absorbing layer having a light absorbing ability, and is characterized in that the light transmittance at a wavelength of 380 nm is 5% or less. According to the polarizing film film laminate of this aspect, the problems of "polyene formation", “color loss”, and “heat reddening" can be comprehensively solved.
  • the film thickness of the polarizing film may be 4 to 30 ⁇ m.
  • the polarizing film made of a polyvinyl alcohol-based resin is optically bonded to at least the visible surface of the polarizing film directly or via another optical film.
  • a polarizing film laminate provided with a transparent polarizing film protective film the x-axis is the iodine concentration (wt.%) Of the polarizing film, and the y-axis is the water content (g / g /) of the polarizing film laminate. In the xy orthogonal coordinate system in which m 2 ) was taken, the iodine concentration was 4.5 wt.
  • the 7th line segment connecting the 7th coordinate point of% and the water content of 3.4 g / m 2 and the 8th line segment connecting the 6th coordinate point and the 7th coordinate point In the area surrounded by the 7th line segment connecting the 7th coordinate point of% and the water content of 3.4 g / m 2 and the 8th line segment connecting the 6th coordinate point and the 7th coordinate point.
  • the polarizing film protective film having an iodine concentration and a water content contained therein is a light absorbing layer having a light absorbing ability, and is characterized in that the light transmittance at a wavelength of 380 nm is 5% or less.
  • the sixth coordinate point has an iodine concentration of 4.0 wt. % And the water content is 2.4 g / m 2 , which is the eighth coordinate point, and the seventh coordinate point is the iodine concentration of 4.0 wt. It may be the ninth coordinate point of% and the water content of 3.7 g / m 2. Further, the sixth coordinate point has an iodine concentration of 3.7 wt. It is the tenth coordinate point of% and the water content of 2.6 g / m 2 , and the seventh coordinate point may be the fourth coordinate point.
  • the film thickness of the polarizing film may be 11 to 30 ⁇ m.
  • the polarizing film made of a polyvinyl alcohol-based resin is optically bonded to at least the visible surface of the polarizing film directly or via another optical film.
  • a polarizing film laminate provided with a transparent polarizing film protective film the x-axis is the iodine concentration (wt.%) Of the polarizing film, and the y-axis is the water content (g / g /) of the polarizing film laminate. In the xy orthogonal coordinate system in which m 2 ) was taken, the iodine concentration was 6.0 wt.
  • the polarizing film protective film having an iodine concentration and a water content contained therein is a light absorbing layer having a light absorbing ability, and is characterized in that the light transmittance at a wavelength of 380 nm is 5% or less.
  • the film thickness of the polarizing film may be 4 to 11 ⁇ m.
  • the polarizing film protective film preferably has a light transmittance of 35% or less at a wavelength of 390 nm, and the polarizing film protective film has a wavelength of 400 nm.
  • the light transmittance is preferably 70% or less.
  • the polarizing film film laminate of the above aspect it is preferable that the polarizing film contains zinc.
  • a sample composed of the polarizing film laminate and the glass plate laminated on both sides of the polarizing film laminate with an adhesive is provided at a black panel temperature of 89 ° C. and 30 ° C. % R. H.
  • the single transmittance after irradiating xenon light in the wavelength range of 300 to 400 nm for 200 hours with an irradiance of 100 W / m 2 is -0.5 or more as compared with the single transmittance before irradiation. Is preferable. Thereby, the problem of polyene formation can be effectively solved.
  • the amount of change in the orthogonal transmittance at a wavelength of 410 nm is less than 1% and at a wavelength of 700 nm. It is preferable that the amount of change in the orthogonal transmittance of is less than 5%. As a result, the problem of color loss can be effectively solved.
  • the amount of change in the orthogonal transmittance at a wavelength of 410 nm is 1% or more, and the wavelength is 700 nm. It is preferable that the amount of change in the orthogonal transmittance of is less than 5%. Thereby, the problem of heating redness can be effectively solved.
  • the optical display panel according to one aspect of the present invention is bonded to the optical display cell directly or via another optical film on one surface of the optical display cell.
  • the optical display cell comprising the polarizing film laminate according to any one of the above and an optically transparent cover plate arranged along the polarizing film laminate on the side opposite to the optical display cell.
  • An optical display panel attached to the vehicle body of a powered vehicle is characterized in that the polarizing film laminate and the transparent cover plate are adhered to each other by a transparent adhesive layer that fills the space between them without any gaps. To do.
  • the transparent cover plate may have the function of a capacitive touch sensor.
  • an ITO layer which is a component of the capacitive touch sensor may be provided between the transparent cover plate and the polarizing film laminate.
  • the polarizing film laminate with a transparent adhesive layer is optically bonded to a polarizing film made of a polyvinyl alcohol-based resin directly or via another optical film on the surface of the polarizing film on at least the visible side.
  • a polarizing film laminate provided with a transparent polarizing film protective film and a transparent adhesive layer laminated on the visual side of the polarizing film laminate are provided, and the iodine concentration (wt) of the polarizing film is provided on the x-axis.
  • the iodine concentration was 6.0 wt.
  • the transparent adhesive layer and the polarizing film protective film having the iodine concentration and the amount of water contained, at least the transparent adhesive layer is a light absorbing layer having a light absorbing ability, and the transparent adhesive layer and the polarizing film It is characterized in that the light transmittance of the laminated body of the protective film at a wavelength of 380 nm is 5% or less.
  • the polarizing film laminate with a transparent adhesive layer is bonded to a polarizing film made of a polyvinyl alcohol-based resin directly or via another optical film on the surface of the polarizing film opposite to the visible side.
  • a polarizing film laminate provided with an optically transparent polarizing film protective film and a transparent adhesive layer laminated on the visual side of the polarizing film laminate are provided, and iodine of the polarizing film is provided on the x-axis.
  • concentration (wt.%) Is the water content (g / m 2 ) of the polarizing film laminate on the y-axis
  • the iodine concentration is 6.0 wt.
  • the transparent adhesive layer having an iodine concentration and a water content contained therein is a light absorbing layer having a light absorbing ability, and is characterized in that the light transmittance of the transparent adhesive layer at a wavelength of 380 nm is 5% or less.
  • the polarizing film assembly is an optically transparent polarized light bonded to a polarizing film made of a polyvinyl alcohol-based resin directly to at least the surface of the polarizing film on the visible side or via another optical film.
  • a polarizing film laminate provided with a film protective film, a transparent adhesive layer laminated on the visual side of the polarizing film laminate, and an optically transparent cover plate laminated on the visual side of the transparent adhesive layer.
  • the x-axis is the iodine concentration (wt.%) Of the polarizing film and the y-axis is the water content (g / m 2) of the polarizing film laminate. Concentration 6.0 wt.
  • the transparent cover plate is a light absorbing layer having a light absorbing ability, and the said. It is characterized in that the light transmittance of the polarizing film protective film, the transparent adhesive layer, and the laminated body of the transparent cover plate at a wavelength of 380 nm is 5% or less.
  • the polarizing film assembly according to another aspect of the present invention is optically bonded to a polarizing film made of a polyvinyl alcohol-based resin directly or via another optical film on the surface of the polarizing film opposite to the visible side.
  • a polarizing film laminate provided with a transparent polarizing film protective film, a transparent adhesive layer laminated on the visible side of the polarizing film laminate, and an optically transparent laminate laminated on the visual side of the transparent adhesive layer.
  • An xy orthogonal coordinate system provided with a cover plate, with the iodine concentration (wt.%) Of the polarizing film on the x-axis and the water content (g / m 2) of the polarizing film laminate on the y-axis.
  • the iodine concentration was 6.0 wt. % And the first coordinate point with a water content of 0.7 g / m 2 and an iodine concentration of 1.8 wt. % And a first line segment connecting a second coordinate point having a water content of 4.2 g / m 2 , the second coordinate point and an iodine concentration of 1.8 wt. % And a second line segment connecting a third coordinate point having a water content of 5.1 g / m 2 , the third coordinate point and an iodine concentration of 5.7 wt.
  • the transparent adhesive layer and the transparent cover plate having the iodine concentration and the amount of water contained at least the transparent cover plate is a light absorption layer having a light absorbing ability, and the transparent adhesive layer and the transparent cover plate. It is characterized in that the light transmittance of the laminated body of the cover plate at a wavelength of 380 nm is 5% or less.
  • the present invention relates to an optical display panel, for example, an optical display panel attached to the vehicle body of an automobile, a train, an airplane, or other powered traveling vehicle, and a polarizing film laminate used for the optical display panel. set to target.
  • an optical display panel for example, an optical display panel attached to the vehicle body of an automobile, a train, an airplane, or other powered traveling vehicle
  • a polarizing film laminate used for the optical display panel. set to target.
  • “attached to the vehicle body” does not necessarily mean that the optical display panel or the polarizing film laminate is fixed to the vehicle body, but also, for example, the optical display panel or the polarizing film laminate used in a smartphone or the like. It also includes the case where they are freely mounted or brought into a powered vehicle like a body.
  • mounted on the vehicle body includes all situations in which an optical display panel or polarizing film laminate is used with a powered vehicle and may be exposed to high temperature or high humidity environments.
  • FIG. 1 is a schematic view showing an example of the layer structure of the optical display panel 1.
  • the optical display panel 1 is at least opposite to the optical display cell 10, the polarizing film laminate 12 laminated on one surface 10a side (visual side) of the optical display cell 10, and the optical display cell 10.
  • the optical display cell 10 and the polarizing film laminate 12 are adhered to each other without any voids by using a transparent adhesive layer made of a transparent adhesive (PSA) 11.
  • PSA transparent adhesive
  • a transparent adhesive layer made of a transparent adhesive (OCA) 13 laminated on the visual side of the polarizing film laminate 12 is used so that there are no voids.
  • Another polarizing film laminate 17 is arranged on the other surface 10b side of the optical display cell 10 via a transparent adhesive (PSA) 16.
  • PSA transparent adhesive
  • the term "adhesive” includes adhesive (pressure sensitive adhesive).
  • the optical display cell 10 and the polarizing film laminate 12 may be directly bonded by the transparent adhesive 11, but if necessary, other optical films such as a retardation film and a viewing angle compensation film (not shown). ) May be adhered.
  • Optical display cell 10 examples include a liquid crystal cell and an organic EL cell.
  • the organic EL cell a cell in which a transparent electrode, an organic light emitting layer, and a metal electrode are sequentially laminated on a transparent substrate to form a light emitting body (organic electroluminescence light emitting body) or the like is preferably used.
  • the organic light emitting layer is a laminate of various organic thin films, for example, a laminate of a hole injection layer made of a triphenylamine derivative or the like and a light emitting layer made of a fluorescent organic solid such as anthracene, or a laminate of these.
  • Various layer configurations can be adopted, such as a laminate of electron injection layers composed of a light emitting layer and a perylene derivative, or a laminate of hole injection layers, light emitting layers, and electron injection layers.
  • the liquid crystal cell includes a reflective liquid crystal cell that uses external light, a transmissive liquid crystal cell that uses light from a light source such as a backlight 18, and a semi-transmissive semi-reflection that uses both external light and light from a light source. Any type liquid crystal cell may be used.
  • the polarizing film laminate 17 is also arranged on the side opposite to the visible side of the optical display cell (liquid crystal cell) 10, and further.
  • a light source 18 such as a backlight is arranged.
  • the polarizing film laminate 17 on the light source side and the liquid crystal cell 10 are adhered by an appropriate layer of a transparent adhesive 16.
  • any type such as VA mode, IPS mode, TN mode, STN mode and bend orientation ( ⁇ type) can be used.
  • cover plate 14 examples include a transparent plate (window layer), a touch panel, and the like.
  • a transparent plate a transparent plate having appropriate mechanical strength and thickness is used.
  • a transparent resin plate such as an acrylic resin or a polycarbonate resin, a glass plate, or the like is used.
  • the surface of the cover plate 14 may be subjected to a low reflection treatment by, for example, a low reflection film (not shown).
  • various touch panels such as a resistive film method, a capacitance method, an optical method, an ultrasonic method, and a glass plate or a transparent resin plate having a touch sensor function are used.
  • the cover plate 14 may contain an ultraviolet absorber to form a light absorbing layer having a light absorbing ability, in other words, the transmittance of the cover plate 14 to ultraviolet rays may be set to a desired value.
  • the cover plate 14 is formed of a transparent resin plate such as an acrylic resin or a polycarbonate resin, or a glass plate, and at the time of its production, for example, benzotriazole-based, benzophenone-based, salicylate phenyl ester-based, or triazine-based. Examples include UV absorbers.
  • benzotriazole-based ultraviolet absorber examples include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazole-2-yl) -p-cresol, and 2- (2H-benzotriazole). -2-yl) -4,6-di-tert-pentylphenol, 2- (2'-hydroxy-5'methacryloxyethylphenyl) -2H-benzotriazole and the like can be mentioned.
  • benzophenone-based ultraviolet absorber examples include 2-hydroxy-4-octoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-4'-chlorobenzophenone, and 2,2-dihydroxy-4-methoxy.
  • Benzophenone, 2,2-dihydroxy-4,4'-dimethoxybenzophenone and the like can be mentioned.
  • Examples of the salicylic acid phenyl ester-based ultraviolet absorber include pt-butylphenyl salicylate ester and the like.
  • Examples of the triazine-based ultraviolet absorber include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine and 2,4-diphenyl-6- (2-hydroxy-).
  • the transmittance of ultraviolet rays in the polarizing film assembly 19 including the polarizing film laminate 12 can be set to a desired value, and more effectively, "polyene formation", “color loss”, and “heated red”. You can comprehensively solve the problem of "oddness".
  • the transmittance at a wavelength of 380 nm is preferably 5% or less, more preferably 3% or less, still more preferably 2% or less.
  • the lower limit is, for example, 0.1% or more and 1% or more.
  • the transmittance at a wavelength of 390 nm is preferably 35% or less, more preferably 30% or less, still more preferably 28% or less.
  • the lower limit is, for example, 10% or more, 20% or more, and 25% or more.
  • the transmittance at a wavelength of 400 nm is preferably 70% or less, more preferably 68% or less.
  • the lower limit is, for example, 50% or more, 60% or more, 65% or more.
  • the transmittance at a wavelength of 420 nm is preferably 90% or less.
  • the lower limit is, for example, 80% or more and 85% or more.
  • phthalocyanine-based light absorbers In addition to ultraviolet absorbers, phthalocyanine-based light absorbers, naphthalocyanine-based light absorbers, polymethine-based light absorbers, diphenylmethane-based light absorbers, triphenylmethane-based light absorbers, quinone-based light absorbers, and azo-based light absorbers.
  • An infrared absorber such as a light absorber may be mixed.
  • a front transparent plate made of glass or a transparent resin plate is provided on the visual side of the touch panel. Further, in this case, an ITO layer (not shown) which is a component of the capacitive touch sensor is provided on the transparent adhesive 13 that joins the cover plate 14 and the polarizing film laminate 12.
  • Transparent Adhesive As the transparent adhesives 11, 13 and 16, for example, various adhesives as disclosed in Japanese Patent No. 6071459 can be appropriately used.
  • a (meth) acrylic adhesive can be used, or a curable adhesive that does not contain (meth) acrylic acid can be used.
  • an isoprene-based UV curable adhesive is preferably used.
  • the isoprene-based UV curable adhesive may contain an isoprene derivative in addition to isoprene as a monomer component.
  • the adhesive may contain a monomer component other than the isoprene-based monomer.
  • a (meth) acrylic acid derivative such as a (meth) acrylic acid ester may be contained as a monomer component. In order to suppress the decrease in transmittance due to polyene formation of polyvinyl alcohol, it is effective to reduce the content of the acid component in the transparent adhesives 11, 13 and 16.
  • the transparent adhesives 11, 13, 16, for example, the transparent adhesive 13 (transparent adhesive layer) laminated on the visual side of the polarizing film laminate 12 contains an ultraviolet absorber to absorb light having a light absorbing ability. It may be a layer, in other words, the transmittance of the transparent adhesive to ultraviolet rays may be set to a desired value.
  • a transparent adhesive is formed of a (meth) acrylic pressure-sensitive adhesive, and at the time of its production, examples thereof include benzotriazole-based, benzophenone-based, salicylate phenyl ester-based, and triazine-based UV absorbers.
  • benzotriazole-based ultraviolet absorber examples include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazole-2-yl) -p-cresol, and 2- (2H-benzotriazole). -2-yl) -4,6-di-tert-pentylphenol, 2- (2'-hydroxy-5'methacryloxyethylphenyl) -2H-benzotriazole and the like can be mentioned.
  • benzophenone-based ultraviolet absorber examples include 2-hydroxy-4-octoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-4'-chlorobenzophenone, and 2,2-dihydroxy-4-methoxy.
  • Benzophenone, 2,2-dihydroxy-4,4'-dimethoxybenzophenone and the like can be mentioned.
  • Examples of the salicylic acid phenyl ester-based ultraviolet absorber include pt-butylphenyl salicylate ester and the like.
  • Examples of the triazine-based ultraviolet absorber include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine and 2,4-diphenyl-6- (2-hydroxy-).
  • the transmittance at a wavelength of 380 nm is preferably 5% or less, more preferably 3% or less, still more preferably 2% or less.
  • the lower limit is, for example, 0.1% or more and 1% or more.
  • the transmittance at a wavelength of 390 nm is preferably 35% or less, more preferably 30% or less, still more preferably 28% or less.
  • the lower limit is, for example, 10% or more, 20% or more, and 25% or more.
  • the transmittance at a wavelength of 400 nm is preferably 70% or less, more preferably 68% or less.
  • the lower limit is, for example, 50% or more, 60% or more, 65% or more.
  • the transmittance at a wavelength of 420 nm is preferably 90% or less.
  • the lower limit is, for example, 80% or more and 85% or more.
  • phthalocyanine-based light absorbers In addition to ultraviolet absorbers, phthalocyanine-based light absorbers, naphthalocyanine-based light absorbers, polymethine-based light absorbers, diphenylmethane-based light absorbers, triphenylmethane-based light absorbers, quinone-based light absorbers, and azo-based light absorbers.
  • An infrared absorber such as a light absorber may be mixed.
  • the polarizing film laminate 12 includes at least a polarizing film 120 and a polarizing film protective film 121 bonded to at least the visible side of the polarizing film 120.
  • the polarizing film laminate 12 may further include a polarizing film protective film 122 on the side opposite to the visible side of the polarizing film 120.
  • the polarizing film protective film 121 may function as the light absorbing layer.
  • the present invention is to comprehensively solve the problems caused by the usage environment such as high temperature or high humidity and by the irradiation of sunlight, particularly the problems of "polyenation", “color loss”, and “heating reddening".
  • the polarizing film 120 is made of a polyvinyl alcohol (PVA) -based resin film containing iodine.
  • PVA polyvinyl alcohol
  • the material of the PVA-based film applied to the polarizing film PVA or a derivative thereof is used.
  • the PVA derivative include polyvinyl formal, polyvinyl acetal and the like, olefins such as ethylene and propylene, unsaturated carboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, alkyl esters thereof, and those modified with acrylamide and the like. Be done.
  • PVA a PVA having a degree of polymerization of about 1000 to 10000 and a degree of saponification of about 80 to 100 mol% is generally used. PVA-based films made of these materials tend to contain moisture.
  • the PVA-based film may contain additives such as plasticizers.
  • the plasticizer include polyols and condensates thereof, and examples thereof include glycerin, diglycerin, triglycerin, ethylene glycol, propylene glycol, polyethylene glycol and the like.
  • the amount of the plasticizer used is not particularly limited, but is preferably 20% by weight or less in the PVA-based film.
  • a polarizing film having a thickness of 6 ⁇ m or more for example, a dyeing treatment in which the PVA-based film is dyed with iodine and a stretching treatment in which the PVA-based film is stretched in at least one direction are performed.
  • a method is adopted in which the PVA-based film is subjected to a series of treatments including swelling, dyeing, cross-linking, stretching, washing with water and drying treatment.
  • the swelling treatment is performed, for example, by immersing a PVA-based film in a swelling bath (water bath).
  • a swelling bath water bath
  • stains on the surface of the PVA-based film and blocking inhibitor are cleaned, and the PVA-based film is swollen to prevent non-uniformity such as uneven dyeing.
  • Glycerin, potassium iodide and the like may be appropriately added to the swelling bath.
  • the temperature of the swelling bath is, for example, about 20 to 60 ° C.
  • the immersion time in the swelling bath is, for example, about 0.1 to 10 minutes.
  • the dyeing treatment is performed, for example, by immersing a PVA-based film in an iodine solution.
  • the iodine solution is usually an aqueous iodine solution and contains iodine and potassium iodide as a solubilizing agent.
  • the iodine concentration is, for example, about 0.01 to 1% by weight, preferably 0.02 to 0.5% by weight.
  • the potassium iodide concentration is, for example, about 0.01 to 10% by weight, preferably 0.02 to 8% by weight.
  • the temperature of the iodine solution is, for example, about 20 to 50 ° C, preferably 25 to 40 ° C.
  • the immersion time is, for example, about 10 to 300 seconds, preferably in the range of 20 to 240 seconds.
  • conditions such as the concentration of the iodine solution, the immersion temperature of the PVA film in the iodine solution, and the immersion time are adjusted so that the iodine content and the potassium content in the PVA film are within the above ranges. Will be done.
  • the cross-linking treatment is performed, for example, by immersing an iodine-dyed PVA-based film in a treatment bath containing a cross-linking agent.
  • a cross-linking agent Any suitable cross-linking agent is adopted as the cross-linking agent.
  • Specific examples of the cross-linking agent include boron compounds such as boric acid and borax, glyoxal, and glutaraldehyde. These may be used alone or in combination.
  • Water is generally used as the solvent used for the solution of the cross-linking bath, but an appropriate amount of an organic solvent compatible with water may be added.
  • the cross-linking agent is used, for example, in a ratio of 1 to 10 parts by weight with respect to 100 parts by weight of the solvent.
  • the solution of the cross-linking bath further contains an auxiliary agent such as iodide.
  • concentration of the auxiliary agent is preferably 0.05 to 15% by weight, more preferably 0.5 to 8% by weight.
  • the temperature of the cross-linking bath is, for example, about 20 to 70 ° C, preferably 40 to 60 ° C.
  • the immersion time in the cross-linking bath is, for example, about 1 second to 15 minutes, preferably 5 seconds to 10 minutes.
  • the stretching treatment is a treatment in which the PVA-based film is stretched in at least one direction.
  • the PVA-based film is uniaxially stretched in the transport direction (longitudinal direction).
  • the stretching method is not particularly limited, and either a wet stretching method or a dry stretching method can be adopted.
  • the wet stretching method is adopted, the PVA-based film is stretched to a predetermined magnification in the treatment bath.
  • a solution in which compounds necessary for various treatments are added to a solvent such as water or an organic solvent (for example, ethanol) is preferably used.
  • the dry stretching method include an inter-roll stretching method, a heating roll stretching method, and a compression stretching method.
  • the stretching treatment may be performed at any stage. Specifically, it may be performed at the same time as swelling, staining, and cross-linking, and may be performed before or after each of these treatments. Further, the stretching may be performed in multiple stages.
  • the cumulative draw ratio of the PVA-based film is, for example, 5 times or more, preferably about 5 to 7 times.
  • the PVA-based film (stretched film) subjected to each of the above treatments is subjected to a water washing treatment and a drying treatment according to a conventional method.
  • the water washing treatment is performed, for example, by immersing a PVA-based film in a water washing bath.
  • the water washing bath may be pure water or an aqueous solution of iodide (for example, potassium iodide, sodium iodide, etc.).
  • the concentration of the aqueous iodide solution is preferably 0.1 to 10% by weight.
  • Auxiliary agents such as zinc sulfate and zinc chloride may be added to the aqueous iodide solution.
  • the washing temperature is, for example, in the range of 5 to 50 ° C, preferably 10 to 45 ° C, and more preferably 15 to 40 ° C.
  • the immersion time is, for example, about 10 to 300 seconds, preferably 20 to 240 seconds.
  • the water washing treatment may be carried out only once, or may be carried out a plurality of times as needed. When the water washing treatment is performed a plurality of times, the type and concentration of the additive contained in the water washing bath used for each treatment are appropriately adjusted.
  • the PVA-based film is dried by any suitable method (for example, natural drying, blast drying, heat drying).
  • a polarizing film having a film thickness of less than 6 ⁇ m can be produced, for example, by the production method disclosed in Japanese Patent No. 4751481.
  • This production method includes a laminate preparation process for forming a PVA-based resin layer on a thermoplastic base material, a stretching treatment for stretching the PVA-based resin layer integrally with the thermoplastic resin base material, and a bicolor substance on the PVA resin layer. Includes dyeing treatment to be adsorbed. If necessary, insolubilization treatment, cross-linking treatment, drying treatment, cleaning treatment and the like of the PVA-based resin layer can also be applied.
  • the stretching treatment can be carried out before or after the dyeing treatment, and either stretching method of air stretching or stretching in water such as an aqueous boric acid solution can be adopted. Further, the stretching may be a one-step stretching or a multi-step stretching of two or more steps.
  • a polarizing film is produced by stretching a PVA-based resin layer formed on a resin base material integrally with the resin base material.
  • an amorphous ester-based thermoplastic resin base material having a glass transition temperature of 75 ° C. and a thickness of 200 ⁇ m for example, isophthalic acid copolymerized polyethylene terephthalate obtained by copolymerizing 6 mol% of isophthalic acid (hereinafter, “acrystalline PET””. 6 and a PVA aqueous solution having a concentration of 4 to 5% by weight in which a PVA powder having a degree of polymerization of 1000 or more and a degree of saponification of 99% or more is dissolved in water are prepared.
  • a PVA aqueous solution is applied to the amorphous PET base material 6 at a temperature of 50 to 60 ° C.
  • a PVA layer 2 having a glass transition temperature of 80 ° C. and a thickness of 7 ⁇ m is formed on the PET substrate 6.
  • the laminated body 7 including the PVA layer having a thickness of 7 ⁇ m is produced.
  • the surface of the amorphous PET base material 6 is corona-treated by the surface modification treatment apparatus 23 to improve the adhesion between the amorphous PET base material 6 and the PVA layer 2 formed on the amorphous PET base material 6. Can be done.
  • the laminate 7 containing the PVA layer is finally produced as a polarizing film having a thickness of 3 ⁇ m through the following treatments including a two-stage stretching treatment of auxiliary stretching in the air and stretching in boric acid in water.
  • the laminated body 7 containing the 7 ⁇ m-thick PVA layer 2 is stretched integrally with the PET base material 6, and the “stretched laminated body 8” containing the 5 ⁇ m-thick PVA layer 2 is formed.
  • the laminate 7 including the PVA layer 2 having a thickness of 7 ⁇ m is stretched in the oven 33 set to a stretching temperature environment of 130 ° C. It is stretched uniaxially at the free end so that the stretching ratio becomes 1.8 times through the means 31, and the stretched laminate 8 is produced.
  • the roll 8'of the stretched laminate 8 can be manufactured by the winding device 32 installed in the oven 30.
  • the dyeing treatment (C) produces a colored laminate 9 in which iodine, which is a dichroic substance, is adsorbed on the 5 ⁇ m-thick PVA layer 2 in which PVA molecules are oriented.
  • the stretched laminate 8 unwound from the feeding device 43 equipped with the roll 8'attached to the dyeing device 40 is iodine at a liquid temperature of 30 ° C.
  • the stretched laminate 8 is immersed in a dyeing solution 41 containing potassium iodide for an arbitrary time so that the single transmittance of the PVA layer constituting the finally produced polarizing film is 40 to 44%.
  • a colored laminate 9 in which iodine is adsorbed on the oriented PVA layer 2 is produced.
  • the dyeing solution 41 uses water as a solvent and has an iodine concentration of 0.30% by weight in order to prevent the PVA layer 2 contained in the stretched laminate 8 from being dissolved. Further, the staining solution 41 has a potassium iodide concentration of 2.1% by weight for dissolving iodine in water. The ratio of iodine to potassium iodide concentrations is 1: 7. More specifically, a 5 ⁇ m-thick PVA layer in which PVA molecules are oriented by immersing the stretched laminate 8 in a staining solution 41 having an iodine concentration of 0.30% by weight and a potassium iodide concentration of 2.1% by weight for 60 seconds. A colored laminate 9 in which iodine is adsorbed on 2 is produced.
  • the optical film laminate 60 including the polarizing film is preferably sent to the cleaning treatment (G) as it is.
  • the purpose of the cleaning treatment (G) is to wash away unnecessary residues adhering to the surface of the polarizing film with the cleaning liquid 81 of the cleaning apparatus 80.
  • the cleaning treatment (G) can be omitted, and the optical film laminate 60 including the removed polarizing film can be directly sent to the drying treatment (H).
  • the washed optical film laminate 60 is sent to a drying process (H), where it is dried.
  • the dried optical film laminate 60 is wound as a continuous web optical film laminate 60 by a winding device 91 attached to the drying apparatus 90, and a roll of the optical film laminate 60 including a polarizing film is rolled. Will be generated.
  • the drying treatment (H) any suitable method, for example, natural drying, blast drying, or heat drying can be adopted.
  • drying can be performed with warm air at 60 ° C. for 240 seconds.
  • the polarizing film preferably contains zinc. Since the polarizing film contains zinc, the decrease in transmittance and the deterioration of hue of the polarizing film laminate after the heating test tend to be suppressed.
  • the zinc content in the polarizing film is preferably 0.002 to 2% by weight, more preferably 0.01 to 1% by weight.
  • the polarizing film also preferably contains sulfate ions. Since the polarizing film contains sulfate ions, a decrease in the transmittance of the polarizing film laminate after the heating test tends to be suppressed.
  • the content of sulfate ions in the polarizing film is preferably 0.02 to 0.45% by weight, more preferably 0.05 to 0.35% by weight, and 0.1 to 0.1 to 0.35% by weight. 0.25% by weight is more preferable.
  • the content of sulfate ions in the polarizing film is calculated from the sulfur atom content.
  • zinc impregnation treatment is performed in the polarizing film manufacturing process.
  • sulfate ions it is preferable that sulfate ion treatment is performed in the polarizing film manufacturing process.
  • the zinc impregnation treatment is performed, for example, by immersing a PVA-based film in a zinc salt solution.
  • a zinc salt solution an inorganic salt compound in an aqueous solution such as zinc halide such as zinc chloride and zinc iodide, zinc sulfate and zinc acetate is suitable.
  • various zinc complex compounds may be used for the zinc impregnation treatment.
  • the zinc salt solution it is preferable to use an aqueous solution containing potassium ions and iodine ions with potassium iodide or the like because it is easy to impregnate the zinc ions.
  • the potassium iodide concentration in the zinc salt solution is preferably about 0.5 to 10% by weight, more preferably 1 to 8% by weight.
  • Sulfate ion treatment is performed, for example, by immersing a PVA-based film in an aqueous solution containing a metal sulfate.
  • the metal sulfate is preferably one in which the sulfate ion and the metal ion are easily separated in the treatment liquid, and the metal sulfate is easily introduced into the PVA-based film in the ion state.
  • the types of metals that form metal sulfates include alkali metals such as sodium and potassium; alkaline earth metals such as magnesium and calcium; transitions such as cobalt, nickel, zinc, chromium, aluminum, copper, manganese, and iron. Metal is mentioned.
  • the zinc impregnation treatment and the sulfate ion treatment may be performed at any stage. That is, the zinc impregnation treatment and the sulfate ion treatment may be performed before the dyeing treatment or after the dyeing treatment. The zinc impregnation treatment and the sulfate ion treatment may be performed at the same time. It is preferable that the zinc impregnation treatment and the sulfate ion treatment are simultaneously performed by immersing the PVA-based film in a treatment bath containing zinc sulfate using zinc sulfate as the zinc salt and the metal sulfate.
  • the zinc salt and the metal sulfate can be allowed to coexist in the dyeing solution, and the zinc impregnation treatment and / or the sulfate ion treatment can be performed at the same time as the dyeing treatment.
  • the zinc impregnation treatment and the sulfate ion treatment may be performed at the same time as the stretching.
  • Polarizing film protective film 2-2-1 Polarizing film protective film located on the side opposite to the viewing side In the polarizing film laminate 12 of FIG. 1, as a material constituting the polarizing film protective film 122 located on the side opposite to the viewing side of the polarizing film 120, for example, , A thermoplastic resin having excellent transparency, mechanical strength, and thermal stability.
  • thermoplastic resins include cellulose-based resins such as triacetyl cellulose, polyester-based resins, polyether sulfone-based resins, polysulfone-based resins, polycarbonate-based resins, polyamide-based resins, polyimide-based resins, and polyolefin-based resins.
  • the polarizing film protective film 122 may also have the function of a retardation film.
  • the thickness of the polarizing film protective film 122 is appropriately adjusted in order to adjust the water content of the polarizing film laminate. From the viewpoint of workability such as strength and handleability, thin layer property, etc., about 1 to 500 ⁇ m is preferable, 2 to 300 ⁇ m is more preferable, and 5 to 200 ⁇ m is further preferable.
  • the polarizing film protective film 122 may contain one or more kinds of arbitrary additives. Examples of additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, color retardants, flame retardants, nucleating agents, antistatic agents, pigments, colorants and the like.
  • the polarizing film protective film 121 located on the viewing side of the polarizing film 120 is configured as a light absorbing layer having a light absorbing ability.
  • the transmittance for ultraviolet rays is set to a desired value.
  • the polarizing film protective film 121 can be configured as a light absorbing layer having a light absorbing ability by containing an ultraviolet absorber, but it is sufficient if the transmittance for ultraviolet rays can be set to a desired value. It is not always necessary to use an ultraviolet absorber.
  • an ultraviolet absorbing filter may be used instead of the ultraviolet absorber to obtain a desired transmittance.
  • the transmittance at a wavelength of 380 nm is preferably 5% or less, more preferably 3% or less, still more preferably 2% or less.
  • the lower limit is, for example, 0.1% or more and 1% or more.
  • the transmittance at a wavelength of 390 nm is preferably 35% or less, more preferably 30% or less, still more preferably 28% or less.
  • the lower limit is, for example, 10% or more, 20% or more, and 25% or more.
  • the transmittance at a wavelength of 400 nm is preferably 70% or less, more preferably 68% or less.
  • the lower limit is, for example, 50% or more, 60% or more, 65% or more.
  • the transmittance at a wavelength of 420 nm is preferably 90% or less.
  • the lower limit is, for example, 80% or more and 85% or more.
  • phthalocyanine-based light absorbers In addition to ultraviolet absorbers, phthalocyanine-based light absorbers, naphthalocyanine-based light absorbers, polymethine-based light absorbers, diphenylmethane-based light absorbers, triphenylmethane-based light absorbers, quinone-based light absorbers, and azo-based light absorbers.
  • An infrared absorber such as a light absorber may be mixed.
  • the polarizing film protective film 121 for example, the configurations shown in FIGS. 3A to 3C can be adopted. Any of the polarizing film protective films 121A to C shown in FIGS. 3A to 3C can be used as the polarizing film protective film 121 shown in FIG.
  • the polarizing film 120 and the polarizing film protective film 122 shown in FIG. 1 are also shown in these figures.
  • the polarizing film protective film 121A shown in FIG. 3A includes a polarizing film protective film layer 121A-1 and a coating layer 121A-2.
  • the polarizing film protective film 121A having a light absorbing ability is obtained, for example, by containing a light absorbing agent in the polarizing film protective film layer 121A-1 and / or by containing a light absorbing agent in the coating layer 121A-2. Can be formed.
  • thermoplastic resin having excellent transparency, mechanical strength, and thermal stability.
  • thermoplastic resins include cellulose-based resins such as triacetyl cellulose, polyester-based resins, polyether sulfone-based resins, polysulfone-based resins, polycarbonate-based resins, polyamide-based resins, polyimide-based resins, and polyolefin-based resins.
  • the polarizing film protective film may have the function of a retardation film.
  • the thickness of the polarizing film protective film layer 121A-1 is appropriately adjusted in order to adjust the water content of the polarizing film laminate 12. It is 20 to 60 ⁇ m, preferably 30 to 50 ⁇ m from the viewpoint of workability such as strength and handleability, and thin layer property.
  • One or more kinds of arbitrary additives may be contained in the polarizing film protective film layer 121A-1. Examples of the additive include antioxidants, lubricants, plasticizers, mold release agents, colorants, flame retardants, nucleating agents, antistatic agents, pigments, colorants and the like.
  • Examples of the light absorber contained in the polarizing film protective film layer 121A-1 include benzotriazole-based, benzophenone-based, salicylate phenyl ester-based, and triazine-based ultraviolet absorbers.
  • Examples of the benzotriazole-based ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazole-2-yl) -p-cresol, and 2- (2H-benzotriazole).
  • -2-yl) -4,6-di-tert-pentylphenol, 2- (2'-hydroxy-5'methacryloxyethylphenyl) -2H-benzotriazole and the like can be mentioned.
  • benzophenone-based ultraviolet absorber examples include 2-hydroxy-4-octoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-4'-chlorobenzophenone, and 2,2-dihydroxy-4-methoxy.
  • benzophenone, 2,2-dihydroxy-4,4'-dimethoxybenzophenone and the like can be mentioned.
  • salicylic acid phenyl ester-based ultraviolet absorber include pt-butylphenyl salicylate ester and the like.
  • Examples of the triazine-based ultraviolet absorber include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine and 2,4-diphenyl-6- (2-hydroxy-). 4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy- 4-Butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- ( 2-Hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4 -Diphenyl-6- (2
  • the coating layer 121A-2 include a hard coat layer, an anti-glare layer, an anti-blocking layer, an antireflection layer, a conductive layer and the like.
  • the production method of the present invention is particularly useful when forming a hard coat layer.
  • Materials constituting the coating layer include resin materials (monomers, oligomers, prepolymers and / or polymers).
  • the resin material comprises a thermosetting or photocurable curable compound.
  • a hard coat layer or an anti-glare layer can be formed by using a coating layer material containing a curable compound.
  • the curable compound may be any of a monomer, an oligomer and a prepolymer.
  • a polyfunctional monomer or oligomer can be used as the curable compound, for example, a monomer or oligomer having two or more (meth) acryloyl groups, a urethane (meth) acrylate or a urethane (meth) acrylate oligomer, an epoxy-based monomer or Examples thereof include oligomers, silicone-based monomers and oligomers.
  • the thickness of the coating layer 121A-2 is 10 ⁇ m or less, preferably 8 ⁇ m or less, and more preferably 6 ⁇ m or less in terms of thinness and the like. The lower limit is, for example, 1 ⁇ m or more, 2 ⁇ m or more, and 4 ⁇ m or more.
  • Examples of the light absorber contained in the coating layer 121A-2 include benzotriazole-based, benzophenone-based, salicylic acid phenyl ester-based, and triazine-based ultraviolet absorbers.
  • Examples of the benzotriazole-based ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazole-2-yl) -p-cresol, and 2- (2H-benzotriazole).
  • -2-yl) -4,6-di-tert-pentylphenol, 2- (2'-hydroxy-5'methacryloxyethylphenyl) -2H-benzotriazole and the like can be mentioned.
  • benzophenone-based ultraviolet absorber examples include 2-hydroxy-4-octoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-4'-chlorobenzophenone, and 2,2-dihydroxy-4-methoxy.
  • benzophenone, 2,2-dihydroxy-4,4'-dimethoxybenzophenone and the like can be mentioned.
  • salicylic acid phenyl ester-based ultraviolet absorber include pt-butylphenyl salicylate ester and the like.
  • Examples of the triazine-based ultraviolet absorber include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine and 2,4-diphenyl-6- (2-hydroxy-). 4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy- 4-Butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- ( 2-Hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4 -Diphenyl-6- (2
  • the total thickness of the light absorbing layer composed of the polarizing film protective film layer 121A-1 and / or the coating layer 121A-2 that is, the polarizing film protection having a light absorbing ability
  • the total thickness of the film layer 121A-1 and / or the coating layer 121A-2 having a light absorbing ability is 25 to 65 ⁇ m, preferably 35 to 55 ⁇ m from the viewpoint of obtaining sufficient light absorbing ability and thinning property.
  • it is more preferably 40 to 50 ⁇ m.
  • Polarizing film protective film 121B The polarizing film protective film 121B shown in FIG. 3 (b) includes a plurality of polarizing film protective film layers 121B-1 and 121B-3, and these polarizing film protective film layers 121B-1 and 121B-. Includes an adhesive layer 121B-2 to which 3 is bonded.
  • the polarizing film protective film 121B having a light absorbing ability can be formed, for example, by including a light absorbing agent in either or both of the polarizing film protective film layers 121B-1 and 121B-3.
  • the same material as the optical film protective film layer 121A-1 can be used.
  • the same light absorber contained in the polarizing film protective film layers 121B-1 and 121B-3 the same light absorber contained in the polarizing film protective film layer 121A-1 can be used. These light absorbers can be contained in the same manner as the polarizing film protective film layer 121A-1.
  • the total thickness of the light absorbing layer composed of the polarizing film protective film layers 121B-1 and 121B-3, that is, the polarizing film protective film layer 121B-1 having a light absorbing ability is 25 to 105 ⁇ m, preferably 60 to 100 ⁇ m, and more preferably 70 to 90 ⁇ m from the viewpoint of obtaining sufficient light absorption capacity and thin layer property.
  • an ultraviolet curable adhesive or a dope curable adhesive which will be described later, can be used.
  • Polarizing film protective film 121C The polarizing film protective film 121C shown in FIG. 3 (c) includes only the polarizing film protective film layer 121C having a light absorbing ability.
  • the same material as that of the optical film protective film layer 121A-1 can be used.
  • the same light absorber contained in the polarizing film protective film layer 121C the same light absorber contained in the polarizing film protective film layer 121A-1 can be used. These light absorbers can be contained in the same manner as the polarizing film protective film layer 121A-1.
  • the thickness of the polarizing film protective film layer 121C is 25 to 105 ⁇ m, preferably 60 to 100 ⁇ m, more preferably 70 to 90 ⁇ m from the viewpoint of obtaining sufficient light absorption ability and thin layer property.
  • the polarizing film protective film layer 121C can also be regarded as a combination of the plurality of polarizing film protective films 121B-1 and 121B-3 shown in FIG. 3B.
  • any of the cover plate 14, the transparent adhesive 13, and the polarizing film protective film 121 may be used, or a combination thereof may be used to form a light absorption layer.
  • the desired transmittance may be appropriately adjusted for the entire device as in the case of a general device.
  • the other optical film The polarizing film and the polarizing film protective films 121 and 122 may be directly bonded or laminated with another optical film.
  • the other optical film is not particularly limited, but for example, a retardation film, a viewing angle compensation film, or the like can be used.
  • the retardation film as another optical film may have a function as a protective film.
  • the polarizing film protective films 121 and 122 may have the function of a retardation film, but in this case, the retardation film as another optical film may be omitted.
  • the retardation film can be provided as another optical film. In this case, substantially two or more retardation films will be included.
  • Adhesive The adhesive used to bond the adhesive layer 121B-2 shown in FIG. 3B, the polarizing film 120 and the polarizing film protective films 121 and 122, or other optical films such as a retardation film and them.
  • a radical polymerization curable (ultraviolet curable) adhesive, a cationic polymerization curable adhesive, or an aqueous (dope type) adhesive can be used.
  • the radical polymerization curable adhesive contains a radical polymerizable compound as a curable compound.
  • the radically polymerizable compound may be a compound that is cured by active energy rays or a compound that is cured by heat. Examples of the active energy ray include an electron beam, ultraviolet rays, visible light and the like.
  • the radically polymerizable compound examples include compounds having a radically polymerizable functional group having a carbon-carbon double bond such as a (meth) acryloyl group and a vinyl group.
  • a polyfunctional radically polymerizable compound is preferably used. Only one type of radically polymerizable compound may be used alone, or two or more types may be used in combination. Further, the polyfunctional radical polymerizable compound and the monofunctional radical polymerizable compound may be used in combination.
  • the polymerizable compound it is preferable to use a compound having a high logP value (octanol / water partition coefficient), and as the radical polymerizable compound, it is preferable to select a compound having a high logP value.
  • the logP value is an index showing the lipophilicity of a substance, and means a logarithmic value of the partition coefficient of octanol / water.
  • a high logP value means that it is lipophilic, that is, it has a low water absorption rate.
  • the logP value can be measured (the flask dipping method described in JIS-Z-7260), and is calculated based on the structure of each compound which is a constituent component (curable component, etc.) of the curable adhesive. It can also be calculated (ChemDraw Ultra manufactured by Cambridge Soft).
  • the logP value of the radically polymerizable compound is preferably 2 or more, more preferably 3 or more, and particularly preferably 4 or more. Within such a range, deterioration of the polarizing element due to moisture can be prevented, and a polarizing film having excellent durability under high temperature and high humidity can be obtained.
  • polyfunctional radical polymerizable compound examples include tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di ().
  • a polyfunctional radical polymerizable compound having a high logP value is preferable.
  • the content ratio of the polyfunctional radical polymerizable is preferably 20 to 97% by weight, preferably 50 to 95% by weight, based on the total amount of the radically polymerizable compound.
  • weight% is more preferable, 75 to 92% by weight is further preferable, and 80 to 92% by weight is particularly preferable. Within such a range, a polarizing film having excellent durability under high temperature and high humidity can be obtained.
  • Examples of the monofunctional radically polymerizable compound include (meth) acrylamide derivatives having a (meth) acrylamide group.
  • the (meth) acrylamide derivative By using the (meth) acrylamide derivative, a pressure-sensitive adhesive layer having excellent adhesiveness can be formed with high productivity.
  • Specific examples of the (meth) acrylamide derivative include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N.
  • N-N-alkyl group-containing (meth) acrylamide derivatives such as butyl (meth) acrylamide and N-hexyl (meth) acrylamide; N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylol-N- N-hydroxyalkyl group-containing (meth) acrylamide derivatives such as propane (meth) acrylamide; N-aminoalkyl group-containing (meth) acrylamide derivatives such as aminomethyl (meth) acrylamide and aminoethyl (meth) acrylamide; N-methoxymethyl N-alkoxy group-containing (meth) acrylamide derivatives such as acrylamide and N-ethoxymethylacrylamide; N-mercaptoalkyl group-containing (meth) acrylamide derivatives such as mercaptomethyl (meth) acrylamide and mercaptoethyl (meth) acrylamide can be mentioned.
  • heterocyclic-containing (meth) acrylamide derivative in which the nitrogen atom of the (meth) acrylamide group forms a heterocycle for example, N-acrylloylmorpholine, N-acrylloylpiperidin, N-methacryloylpiperidin, N-acrylloylpyridine and the like. May be used. Among these, an N-hydroxyalkyl group-containing (meth) acrylamide derivative is preferable, and N-hydroxyethyl (meth) acrylamide is more preferable.
  • a (meth) acrylic acid derivative having a (meth) acryloyloxy group a (meth) acrylic acid derivative having a (meth) acryloyloxy group; (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, croton.
  • Carboxyl group-containing monomers such as acid and isocrotonic acid; lactam-based vinyl monomers such as N-vinylpyrrolidone, N-vinyl- ⁇ -caprolactam and methylvinylpyrrolidone; vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole , Vinyl imidazole, vinyl oxazole, vinyl morpholin, and other vinyl-based monomers having a nitrogen-containing heterocycle may be used.
  • the content ratio of the monofunctional radical polymerizable is preferably 3 to 80% by weight based on the total amount of the radical polymerizable compound, and 5 to 50% by weight. By weight% is more preferred, 8 to 25% by weight is even more preferred, and 8 to 20% by weight is particularly preferred. Within such a range, a polarizing film having excellent durability under high temperature and high humidity can be obtained.
  • the radical polymerization curable adhesive may further contain other additives.
  • the adhesive may further contain, for example, a photopolymerization initiator, a photoacid generator, a silane coupling agent, and the like.
  • the adhesive may further contain a thermal polymerization initiator, a silane coupling agent, and the like.
  • examples of other additives include polymerization inhibitors, polymerization initiators, leveling agents, wettability improvers, surfactants, plasticizers, ultraviolet absorbers, inorganic fillers, pigments, dyes and the like. ..
  • the cationically polymerizable curable adhesive contains a cationically polymerizable compound as a curable compound.
  • the cationically polymerizable compound include compounds having an epoxy group and / or an oxetanyl group.
  • the compound having an epoxy group a compound having at least two epoxy groups in the molecule is preferably used.
  • the compound having an epoxy group include a compound having at least two epoxy groups and at least one aromatic ring (aromatic epoxy compound), and at least two epoxy groups in the molecule, of which at least.
  • One is a compound (alicyclic epoxy compound) formed between two adjacent carbon atoms constituting an alicyclic ring.
  • the cationic polymerization curable adhesive preferably contains a photocationic polymerization initiator.
  • the photocationic polymerization initiator generates a cationic species or Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and initiates a polymerization reaction of an epoxy group or an oxetanyl group.
  • the cationic polymerization curable adhesive may further contain the above-mentioned additive.
  • water-based adhesive examples include aqueous solutions of water-based adhesives such as isocyanate-based adhesives, PVA-based adhesives, gelatin-based adhesives, vinyl-based latex-based adhesives, and water-based polyesters (for example, solid content concentration of 0.5 to 60% by weight). ) Is preferably used.
  • the adhesive may be applied to any of the polarizing film 120, the polarizing film protective films 121 and 122, and other optical films, or both of them.
  • a method in which the polarizing film is immersed in an aqueous adhesive solution and then laminated with the polarizing film protective films 121 and 122 by a roll laminator or the like is preferable.
  • the thickness of the adhesive layer is not particularly limited, but is, for example, about 30 nm to 1000 nm after drying.
  • this laminate is subjected to a drying treatment.
  • the purpose is to reduce the amount of water that improves the initial optical characteristics of the polarizing film laminated body.
  • heat drying is common.
  • the drying conditions are preferably in the range of 50 to 95 ° C and more preferably in the range of 60 to 85 ° C.
  • the drying conditions of the laminate are not particularly limited, but considering the efficiency and practicality of the treatment, the drying temperature is preferably 50 ° C. or higher, and 95 from the viewpoint of making the optical characteristics of the polarizing film laminate uniform. °C or less is preferable.
  • the drying temperature can be raised stepwise within the above temperature range.
  • the laminate can be dried continuously with the bonding treatment of the polarizing film, the polarizing film protective film, and other optical films. Further, after the laminate of the polarizing film, the polarizing film protective film, and other optical films is once wound in a roll state, drying may be performed as another treatment.
  • the water content of the polarizing film laminate can be adjusted within the desired range without adopting harsh drying conditions. Can be done.
  • Adhesive The adhesive described in "1-3. Transparent Adhesive" described above can be used in the same manner.
  • ⁇ Polyene> In a high temperature and high humidity environment, the single transmittance of the polarizing film laminate decreases. Further, even when light is irradiated in the ultraviolet region or the visible light region, the single transmittance of the polarizing film laminate is similarly lowered. This decrease is presumed to be due to polyene formation of PVA.
  • PVA is polyene-ized by the iodine (I 2 ) generated in a high-temperature and high-humidity environment or in a light irradiation environment in the ultraviolet region or visible light region, and heating or light energy. It is thought to occur when the dehydration reaction is promoted.
  • I 2 generated when the PVA-polyiodine complex existing in the polarizing film is broken by heating or light energy and the OH group in PVA form a charge transfer complex (HO ... I 2 ), and then the OI group is formed. It is thought that it will become polyene via.
  • ⁇ Color loss> It is iodine staining, and the stretched PVA-based film (polarizer), iodine I 3 - and I 5 - in the form of a polyiodine ion, to form a oriented PVA complexes (PVA polyiodine complex ).
  • the PVA has a cross-linking point formed by a cross-linking agent such as boric acid, whereby the orientation is maintained.
  • a cross-linking agent such as boric acid
  • the visible light absorption based on the PVA polyiodine complex is reduced, and the transmittance on the long wavelength side of about 700 nm and the short wavelength side of about 410 nm is increased.
  • color loss occurs in a black display.
  • I 3 - has a broad absorption peak near 470 nm
  • I 5 - has a broad absorption peak near 600 nm. That is, the PVA-I 3 - complex is responsible for absorption on the short wavelength side (blue side), and the PVA-I 5 - complex is responsible for absorption on the long wavelength side (red side).
  • the PVA-I 5 - complexes weakly to the heat or light energy, the polarizing film and a high temperature, when placed under light irradiation environment in the ultraviolet region or visible region PVA and I 5 - is complexation with collapse, I 5 - would decompose. Therefore, in a polarizing film placed at a high temperature or in a light irradiation environment in an ultraviolet region or a visible light region, the PVA-I 5 - complex responsible for absorption on the long wavelength side is reduced, that is, the length is about 700 nm. The transmittance on the wavelength side increases, and the polarizing film turns red.
  • ⁇ Film thickness of polarizing film The film thickness ( ⁇ m) of the polarizing film is measured using a spectroscopic film thickness meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.). The thickness of the polarizing film protective film is also measured using this.
  • the polarizing film contained in the sample can be taken out by immersing the sample in a solvent and dissolving the polarizing film protective film.
  • the solvent for example, dichloromethane is used when the polarizing film protective film is a triacetyl cellulose resin, cyclohexane is used when the polarizing film protective film is a cycloolefin resin, and methyl ethyl ketone is used when the polarizing film protective film is an acrylic resin. , Can be used respectively. If the resin of the polarizing film protective film provided on one surface of the polarizing film and the resin of the polarizing film protective film provided on the other surface are different, the respective resins are used as the above-mentioned solvent. Dissolve in sequence using.
  • the iodine concentration (wt.%) Of the polarizing film can be changed, for example, by adjusting the concentration of the iodine aqueous solution for immersing the PVA-based film or the PVA layer and the immersion time during the production of the polarizing film.
  • the iodine concentration of the polarizing film is measured by the following method.
  • the polarizing film contained in the sample can be taken out by immersing the sample in a solvent and dissolving the polarizing film protective film in the same manner as when measuring the film thickness of the polarizing film.
  • the iodine concentration of the polarizing film is quantified by using the calibration curve method of fluorescent X-ray analysis.
  • a fluorescent X-ray analyzer ZSX-PRIMUS IV manufactured by Rigaku Co., Ltd.
  • the value directly obtained by the fluorescent X-ray analyzer is not the concentration of each element, but the fluorescent X-ray intensity (kcps) of the wavelength peculiar to each element. Therefore, in order to determine the iodine concentration contained in the polarizing film, it is necessary to convert the fluorescent X-ray intensity into a concentration using a calibration curve.
  • the iodine concentration of the polarizing film in the present specification and the like means the iodine concentration (wt%) based on the weight of the polarizing film.
  • Iodine concentration (wt%) ⁇ potassium iodide amount (g) / (potassium iodide amount (g) + PVA amount (g)) ⁇ x (127/166) (Molecular weight of iodine: 127 Molecular weight of potassium: 39)
  • the fluorescent X-ray intensity (kcps) corresponding to iodine is measured on the produced PVA film using a fluorescent X-ray analyzer ZSX-PRIMUS IV (manufactured by Rigaku Co., Ltd.).
  • the fluorescent X-ray intensity (kcps) is the peak value of the fluorescent X-ray spectrum.
  • the film thickness of the produced PVA film is measured using a spectroscopic film thickness meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.).
  • the fluorescent X-ray intensity is divided by the thickness of the PVA film ( ⁇ m) to obtain the fluorescent X-ray intensity per unit thickness of the film (kcps / ⁇ m).
  • Table 1 shows the iodine concentration of each sample and the fluorescent X-ray intensity per unit thickness.
  • the fluorescent X-ray intensity obtained in the sample measurement is divided by the thickness to obtain the fluorescent X-ray intensity (kcps / ⁇ m) per unit thickness.
  • the iodine concentration is obtained by substituting the fluorescent X-ray intensity per unit thickness of each sample into Equation 2.
  • the water content (g / m 2 ) of the polarizing film laminate can be determined mainly by adjusting the film thickness of the polarizing film, the material and thickness of the polarizing film protective film bonded to the polarizing film, and the like. It can also be adjusted by a cross-linking treatment (boric acid content, etc.) at the time of manufacturing the polarizing film.
  • the water content of the polarizing film laminate is measured by the following method. First, the polarizing film laminates obtained in Examples and Comparative Examples are cut into a square of 0.1 m ⁇ 0.1 m. The cut sample is placed in a constant temperature and humidity chamber and left for 48 hours in an environment with a temperature of 23 ° C.
  • the sample is taken out in the same environment as in the constant temperature and humidity chamber, that is, in a clean room set to a temperature of 23 ° C. and a relative humidity of 55%, and the weight is measured within 5 minutes after taking out.
  • the sample weight at this time is defined as the initial weight W1 (g). If it is within about 15 minutes after taking out, even if the temperature in the clean room fluctuates by about 2 ° C to 3 ° C, or even if the relative humidity in the clean room fluctuates by about ⁇ 10%, the initial weight Has no substantial effect on.
  • the taken-out sample is put into a dryer and dried at 120 ° C. for 2 hours.
  • the sample dried in a clean room set to the above-mentioned temperature of 23 ° C. and relative humidity of about 55% is taken out, and the weight is measured within 10 minutes after taking out.
  • the sample weight at this time is the weight W2 (g) after drying.
  • the reason why it is set within 10 minutes instead of within 5 minutes is in consideration of the cooling time.
  • the weight after drying is not substantially affected.
  • the equilibrium water content M (g / m 2 ) of the polarizing film laminate is calculated from the following formula.
  • (Equation) M (W1-W2) / (0.1 ⁇ 0.1)
  • the "moisture content of the polarizing film laminate" as used in the present invention means the equilibrium moisture content calculated by the above method.
  • the polarizing film protection located on the visual side of the polarizing film according to the JIS-Z-8701 color display method for each of the wavelengths of 380 ⁇ m, 390 ⁇ m, 400 ⁇ m, and 420 ⁇ m
  • the transmittance of the film was measured.
  • U-4100 manufactured by Hitachi, Ltd. was used.
  • Example 1 (Creation of polarizing film)
  • a long amorphous isophthalic copolymerized polyethylene terephthalate film (isophthalic acid group modification degree 5 mol%, thickness: 100 ⁇ m) was used.
  • (Degree of polymerization ethylene isophthalate unit / (ethylene terephthalate unit + ethylene isophthalate unit))
  • One surface of the resin base material is subjected to corona treatment (treatment condition: 55 W ⁇ min / m2), and the corona treated surface is subjected to corona treatment.
  • An aqueous solution containing potassium iodide so as to be 13 parts by weight was applied at room temperature. Then, it was dried at 60 ° C. to form a PVA-based resin layer having a thickness of 13 ⁇ m, and a laminate was prepared. The obtained laminate was stretched 2.4 times in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds in an oven at 130 ° C.
  • the laminate was immersed in an insolubilizing bath at a liquid temperature of 40 ° C. (an aqueous boric acid solution obtained by blending 4 parts by weight of boric acid with 100 parts by weight of water) for 30 seconds (insolubilization treatment).
  • a dyeing bath having a liquid temperature of 30 ° C. an aqueous iodine solution obtained by mixing iodine and potassium iodide in a weight ratio of 1: 7 with respect to 100 parts by weight of water
  • a polarizing film protective film is not provided on the surface of the obtained polarizing film opposite to the resin substrate (one surface of the polarizing film, in other words, the surface opposite to the visible side of the polarizing film).
  • the other surface of the polarizing film in other words, the surface on the visual side of the polarizing film
  • triacetyl cellulose containing a light absorber as a polarizing film protective film having a light absorbing ability.
  • An ultraviolet curable type polarizing film protective film composed of a film (manufactured by Konica Minolta, trade name "KC4UY", thickness 40 ⁇ m) and a hard coat layer (thickness 5 ⁇ m) containing a light absorber arranged on the visible side thereof. They were joined via an adhesive. Specifically, the curable adhesive was coated so that the total thickness was 1.0 ⁇ m, and the adhesive was joined using a roll machine. Then, UV light is irradiated from the other surface side to cure the adhesive to obtain a polarizing film laminate containing a polarizing film and a polarizing film protective film having a light absorbing ability on the other surface of the polarizing film. It was.
  • the above-mentioned triacetyl cellulose film contains a predetermined amount of a light absorber (ultraviolet absorber).
  • the hard coat layer is a light absorber Tinosorb S (manufactured by BASF) so that the triacetyl cellulose film and the entire hard coat layer have the transmittances shown in Tables 2 and 3 described later. Was contained.
  • the details of the UV curable adhesive are as follows. An adhesive was prepared by mixing 40 parts by weight of N-hydroxyethylacrylamide (HEAA), 60 parts by weight of acryloyl morpholine (ACMO), and 3 parts by weight of the photoinitiator "IRGACURE 819" (manufactured by BASF).
  • the adhesive layer was applied onto a polarizing film so that the thickness of the adhesive layer after curing was 1.0 ⁇ m, and was irradiated with ultraviolet rays as active energy rays to cure the adhesive.
  • ultraviolet irradiation gallium-filled metal halide lamp, irradiation device: Fusion UV Systems, Light HAMMER10 manufactured by Inc., valve: V valve, peak illuminance: 1600 mW / cm 2 , cumulative irradiation amount 1000 / mJ / cm 2 (wavelength 380 to 440 nm). ), And the illuminance of ultraviolet rays was measured using a Solar-Check system manufactured by Solartell.
  • the polarizing film protective film located on the visual side of the polarizing film that is, the polarizing film protective film composed of the triacetyl cellulose film and the hard coat layer is peeled off from the polarizing film laminate to increase the transmittance of the polarizing film protective film. It was measured.
  • Example 2 In the preparation of the polarizing film of Example 1, the concentration of the iodine aqueous solution and the immersion time were adjusted in the dyeing treatment to change the iodine concentration. Further, when producing the polarizing film laminate of Example 1, a cycloolefin-based film (Zeonoa film, 13 ⁇ m, manufactured by Nippon Zeon Co., Ltd.) was applied as a polarizing film protective film on one surface of the polarizing film, and an ultraviolet curable adhesive was applied. It was joined through. Since this cycloolefin-based film is provided on one surface of the polarizing film, it does not affect the value of the light absorption capacity. On the other hand, the other surface of the polarizing film has the same configuration as the other surface of the first embodiment. In addition, the water content of the polarizing film laminate was changed. Others are the same as in Example 1.
  • Example 1 In producing the polarizing film laminate of Example 1, one surface of the polarizing film has the same configuration as the above-mentioned one surface of Example 1, while the other surface of the polarizing film has a lactone ring structure.
  • a transparent protective film manufactured by Nitto Denko Co., Ltd.
  • a transparent protective film having a thickness of 20 ⁇ m made of a modified acrylic polymer was applied through an ultraviolet curable adhesive in the same manner as in Example 1 so that the total thickness of the curable adhesive was 1.0 ⁇ m. It was joined.
  • the water content of the polarizing film laminate was changed. Others are the same as in Example 1.
  • Example 2 In producing the polarizing film laminate of Example 2, one surface of the polarizing film has the same configuration as the above one surface of Example 2, while the other surface of the polarizing film has a cycloolefin film (Japan). Zeon Co., Ltd., Zeonoa film, 25 ⁇ m) was bonded via an ultraviolet curable adhesive in the same manner as in Example 1 so that the total thickness of the curable adhesive was 1.0 ⁇ m. In addition, the water content of the polarizing film laminate was changed. Others are the same as in Example 2.
  • Example 3 In the preparation of the polarizing film of Example 1, the concentration of the iodine aqueous solution and the immersion time were adjusted in the dyeing treatment to change the iodine concentration. Further, in producing the polarizing film laminate of Example 1, a cycloolefin-based film (Zeonoa film, 17 ⁇ m, manufactured by Nippon Zeon Co., Ltd.) was used as a polarizing film protective film on one surface of the polarizing film. In the same manner, the curable adhesives were bonded via an ultraviolet curable adhesive so that the total thickness of the curable adhesive was 1.0 ⁇ m. On the other hand, the other surface of the polarizing film has the same configuration as the other surface of the first embodiment. Furthermore, the water content of the polarizing film laminate was changed. Others are the same as in Example 1.
  • Example 3 (Creation of polarizing film) A PVA film having an average degree of polymerization of 2700 and a thickness of 30 ⁇ m was stretched and conveyed while being dyed between rolls having different peripheral speed ratios. First, the PVA film was swelled by immersing it in a water bath at 30 ° C. for 1 minute, stretched 1.2 times in the transport direction, and then potassium iodide (0.03% by weight) and iodine (0.3% by weight). ) was immersed in an aqueous solution (liquid temperature 30 ° C.) for 1 minute to stretch the film three times in the transport direction (based on unstretched film) while dyeing.
  • aqueous solution liquid temperature 30 ° C.
  • a dope-curable curable adhesive more specifically, a polyvinyl alcohol resin containing an acetoacetyl group (average degree of polymerization 1200, saponification degree 98.5 mol%, acetoacetylation degree 5 mol%).
  • An aqueous solution containing methylol melamine at a weight ratio of 3: 1 was used.
  • a transparent protective film manufactured by Nitto Denko KK
  • Nitto Denko KK with a thickness of 20 ⁇ m made of a modified acrylic polymer having a lactone ring structure was bonded to one surface of a polarizing film under a temperature condition of 30 ° C. ..
  • the dope-curable adhesive was coated so as to have a total thickness of 1.0 ⁇ m, and bonded using a roll machine.
  • the polarizing film protective film used in Example 1 that is, a triacetyl cellulose film containing a light absorber, and a visible side thereof.
  • the polarizing film protective film composed of the hard coat layer containing the light absorber arranged in the above was bonded not with the ultraviolet curable adhesive but with the same dope curable curable adhesive in the same manner as one surface. .. Then, it is heated and dried in an oven at 70 ° C.
  • a polarizing film laminate having a polarizing film protective film was obtained. (Measurement of iodine concentration) By using dichloromethane and methyl ethyl ketone as solvents, the polarizing film was taken out from the polarizing film laminate, and the iodine concentration of the polarizing film was measured.
  • Example 5 In producing the polarizing film laminate of Example 3, one of the above surfaces has the same configuration as that of Example 3, and the other surface contains a light absorber as a polarizing film protective film having a light absorbing ability.
  • KC2UA acetyl cellulose film
  • a hard coat layer manufactured by Nitto Denko Co., Ltd., thickness 9 ⁇ m
  • the hard coat layer was formed by the following method. First, a hard coat layer forming material is prepared. This is a resin solution in which an ultraviolet curable resin monomer or oligomer containing urethane acrylate as a main component is dissolved in butyl acetate (manufactured by DIC Corporation, trade name "Unidic 17-806". Solid content concentration 80% by weight).
  • the hard coat layer forming material thus produced was coated on a transparent protective film so that the thickness of the hard coat after curing was 9 ⁇ m to form a coating film. Then, it was dried at 90 ° C. for 1 minute, and then irradiated with ultraviolet rays having an integrated light intensity of 300 mJ / cm2 with a high-pressure mercury lamp to cure the coating film. Others are the same as in Example 3.
  • Example 4 (Creation of polarizing film) A PVA film having an average degree of polymerization of 2700 and a thickness of 45 ⁇ m was stretched and conveyed while being dyed between rolls having different peripheral speed ratios. First, the PVA film was swelled by immersing it in a water bath at 30 ° C. for 1 minute, stretched 1.2 times in the transport direction, and then potassium iodide (0.03% by weight) and iodine (0.3% by weight). ) was immersed in an aqueous solution (liquid temperature 30 ° C.) for 1 minute to stretch the film three times in the transport direction (based on unstretched film) while dyeing.
  • aqueous solution liquid temperature 30 ° C.
  • the stretched film is immersed in an aqueous solution (bath) of boric acid (4% by weight), potassium iodide (5% by weight) and zinc sulfate (3.5% by weight) for 30 seconds in the transport direction.
  • Bath aqueous solution
  • boric acid 4% by weight
  • potassium iodide 5% by weight
  • zinc sulfate 3.5% by weight
  • Example 5 In producing the polarizing film laminate of Example 4, one of the above surfaces has the same configuration as that of Example 4, and the other surface contains a light absorber as a polarizing film protective film having a light absorbing ability.
  • Acetylcellulose film (manufactured by Fujifilm, trade name "TJ40ULF", thickness 40 ⁇ m), triacetylcellulose film containing a light absorber placed on the visible side (manufactured by Konica Minolta, trade name "KC4UY”, thickness 40 ⁇ m),
  • a polarizing film protective film composed of a hard coat layer manufactured by Nitto Denko Co., Ltd., thickness 9 ⁇ m
  • the polarizing film protective film located on the visual side of the polarizing film that is, the polarizing film protective film composed of a triacetyl cellulose film, another triacetyl cellulose film, and a hard coat layer is peeled off. , The transmittance of the polarizing film protective film was measured.
  • a polarizing film protective film having a hard coat layer (manufactured by Nitto Denko Co., Ltd., thickness 9 ⁇ m) formed with no function is dope-cured by the same method as in Example 3 so that the total thickness of the curable adhesive is 1.0 ⁇ m. They were joined via an adhesive. In addition, the water content of the polarizing film laminate was changed. Others are the same as in Example 4.
  • Example 8 In the preparation of the polarizing film laminate of Example 4, the iodine concentration was changed by adjusting the concentration of the iodine aqueous solution and the immersion time in the dyeing treatment. In addition, the water content of the polarizing film laminate was changed. Others are the same as in Example 4.
  • Example 6 In the preparation of the polarizing film laminate of Example 4, the iodine concentration was changed by adjusting the concentration of the iodine aqueous solution and the immersion time in the dyeing treatment. In addition, the water content of the polarizing film laminate was changed. Others are the same as in Example 4.
  • Example 7 (Creation of polarizing film)
  • a PVA film having a thickness of 75 ⁇ m was stretched and conveyed to obtain a polarizing film having a thickness of 28 ⁇ m.
  • the iodine concentration was changed by adjusting the concentration of the iodine aqueous solution and the immersion time.
  • the other surface of one surface of the polarizing film has the same configuration as the one surface and the other surface of the polarizing film of Example 4, respectively.
  • the water content of the polarizing film laminate was changed. Others are the same as in Example 4.
  • Example 8 In producing the polarizing film laminate of Example 7, the water content of the polarizing film laminate was changed. Further, in Example 7, similarly to Example 4, when the film was stretched 6 times in the transport direction (based on the unstretched film), it was immersed in an aqueous solution (bath) of zinc sulfate (3.5% by weight). .. Other conditions are the same as in Example 7.
  • a polarizing film protective film composed of a hard coat layer having no light absorbing ability arranged on the visible side is doped and cured by the same method as in Example 3 so that the total thickness of the curing adhesive is 1.0 ⁇ m. They were joined via an agent. In addition, the water content of the polarizing film laminate was changed. Other conditions are the same as in Example 7.
  • Example 9 In the preparation of the polarizing film of Example 4, the concentration of the iodine aqueous solution and the immersion time were adjusted in the dyeing treatment to change the iodine concentration. Others are the same as in Example 4.
  • Example 10 In the preparation of the polarizing film of Example 3, the iodine concentration was changed by adjusting the concentration of the iodine aqueous solution and the immersion time in the dyeing treatment. Further, in producing the polarizing film laminate of Example 3, as a transparent protective film made of a modified acrylic polymer having a lactone ring structure to be bonded to one surface of the polarizing film, instead of the transparent protective film having a thickness of 20 ⁇ m, A transparent protective film (manufactured by Nitto Denko Co., Ltd.) having a thickness of 30 ⁇ m was used. Furthermore, the water content of the polarizing film laminate was changed. Others are the same as in Example 3.
  • a triacetyl cellulose film (manufactured by Fuji Film Co., Ltd., trade name "TJ40ULF", thickness 40 ⁇ m) containing a light absorber as a polarizing film protective film having a light absorbing ability on the other surface of the polarizing film absorbs light.
  • a polarizing film protective film having a hard coat layer (manufactured by Nitto Denko Co., Ltd., thickness 9 ⁇ m) formed with no function is dope-cured by the same method as in Example 3 so that the total thickness of the curable adhesive is 1.0 ⁇ m. They were joined via an adhesive. In addition, the water content of the polarizing film laminate was changed. Others are the same as in Example 9.
  • Example 11 In the preparation of the polarizing film of Example 3, the iodine concentration was changed by adjusting the concentration of the iodine aqueous solution and the immersion time in the dyeing treatment. Further, in producing the polarizing film laminate of Example 3, a dope-curable curable adhesive was used as an adhesive, and more specifically, a polyvinyl alcohol resin containing an acetoacetyl group (average degree of polymerization 1200, saponification degree 98). An aqueous solution containing .5 mol%, acetoacetylation degree 5 mol%) and methylol melamine in a weight ratio of 3: 1 was used.
  • a dope-curable curable adhesive was used as an adhesive, and more specifically, a polyvinyl alcohol resin containing an acetoacetyl group (average degree of polymerization 1200, saponification degree 98).
  • a transparent protective film having a thickness of 25 ⁇ m made of triacetyl cellulose was bonded to one surface of the polarizing film.
  • the dope-curable adhesive was coated so as to have a total thickness of 1.0 ⁇ m, and bonded using a roll machine.
  • the polarizing film protective film used in Example 1 that is, a triacetyl cellulose film containing a light absorber, and a visible side thereof.
  • the polarizing film protective film composed of the hard coat layer containing the light absorber arranged in the above was bonded not with the ultraviolet curable adhesive but with the same dope curable curable adhesive in the same manner as one surface. .. Then, it is heated and dried in an oven at 70 ° C. for 5 minutes to have a polarizing film and a polarizing film protective film having no light absorbing ability on one surface of the polarizing film and having light absorbing ability on the other surface.
  • a polarizing film laminate having a polarizing film protective film was obtained.
  • a dope-curable curable adhesive In producing the polarizing film laminate of Example 11, as an adhesive, a dope-curable curable adhesive, more specifically, a polyvinyl alcohol resin containing an acetoacetyl group (average degree of polymerization 1200, saponification degree 98.5). An aqueous solution containing methylol melamine and methylol melamine at a weight ratio of 3: 1 was used. Using this adhesive, a transparent protective film having a thickness of 25 ⁇ m made of triacetyl cellulose was bonded to one surface of the polarizing film. Specifically, the dope-curable adhesive was coated so as to have a total thickness of 1.0 ⁇ m, and bonded using a roll machine.
  • the polarizing film protective film used in Comparative Example 5 that is, a triacetyl cellulose film containing a light absorber, and a visible side thereof.
  • a polarizing film protective film composed of a hard coat layer containing no light absorber was bonded to one surface using the same dope-curable curable adhesive in the same manner as one surface, instead of the ultraviolet-curable adhesive. ..
  • Example 12 In the preparation of the polarizing film of Example 11, the concentration of the iodine aqueous solution and the immersion time were adjusted in the dyeing treatment to change the iodine concentration. Others are the same as in Example 11.
  • Comparative Example 13 In the preparation of the polarizing film of Comparative Example 11, the concentration of the iodine aqueous solution and the immersion time were adjusted in the dyeing treatment to change the iodine concentration. Others are the same as in Comparative Example 11.
  • CS98210US manufactured by Nitto Denko
  • a thickness of 200 ⁇ m was used on one surface of the polarizing film laminate, and used for the polarizing film laminate (manufactured by Nitto Denko) of CRT1794YCU on the other surface of the polarizing film laminate.
  • An acrylic adhesive (thickness 20 ⁇ m) was used.
  • the acrylic pressure-sensitive adhesive used on the other side was prepared by placing 99 parts by weight of butyl acrylate (the same applies hereinafter) and 4-hydroxybutyl acrylate in a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer.
  • a xenon light irradiation test was performed on each sample using a xenon weather meter (manufactured by Suga Test Instruments Co., Ltd .: NX75).
  • (Xenon light irradiation test) Black panel temperature 89 ° C., 30% R. H.
  • the sample is irradiated with xenon light for 200 hours at an irradiance of 100 W / m 2 integrated in a wavelength range of 300 to 400 nm.
  • the light source used was a xenon lamp (manufactured by Suga Test Instruments Co., Ltd.) with a daylight filter (manufactured by Suga Test Instruments Co., Ltd.) attached. After 200 hours of irradiation, color loss and heat redness were evaluated, and after 200 hours of irradiation, polyene formation was also evaluated.
  • the single transmittance after irradiation with xenon light for 200 hours is the same as or larger than the single transmittance before irradiation with xenon light, it was evaluated that the problem of polyene formation is not a problem.
  • the single transmittance was measured for the above sample using a spectrophotometer (product name "DOT-3" manufactured by Murakami Color Technology Research Institute Co., Ltd.).
  • the simple substance transmittance can be obtained according to JlS Z 8701.
  • -Change amount ⁇ Hs 410 is 1% or more-Change amount ⁇ Hs 700 is 5% or more
  • the change amount of the orthogonal transmittance at a wavelength of 410 nm after irradiation with xenone light for 200 hours is less than 1% and the wavelength is 700 nm.
  • the amount of change in the orthogonal transmittance in was less than 5%, it was evaluated that there was no problem of color loss.
  • those satisfying the following conditions were evaluated as "heated redness" of the sample.
  • -Change amount ⁇ Hs 410 is less than 1% -Change amount ⁇ Hs 700 is 5% or more
  • the amount of change in orthogonal transmittance at a wavelength of 410 nm after irradiation with xenone light for 200 hours is 1% or more and a wavelength of 700 nm.
  • the amount of change in the orthogonal transmittance in was less than 5%, it was evaluated that the problem of heating redness did not exist.
  • FIG. 6 is a plot of the results of Examples and Comparative Examples centered on the Examples in the xy orthogonal coordinate system. Furthermore, when the results of the Examples and the Comparative Examples overlap, " The results of "Examples” are shown, and conversely, FIG. 7 is a plot of the results of Examples and Comparative Examples centered on Comparative Examples, and more specifically, the results of Examples and Comparative Examples. When are duplicated, the result of "comparative example” is shown.
  • the x-axis (horizontal axis) indicates the iodine concentration (wt.%) Of the polarizing film
  • the y-axis vertical axis indicates the water content (g / m 2 ) of the polarizing film laminate.
  • Example 7 a coordinate point of 0.7 g / m 2 (hereinafter referred to as the first coordinate point) and the periphery of the plot showing the result of Example 7 in which the iodine concentration is (most) small but the water content is large, that is, the iodine concentration.
  • the coordinate point that can be connected to each of the third coordinate point and the fifth coordinate point without including the comparative example that is, the iodine concentration is 5.7 wt.
  • these partition lines " ⁇ ", “ ⁇ ", “ ⁇ 1", and “ ⁇ 2" are all polarizing films having a film thickness of about 4 to 30 ⁇ m, regardless of the film thickness of the polarizing film. It is to be applied with respect to.
  • the iodine concentration and the water content of the polarizing film laminate are, for example, the region surrounded by a to e, and further details.
  • the iodine concentration is 6.0 wt. %
  • the first coordinate point (“a” in the figure) having a water content of 0.7 g / m 2 and an iodine concentration of 1.8 wt.
  • the iodine concentration and the water content of the polarizing film laminate are surrounded by f, b, c, and g, and more specifically. , Iodine concentration 4.5 wt.
  • the sixth coordinate point "f” has an iodine concentration of 4.0 wt. %
  • the water content is 2.4 g / m 2 , which is the 8th coordinate point (“f-1” in the figure)
  • the 7th coordinate point “g” is the iodine concentration of 4.0 wt.
  • the sixth coordinate point “f” has an iodine concentration of 3.7 wt. % And the water content is 2.6 g / m 2 , which is the 10th coordinate point (“h” in the figure), and the 7th coordinate point “g” is also the 4th coordinate point “d”, which is a preferable result. Is considered to be obtained.
  • Optical display panel 10 Optical display cell 11
  • Transparent adhesive 12 Polarizing film laminate 13
  • Transparent adhesive 14 Transparent cover plate 120
  • Polarizing film 121 Polarizing film protective film with light absorption capacity 122

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • Polarising Elements (AREA)

Abstract

L'invention concerne, entre autres, un stratifié de film polarisant dans lequel l'effet de l'irradiation solaire est supprimé, ce qui permet de résoudre complètement les problèmes de formation de polyène, de perte de couleur et de rougissement induit par la chaleur. Dans un système de coordonnées orthogonales ayant la concentration en iode (% en poids) d'une membrane polarisante le long de l'axe x et la teneur en humidité (g/m2) du stratifié de film polarisant le long de l'axe y, la concentration en iode et la teneur en humidité sont contenues dans la région entourée par un premier segment de ligne reliant un premier point de coordonnées (x : 6,0, y : 0,7) et un deuxième point de coordonnées (x : 1,8, y : 4,2), un deuxième segment de ligne reliant le deuxième point de coordonnées et un troisième point de coordonnées (x : 1,8, y : 5,1), un troisième segment de ligne reliant le troisième point de coordonnées et un quatrième point de coordonnées (x : 5,7, y : 2,6), un quatrième segment de ligne reliant le quatrième point de coordonnées et un cinquième point de coordonnées (x : 7,0, y : 0,7), et un cinquième segment de ligne reliant le premier point de coordonnées et le cinquième point de coordonnées. Dans la présente invention, un film protecteur de membrane de polarisation est une couche absorbant la lumière ayant une fonction d'absorption de lumière, le film ne transmettant pas plus de 5 % d'une lumière ayant une longueur d'onde de 380 nm.
PCT/JP2020/032666 2019-08-28 2020-08-28 Stratifié de film polarisant, panneau d'affichage optique dans lequel ledit stratifié de film polarisant est utilisé, stratifié de film polarisant avec couche adhésive transparente, et ensemble film polarisant WO2021039987A1 (fr)

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CN202080060899.XA CN114303080A (zh) 2019-08-28 2020-08-28 偏振膜层叠体、使用该偏振膜层叠体的光学显示面板、带透明粘接层的偏振膜层叠体、及偏振膜组装体
KR1020227007841A KR20220054320A (ko) 2019-08-28 2020-08-28 편광 필름 적층체, 그 편광 필름 적층체가 사용되는 광학 표시 패널, 투명 접착층 부착의 편광 필름 적층체, 및 편광 필름 조립체

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JP2020140953A JP2021039339A (ja) 2019-08-28 2020-08-24 偏光フィルム積層体、該偏光フィルム積層体が使用される光学表示パネル、透明接着層付きの偏光フィルム積層体、及び偏光フィルム組立体

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