WO2016052549A1 - Film polarisant protégé d'un seul côté, film polarisant doté d'une couche adhésive, dispositif d'affichage d'image, et leur procédé de production en continu - Google Patents

Film polarisant protégé d'un seul côté, film polarisant doté d'une couche adhésive, dispositif d'affichage d'image, et leur procédé de production en continu Download PDF

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Publication number
WO2016052549A1
WO2016052549A1 PCT/JP2015/077590 JP2015077590W WO2016052549A1 WO 2016052549 A1 WO2016052549 A1 WO 2016052549A1 JP 2015077590 W JP2015077590 W JP 2015077590W WO 2016052549 A1 WO2016052549 A1 WO 2016052549A1
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WIPO (PCT)
Prior art keywords
polarizing film
adhesive layer
protective
film
meth
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PCT/JP2015/077590
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English (en)
Japanese (ja)
Inventor
聡司 三田
友徳 上野
菁▲王番▼ 徐
佑輔 茂手木
岸　敦史
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.)
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Priority claimed from JP2015189276A external-priority patent/JP6077619B2/ja
Priority claimed from JP2015189281A external-priority patent/JP6931518B2/ja
Priority claimed from JP2015189275A external-priority patent/JP6018276B2/ja
Priority claimed from JP2015189278A external-priority patent/JP6077620B2/ja
Priority claimed from JP2015189273A external-priority patent/JP6078132B1/ja
Priority claimed from JP2015189274A external-priority patent/JP6077618B2/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN201580053066.XA priority Critical patent/CN107076908B/zh
Priority to SG11201706552PA priority patent/SG11201706552PA/en
Priority to US15/515,948 priority patent/US11137522B2/en
Priority to KR1020177009091A priority patent/KR102567394B1/ko
Publication of WO2016052549A1 publication Critical patent/WO2016052549A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors

Definitions

  • the present invention relates to a piece protective polarizing film in which a protective film is provided only on one side of a polarizer and a polarizing film with a pressure sensitive adhesive layer having the piece protective polarizing film and a pressure sensitive adhesive layer.
  • the single-protective polarizing film and the polarizing film with the pressure-sensitive adhesive layer can form an image display device such as a liquid crystal display device (LCD) or an organic EL display device as a single or a laminated optical film.
  • LCD liquid crystal display device
  • organic EL display device as a single or a laminated optical film.
  • polarizing films In a liquid crystal display device, it is indispensable to dispose polarizing films on both sides of a glass substrate that forms the surface of a liquid crystal panel because of its image forming method.
  • a polarizing film in which a protective film is bonded to one or both sides of a polarizer made of a dichroic material such as a polyvinyl alcohol film and iodine with a polyvinyl alcohol adhesive or the like is used. .
  • an adhesive is usually used.
  • the polarizing film can be fixed instantaneously and has a merit such that a drying step is not required to fix the polarizing film
  • the adhesive is provided in advance as an adhesive layer on one side of the polarizing film. . That is, a polarizing film with an adhesive layer is generally used for attaching the polarizing film.
  • a polarizing film or a polarizing film with a pressure-sensitive adhesive layer can cause the polarizer to contract in a severe environment of thermal shock (for example, a heat shock test in which temperature conditions of ⁇ 30 ° C. and 80 ° C. are repeated or a test at a high temperature of 100 ° C.)
  • thermal shock for example, a heat shock test in which temperature conditions of ⁇ 30 ° C. and 80 ° C. are repeated or a test at a high temperature of 100 ° C.
  • cracks through cracks
  • the polarizing film with an adhesive layer was not sufficiently durable due to thermal shock in the harsh environment.
  • a polarizing film with a pressure-sensitive adhesive layer using a piece protective polarizing film in which a protective film is provided only on one side of a polarizer has insufficient durability due to the thermal shock.
  • the penetration crack produced by the said thermal shock was easy to generate
  • Patent Document 1 a polarizing film with an adhesive layer in which a protective layer having a tensile modulus of 100 MPa or more is provided on a single protective polarizing film and an adhesive layer is further provided on the protective layer has been proposed.
  • Patent Document 2 a protective layer made of a cured product of the curable resin composition on one side of a polarizer having a thickness of 25 ⁇ m or less, a protective film on the other side of the polarizer, and an adhesive on the outside of the protective layer
  • Patent Document 2 a polarizing film with an adhesive layer having a layer has been proposed.
  • Patent Document 3 The polarizing film with the pressure-sensitive adhesive layer described in Patent Documents 1 and 2 is effective in terms of suppressing the occurrence of through cracks. Thinning is also performed for polarizers, and for example, a thin polarizer exhibiting high orientation in which optical characteristics of single transmittance and polarization degree are controlled has been proposed (Patent Document 3).
  • the thickness is reduced by using a piece protective polarizing film having a protective film only on one side of a polarizer, and on the other hand, by providing a protective layer, the piece protective polarizing film is used. Generation of through cracks in the direction of the absorption axis of the polarizer is suppressed.
  • thinning is also done for polarizers.
  • the polarizer used for the polarizing film or the polarizing film with the pressure-sensitive adhesive layer is thinned, the change in the contraction stress of the polarizer becomes small. Therefore, it has been found that the thinned polarizer can suppress the occurrence of the through cracks.
  • the optical characteristics are controlled as in Patent Document 3 and the polarizer is thinned (for example, When the thickness is 10 ⁇ m or less), when a mechanical shock is applied to the one-side protective polarizing film or the polarizing film with an adhesive layer using the same (including the case where a load due to convex folding is applied to the polarizer side), It was found that a very fine slit (hereinafter also referred to as nano slit) is generated in the absorption axis direction of the polarizer.
  • nano slit very fine slit
  • the nano slits occur regardless of the size of the polarizing film. Furthermore, it was also found that the nano slit does not occur when both protective polarizing films having protective films on both sides of the polarizer are used. In addition, when a through crack occurs in the polarizer, the stress around the through crack is released, so the through crack does not occur adjacently. I found it to happen. Moreover, although the penetration crack has the progressive property extended in the absorption-axis direction of the polarizer in which the crack generate
  • the nano slit is a new problem that occurs when the polarizer is thin and the optical characteristics are controlled within a predetermined range in the single-protective polarizing film in which the generation of through cracks is suppressed. It has been found that this is a problem caused by a phenomenon different from the above-described through crack.
  • the nano slit is extremely thin, it cannot be detected under a normal environment. Therefore, even if nanoslits are generated in the polarizer, it is difficult to confirm the defects due to light leakage of the one-side protective polarizing film and the polarizing film with the pressure-sensitive adhesive layer using it. That is, usually, the piece-protecting polarizing film is produced in the form of a long film and automatically inspected for defects by optical inspection, but it is difficult to detect nanoslits as defects by this defect inspection.
  • the defect caused by the nano slit is that the nano slit spreads in the width direction when the single protective polarizing film or the polarizing film with the adhesive layer is bonded to the glass substrate of the image display panel and placed in a heating environment. It was also found that detection is possible (for example, the presence or absence of light leakage).
  • the polarizing film is likely to be broken or broken during handling because it is thin compared to the polarizing film having both protective structures having protective films on both sides. . Therefore, at the time of handling, it is desired that the polarizing film or the polarizing film with an adhesive layer using the same is not curled.
  • the material forming the protective layer shrinks during the formation of the protective layer, so that there is a gap between the polarizer and the protective layer. Stress easily accumulates and curls are likely to occur. For this reason, it is desirable that no curling occurs in the single-protective polarizing film or the polarizing film with the pressure-sensitive adhesive layer using the same from the viewpoint of handleability.
  • the present invention provides a single protective polarizing film having a protective film only on one surface of a thin polarizer, the polarizer having predetermined optical characteristics, and suppressing the occurrence of defects and curls due to through cracks and nano slits.
  • An object of the present invention is to provide a piece protective polarizing film that can be used. Moreover, this invention aims at providing the polarizing film with an adhesive layer which has the said piece protection polarizing film and an adhesive layer.
  • Another object of the present invention is to provide an image display device having the piece protective polarizing film or the pressure-sensitive adhesive layer-attached polarizing film, and a continuous production method thereof.
  • the present invention is a piece protective polarizing film having a protective film only on one side of the polarizer
  • the transparent resin layer preferably has a compression elastic modulus at 80 ° C. of 0.1 GPa or more.
  • the transparent resin layer is preferably formed of an ultraviolet curable acrylic resin, an ultraviolet curable epoxy resin, a urethane resin, or a polyvinyl alcohol resin.
  • the piece protective polarizing film preferably has an adhesive layer between the polarizer and the protective film.
  • the thickness of the adhesive layer is preferably 0.1 ⁇ m or more and 5 ⁇ m or less.
  • the adhesive layer preferably has a compressive elastic modulus at 80 ° C. of 0.1 GPa or more and 10 GPa or less.
  • the adhesive layer is preferably formed of an ultraviolet curable acrylic resin, an ultraviolet curable epoxy resin, a urethane resin, or a polyvinyl alcohol resin.
  • the thickness of the protective film is preferably 10 ⁇ m or more and 100 ⁇ m or less.
  • each protective film when there are two protective films, the thickness of each protective film is 10 ⁇ m or more, and the total thickness of the protective films is 100 ⁇ m or less. It preferably has an agent layer or an adhesive layer.
  • the polarizer preferably contains boric acid in an amount of 25% by weight or less based on the total amount of the polarizer.
  • the present invention also relates to the above-mentioned piece protective polarizing film and a polarizing film with an adhesive layer, characterized by having an adhesive layer.
  • the thickness of the adhesive layer is preferably 1 ⁇ m or more and 40 ⁇ m or less.
  • the pressure-sensitive adhesive layer preferably has a storage elastic modulus at 23 ° C. of 1.0 ⁇ 10 4 Pa or more.
  • the polarizing film with the pressure-sensitive adhesive layer can be used in a mode in which the pressure-sensitive adhesive layer is provided on the transparent resin layer of the piece protective polarizing film. Moreover, the said polarizing film with an adhesive layer can be used in the aspect by which the said adhesive layer is provided in the protective film of the said piece protection polarizing film. Moreover, a separator can be provided in the adhesive layer of the polarizing film with an adhesive layer. The polarizing film with an adhesive layer provided with a separator can be used as a wound body.
  • the present invention also relates to an image display device having the piece protective polarizing film or the polarizing film with an adhesive layer.
  • the polarizing film with the pressure-sensitive adhesive layer fed out from the wound body of the polarizing film with the pressure-sensitive adhesive layer and conveyed by the separator is continuously applied to the surface of the image display panel via the pressure-sensitive adhesive layer.
  • the present invention relates to a continuous manufacturing method of an image display device including a step of bonding to a substrate.
  • the piece-protecting polarizing film and the polarizing film with a pressure-sensitive adhesive layer of the present invention use a polarizer having a thickness of 12 ⁇ m or less, and are thinned.
  • the thin polarizer having a thickness of 12 ⁇ m or less has a smaller change in shrinkage stress applied to the polarizer due to thermal shock than in the case where the thickness of the polarizer is large, the occurrence of through cracks can be suppressed.
  • the nano-slit is a process for producing a piece-protecting polarizing film, a step for producing a polarizing film with a pressure-sensitive adhesive layer in which a pressure-sensitive adhesive layer is provided on the piece-protecting polarizing film, and various steps after producing a polarizing film with a pressure-sensitive adhesive layer. It is considered to occur when a mechanical shock is applied to the polarizing film or the polarizing film with the pressure-sensitive adhesive layer using the polarizing film, and is assumed to be generated by a mechanism different from the through crack generated by the thermal shock.
  • the defect due to the nano slit is that when the single protective polarizing film or the polarizing film with the pressure-sensitive adhesive layer is bonded to the glass substrate of the image display panel and placed in a heating environment, the nano slit is in the width direction. Detection is possible by spreading (for example, the presence or absence of light leakage).
  • a piece before provision of the transparent resin layer is provided by providing a transparent resin layer on the other side of the polarizer (the side having no protective film). Even when the nano slits are generated in the polarizer in the state of the protective polarizing film, the generation of defects due to the spread of the nano slits in the width direction can be suppressed.
  • a transparent resin layer having a compression elastic modulus at 80 ° C. of 0.1 GPa or more is effective.
  • the piece-protecting polarizing film of the present invention and the polarizing film with the pressure-sensitive adhesive layer using the same have a transparent resin layer, satisfying a reduction in thickness, and having through cracks and nano-particles generated in the polarizer. Defects due to slits can be suppressed.
  • the single protective polarizing film 10 (in the case where the transparent resin layer 3 is not provided) has the protective film 2 only on one surface of the polarizer 1, for example, as shown in FIG.
  • the polarizer 1 and the protective film 2 are laminated via an adhesive layer 2a (other intervening layers such as a pressure-sensitive adhesive layer and an undercoat layer (primer layer)).
  • the piece protection polarizing film 10 can laminate
  • the single-protective polarizing film 11 (with the transparent resin layer 3) of the present invention has, on the single-sided protective polarizing film 10, the other surface of the polarizer 1 (the surface not having the protective film 2).
  • a transparent resin layer 3 is provided (directly).
  • a plurality of protective films 2 can be provided.
  • FIG. 1B shows a single protective polarizing film (with a transparent resin layer) 11 ′ provided with two protective films 2 and 2 ′.
  • the protective film 2 and the protective film 2 ′ can be laminated by an adhesive layer 2a (other intervening layers such as a pressure-sensitive adhesive layer and an undercoat layer (primer layer)).
  • the thickness of the polarizer is X ( ⁇ m), and the thickness Y ( ⁇ m) of the transparent resin layer satisfies X ⁇ 12, Y ⁇ 15, and 0.15 ⁇ (Y / X) ⁇ 3.
  • the value (Y / X) is preferably 0.24 or more.
  • the value (Y / X) is preferably 0.8 or less, and more preferably 0.5 or less.
  • the value (Y / X) is preferably 0.24 ⁇ (Y / X) ⁇ 0.8, and more preferably 0.24 ⁇ (Y / X) ⁇ 0.5. .
  • the polarizing film 12 with an adhesive layer of this invention has the piece protection polarizing film (with transparent resin layer) 11 and the adhesive layer 4, as shown in FIG.
  • the pressure-sensitive adhesive layer 4 is provided on the transparent resin layer 3 side in FIG. 2A and on the protective film 2 side in FIG.
  • the separator 5 can be provided in the adhesive layer 4 of the polarizing film 12 with an adhesive layer of this invention, and the surface protection film 6 can be provided in the other side.
  • the polarizing film 12 with an adhesive layer of FIG. 2 the case where both the separator 5 and the surface protection film 6 are provided is shown.
  • the pressure-sensitive adhesive layer-attached polarizing film 12 having at least the separator 5 (and further having the surface protective film 6) can be used as a wound body, and as described later, for example, the separator 5 is fed out from the wound body.
  • the polarizing film 12 with the pressure-sensitive adhesive layer conveyed by the above is also referred to as a “roll-to-panel method” (hereinafter referred to as “roll-to-panel method”). This is advantageous for application to the specification No. 4406043.
  • the aspect shown to FIG. 2 (A) is preferable from viewpoints, such as suppression of the curvature of the display panel after bonding, generation
  • the surface protective film 6 can be provided on the piece protective polarizing film 10 and the piece protective polarizing film 11 (with a transparent resin layer).
  • the piece protection polarizing film 11 (with a transparent resin layer) 11 of FIG. 1 (A) is used is illustrated, the piece protection polarizing film (with a transparent resin layer) of FIG. 11 'can also be used.
  • FIG. 3 is a conceptual diagram comparing the nano slit a and the through crack b generated in the polarizer.
  • 3A shows a nano slit a generated in the polarizer 1
  • FIG. 3B shows a through crack b generated in the polarizer 1.
  • the nano slit a is generated by mechanical impact and is partially generated in the absorption axis direction of the polarizer 1.
  • the nano slit a cannot be confirmed at the beginning, but is in a thermal environment (for example, 80 ° C. or 60 ° C., 90% RH), it can be confirmed by the spread in the width direction.
  • it is considered that the nano slit a does not have a progressive property extending in the absorption axis direction of the polarizer.
  • the said nano slit a arises irrespective of the size of a polarizing film.
  • the nano slits a may occur not only independently but also adjacent to each other.
  • the through crack b is generated by a thermal shock (for example, a heat shock test).
  • the through crack has a process of extending in the absorption axis direction of the polarizer where the crack has occurred.
  • the peripheral stress is released, so that the through crack does not occur adjacently.
  • FIG. 4 is an example of a photograph of a cross-sectional view of the piece protective polarizing film 10 or the piece protective polarizing film 11 with a transparent resin layer related to generation, expansion, and repair of nano slits a generated in the polarizer.
  • FIG. 4 (A) is an example of a case where the single protective polarizing film 10 having the protective film 2 on only one surface of the polarizer 1 via the adhesive layer 2a and no nanoslit is generated.
  • FIG. 4B is an example when nano slits a are generated in the piece protective polarizing film 10. 4A and 4B are both before heating.
  • FIG.4 (C) is an example of the photograph of sectional drawing after heating the piece protection polarizing film 10 in which the nano slit a has generate
  • FIG.4 (C) it turns out that the nano slit a of the polarizer 1 is expanded by heating.
  • FIG. 4 (D) is an example of a photograph of a cross-sectional view of the piece protective polarizing film 11 with a transparent resin layer in which the transparent resin layer 3 is formed on the piece protective polarizing film 10 in which the nano slits a are generated.
  • FIG. 4D it can be seen that the nano slits a generated in the polarizer 1 are repaired (a ′) by the transparent resin layer 3.
  • FIG.4 (E) is an example of the photograph of sectional drawing after heating the piece protection polarizing film 11 with the transparent resin layer in which the transparent resin layer 3 was formed.
  • FIG. 4E it can be seen that there is no expansion of the repaired (a ′) nanoslit after heating.
  • the section was cut with a cross session polisher or a microtome perpendicular to the absorption axis direction of the sample, and observed with a scanning electron microscope.
  • a polarizer having a thickness of 12 ⁇ m or less is used.
  • the thickness of the polarizer is preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less, further preferably 7 ⁇ m or less, and further preferably 6 ⁇ m or less from the viewpoint of reducing the thickness and preventing the occurrence of through cracks.
  • the thickness of the polarizer is preferably 2 ⁇ m or more, and more preferably 3 ⁇ m or more.
  • Such a thin polarizer has less thickness unevenness, excellent visibility, and less dimensional change, and therefore excellent durability against thermal shock.
  • a polarizer using a polyvinyl alcohol resin is used.
  • polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
  • hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
  • examples thereof include polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products.
  • a polarizer composed of a polyvinyl alcohol film and a dichroic material such as iodine is preferable.
  • a polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. If necessary, it may contain boric acid, zinc sulfate, zinc chloride, or the like, or may be immersed in an aqueous solution such as potassium iodide. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing.
  • Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching.
  • the film can be stretched even in an aqueous solution such as boric acid or potassium iodide or in a water bath.
  • the polarizer preferably contains boric acid from the viewpoint of stretching stability and optical durability.
  • the content of boric acid contained in the polarizer is preferably 25% by weight or less, more preferably 20% by weight or less, based on the total amount of the polarizer, from the viewpoint of suppressing the generation of through cracks and nano slits and suppressing expansion. Preferably, it is 18% by weight or less, and more preferably 16% by weight or less.
  • the boric acid content with respect to the total amount of the polarizer is preferably 10% by weight or more, and more preferably 12% by weight or more.
  • Patent No. 4751486 Japanese Patent No. 4751481, Patent No. 4815544, Patent No. 5048120, Japanese Patent No. 5587517, International Publication No. 2014/077599 pamphlet, International Publication No. 2014/077636 Pamphlet, And the thin polarizers obtained from the production methods described therein.
  • the polarizer has an optical characteristic expressed by a single transmittance T and a polarization degree P of the following formula P> ⁇ (10 0.929T-42.4 ⁇ 1) ⁇ 100 (where T ⁇ 42.3), Or It is configured to satisfy the condition of P ⁇ 99.9 (however, T ⁇ 42.3).
  • a polarizer configured so as to satisfy the above-described conditions uniquely has performance required as a display for a liquid crystal television using a large display element. Specifically, the contrast ratio is 1000: 1 or more and the maximum luminance is 500 cd / m 2 or more. As other uses, for example, it is bonded to the viewing side of the organic EL display device.
  • a polarizer configured to satisfy the above conditions has a high orientation of a polymer (for example, a polyvinyl alcohol-based molecule), so that the thickness of the polarizer is 10 ⁇ m or less.
  • the tensile breaking stress in the direction orthogonal to the absorption axis direction is significantly reduced.
  • this invention is especially suitable for the piece protection polarizing film (or polarizing film with an adhesive layer using the same) which employ
  • Patent No. 4751486, Patent in that it can be stretched at a high magnification and the polarization performance can be improved.
  • stretching in a boric-acid aqueous solution as described in the 4751481 specification and the patent 4815544 specification is preferable, and it describes especially in the patent 4751481 specification and the patent 4815544 specification.
  • stretching in the boric-acid aqueous solution which has this is preferable.
  • a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is preferable.
  • polyester polymers such as polyethylene terephthalate and polyethylene naphthalate
  • cellulose polymers such as diacetyl cellulose and triacetyl cellulose
  • acrylic polymers such as polymethyl methacrylate
  • styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin)
  • AS resin acrylonitrile / styrene copolymer
  • polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or the above Polymer blends and the like can also be mentioned as examples of the polymer forming the protective film.
  • thermoplastic resin in the protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight.
  • content of the said thermoplastic resin in a protective film is 50 weight% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.
  • a retardation film As the protective film, a retardation film, a brightness enhancement film, a diffusion film, and the like can also be used.
  • the retardation film include those having a front retardation of 40 nm or more and / or a retardation having a thickness direction retardation of 80 nm or more.
  • the front phase difference is usually controlled in the range of 40 to 200 nm
  • the thickness direction phase difference is usually controlled in the range of 80 to 300 nm.
  • the retardation film functions also as a polarizer protective film, so that the thickness can be reduced.
  • the retardation film examples include a birefringent film obtained by uniaxially or biaxially stretching a thermoplastic resin film.
  • the stretching temperature, stretching ratio, and the like are appropriately set depending on the retardation value, film material, and thickness.
  • the thickness of the protective film can be appropriately determined, but is generally about 1 to 500 ⁇ m from the viewpoints of workability such as strength and handleability, and thin layer properties. 1 to 300 ⁇ m is particularly preferable, and 5 to 200 ⁇ m is more preferable. In particular, in the case of a single protective film, the thickness is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, and further preferably 60 ⁇ m or less from the viewpoint of thinning. Moreover, 10 micrometers or more are preferable from a viewpoint of protecting a polarizing film from a break and a fracture
  • the thickness of the protective film was V ( ⁇ m)
  • mechanical stress was applied to the polarizing film in relation to the thickness X ( ⁇ m) of the polarizer and the thickness Y ( ⁇ m) of the transparent resin layer.
  • two protective films can be used.
  • the two protective films preferably have a total thickness of 10 ⁇ m or more, more preferably 20 ⁇ m or more, and from the viewpoint of reducing the thickness of the single protective polarizing film. It is preferable to control the total thickness of each protective film to be 100 ⁇ m or less.
  • a functional layer such as a hard coat layer, an antireflection layer, an antisticking layer, a diffusion layer or an antiglare layer can be provided on the surface of the protective film on which the polarizer is not adhered (particularly, the embodiment shown in FIG. 1).
  • the hard coat layer, the antireflection layer, the antisticking layer, the diffusion layer, the antiglare layer, and other functional layers can be provided on the protective film itself, or can be provided separately from the protective film. it can.
  • the protective film and the polarizer are laminated via an intervening layer such as an adhesive layer, an adhesive layer, and an undercoat layer (primer layer). At this time, it is desirable that the both are laminated without an air gap by an intervening layer.
  • the protective film and the polarizer are preferably laminated via an adhesive layer.
  • the adhesive layer is formed with an adhesive.
  • the type of the adhesive is not particularly limited, and various types can be used.
  • the adhesive layer is not particularly limited as long as it is optically transparent. Examples of the adhesive include water-based, solvent-based, hot-melt-based, active energy ray-curable types, and the like. Or an active energy ray hardening-type adhesive agent is suitable.
  • water-based adhesives examples include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, vinyl-based latex systems, and water-based polyesters.
  • the water-based adhesive is usually used as an adhesive composed of an aqueous solution, and usually contains 0.5 to 60% by weight of solid content. Of these, isocyanate adhesives and polyvinyl alcohol adhesives are preferred. From the isocyanate adhesive, a urethane resin layer is formed as an adhesive layer.
  • the active energy ray curable adhesive is an adhesive that cures by an active energy ray such as an electron beam or ultraviolet rays (radical curable type, cationic curable type), for example, in an electron beam curable type or an ultraviolet curable type. Can be used.
  • an active energy ray such as an electron beam or ultraviolet rays (radical curable type, cationic curable type), for example, in an electron beam curable type or an ultraviolet curable type.
  • a photo radical curable adhesive can be used.
  • the adhesive contains a radical polymerizable compound and a photo polymerization initiator.
  • the radical curable ultraviolet curable adhesive is preferably an ultraviolet curable acrylic resin
  • the cationic curable ultraviolet curable adhesive is preferably an ultraviolet curable epoxy resin.
  • the adhesive coating method is appropriately selected depending on the viscosity of the adhesive and the target thickness.
  • coating methods include reverse coaters, gravure coaters (direct, reverse and offset), bar reverse coaters, roll coaters, die coaters, bar coaters, rod coaters and the like.
  • a method such as a dapping method can be appropriately used.
  • the thickness of the adhesive layer is preferably 0.1 ⁇ m or more and 5 ⁇ m or less, and a preferable range can be set depending on the type of the water-based adhesive or the active energy ray-curable adhesive.
  • the thickness of 0.1 ⁇ m or more is preferable from the viewpoint of maintaining the adhesive force, and the thickness of 5 ⁇ m or less is preferable from the viewpoint of ensuring optical reliability.
  • the adhesive is preferably applied so that the finally formed adhesive layer has a thickness of 100 to 300 nm.
  • the thickness of the adhesive layer is more preferably 100 to 250 nm.
  • the thickness of the adhesive layer is preferably 0.2 to 5 ⁇ m. More preferably, it is 0.2 to 2 ⁇ m, and still more preferably 0.5 to 1.5 ⁇ m.
  • the adhesive layer preferably has a compressive elastic modulus at 80 ° C. of 0.1 GPa or more and 10 GPa or less in order to suppress penetration cracks while relaxing the force applied to the polarizer.
  • the compression elastic modulus of 0.1 GPa or more is preferable for absorbing cracks and ensuring crack resistance (inhibition of generation of nanoslits and suppression of through cracks), and the compression elastic modulus of 10 GPa or less. This is preferable from the viewpoint of preventing penetration cracks.
  • the compression elastic modulus is preferably 1 GPa or more, and more preferably 3 GPa or more.
  • the compression elastic modulus is preferably 8 GPa or less.
  • an easily bonding layer can be provided between a protective film and an adhesive bond layer.
  • the easy adhesion layer can be formed of, for example, various resins having a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, a silicone-based, a polyamide skeleton, a polyimide skeleton, a polyvinyl alcohol skeleton, and the like. These polymer resins can be used alone or in combination of two or more. Moreover, you may add another additive for formation of an easily bonding layer. Specifically, a stabilizer such as a tackifier, an ultraviolet absorber, an antioxidant, and a heat resistance stabilizer may be used.
  • the easy-adhesion layer is usually provided in advance on a protective film, and the easy-adhesion layer side of the protective film and the polarizer are laminated with an adhesive layer.
  • the easy-adhesion layer is formed by applying and drying a material for forming the easy-adhesion layer on a protective film by a known technique.
  • the material for forming the easy-adhesion layer is usually adjusted as a solution diluted to an appropriate concentration in consideration of the thickness after drying and the smoothness of coating.
  • the thickness of the easy-adhesion layer after drying is preferably 0.01 to 5 ⁇ m, more preferably 0.02 to 2 ⁇ m, and still more preferably 0.05 to 1 ⁇ m. Note that a plurality of easy-adhesion layers can be provided, but also in this case, the total thickness of the easy-adhesion layers is preferably in the above range.
  • the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive.
  • Various pressure-sensitive adhesives can be used as the pressure-sensitive adhesive, such as rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, vinyl alkyl ether-based pressure-sensitive adhesives, polyvinylpyrrolidone-based pressure-sensitive adhesives, Examples include acrylamide-based adhesives and cellulose-based adhesives.
  • An adhesive base polymer is selected according to the type of the adhesive.
  • acrylic pressure-sensitive adhesives are preferably used because they are excellent in optical transparency, exhibit appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and are excellent in weather resistance and heat resistance.
  • the undercoat layer (primer layer) is formed to improve the adhesion between the polarizer and the protective film.
  • the material constituting the primer layer is not particularly limited as long as the material exhibits a certain degree of strong adhesion to both the base film and the polyvinyl alcohol-based resin layer.
  • a thermoplastic resin excellent in transparency, thermal stability, stretchability, etc. is used.
  • the thermoplastic resin include an acrylic resin, a polyolefin resin, a polyester resin, a polyvinyl alcohol resin, or a mixture thereof.
  • each protective film is preferably laminated via an adhesive layer or a pressure-sensitive adhesive layer.
  • the thickness of the adhesive layer is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more from the viewpoint of adhesive strength.
  • the thickness of the adhesive layer is preferably 5 ⁇ m or less, and more preferably 2 ⁇ m or less from the viewpoint of thinning.
  • thickness is 2 micrometers or more from a viewpoint of adhesive force.
  • the thickness of the pressure-sensitive adhesive layer is preferably 20 ⁇ m or less.
  • the transparent resin layer is provided on the other surface of the polarizer (the surface on which the protective film is not laminated) in the single-protective polarizing film in which the protective film is provided only on one surface of the polarizer.
  • the transparent resin layer preferably has a compression elastic modulus at 80 ° C. of 0.1 GPa or more. Even if nano slits are generated in the polarizer due to mechanical impact and the nano slits are about to expand in the width direction under a thermal environment, by controlling the compression elastic modulus at 80 ° C.
  • the compressive elastic modulus of the transparent resin layer is preferably 0.5 GPa or more, more preferably 2 GPa or more, further 3 GPa or more, further 5 GPa or more, further 6 GPa or more, and further preferably 10 GPa or more.
  • the compression elastic modulus of the transparent resin layer can be adjusted by material selection.
  • the compression elastic modulus in 80 degreeC of a transparent resin layer is a value measured based on description of an Example.
  • the thickness of the transparent resin layer is 15 ⁇ m or less from the viewpoint of thinning and optical reliability. Further, when the transparent resin layer is thick, curling tends to occur in the piece protective polarizing film after storage.
  • the thickness (Y) of the transparent resin layer is preferably 12 ⁇ m or less, more preferably 5 ⁇ m or less, and further preferably 1.5 ⁇ m or less.
  • the thickness (Y) of the transparent resin layer is preferably 0.2 ⁇ m or more, more preferably 0.5 ⁇ m or more, and further preferably 0.6 ⁇ m or more from the viewpoint of the effect of suppressing the expansion of the nanoslit. Further, it is preferably 0.8 ⁇ m or more.
  • the thickness (Y) of the transparent resin layer is controlled so as to satisfy 0.15 ⁇ (Y / X) ⁇ 3 in relation to the thickness X ( ⁇ m) of the polarizer.
  • the transparent resin layer can be formed from a curable forming material containing a curable component.
  • the curable component can be roughly classified into an active energy ray curable type such as an electron beam curable type, an ultraviolet ray curable type, and a visible light curable type, and a thermosetting type.
  • the ultraviolet curable type and the visible light curable type can be classified into a radical polymerization curable type and a cationic polymerization curable type.
  • an active energy ray having a wavelength range of 10 nm to less than 380 nm is expressed as ultraviolet light
  • an active energy ray having a wavelength range of 380 nm to 800 nm is expressed as visible light.
  • the radical polymerization curable component can be used as a thermosetting curable component.
  • the curable component examples include a radical polymerizable compound.
  • the radical polymerizable compound examples include compounds having a radical polymerizable functional group of a carbon-carbon double bond such as a (meth) acryloyl group and a vinyl group.
  • these curable components either a monofunctional radical polymerizable compound or a bifunctional or higher polyfunctional radical polymerizable compound can be used.
  • these radically polymerizable compounds can be used individually by 1 type or in combination of 2 or more types.
  • compounds having a (meth) acryloyl group are suitable.
  • (meth) acryloyl means an acryloyl group and / or methacryloyl group, and “(meth)” has the same meaning hereinafter.
  • Examples of the monofunctional radical polymerizable compound include (meth) acrylamide derivatives having a (meth) acrylamide group.
  • the (meth) acrylamide derivative is preferable in terms of ensuring adhesion with the polarizer and having a high polymerization rate and excellent productivity.
  • (meth) acrylamide derivatives include, for example, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, 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
  • heterocyclic-containing (meth) acrylamide derivative in which the nitrogen atom of the (meth) acrylamide group forms a heterocyclic ring examples include, for example, N-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine. Etc.
  • an N-hydroxyalkyl group-containing (meth) acrylamide derivative is preferable from the viewpoint of adhesion to a polarizer, and N-hydroxyethyl (meth) acrylamide is particularly preferable.
  • examples of the monofunctional radical polymerizable compound include various (meth) acrylic acid derivatives having a (meth) acryloyloxy group. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-methyl-2-nitropropyl (meth) acrylate, n-butyl ( (Meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, t-pentyl (meth) acrylate, 3-pentyl (meth) acrylate, 2,2-dimethylbutyl (meth) acrylate, n-hexyl (meth) acrylate, cetyl (meth) acrylate, n-
  • Examples of the (meth) acrylic acid derivative include cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and cyclopentyl (meth) acrylate; Aralkyl (meth) acrylates such as benzyl (meth) acrylate; 2-isobornyl (meth) acrylate, 2-norbornylmethyl (meth) acrylate, 5-norbornen-2-yl-methyl (meth) acrylate, 3-methyl-2-norbornylmethyl (meth) acrylate, dicyclo Polycyclic (meth) acrylates such as pentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxymethoxyethyl (
  • Examples of the (meth) acrylic acid derivative include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, etc.
  • hydroxyl groups such as [4- (hydroxymethyl) cyclohexyl] methyl acrylate, cyclohexanedimethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc.
  • Meth) acrylate Epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether; 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2-trifluoroethylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) ) Halogen-containing (meth) acrylates such as acrylate, heptadecafluorodecyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate; Alkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate; 3-Oxetanylmethyl (meth) acrylate
  • examples of the monofunctional radically polymerizable compound include carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
  • carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
  • Examples of the monofunctional radical polymerizable compound include lactam vinyl monomers such as N-vinyl pyrrolidone, N-vinyl- ⁇ -caprolactam, and methyl vinyl pyrrolidone; vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinyl pyrazine, Examples thereof include vinyl monomers having a nitrogen-containing heterocyclic ring such as vinyl pyrrole, vinyl imidazole, vinyl oxazole and vinyl morpholine.
  • lactam vinyl monomers such as N-vinyl pyrrolidone, N-vinyl- ⁇ -caprolactam, and methyl vinyl pyrrolidone
  • vinyl pyridine vinyl piperidone
  • vinyl pyrimidine vinyl piperazine
  • vinyl pyrazine examples thereof include vinyl monomers having a nitrogen-containing heterocyclic ring such as vinyl pyrrole, vinyl imidazole, vinyl oxazole and vinyl morpholine.
  • a radically polymerizable compound having an active methylene group can be used as the monofunctional radically polymerizable compound.
  • the radical polymerizable compound having an active methylene group is a compound having an active methylene group having an active double bond group such as a (meth) acryl group at the terminal or in the molecule.
  • the active methylene group include an acetoacetyl group, an alkoxymalonyl group, and a cyanoacetyl group.
  • the active methylene group is preferably an acetoacetyl group.
  • radical polymerizable compound having an active methylene group examples include 2-acetoacetoxyethyl (meth) acrylate, 2-acetoacetoxypropyl (meth) acrylate, 2-acetoacetoxy-1-methylethyl (meth) acrylate, and the like.
  • Examples include acrylamide, N- (4-acetoacetoxymethylbenzyl) acrylamide, and N- (2-acetoacetylaminoethyl) acrylamide.
  • the radical polymerizable compound having an active methylene group is preferably acetoacetoxyalkyl (meth) acrylate.
  • Examples of the bifunctional or higher polyfunctional radical polymerizable compound include tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 -Nonanediol di (meth) acrylate, 1,10-decanediol diacrylate, 2-ethyl-2-butylpropanediol di (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) ) Acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) Acryte, cyclic trimethylol
  • Aronix M-220, M-306 manufactured by Toagosei Co., Ltd.
  • light acrylate 1,9ND-A manufactured by Kyoeisha Chemical Co., Ltd.
  • light acrylate DGE-4A manufactured by Kyoeisha Chemical Co., Ltd.
  • light acrylate DCP- A manufactured by Kyoeisha Chemical Co., Ltd.
  • SR-531 manufactured by Sartomer
  • CD-536 manufactured by Sartomer
  • various epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, various (meth) acrylate monomers, and the like are included as necessary.
  • the radical polymerizable compound is preferably used in combination with a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound from the viewpoint of achieving both adhesion to the polarizer and optical durability.
  • the radical polymerization curable forming material can be used as an active energy ray curable forming material or a thermosetting forming material.
  • the active energy ray curable forming material does not need to contain a photopolymerization initiator, but when using ultraviolet rays or visible light for the active energy ray, It preferably contains a photopolymerization initiator.
  • the curable component when used as a thermosetting component, the forming material preferably contains a thermal polymerization initiator.
  • the photopolymerization initiator in the case of using the radical polymerizable compound is appropriately selected depending on the active energy ray.
  • a photopolymerization initiator for ultraviolet light or visible light cleavage is used.
  • photopolymerization initiator examples include benzophenone compounds such as benzyl, benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone; 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2 -Propyl) ketone, aromatic ketone compounds such as ⁇ -hydroxy- ⁇ , ⁇ '-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, ⁇ -hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy- Acetophenone compounds such as 2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) -phenyl] -2-morpholinopropane-1; benzoin methyl ether; Benzoin ethyl ether, benzoin Benzoin ether compounds such as isopropyl ether, benzoin butyl ether and ani
  • the blending amount of the photopolymerization initiator is 20 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component (radical polymerizable compound).
  • the blending amount of the photopolymerization initiator is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, and further preferably 0.1 to 5 parts by weight.
  • a photopolymerization initiator that is particularly sensitive to light of 380 nm or more is used. It is preferable to use it.
  • a photopolymerization initiator that is highly sensitive to light of 380 nm or more will be described later.
  • the compound represented by following General formula (1) (Wherein R 1 and R 2 represent —H, —CH 2 CH 3 , —iPr or Cl, and R 1 and R 2 may be the same or different), respectively, or a general formula ( It is preferable to use together the compound represented by 1) and a photopolymerization initiator that is highly sensitive to light of 380 nm or more, which will be described later.
  • the adhesion is excellent as compared with the case where a photopolymerization initiator having high sensitivity to light of 380 nm or more is used alone.
  • diethylthioxanthone in which R 1 and R 2 are —CH 2 CH 3 is particularly preferable.
  • the composition ratio of the compound represented by the general formula (1) in the forming material is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable component, and preferably 0.5 to 4 parts. More preferred are parts by weight, and even more preferred is 0.9 to 3 parts by weight.
  • polymerization initiators include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, etc. Among them, ethyl 4-dimethylaminobenzoate is particularly preferable.
  • a polymerization initiation assistant When a polymerization initiation assistant is used, its addition amount is usually 0 to 5 parts by weight, preferably 0 to 4 parts by weight, most preferably 0 to 3 parts by weight, based on 100 parts by weight of the total amount of the curable component. is there.
  • a known photopolymerization initiator can be used in combination as necessary. Since the protective film having UV absorbing ability does not transmit light of 380 nm or less, it is preferable to use a photopolymerization initiator that is highly sensitive to light of 380 nm or more as the photopolymerization initiator.
  • 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine Oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) 1-yl) -phenyl) titanium and the like.
  • a photopolymerization initiator in addition to the photopolymerization initiator of the general formula (1), a compound represented by the following general formula (2); Wherein R 3 , R 4 and R 5 represent —H, —CH 3 , —CH 2 CH 3 , —iPr or Cl, and R 3 , R 4 and R 5 may be the same or different. It is preferable to use it.
  • the compound represented by the general formula (2) 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: IRGACURE907 manufacturer: BASF) which is also a commercial product is suitable. Can be used.
  • 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE369 manufacturer: BASF)
  • 2- (dimethylamino) -2-[(4-methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE379 manufacturer: BASF) is preferred because of its high sensitivity.
  • a radical polymerizable compound having an active methylene group when used as the radical polymerizable compound, it is preferably used in combination with a radical polymerization initiator having a hydrogen abstraction function.
  • radical polymerization initiator having a hydrogen abstracting action examples include thioxanthone radical polymerization initiators and benzophenone radical polymerization initiators.
  • the radical polymerization initiator is preferably a thioxanthone radical polymerization initiator.
  • examples of the thioxanthone radical polymerization initiator include compounds represented by the above general formula (1).
  • Specific examples of the compound represented by the general formula (1) include thioxanthone, dimethylthioxanthone, diethylthioxanthone, isopropylthioxanthone, and chlorothioxanthone.
  • diethylthioxanthone in which R 1 and R 2 are —CH 2 CH 3 is particularly preferable.
  • the radical polymerizable compound having an active methylene group and a radical polymerization initiator having a hydrogen abstraction function when the total amount of the curable component is 100% by weight, It is preferable to contain 1 to 50% by weight of the radical polymerizable compound having an active methylene group and 0.1 to 10 parts by weight of the radical polymerization initiator with respect to 100 parts by weight of the total amount of the curable component.
  • thermal polymerization initiator those in which polymerization does not start by thermal cleavage when the adhesive layer is formed are preferable.
  • thermal polymerization initiator those having a 10-hour half-life temperature of 65 ° C. or higher, more preferably 75 to 90 ° C. are preferable.
  • the half-life is an index representing the decomposition rate of the polymerization initiator and refers to the time until the remaining amount of the polymerization initiator is halved.
  • the decomposition temperature for obtaining a half-life at an arbitrary time and the half-life time at an arbitrary temperature are described in the manufacturer catalog, for example, “Organic peroxide catalog 9th edition by Nippon Oil & Fats Co., Ltd.” (May 2003) ".
  • thermal polymerization initiator examples include lauroyl peroxide (10 hour half-life temperature: 64 ° C.), benzoyl peroxide (10 hour half-life temperature: 73 ° C.), 1,1-bis (t-butylperoxy) -3.
  • thermal polymerization initiator examples include 2,2′-azobisisobutyronitrile (10 hour half-life temperature: 67 ° C.), 2,2′-azobis (2-methylbutyronitrile) (10 hours). And azo compounds such as 1,1-azobis-cyclohexane-1-carbonitrile (10 hour half-life temperature: 87 ° C.).
  • the blending amount of the thermal polymerization initiator is 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of the curable component (radical polymerizable compound).
  • the blending amount of the thermal polymerization initiator is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 3 parts by weight.
  • Examples of the curable component of the cationic polymerization curable forming material include compounds having an epoxy group or an oxetanyl group.
  • the compound having an epoxy group is not particularly limited as long as it has at least two epoxy groups in the molecule, and various generally known curable epoxy compounds can be used.
  • a preferable epoxy compound a compound having at least two epoxy groups and at least one aromatic ring in the molecule (aromatic epoxy compound), or at least two epoxy groups in the molecule, at least one of them. Examples thereof include a compound (alicyclic epoxy compound) formed between two adjacent carbon atoms constituting an alicyclic ring.
  • the curable forming material according to the present invention preferably contains the following components.
  • the active energy ray-curable forming material according to the present invention can contain an acrylic oligomer obtained by polymerizing a (meth) acrylic monomer, in addition to the curable component related to the radical polymerizable compound.
  • an acrylic oligomer in the active energy ray curable forming material curing shrinkage when irradiating and curing the active energy ray to the transparent resin layer is reduced, and the transparent resin layer and the polarizer are attached. Interfacial stress with the body can be reduced. As a result, it is possible to suppress a decrease in adhesiveness between the adhesive layer and the adherend.
  • the content of the acrylic oligomer is preferably 20 parts by weight or less and more preferably 15 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component.
  • the acrylic oligomer is preferably contained in an amount of 3 parts by weight or more, more preferably 5 parts by weight or more, based on 100 parts by weight of the total amount of the curable component.
  • the active energy ray-curable forming material preferably has a low viscosity in consideration of workability and uniformity during coating, and thus an acrylic oligomer obtained by polymerizing a (meth) acrylic monomer also has a low viscosity. It is preferable.
  • the acrylic oligomer having a low viscosity and capable of preventing curing shrinkage of the transparent resin layer preferably has a weight average molecular weight (Mw) of 15000 or less, more preferably 10,000 or less, and particularly preferably 5000 or less. preferable.
  • the weight average molecular weight (Mw) of the acrylic oligomer is preferably 500 or more, more preferably 1000 or more, and 1500 or more. Is particularly preferred.
  • Specific examples of the (meth) acrylic monomer constituting the acrylic oligomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-methyl- 2-nitropropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, S-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, t-pentyl (Meth) acrylate, 3-pentyl (meth) acrylate, 2,2-dimethyl
  • acrylic oligomer examples include “ARUFON” manufactured by Toagosei Co., Ltd., “Act Flow” manufactured by Soken Chemical Co., Ltd., “JONCRYL” manufactured by BASF Japan.
  • the active energy ray-curable forming material may contain a photoacid generator.
  • the active energy ray-curable forming material contains a photoacid generator, the water resistance and durability of the transparent resin layer can be drastically improved as compared with the case where no photoacid generator is contained.
  • the photoacid generator can be represented by the following general formula (3).
  • onium salts constituting the photoacid generator include PF 6 ⁇ , SbF 6 ⁇ , AsF 6 ⁇ , SbCl 6 ⁇ , BiCl 5 ⁇ , SnCl 6 ⁇ , ClO 4 ⁇ , dithiocarbamate anion, SCN ⁇ . It is an onium salt comprising an anion selected from more.
  • the content of the photoacid generator is 10 parts by weight or less, preferably 0.01 to 10 parts by weight, and preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable component. More preferred is 0.1 to 3 parts by weight.
  • the cationic polymerization curable forming material contains the epoxy compound and the oxetane compound described above as the curable component, and both of these are cured by cationic polymerization, and therefore, a photocationic polymerization initiator is blended therein.
  • This cationic photopolymerization initiator generates a cationic species or a Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and starts a polymerization reaction of an epoxy group or an oxetanyl group.
  • the formation of the transparent resin layer by the curable forming material is performed by coating the curable forming material on the surface of the polarizer and then curing.
  • the polarizer may be subjected to a surface modification treatment before coating the curable forming material.
  • Specific examples of the treatment include corona treatment, plasma treatment, and saponification treatment.
  • the coating method of the curable forming material is appropriately selected depending on the viscosity of the curable forming material and the target thickness.
  • coating methods include reverse coaters, gravure coaters (direct, reverse and offset), bar reverse coaters, roll coaters, die coaters, bar coaters, rod coaters and the like.
  • a method such as a dapping method can be appropriately used.
  • the curable forming material is used as an active energy ray curable forming material or a thermosetting forming material.
  • the active energy ray curable forming material can be used in an electron beam curable type, an ultraviolet curable type, or a visible light curable type.
  • the aspect of the curable forming material is preferably an active energy ray curable forming material rather than a thermosetting forming material from the viewpoint of productivity, and moreover, the active energy ray curable forming material is a visible light curable forming material. It is preferable from the viewpoint of productivity.
  • active energy ray curing type In the active energy ray curable forming material, after applying the active energy ray curable forming material to the polarizer, the active energy ray (electron beam, ultraviolet ray, visible light, etc.) is irradiated, and the active energy ray curable forming material is applied. Curing to form a transparent resin layer.
  • the irradiation direction of active energy rays can be irradiated from any appropriate direction. Preferably, it irradiates from the transparent resin layer side.
  • the acceleration voltage is preferably 5 kV to 300 kV, and more preferably 10 kV to 250 kV. If the acceleration voltage is less than 5 kV, the electron beam may not reach the deepest part of the transparent resin layer and may be insufficiently cured. If the acceleration voltage exceeds 300 kV, the penetration force through the sample is too strong, and a protective film or polarizer May cause damage.
  • the irradiation dose is 5 to 100 kGy, more preferably 10 to 75 kGy.
  • the adhesive When the irradiation dose is less than 5 kGy, the adhesive is insufficiently cured, and when it exceeds 100 kGy, the protective film and the polarizer are damaged, resulting in a decrease in mechanical strength and yellowing, thereby obtaining predetermined optical characteristics. Can not.
  • the electron beam irradiation is usually performed in an inert gas, but if necessary, it may be performed in the atmosphere or under a condition where a little oxygen is introduced.
  • active energy rays containing visible light having a wavelength range of 380 nm to 450 nm, particularly active energy rays having the largest irradiation amount of visible light having a wavelength range of 380 nm to 450 nm are used as active energy rays. It is preferable.
  • active energy ray according to the present invention a gallium-encapsulated metal halide lamp and an LED light source that emits light in the wavelength range of 380 to 440 nm are preferable.
  • low pressure mercury lamp medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, incandescent lamp, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, gallium lamp, excimer laser or sunlight
  • a light source including visible light can be used, and ultraviolet light having a wavelength shorter than 380 nm can be blocked using a band pass filter.
  • thermosetting type forming material after bonding a polarizer and a protective film, by heating, polymerization is started by a thermal polymerization initiator to form a cured product layer.
  • the heating temperature is set according to the thermal polymerization initiator, but is about 60 to 200 ° C., preferably 80 to 150 ° C.
  • a material for forming the transparent resin layer for example, a cyanoacrylate-based forming material, an epoxy-based forming material, or an isocyanate-based forming material can be used.
  • Examples of the cyanoacrylate-based forming material include alkyl- ⁇ -cyanoacrylates such as methyl- ⁇ -cyanoacrylate, ethyl- ⁇ -cyanoacrylate, butyl- ⁇ -cyanoacrylate, octyl- ⁇ -cyanoacrylate, and cyclohexyl- ⁇ -. And cyanoacrylate and methoxy- ⁇ -cyanoacrylate.
  • alkyl- ⁇ -cyanoacrylates such as methyl- ⁇ -cyanoacrylate, ethyl- ⁇ -cyanoacrylate, butyl- ⁇ -cyanoacrylate, octyl- ⁇ -cyanoacrylate, and cyclohexyl- ⁇ -.
  • cyanoacrylate and methoxy- ⁇ -cyanoacrylate methoxy- ⁇ -cyanoacrylate.
  • those used as a cyanoacrylate-based adhesive can be used as the cyanoacrylate-based adhesive can be used.
  • the epoxy-based forming material may be used alone as an epoxy resin or may contain an epoxy curing agent. When the epoxy resin is used alone, it is cured by adding a photopolymerization initiator and irradiating active energy rays. When an epoxy curing agent is added as an epoxy-based forming material, for example, those used as an epoxy-based adhesive can be used.
  • the usage form of the epoxy-based forming material can be used as a one-component type containing an epoxy resin and its curing agent, but it is used as a two-component type in which a curing agent is blended with the epoxy resin.
  • Epoxy-based forming materials are usually used as solutions.
  • the solution may be a solvent system or an aqueous system such as an emulsion, a colloidal dispersion, or an aqueous solution.
  • the epoxy resin examples include various compounds containing two or more epoxy groups in the molecule.
  • the epoxy resin examples include various compounds containing two or more epoxy groups in the molecule.
  • bisphenol type epoxy resin aliphatic type epoxy resin, aromatic type epoxy resin, halogenated bisphenol type epoxy resin, biphenyl And epoxy resin.
  • an epoxy resin can be suitably determined according to an epoxy equivalent and the number of functional groups, the epoxy equivalent of 500 or less is used suitably from a durable viewpoint.
  • the curing agent for the epoxy resin is not particularly limited, and various types such as phenol resin type, acid anhydride type, carboxylic acid type, and polyamine type can be used.
  • phenol resin-based curing agent for example, phenol novolak resin, bisphenol novolak resin, xylylene phenol resin, cresol novolak resin, or the like is used.
  • acid anhydride-based curing agents include: maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and the like.
  • carboxylic acid-based curing agents include carboxylic acids such as pyromellitic acid and trimellitic acid.
  • Examples thereof include block carboxylic acids added with acids and vinyl ether.
  • an epoxy-type two-component formation material what consists of two liquids of an epoxy resin and a polythiol, what consists of two liquids of an epoxy resin and polyamide, etc. can be used, for example.
  • the blending amount of the curing agent varies depending on the equivalent to the epoxy resin, but is preferably 30 to 70 parts by weight, more preferably 40 to 60 parts by weight with respect to 100 parts by weight of the epoxy resin.
  • curing accelerators can be used for the epoxy-based forming material.
  • the curing accelerator include various imidazole compounds and derivatives thereof, dicyandiamide, and the like.
  • Examples of the isocyanate-based forming material include those used as a crosslinking agent in the formation of the pressure-sensitive adhesive layer.
  • As the isocyanate-based crosslinking agent a compound having at least two isocyanate groups can be used.
  • the polyisocyanate compound can be used as an isocyanate-based forming material.
  • Examples include those reacted with polyhydric alcohols and polyhydric amines.
  • isocyanate-based crosslinking agent those having three or more isocyanate groups such as isocyanuric acid tris (6-inocyanate hexyl) are preferable.
  • isocyanate type formation material what is used as an isocyanate type adhesive agent is mention
  • the isocyanate-based forming materials in the present invention, it is preferable to use those having a rigid structure in which a cyclic structure (benzene ring, cyanurate ring, isocyanurate ring, etc.) accounts for a large proportion in the structure.
  • a cyclic structure benzene ring, cyanurate ring, isocyanurate ring, etc.
  • the isocyanate-based forming material for example, trimethylolpropane-tri-tolylene isocyanate, tris (hexamethylene isocyanate) isocyanurate and the like are preferably used.
  • the said isocyanate type crosslinking agent can also use what provided the protective group to the terminal isocyanate group.
  • Protecting groups include oximes and lactams. In the case where the isocyanate group is protected, the protecting group is dissociated from the isocyanate group by heating, and the isocyanate group reacts.
  • a reaction catalyst can be used to increase the reactivity of the isocyanate group.
  • the reaction catalyst is not particularly limited, but a tin-based catalyst or an amine-based catalyst is suitable.
  • the reaction catalyst can use 1 type (s) or 2 or more types.
  • the amount of the reaction catalyst used is usually 5 parts by weight or less with respect to 100 parts by weight of the isocyanate-based crosslinking agent. When the amount of the reaction catalyst is large, the crosslinking reaction rate increases and foaming of the forming material occurs. Even if the forming material after foaming is used, sufficient adhesion cannot be obtained.
  • a reaction catalyst it is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 4 parts by weight.
  • the tin-based catalyst both inorganic and organic catalysts can be used, but an organic catalyst is preferred.
  • the inorganic tin-based catalyst include stannous chloride and stannic chloride.
  • the organic tin-based catalyst is preferably one having at least one organic group such as an aliphatic group or alicyclic group having a skeleton such as a methyl group, an ethyl group, an ether group or an ester group. Examples include tetra-n-butyltin, tri-n-butyltin acetate, n-butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride, dibutyltin dilaurate and the like.
  • the amine catalyst is not particularly limited. For example, those having at least one organic group such as an alicyclic group such as quinoclidine, amidine, and diazabicycloundecene are preferable.
  • examples of the amine catalyst include triethylamine.
  • reaction catalysts other than the above include cobalt naphthenate and benzyltrimethylammonium hydroxide.
  • the isocyanate-based forming material is usually used as a solution.
  • the solution may be a solvent system or an aqueous system such as an emulsion, a colloidal dispersion, or an aqueous solution.
  • the organic solvent is not particularly limited as long as the components constituting the forming material are uniformly dissolved. Examples of the organic solvent include toluene, methyl ethyl ketone, ethyl acetate and the like.
  • alcohols such as n-butyl alcohol and isopropyl alcohol and ketones such as acetone can be blended.
  • a dispersant is used, or an isocyanate-based crosslinking agent, a functional group having low reactivity with an isocyanate group such as a carboxylate, a sulfonate, or a quaternary ammonium salt, or an aqueous dispersion such as polyethylene glycol. It can carry out by introduce
  • the formation of the transparent resin layer by the cyanoacrylate-based forming material, the epoxy-based forming material, or the isocyanate-based forming material can be appropriately selected according to the type of the forming material, but is usually about 30 to 100 ° C., The drying is preferably performed at 50 to 80 ° C. for about 0.5 to 15 minutes. In the case of a cyanoacrylate-based forming material, since the curing is fast, the transparent resin layer can be formed in a time shorter than the above time.
  • the transparent resin layer may be formed from a forming material that does not contain a curable component.
  • the transparent resin layer may be formed from a forming material that contains the polyvinyl alcohol-based resin as a main component.
  • the polyvinyl alcohol resin forming the transparent resin layer may be the same as or different from the polyvinyl alcohol resin contained in the polarizer as long as it is a “polyvinyl alcohol resin”.
  • polyvinyl alcohol resin examples include polyvinyl alcohol.
  • Polyvinyl alcohol is obtained by saponifying polyvinyl acetate.
  • polyvinyl alcohol-based resin examples include a saponified product of a copolymer of vinyl acetate and a monomer having copolymerizability.
  • the copolymerizable monomer is ethylene
  • an ethylene-vinyl alcohol copolymer is obtained.
  • the copolymerizable monomer include unsaturated carboxylic acids such as (anhydrous) maleic acid, fumaric acid, crotonic acid, itaconic acid, (meth) acrylic acid, and esters thereof; ethylene, propylene, and the like.
  • ⁇ -olefin (meth) allylsulfonic acid (soda), sulfonic acid soda (monoalkylmalate), disulfonic acid soda alkylmalate, N-methylolacrylamide, acrylamide alkylsulfonic acid alkali salt, N-vinylpyrrolidone, N- Examples include vinyl pyrrolidone derivatives.
  • These polyvinyl alcohol resins can be used alone or in combination of two or more.
  • Polyvinyl alcohol obtained by saponifying polyvinyl acetate is preferable from the viewpoint of controlling the heat of crystal fusion of the transparent resin layer to 30 mj / mg or more and satisfying heat and moisture resistance and water resistance.
  • the degree of saponification of the polyvinyl alcohol resin can be, for example, 95% or more, and the heat of crystal melting of the transparent resin layer is controlled to 30 mj / mg or more to satisfy the heat and moisture resistance and water resistance. Therefore, the degree of saponification is preferably 99.0% or more, and more preferably 99.7% or more.
  • the degree of saponification represents the proportion of units that are actually saponified to vinyl alcohol units among the units that can be converted to vinyl alcohol units by saponification, and the residue is a vinyl ester unit.
  • the degree of saponification can be determined according to JIS K 6726-1994.
  • the average degree of polymerization of the polyvinyl alcohol-based resin can be, for example, 500 or more, and the heat of crystal melting of the transparent resin layer is controlled to 30 mj / mg or more to satisfy the moisture and heat resistance and water resistance. From the viewpoint, the average degree of polymerization is preferably 1000 or more, more preferably 1500 or more, and further preferably 2000 or more. The average degree of polymerization of the polyvinyl alcohol resin is measured according to JIS-K6726.
  • a modified polyvinyl alcohol resin having a hydrophilic functional group in the side chain of the polyvinyl alcohol or a copolymer thereof can be used.
  • the hydrophilic functional group include an acetoacetyl group and a carbonyl group.
  • modified polyvinyl alcohol obtained by acetalization, urethanization, etherification, grafting, phosphoric esterification or the like of a polyvinyl alcohol resin can be used.
  • the forming material containing the polyvinyl alcohol-based resin as a main component can contain a curable component (crosslinking agent) and the like.
  • the proportion of the polyvinyl alcohol-based resin in the transparent resin layer or the forming material (solid content) is preferably 80% by weight or more, more preferably 90% by weight or more, and further preferably 95% by weight or more.
  • the forming material does not contain a curable component (crosslinking agent) from the viewpoint of easily controlling the heat of crystal fusion of the transparent resin layer to 30 mj / mg or more.
  • a compound having at least two functional groups having reactivity with the polyvinyl alcohol resin can be used.
  • alkylenediamine having two alkylene groups and two amino groups such as ethylenediamine, triethylenediamine, hexamethylenediamine; tolylene diisocyanate, hydrogenated tolylene diisocyanate, trimethylolpropane tolylene diisocyanate adduct, triphenylmethane triisocyanate, methylene bis (4-Phenylmethane triisocyanate, isophorone diisocyanate and isocyanates such as ketoxime block product or phenol block product thereof; ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin di or triglycidyl ether, 1,6-hexane Diol diglycidyl ether, trimethylolpropane triglycidyl ether, di Epoxies
  • amino-formaldehyde resins and water-soluble dihydrazine are preferred, and the amino-formaldehyde resin is preferably a compound having a methylol group, particularly methylol melamine, which is a compound having a methylol group.
  • hardenable component crosslinking agent
  • the ratio is 20 weight part or less, 10 weight part or less, 5 weight part with respect to 100 weight part of polyvinyl alcohol-type resin. It is preferable that:
  • the forming material is prepared as a solution in which the polyvinyl alcohol resin is dissolved in a solvent.
  • the solvent include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide N-methylpyrrolidone, various glycols, polyhydric alcohols such as alcohols, and amines such as ethylenediamine and diethylenetriamine. These may be used alone or in combination of two or more. Among these, it is preferable to use it as an aqueous solution using water as a solvent.
  • the concentration of the polyvinyl alcohol-based resin in the forming material is not particularly limited, but is 0.1 to 15% by weight, preferably 0.5%, in consideration of coating properties and storage stability. ⁇ 10% by weight.
  • a plasticizer for example, polyhydric alcohols such as ethylene glycol and glycerin.
  • the surfactant include nonionic surfactants.
  • coupling agents such as silane coupling agents and titanium coupling agents, various tackifiers, ultraviolet absorbers, antioxidants, heat stabilizers, hydrolysis stabilizers, and other stabilizers can be added.
  • the transparent resin layer can be formed by applying and drying the forming material on the other surface of the polarizer (the surface on which the protective film is not laminated).
  • the application operation is not particularly limited, and any appropriate method can be adopted.
  • various means such as a roll coating method, a spin coating method, a wire bar coating method, a dip coating method, a die coating method, a curtain coating method, a spray coating method, a knife coating method (comma coating method, etc.) can be employed.
  • the transparent resin layer is preferably formed of an ultraviolet curable acrylic resin, an ultraviolet curable epoxy resin, a urethane resin, or a polyvinyl alcohol resin.
  • the urethane-based resin layer is formed from the isocyanate-based forming material.
  • Adhesive layer An appropriate pressure-sensitive adhesive can be used for forming the pressure-sensitive adhesive layer, and the type thereof is not particularly limited.
  • Adhesives include rubber adhesives, acrylic adhesives, silicone adhesives, urethane adhesives, vinyl alkyl ether adhesives, polyvinyl alcohol adhesives, polyvinyl pyrrolidone adhesives, polyacrylamide adhesives, Examples thereof include cellulose-based pressure-sensitive adhesives.
  • pressure-sensitive adhesives those having excellent optical transparency, suitable wettability, cohesiveness, and adhesive pressure characteristics, and excellent weather resistance and heat resistance are preferably used.
  • An acrylic pressure-sensitive adhesive is preferably used as one exhibiting such characteristics.
  • the polymerization solvent is dried and removed to form the pressure-sensitive adhesive layer, and then in the embodiment of FIG.
  • a method of transferring to a polarizer (or a protective film in the embodiment of FIG. 2B), or a polarizer (or a protective film in the embodiment of FIG. 2B) in the embodiment of FIG. It is produced by a method of drying and removing a polymerization solvent and the like to form an adhesive layer on a polarizer.
  • one or more solvents other than the polymerization solvent may be added as appropriate.
  • a silicone release liner is preferably used as the release-treated separator.
  • an appropriate method may be adopted as appropriate according to the purpose.
  • a method of heating and drying the coating film is used.
  • the heating and drying temperature is preferably 40 ° C to 200 ° C, more preferably 50 ° C to 180 ° C, and particularly preferably 70 ° C to 170 ° C.
  • the drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.
  • Various methods are used as a method for forming the pressure-sensitive adhesive layer. Specifically, for example, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples thereof include an extrusion coating method.
  • the thickness of the pressure-sensitive adhesive layer is preferably 1 ⁇ m or more, and more preferably 5 ⁇ m or more from the viewpoint of suppressing peeling.
  • the thickness of the pressure-sensitive adhesive is 40 ⁇ m because nanoslits are likely to be generated due to the bending of the polarizer due to mechanical impact applied after the polarizing film is bonded to the liquid crystal cell. It is 35 ⁇ m or less, more preferably 25 ⁇ m or less.
  • the thickness of an adhesive layer is 35 micrometers or less also from a viewpoint of suppressing the shrinkage
  • the pressure-sensitive adhesive layer has a storage elastic modulus at 23 ° C. of 1.0 ⁇ 10 4 Pa or more, so that the polarizing film with the pressure-sensitive adhesive layer is not subjected to a load due to convex folding on the polarizer side, and is resistant to cracking. This is preferable for ensuring (suppression of nanoslit generation).
  • the storage elastic modulus of the pressure-sensitive adhesive layer is preferably 5.0 ⁇ 10 4 Pa or more.
  • the storage elastic modulus of the pressure-sensitive adhesive layer is preferably 1 ⁇ 10 8 Pa or less. Further, it is preferably 1 ⁇ 10 7 PaPa or less.
  • the pressure-sensitive adhesive layer When the pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a peeled sheet (separator) until practical use.
  • constituent material of the separator examples include, for example, plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof.
  • plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films
  • porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof.
  • a thin film can be used, but a plastic film is preferably used because of its excellent surface smoothness.
  • the plastic film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer.
  • a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, and a vinyl chloride co-polymer are used.
  • examples thereof include a polymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
  • the thickness of the separator is usually about 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
  • mold release and antifouling treatment with a silicone type, fluorine type, long chain alkyl type or fatty acid amide type release agent, silica powder, etc., coating type, kneading type, vapor deposition type It is also possible to carry out antistatic treatment such as.
  • the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the separator.
  • a surface protective film can be provided on the single protective polarizing film and the polarizing film with the pressure-sensitive adhesive layer.
  • the surface protective film usually has a base film and an adhesive layer, and protects the polarizer via the adhesive layer.
  • a film material having isotropic property or close to isotropic property is selected from the viewpoints of inspection property and manageability.
  • film materials include polyester resins such as polyethylene terephthalate film, cellulose resins, acetate resins, polyether sulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, acrylic resins, and the like. Examples thereof include transparent polymers such as resins. Of these, polyester resins are preferred.
  • the base film can be used as a laminate of one kind or two or more kinds of film materials, and a stretched product of the film can also be used.
  • the thickness of the base film is generally 500 ⁇ m or less, preferably 10 to 200 ⁇ m.
  • the pressure-sensitive adhesive that forms the pressure-sensitive adhesive layer of the surface protective film includes a (meth) acrylic polymer, a silicone-based polymer, a polyester, a polyurethane, a polyamide, a polyether, a fluorine-based or a rubber-based pressure-sensitive adhesive. Can be appropriately selected and used. From the viewpoints of transparency, weather resistance, heat resistance and the like, an acrylic pressure-sensitive adhesive having an acrylic polymer as a base polymer is preferable.
  • the thickness (dry film thickness) of the pressure-sensitive adhesive layer is determined according to the required adhesive force. Usually, it is about 1 to 100 ⁇ m, preferably 5 to 50 ⁇ m.
  • the surface protective film can be provided with a release treatment layer on the surface opposite to the surface on which the pressure-sensitive adhesive layer is provided on the base film, using a low adhesion material such as silicone treatment, long-chain alkyl treatment, or fluorine treatment. .
  • the piece-protecting polarizing film and the polarizing film with a pressure-sensitive adhesive layer of the present invention can be used as an optical film laminated with another optical layer in practical use.
  • the optical layer is not particularly limited.
  • a liquid crystal display device such as a reflection plate, a semi-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), and a viewing angle compensation film.
  • One or more optical layers that may be used can be used.
  • a reflective polarizing film or a semi-transmissive polarizing film in which a reflective plate or a semi-transmissive reflective plate is further laminated on the piece protective polarizing film of the present invention an elliptical polarizing film in which a retardation plate is further laminated on the polarizing film, or A circular viewing film, a wide viewing angle polarizing film in which a viewing angle compensation film is further laminated on the polarizing film, or a polarizing film in which a brightness enhancement film is further laminated on the polarizing film are preferable.
  • An optical film obtained by laminating the above optical layer on a single protective polarizing film or a polarizing film with a pressure-sensitive adhesive layer can be formed by a method of sequentially laminating separately in the manufacturing process of a liquid crystal display device, etc.
  • the optical film is excellent in quality stability and assembly work, and has the advantage of improving the manufacturing process of liquid crystal display devices and the like.
  • an appropriate adhesive means such as a pressure-sensitive adhesive layer can be used.
  • their optical axes can be arranged at an appropriate angle depending on the intended retardation characteristics and the like.
  • the piece protective polarizing film, the polarizing film with an adhesive layer or the optical film of the present invention can be preferably used for forming various image display devices such as a liquid crystal display device and an organic EL display device.
  • the liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device is generally formed by appropriately assembling components such as a liquid crystal cell, a polarizing film with an adhesive layer or an optical film, and an illumination system as necessary, and incorporating a drive circuit.
  • a piece-protecting polarizing film, a polarizing film with a pressure-sensitive adhesive layer or an optical film according to the present invention is used.
  • As the liquid crystal cell an arbitrary type such as an IPS type or a VA type can be used, but is particularly suitable for the IPS type.
  • liquid crystal display devices such as a liquid crystal display device in which a single protective polarizing film, a polarizing film with an adhesive layer or an optical film are arranged on one or both sides of a liquid crystal cell, or a backlight or reflector used in an illumination system are formed.
  • the polarizing film with a pressure-sensitive adhesive layer or the optical film according to the present invention can be installed on one side or both sides of the liquid crystal cell.
  • a single protective polarizing film, a polarizing film with an adhesive layer, or an optical film on both sides they may be the same or different.
  • a single layer or a suitable part such as a diffusing plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusing plate, a backlight, etc.
  • a diffusing plate for example, a diffusing plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusing plate, a backlight, etc.
  • a protective plate such as a prism array, a lens array sheet, a light diffusing plate, a backlight, etc.
  • a prism array such as a prism array, a lens array sheet, a light diffusing plate, a backlight, etc.
  • the above image display device is an image of the polarizing film with the pressure-sensitive adhesive layer fed out from the wound body (roll) of the polarizing film with the pressure-sensitive adhesive layer of the present invention and conveyed by the separator through the pressure-sensitive adhesive layer. It is preferably manufactured by a continuous manufacturing method (roll-to-panel method) including a step of continuously bonding to the surface of the display panel.
  • the polarizing film with a pressure-sensitive adhesive layer of the present invention is a very thin film, it is cut into a sheet (sheet-fed) and then bonded to the image display panel one by one (“sheet-to-panel method”) According to the above), it is difficult to handle the sheet when it is transported or bonded to the display panel, and the polarizing film (sheet) with the adhesive layer is subjected to a large mechanical impact (for example, bending due to adsorption) in these processes. Risk increases. In order to reduce such a risk, it is necessary to take another measure such as using a thick surface protective film having a thickness of 50 ⁇ m or more.
  • the polarizing film with the pressure-sensitive adhesive layer is stably conveyed from the roll to the image display panel by the continuous separator without being cut into a sheet (sheet cutting), Since it is directly bonded to the image display panel, the risk can be greatly reduced without using a thick surface protective film. As a result, coupled with the ability to mitigate mechanical impacts with the transparent resin layer, it is possible to continuously produce an image display panel in which the generation of nanoslits is effectively suppressed.
  • FIG. 8 is a schematic diagram showing an example of a continuous manufacturing system of a liquid crystal display device adopting a roll-to-panel method.
  • the continuous manufacturing system 100 of the liquid crystal display device includes a series of transport units X that transport the liquid crystal display panel P, a first polarizing film supply unit 101a, a first bonding unit 201a, and a second polarizing film supply. Part 101b and 2nd pasting part 201b are included.
  • the wound body (first roll) 20a of the polarizing film with the first pressure-sensitive adhesive layer and the wound body (second roll) 20b of the polarizing film with the second pressure-sensitive adhesive layer have an absorption axis in the longitudinal direction. And the thing of the aspect as described in FIG. 2 (A) is used.
  • the transport unit X transports the liquid crystal display panel P.
  • the conveyance unit X is configured to include a plurality of conveyance rollers, a suction plate, and the like.
  • the transport unit X is an arrangement in which the placement relationship between the long side and the short side of the liquid crystal display panel P is switched between the first bonding unit 201a and the second bonding unit 201b with respect to the transport direction of the liquid crystal display panel P.
  • a replacement unit for example, the liquid crystal display panel P is rotated 90 ° horizontally 300 is included. Thereby, with respect to the liquid crystal display panel P, the polarizing film 21a with the 1st adhesive layer and the polarizing film 21b with the 2nd adhesive layer can be bonded together in the crossed Nicols relationship.
  • the first polarizing film supply unit 101a continuously feeds the first adhesive layer-attached polarizing film (with a surface protective film) 21a fed from the first roll 20a and conveyed by the separator 5a to the first bonding unit 201a. To do.
  • the first polarizing film supply unit 101a includes a first feeding unit 151a, a first cutting unit 152a, a first peeling unit 153a, a first winding unit 154a, and a plurality of conveying roller units, an accumulating unit such as a dancer roll, and the like. Have.
  • the first feeding portion 151a has a feeding shaft on which the first roll 20a is installed, and feeds the strip-shaped pressure-sensitive adhesive layer-attached polarizing film 21a provided with the separator 5a from the first roll 20a.
  • the first cutting unit 152a has cutting means and suction means such as a cutter and a laser device.
  • a strip-like pressure-sensitive adhesive layer-attached polarizing film 21a in which a plurality of score lines are formed in the width direction with a predetermined length is laminated on the separator 5a (an optical film roll with a notch). ) Is not required (the same applies to the second cutting portion 152b described later).
  • the 1st peeling part 153a peels the polarizing film 21a with a 1st adhesive layer from the separator 5a by folding up with the separator 5a inside.
  • Examples of the first peeling portion 153a include a wedge-shaped member and a roller.
  • the first winding unit 154a winds up the separator 5a from which the first pressure-sensitive adhesive layer-attached polarizing film 21a has been peeled off.
  • the first winding unit 154a has a winding shaft on which a roll for winding the separator 5a is installed.
  • the 1st bonding part 201a is the liquid crystal display panel P conveyed by the conveyance part X, the polarizing film 21a with the 1st adhesive layer which peeled the polarizing film 21a with the 1st adhesive layer peeled by the 1st peeling part 153a. Are continuously bonded through the pressure-sensitive adhesive layer (first bonding step).
  • the 1st bonding part 81 has a pair of bonding rollers, and at least one of the bonding rollers is configured by a drive roller.
  • the 2nd polarizing film supply part 101b is continuously supplied to the 2nd bonding part 201b by the 2nd bonding part 201b with the 2nd adhesive film layered polarizing film (with surface protection film) 21b which was drawn
  • the second polarizing film supply unit 101b includes a second feeding unit 151b, a second cutting unit 152b, a second peeling unit 153b, a second winding unit 154b, and a plurality of conveying roller units, an accumulating unit such as a dancer roll, and the like. Have.
  • the second feeding portion 151b, the second cutting portion 152b, the second peeling portion 153b, and the second winding portion 154b are respectively the first feeding portion 151a, the first cutting portion 152a, the first peeling portion 153a, and the first winding. It has the same configuration and function as the taking part 154a.
  • the 2nd bonding part 201b is the liquid crystal display panel P conveyed by the conveyance part X.
  • the 2nd adhesive layer-attached polarizing film 21b peeled off by the 2nd peeling part 153b, the 2nd adhesive layer-attached polarizing film 21b Are continuously bonded through the pressure-sensitive adhesive layer (second bonding step).
  • the 2nd bonding part 201b has a pair of bonding rollers, and at least one of the bonding rollers is comprised with a drive roller.
  • polarizer A0 amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA copolymerized PET) film (thickness: 100 ⁇ m) having a water absorption of 0.75% and Tg of 75 ° C. is subjected to corona treatment.
  • Alcohol polymerization degree 4200, saponification degree 99.2 mol%) and acetoacetyl-modified PVA (polymerization degree 1200, acetoacetyl modification degree 4.6%, saponification degree 99.0 mol% or more, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
  • aqueous solution containing 9: 1 ratio of the trade name “Gosefimer Z200”) was applied and dried at 25 ° C. to form a PVA-based resin layer having a thickness of 11 ⁇ m, thereby preparing a laminate.
  • the obtained laminate was uniaxially stretched in the longitudinal direction (longitudinal direction) 2.0 times between rolls having different peripheral speeds in an oven at 120 ° C. (air-assisted stretching process).
  • the laminate was immersed in an insolubilization bath (a boric acid aqueous solution obtained by blending 4 parts by weight of boric acid with respect to 100 parts by weight of water) for 30 seconds (insolubilization treatment).
  • boric acid aqueous solution obtained by blending 3 parts by weight of potassium iodide and 3 parts by weight of boric acid with respect to 100 parts by weight of water.
  • Crosslinking treatment Thereafter, the laminate was immersed in a boric acid aqueous solution (an aqueous solution obtained by blending 4 parts by weight of boric acid and 5 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 70 ° C.
  • uniaxial stretching was performed between rolls having different peripheral speeds in the longitudinal direction (longitudinal direction) so that the total stretching ratio was 5.5 times (in-water stretching treatment).
  • the laminate was immersed in a cleaning bath (an aqueous solution obtained by blending 4 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 30 ° C. (cleaning treatment).
  • a cleaning bath an aqueous solution obtained by blending 4 parts by weight of potassium iodide with respect to 100 parts by weight of water
  • cleaning treatment a liquid temperature of 30 ° C.
  • Polarizers A1 to A3 were produced in the same manner as the production of the polarizer A0 except that the production conditions for the polarizer A0 were changed as shown in Table 1.
  • Table 1 shows the thickness, optical characteristics (single transmittance, polarization degree), and boric acid concentration of the polarizers A1 to A3.
  • polarizer B (12 ⁇ m thick polarizer)
  • a polyvinyl alcohol film having an average polymerization degree of 2400 and a saponification degree of 99.9 mol% and a thickness of 30 ⁇ m was immersed in warm water at 30 ° C. for 60 seconds to swell.
  • the thickness of the obtained polarizer was 12 ⁇ m.
  • IPA copolymerized PET amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA copolymerized PET) film (thickness: 130 ⁇ m) having a water absorption of 0.75% and Tg of 75 ° C. is subjected to corona treatment.
  • Alcohol polymerization degree 4200, saponification degree 99.2 mol%) and acetoacetyl-modified PVA (polymerization degree 1200, acetoacetyl modification degree 4.6%, saponification degree 99.0 mol% or more, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
  • aqueous solution containing 9: 1 ratio of the trade name “Gosefimer Z200”) was applied and dried at 25 ° C. to form a PVA-based resin layer having a thickness of 11 ⁇ m, thereby preparing a laminate.
  • the obtained laminate was contracted 30% in the first direction (MD) at 110 ° C. using a simultaneous biaxial stretching machine, and at the same time, it was stretched in the air in the second direction (TD) by a factor of 5.0. (Stretching treatment).
  • the laminate was immersed for 40 seconds in an iodine aqueous solution (iodine concentration: 0.2 wt%, potassium iodide concentration: 1.4 wt%) at 25 ° C. (dyeing treatment).
  • the layered product after dyeing was immersed in a 60 ° C. boric acid aqueous solution (boric acid concentration: 5% by weight, potassium iodide concentration: 5% by weight) for 80 seconds (crosslinking treatment).
  • the laminate was immersed in a 25 ° C. aqueous potassium iodide solution (potassium iodide concentration: 5% by weight) for 20 seconds (cleaning treatment).
  • cleaning treatment As a result, an optical film laminate including a polarizer having a thickness of 3 ⁇ m was obtained.
  • Acrylic film 1 A (meth) acrylic resin film having a lactone ring structure with a thickness of 40 ⁇ m was subjected to corona treatment on the easy adhesion treated surface.
  • Acrylic film 2 A (meth) acrylic resin film having a lactone ring structure with a thickness of 60 ⁇ m was subjected to corona treatment on the easy adhesion treated surface.
  • Acrylic film 3 A (meth) acrylic resin film having a lactone ring structure with a thickness of 20 ⁇ m was subjected to corona treatment on the easy adhesion treated surface.
  • TAC1 A triacetyl cellulose film having a thickness of 60 ⁇ m was used.
  • TAC 2 A triacetyl cellulose film having a thickness of 40 ⁇ m was used.
  • Epoxy adhesive 3 It is the same as the composition (epoxy 1) of the epoxy-based forming material of the transparent resin layer forming material.
  • PVA adhesive Polyvinyl alcohol-based resin containing acetoacetyl group (average polymerization degree: 1200, saponification degree: 98.5 mol%, acetoacetylation degree: 5 mol%) to 100 parts, Under temperature conditions, an aqueous solution dissolved in pure water and adjusted to a solid content concentration of 3.7% was prepared. A PVA adhesive was prepared by adding 18 parts of an aqueous colloidal alumina solution (average particle size 15 nm, solid content concentration 10%, positive charge) to 100 parts of the aqueous solution.
  • ⁇ Forming material for transparent resin layer> (Polyvinyl alcohol-based forming material: PVA1) A polyvinyl alcohol resin having a polymerization degree of 2500 and a saponification degree of 99.7 mol% was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight.
  • composition of acrylic forming material acrylic 1
  • N-hydroxyethylacrylamide (trade name “HEAA” manufactured by Kojin Co., Ltd.) 20 parts Urethane acrylate (trade name “UV-1700B” manufactured by Nippon Synthetic Chemical Co., Ltd.) 80 parts
  • Photoradical polymerization initiator (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, manufactured by BASF, trade name “IRGACURE907”) 3 parts
  • Photosensitizer diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd., trade name “KAYACURE DETX-S” ]) 2 parts
  • Epoxy-based material composition Epoxy 1
  • 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Daicel Chemical Industries, trade name “Celoxide 2021P”) 100 parts Photocationic polymerization initiator (4- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate , Made by Sun Apro, trade name "CPI-100P”)
  • ⁇ Preparation of adhesive composition >> 0.2 parts of ethylmethylpyrrolidinium-bis (trifluoromethanesulfonyl) imide (manufactured by Tokyo Chemical Industry) and lithium bis (trifluoromethanesulfonyl) imide (Mitsubishi Materials Electronics) with respect to 100 parts of the solid content of the acrylic polymer solution 1 part), 0.1 part trimethylolpropane xylylene diisocyanate (Mitsui Chemicals: Takenate D110N), 0.3 part dibenzoyl peroxide, and ⁇ -glycidoxypropylmethoxy An acrylic pressure-sensitive adhesive solution was prepared by blending 0.075 part of silane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-403).
  • (Acrylic adhesive 2) In the preparation of the acrylic polymer of the above acrylic pressure-sensitive adhesive 1, a monomer mixture containing 65 parts of butyl acrylate, 34 parts of methyl methacrylate and 1 part of 4-hydroxybutyl acrylate was used instead of ethyl acetate as a solvent. A solution of an acrylic polymer having a weight average molecular weight of 1.1 million was prepared using toluene.
  • the preparation of the pressure-sensitive adhesive composition instead of 0.1 part of trimethylolpropane xylylene diisocyanate (Mitsui Chemicals Co., Ltd .: Takenate D110N), a cross-linking agent containing a compound having an isocyanate group as a main component (Nippon Polyurethane Co., Ltd.)
  • An acrylic pressure-sensitive adhesive solution was prepared in the same manner as the acrylic pressure-sensitive adhesive 1 except that 1 part of manufactured product name “Coronate L”) was used.
  • (Acrylic adhesive 3) In the preparation of the acrylic polymer of the acrylic pressure-sensitive adhesive 1, a monomer mixture containing 95 parts of butyl acrylate, 4 parts of acrylic acid and 1 part of 4-hydroxybutyl acrylate was used instead of ethyl acetate as a solvent. A solution of an acrylic polymer having a weight average molecular weight of 2.2 million was prepared using toluene.
  • the preparation of the pressure-sensitive adhesive composition instead of 0.1 part of trimethylolpropane xylylene diisocyanate (Mitsui Chemicals Co., Ltd .: Takenate D110N), a cross-linking agent containing a compound having an isocyanate group as a main component (Nippon Polyurethane Co., Ltd.)
  • An acrylic pressure-sensitive adhesive solution was prepared in the same manner as the acrylic pressure-sensitive adhesive 1 except that 0.6 part of the product, trade name “Coronate L”) was used.
  • Examples 1 to 28, Comparative Examples 1 to 5 (Production of single-protective polarizing film)
  • a piece protective polarizing film was prepared using the polarizer, adhesive, and protective film shown in Table 1.
  • Table 2 shows the optical properties (single transmittance, degree of polarization) of the obtained piece-protecting polarizing film.
  • two protective films were used, but the adhesive layers shown in Table 1 were also used for the lamination of the two protective films.
  • a protective film was bonded to the surface of the polarizer of the optical film laminate through an adhesive layer having a thickness shown in Table 1. Subsequently, the amorphous PET base material was peeled off to produce a piece protective polarizing film using a thin polarizer. In the case of using the polarizer B, a protective film was bonded to one side of the PVA polarizer through a thickness adhesive layer shown in Table 1.
  • the adhesive when the adhesive is acrylic adhesives 1 to 3 and epoxy adhesive 1 (in the case of an ultraviolet curable adhesive), the adhesive is shown in Table 1 with the thickness of the adhesive layer after curing.
  • the protective film was laminated while being applied to the surface of the polarizer, and then the adhesive was cured by irradiating ultraviolet rays as active energy rays. Ultraviolet irradiation is performed using a gallium-encapsulated metal halide lamp, an irradiation device: Fusion UV Systems, Inc.
  • the adhesive is a PVA-based adhesive
  • the protective film is bonded to the surface of the polarizer so that the adhesive has the thickness of the adhesive layer after drying shown in Table 1. After that, it was dried at 60 ° C. for 1 minute.
  • the acrylic 1 or epoxy 1 forming material as the transparent resin layer forming material, it is applied to the surface of the polarizer using a wire bar coater and then irradiated with active energy rays in a nitrogen atmosphere. As a result, a transparent resin layer was formed. In addition, irradiation of the active energy ray was performed in the same manner as that used in the production of the piece protective polarizing film.
  • ⁇ Preparation of polarizing film with adhesive layer> On the surface of the polyethylene terephthalate film (separator film) treated with the silicone release agent so that the thickness of the acrylic adhesives 1 to 3 is 5 ⁇ m, 15 ⁇ m, 20 ⁇ m, or 40 ⁇ m after drying.
  • the coating was uniformly applied with a fountain coater and dried for 2 minutes in an air circulation type thermostatic oven at 155 ° C. to form an adhesive layer on the surface of the separator film.
  • the adhesive layer formed on the release treatment surface of the release sheet was bonded to the transparent resin layer formed on the piece protective polarizing film so as to have the types and thicknesses shown in Table 2, A polarizing film with an adhesive layer was prepared.
  • the single transmittance T and polarization degree P of the obtained piece-protecting polarizing film were measured using a spectral transmittance measuring device with an integrating sphere (Dot-3c, Murakami Color Research Laboratory).
  • the degree of polarization P is the transmittance when two identical polarizing films are overlapped so that their transmission axes are parallel (parallel transmittance: Tp), and overlapped so that their transmission axes are orthogonal to each other. It is calculated
  • Polarization degree P (%) ⁇ (Tp ⁇ Tc) / (Tp + Tc) ⁇ 1/2 ⁇ 100
  • Each transmittance is represented by a Y value obtained by correcting visibility with a two-degree field of view (C light source) of JIS Z8701, with 100% of the completely polarized light obtained through the Granteller prism polarizer.
  • FTIR Fourier transform infrared spectrophotometer
  • SPECTRUM2000 the total reflection attenuation spectroscopy using the polarized light as the measurement light for the polarizers obtained in the examples and comparative examples
  • the intensity of the boric acid peak (665 cm ⁇ 1 ) and the intensity of the reference peak (2941 cm ⁇ 1 ) were measured by ATR) measurement.
  • the boric acid content index was calculated from the obtained boric acid peak intensity and the reference peak intensity by the following formula, and the boric acid content (% by weight) was determined from the calculated boric acid index by the following formula.
  • the storage elastic modulus at 23 ° C. was measured using a viscoelastic spectrometer (trade name: RSA-II) manufactured by Rheometric.
  • the measurement conditions were a measurement value at 23 ° C. in the range of ⁇ 50 ° C. to 200 ° C. at a frequency of 1 Hz, a sample thickness of 2 mm, a pressure bonding load of 100 g, and a temperature increase rate of 5 ° C./min.
  • a base molding material made of low density polyethylene having a density of 0.924 g / cm 3 and a melt flow rate at 190 ° C. of 2.0 g / 10 min was supplied to a coextrusion inflation molding machine.
  • a surface protective film consisting of a 33 ⁇ m thick base material layer and a 5 ⁇ m thick adhesive layer was produced.
  • the release sheet (separator) is peeled from the sample, and the glass plate 20 is interposed through the exposed adhesive layer 4. Pasted on top.
  • a load of 200 g is applied to the central portion of the sample 11 (surface protective film 6 side) by a guitar pick (manufactured by HISTROY, model number “HP2H (HARD)”), and the absorption axis of the polarizer 1 in the sample 11 is applied.
  • the load load of 50 reciprocations was repeated at a distance of 100 mm in the orthogonal direction. The load was applied at one place.
  • the sample 11 was left in an environment of 80 ° C. for 1 hour, the presence or absence of light leakage cracks in the sample 11 was confirmed according to the following criteria.
  • X 21 or more.
  • FIG. 6 shows the following index for the confirmation of the light leakage crack (nano slit a) in the guitar pick test of the piece protective polarizing film 10 or the piece protective polarizing film 11 with a transparent resin layer. It is an example of no.
  • FIG. 6A no light leakage crack due to the nano slit a is confirmed.
  • the state shown in FIG. 6A corresponds to before the heating of the guitar pick test of the comparative example and after the heating of the rock and roll test of the example (because of the expansion suppressing effect, the nano slit does not leak light).
  • FIG. 6B shows a case where three cracks of light leakage due to the nano slits a are generated in the absorption axis direction of the polarizer by heating.
  • the state as shown in FIG. 6B corresponds to after heating in the guitar pick test of the comparative example.
  • the sample in which the nano slits are generated was observed with a differential interference microscope.
  • the sample without nano slits was set to cross Nicole on the lower side (transmission light source side) of the sample where nano slits were generated and observed with transmitted light. .
  • FIG. 7 is an example of a microphotograph of the surface of the polarizing film, which serves as an index for confirming the penetration crack b of the piece protective polarizing film 10 or the piece protective polarizing film 11 with a transparent resin layer.
  • the sample in which the through crack was generated was observed with a differential interference microscope.
  • the optical characteristics represented by the single transmittance T and the polarization degree P are represented by the following formula: P> ⁇ (10 0.929T-42.4 ⁇ 1) ⁇ 100 (however, If the condition of T ⁇ 42.3) or P ⁇ 99.9 (however, T ⁇ 42.3) is not satisfied, the problem of the present application (occurrence of through cracks and nano slits) did not occur. .
  • Example 29 Using a long film as a single protective polarizing film, coating a forming material using a micro gravure coater, a long film as the release sheet (separator) and the following surface protective film It is the same as that of Example 1 except having used.
  • the wound body of the piece protective polarizing film with the transparent resin layer corresponds to the short side and the long side of the 32-inch non-alkali glass by slit processing in which the cutting proceeds by continuous conveyance of the piece protective polarizing film with the transparent resin layer, respectively.
  • the polarizing film was continuously bonded to both sides of 100 sheets of 0.5 mm thick 32 inch non-alkali glass so as to have a crossed Nicols relationship.
  • Example 30 In the same manner as in Example 29, except that a piece-protecting polarizing film with a transparent resin layer was produced in the same manner as in Examples 2 and 3, respectively.

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Abstract

La présente invention se rapporte à un film polarisant protégé d'un seul côté comportant un film protecteur sur une seule surface d'un polariseur : le polariseur contenant une résine d'alcool polyvinylique, et étant conçu de telle manière que ses propriétés optiques, représentées par la transmittance T d'un corps unique et le degré de polarisation P, satisfont à la condition P > -(100,929T-42,4-1) × 100 (cependant, T < 42,3) ou P ≥ 99,9 (cependant, T ≥ 42,3) ; et X ≤ 12, Y ≤ 15, 0,15 ≤ (Y/X) ≤ 3 étant satisfaites, étant donné que l'épaisseur du polariseur est X (µm) et l'épaisseur de la couche de résine transparente est Y (μm). Même lorsque le polariseur de type mince présente les propriétés optiques recommandées, ce film polarisant protégé d'un seul côté est susceptible de supprimer l'apparition d'enroulements et de défauts causés par des fissures traversantes et des nanofentes.
PCT/JP2015/077590 2014-09-30 2015-09-29 Film polarisant protégé d'un seul côté, film polarisant doté d'une couche adhésive, dispositif d'affichage d'image, et leur procédé de production en continu WO2016052549A1 (fr)

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CN201580053066.XA CN107076908B (zh) 2014-09-30 2015-09-29 单侧保护偏振膜、带粘合剂层的偏振膜、图像显示装置及其连续制造方法
SG11201706552PA SG11201706552PA (en) 2014-09-30 2015-09-29 One-side-protected polarizing film, pressure-sensitive-adhesive-layer-attached polarizing film, image display device, and method for continuously producing same
US15/515,948 US11137522B2 (en) 2014-09-30 2015-09-29 One-side-protected polarizing film, pressure-sensitive-adhesive-layer-attached polarizing film, image display device, and method for continuously producing same
KR1020177009091A KR102567394B1 (ko) 2014-09-30 2015-09-29 편보호 편광 필름, 점착제층 부착 편광 필름, 화상 표시 장치 및 그 연속 제조 방법

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WO2017122732A1 (fr) * 2016-01-15 2017-07-20 日東電工株式会社 Film polarisant protégé sur un côté à couche adhésive, dispositif d'affichage d'image, et procédé de production en continu associé
WO2018038028A1 (fr) * 2016-08-22 2018-03-01 株式会社クラレ Plaque polarisante
WO2018181715A1 (fr) * 2017-03-29 2018-10-04 日東電工株式会社 Couche adhésive autocollante, film polarisant protégé sur un côté comportant une couche adhésive autocollante, dispositif d'affichage d'image, et procédé de production continue associé
CN110192131A (zh) * 2017-01-27 2019-08-30 住友化学株式会社 偏振板和图像显示装置
JP2019172839A (ja) * 2018-03-28 2019-10-10 日東電工株式会社 粘着剤層、粘着剤層付片保護偏光フィルム、画像表示装置およびその連続製造方法
KR20190128629A (ko) * 2017-03-29 2019-11-18 닛토덴코 가부시키가이샤 점착제층, 점착제층을 구비한 편보호 편광 필름, 화상 표시 장치 및 그 연속 제조 방법
WO2020003857A1 (fr) * 2018-06-26 2020-01-02 日東電工株式会社 Film de polarisation protégé d'un seul côté avec une couche adhésive, dispositif d'affichage d'image et procédé de production continu associé
IT202000022819A1 (it) * 2020-09-28 2022-03-28 Neos S R L Composizione adesiva a polimerizzazione u.v. per stampa digitale

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WO2018038028A1 (fr) * 2016-08-22 2018-03-01 株式会社クラレ Plaque polarisante
JPWO2018038028A1 (ja) * 2016-08-22 2019-06-20 株式会社クラレ 偏光板
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WO2018181715A1 (fr) * 2017-03-29 2018-10-04 日東電工株式会社 Couche adhésive autocollante, film polarisant protégé sur un côté comportant une couche adhésive autocollante, dispositif d'affichage d'image, et procédé de production continue associé
KR20190128629A (ko) * 2017-03-29 2019-11-18 닛토덴코 가부시키가이샤 점착제층, 점착제층을 구비한 편보호 편광 필름, 화상 표시 장치 및 그 연속 제조 방법
KR102460885B1 (ko) * 2017-03-29 2022-11-01 닛토덴코 가부시키가이샤 점착제층, 점착제층을 구비한 편보호 편광 필름, 화상 표시 장치 및 그 연속 제조 방법
JP7153459B2 (ja) 2018-03-28 2022-10-14 日東電工株式会社 粘着剤層、粘着剤層付片保護偏光フィルム、画像表示装置およびその連続製造方法
JP2019172839A (ja) * 2018-03-28 2019-10-10 日東電工株式会社 粘着剤層、粘着剤層付片保護偏光フィルム、画像表示装置およびその連続製造方法
JP2020003576A (ja) * 2018-06-26 2020-01-09 日東電工株式会社 粘着剤層付片保護偏光フィルム、画像表示装置およびその連続製造方法
JP7142497B2 (ja) 2018-06-26 2022-09-27 日東電工株式会社 粘着剤層付片保護偏光フィルム、画像表示装置およびその連続製造方法
CN112119332A (zh) * 2018-06-26 2020-12-22 日东电工株式会社 带粘合剂层的单侧保护偏振膜、图像显示装置及其连续制造方法
WO2020003857A1 (fr) * 2018-06-26 2020-01-02 日東電工株式会社 Film de polarisation protégé d'un seul côté avec une couche adhésive, dispositif d'affichage d'image et procédé de production continu associé
CN112119332B (zh) * 2018-06-26 2022-11-08 日东电工株式会社 带粘合剂层的单侧保护偏振膜、图像显示装置及其连续制造方法
IT202000022819A1 (it) * 2020-09-28 2022-03-28 Neos S R L Composizione adesiva a polimerizzazione u.v. per stampa digitale
WO2022064461A1 (fr) * 2020-09-28 2022-03-31 Neos S.R.L. Composition adhésive durcissable aux uv pour impression numérique

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