WO2016052536A1 - Polarizing film protected on one side, polarizing film with pressure-sensitive adhesive layer, image display device, and continuous production process therefor - Google Patents
Polarizing film protected on one side, polarizing film with pressure-sensitive adhesive layer, image display device, and continuous production process therefor Download PDFInfo
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- WO2016052536A1 WO2016052536A1 PCT/JP2015/077576 JP2015077576W WO2016052536A1 WO 2016052536 A1 WO2016052536 A1 WO 2016052536A1 JP 2015077576 W JP2015077576 W JP 2015077576W WO 2016052536 A1 WO2016052536 A1 WO 2016052536A1
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- polarizing film
- adhesive layer
- polarizer
- film
- pressure
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- 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 transparent 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.
- a polarizing film is used in which a transparent 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.
- 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 single protective polarizing film provided with a transparent protective film only on one surface of a polarizer has insufficient durability due to the thermal shock.
- the penetration crack produced by the said thermal shock was easy to generate
- 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 1 Moreover, it has 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, has a transparent protective film on the other side of the polarizer, and adheres to the outside of the protective layer.
- a polarizing film with an adhesive layer having an adhesive layer has been proposed (Patent Document 2).
- 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.
- a protective layer made of a water-soluble film-forming composition (polyvinyl alcohol-based resin composition) is provided on at least one surface of the polarizer from the viewpoint of thinning and weight reduction.
- 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 4).
- Patent Documents 1 and 2 the thickness is reduced by using a piece protective polarizing film having a transparent protective film only on one side of the polarizer, and on the other hand, by using a piece protective polarizing film by providing a protective layer.
- the occurrence of through cracks in the absorption axis direction of the generated polarizer is suppressed.
- production of the through crack to the absorption-axis direction of a polarizer is suppressed by providing a protective layer in a polarizer.
- 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 (for example, when the thickness is 10 ⁇ m or less), the change in the contraction stress of the polarizer is small. Therefore, it was found that the thinning can suppress the occurrence of the through cracks according to the polarizer.
- the optical characteristics are controlled as in Patent Document 4 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 has also been found that the nano slit does not occur when both protective polarizing films having transparent 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 present invention is a piece protective polarizing film having a transparent protective film only on one side of a polarizer, wherein the polarizer has predetermined optical properties and has a thickness of 10 ⁇ m or less, and through cracks and nano slits. It aims at providing the piece protection polarizing film which can suppress the defect by this. 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 transparent protective film only on one side of the polarizer
- the polarizer contains a polyvinyl alcohol-based resin, has a thickness of 10 ⁇ m or less, and 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 P ⁇ 99.9 (provided that T ⁇ 42.3) is satisfied,
- the present invention relates to a single-protective polarizing film, which is a formed material formed of a polyvinyl alcohol-based resin on the other surface of the polarizer and has a transparent resin layer having a thickness of 0.2 ⁇ m or more.
- the transparent resin layer has a heat of crystal melting of 30 mj / mg or more.
- the transparent resin layer preferably has a thickness of less than 3 ⁇ m.
- the polyvinyl alcohol resin preferably has a saponification degree of 99.0% or more and an average polymerization degree of 1000 or more.
- the said piece protection polarizing film WHEREIN The said formation material can be formed by what does not contain a sclerosing
- the polyvinyl alcohol resin is preferably a polyvinyl alcohol resin.
- 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 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 transparent 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 10 ⁇ m or less, and are thinned.
- the thin polarizer having a thickness of 10 ⁇ 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, generation of a through crack 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).
- the nano resin is provided by providing a transparent resin layer having a thickness of 0.2 ⁇ m or more on the other surface of the polarizer (the surface having no transparent protective film). Generation of slits can be suppressed.
- the piece protective polarizing film of the present invention and the polarizing film with an adhesive layer using the same have a transparent resin layer having a thickness of 0.2 ⁇ m or more formed from a forming material containing a polyvinyl alcohol-based resin.
- production of the penetration crack and nano slit which arise in a polarizer can be suppressed, satisfying thickness reduction.
- 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.
- the defect due to the nano slit can be detected by spreading the nano slit in the width direction when the single protective polarizing film or the polarizing film with the pressure-sensitive adhesive layer is placed in a heating environment (for example, the presence or absence of light leakage).
- the transparent resin layer constitutes a part of the piece protective polarizing film, it is desired to maintain the polarization degree of the polarizing film even in a high-temperature and high-humidity environment or a hot water environment.
- it is a layer formed from a forming material containing a water-soluble polyvinyl alcohol resin as a main component, by controlling the heat of crystal melting of the transparent resin layer to 30 mj / mg or more, defects due to through cracks and nano slits While suppressing generation
- a polyvinyl alcohol resin having a saponification degree of 99.0% or more and an average polymerization degree of 1000 or more can be used.
- the piece protective polarizing film 11 and the polarizing film 12 with an adhesive layer of the present invention will be described with reference to FIGS.
- the single protective polarizing film 10 (in the case where the transparent resin layer 3 is not provided) has the transparent protective film 2 only on one surface of the polarizer 1.
- the polarizer 1 and the transparent protective film 2 are laminated via intervening layers such as an adhesive layer, 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 a transparent resin layer 3) of the present invention is provided on the other single surface of the polarizer 1 (the surface without the transparent protective film 2) in the single protective polarizing film 10.
- a transparent resin layer 3 formed from a forming material containing a polyvinyl alcohol-based resin is provided (directly).
- 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. 2 (A) and on the transparent protective film 2 side in FIG. 2 (B).
- 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.
- As a polarizing film with an adhesive layer 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).
- 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 in which a single protective polarizing film 10 having a transparent protective film 2 via an adhesive layer 2a only on one side of the polarizer 1 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 a photograph of a sectional view of a piece protective polarizing film 11 with a transparent resin layer in which a transparent resin layer 3 (thickness 1 ⁇ m) is formed on the piece protective polarizing film 10 in which nano slits a are generated. It is an example.
- FIG. 4 (D) is a photograph of a sectional view of a piece protective polarizing film 11 with a transparent resin layer in which a transparent resin layer 3 (thickness 1 ⁇ m) is formed on the piece protective polarizing film 10 in which nano slits a are generated. It is an example.
- FIG. 4 (D) is a photograph of a sectional view of a piece protective
- FIG. 4E is an example of a photograph of a cross-sectional view after heating the piece protective polarizing film 11 with the transparent resin layer on which the transparent resin layer 3 (thickness 1 ⁇ m) is formed.
- FIG. 4E it can be seen that there is no expansion of the repaired (a ′) nanoslit after heating.
- FIG. 4F is a cross-sectional view of a piece protective polarizing film 11 ′ with a transparent resin layer in which a transparent resin layer 3 ′ (thickness 0.1 ⁇ m) is formed on the piece protective polarizing film 10 in which nano slits a are generated.
- FIG. 4F It is an example of a photograph.
- FIG. 4F it can be seen that although the transparent resin layer 3 'is provided, the nano slit a of the polarizer 1 is expanded by heating because the thickness is thin.
- 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 10 ⁇ m or less is used.
- the thickness of the polarizer is preferably 8 ⁇ m or less, more 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, 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.
- These thin polarizers can be obtained by a production method including a step of stretching and dyeing a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin base material in a laminated state.
- PVA-based resin polyvinyl alcohol-based resin
- a stretching resin base material in a laminated state.
- Transparent protective film As the material constituting the transparent protective film, 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 that forms the transparent protective film include polymer blends.
- the transparent protective film may contain one or more arbitrary appropriate additives.
- the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a release agent, a coloring inhibitor, a flame retardant, a nucleating agent, an antistatic agent, a pigment, and a coloring agent.
- the content of the thermoplastic resin in the transparent 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 transparent 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 transparent 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 transparent 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. In particular, it is preferably 1 to 300 ⁇ m, more preferably 5 to 200 ⁇ m, and further preferably 5 to 150 ⁇ m, particularly 20 to 100 ⁇ m.
- Functional surfaces such as a hard coat layer, an antireflection layer, an anti-sticking layer, a diffusion layer or an antiglare layer can be provided on the surface of the transparent protective film to which the polarizer is not adhered (particularly the embodiment shown in FIG. 1).
- the functional layers such as the hard coat layer, antireflection layer, antisticking layer, diffusion layer and antiglare layer can be provided on the transparent protective film itself, and separately provided separately from the transparent protective film. You can also
- the transparent 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.
- an intervening layer such as an adhesive layer, an adhesive layer, and an undercoat layer (primer 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.
- 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.
- an active energy ray curable adhesive for example, a photo radical curable adhesive can be used.
- the photo radical curable active energy ray curable adhesive is used as an ultraviolet curable adhesive, the adhesive contains a radical polymerizable compound and a photo polymerization initiator.
- 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 adhesive is preferably applied so that the finally formed adhesive layer has a thickness of 30 to 300 nm.
- the thickness of the adhesive layer is more preferably 60 to 250 nm.
- the thickness of the adhesive layer is preferably 0.1 to 200 ⁇ m. More preferably, it is 0.5 to 50 ⁇ m, and still more preferably 0.5 to 10 ⁇ m.
- an easily bonding layer can be provided between a transparent 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 transparent protective film, and the easy-adhesion layer side of the transparent protective film and the polarizer are laminated with an adhesive layer.
- the easy-adhesion layer is formed by coating and drying the material for forming the easy-adhesion layer on the transparent 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.
- the transparent resin layer is formed from a forming material containing a polyvinyl alcohol-based resin.
- 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”.
- the transparent resin layer can be formed by applying the forming material to, for example, a polarizer.
- the transparent resin layer is provided on the other surface of the polarizer (the surface not having the transparent protective film) in the single-protective polarizing film having the transparent protective film only on one surface of the polarizer.
- a mechanical impact may be applied so that the polarizer is bent convexly toward the image display panel during handling. At this time, stress concentrates on the tip of the convex side of the polarizer, and the polarizer breaks to form a nano slit.
- the transparent resin layer is formed of a forming material made of polyvinyl alcohol resin, for example, the transparent resin layer is formed on the convex side of the polarizer. Since the said transparent resin layer is a layer which consists of polyvinyl alcohol with low boric acid content, it is hard to generate
- the transparent resin layer when a polyvinyl alcohol-based resin is used as the transparent resin layer, boric acid contained in the polarizer is partially oozed out in the transparent resin layer formation process, so that the boric acid content in the polarizer is reduced. Therefore, the nanoslit is hardly generated in the polarizer itself. If the thickness of the transparent resin layer is 0.2 ⁇ m or more, as described above, the generation of nano slits due to handling after being attached to an image display panel or the like can be effectively suppressed.
- the thickness of the transparent resin layer is preferably 0.5 ⁇ m or more, and more preferably 0.7 ⁇ m or more. On the other hand, if the transparent resin layer becomes too thick, the optical reliability and water resistance are lowered.
- the thickness of the transparent resin layer is preferably less than 3 ⁇ m, and more preferably 2 ⁇ m or less.
- the said transparent resin layer can suppress generation
- the nano slit generated in the polarizer is caused by mechanical impact, and the nano slit tends to spread in the width direction under a thermal environment.
- the transparent resin layer formed from the forming material containing the polyvinyl alcohol resin is under a thermal environment. The mechanical holding ability of the transparent resin layer can be maintained and the spread of the nano slits in the width direction can be suppressed.
- the transparent resin layer is preferably controlled to have a heat of crystal melting of 30 mj / mg or more.
- the transparent resin layer is formed of a forming material mainly composed of a water-soluble polyvinyl alcohol-based resin. By controlling the heat of crystal melting of the transparent resin layer to 30 mj / mg or more, the moisture and heat resistance of the transparent resin layer Water resistance can be satisfied.
- the crystal melting heat quantity of the transparent resin layer is a value measured based on the description of the examples.
- the crystal melting heat quantity of the transparent resin layer is preferably 40 mj / mg or more, more preferably 50 mj / mg or more.
- the amount of heat of crystal melting of the transparent resin layer is the type of polyvinyl alcohol resin, the degree of saponification of the polyvinyl alcohol resin, the degree of polymerization, and the curable component (the ratio of use of a crosslinking agent, etc.) that can be used as a forming material, Etc.).
- 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 saponification degree of the polyvinyl alcohol resin can be, for example, 88% or more, but preferably 95% or more. From the viewpoint of satisfying moisture heat resistance and water resistance by controlling the heat of crystal fusion of the transparent resin layer to 30 mj / mg or more, the saponification degree is more preferably 99% or more, and further 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 transparent resin layer of the present invention is formed from a forming material containing the polyvinyl alcohol-based resin as a main component, and the forming material 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 compounds having a methylol group are preferred as the amino-formaldehyde resin, and methylol melamine, which is a compound having a methylol group, is particularly preferred.
- 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, alcohols, 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 (for example, an aqueous solution) 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 not having the transparent protective film).
- the forming material is applied so that the thickness after drying is 0.2 ⁇ m or more.
- 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.
- 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.
- the adhesive or the transparent protective film in the embodiment of FIG. 2B or the polarizer (or the transparent protective film in the embodiment of FIG. 2B) in the embodiment of FIG. It is produced by, for example, a method of forming a pressure-sensitive adhesive layer on a polarizer by applying and removing a polymerization solvent by drying.
- 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 not particularly limited, and is, for example, about 1 to 100 ⁇ m.
- the thickness is preferably 2 to 50 ⁇ m, more preferably 2 to 40 ⁇ m, and still more preferably 5 to 35 ⁇ m.
- 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, it is possible to continuously produce an image display device in which not only defects due to the generation of nanoslits before the formation of the transparent resin layer but also defects due to the generation of nanoslits after the formation of the transparent resin layer are effectively suppressed.
- FIG. 9 is a schematic view 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.
- ⁇ Strip protection polarizing film A> (Preparation of polarizer A0)
- IPA copolymerized PET 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
- 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 A8 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 A8.
- Transparent protective film A (meth) acrylic resin film having a lactone ring structure having a thickness of 40 ⁇ m was subjected to corona treatment on the easy adhesion treated surface.
- An ultraviolet curable adhesive was prepared by mixing 40 parts by weight of N-hydroxyethylacrylamide (HEAA), 60 parts by weight of acryloylmorpholine (ACMO), and 3 parts by weight of a photoinitiator “IRGACURE 819” (manufactured by BASF).
- HEAA N-hydroxyethylacrylamide
- ACMO acryloylmorpholine
- UVGACURE 819 a photoinitiator
- ⁇ Single protective polarizing film C> Preparation of polarizer C
- IPA copolymerized PET film 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
- 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.
- a protective film (thickness: 40 ⁇ m, manufactured by Fuji Film, trade name “Z-TAC ZRD40SL”) was bonded to the polarizer side of the laminate through a vinyl alcohol adhesive. Subsequently, the amorphous PET base material was peeled off to produce a piece protective polarizing film C using a thin polarizer.
- the optical properties of the obtained piece-protecting polarizing film C were a transmittance of 38.4% and a degree of polarization of 99.99%.
- ⁇ Preparation of single protective polarizing film D> (Preparation of polarizer D (12 ⁇ m thick polarizer))
- polarizer D (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.
- ⁇ Forming material for transparent resin layer> (Polyvinyl alcohol-based forming material A) A polyvinyl alcohol resin having a polymerization degree of 2500 and a saponification degree of 99.0 mol% (trade name: JC-25, manufactured by Nihon Acetate / Poval) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
- Polyvinyl alcohol-based forming material B A polyvinyl alcohol resin having a degree of polymerization of 2500 and a degree of saponification of 99.7 mol% (trade name: JC-25H, manufactured by Nippon Vinegar Poval Co., Ltd.) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
- Polyvinyl alcohol-based forming material C A polyvinyl alcohol resin having a polymerization degree of 1700 and a saponification degree of 99.0 mol% (trade name: JC-17, manufactured by Nihon Acetate / Poval) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
- Polyvinyl alcohol-based forming material D A polyvinyl alcohol resin having a polymerization degree of 1000 and a saponification degree of 99.0 mol% (trade name: JC-10, manufactured by Nippon Vinegar Pover Co., Ltd.) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
- Polyvinyl alcohol-based forming material E A polyvinyl alcohol resin having a degree of polymerization of 500 and a saponification degree of 99.0 mol% (trade name: JC-05, manufactured by Nihon Acetate / Poval) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
- Polyvinyl alcohol-based forming material F A polyvinyl alcohol resin having a degree of polymerization of 2500 and a degree of saponification of 98.0 mol% (trade name: JF-2500, manufactured by Nippon Acetate / Poval) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
- Polyvinyl alcohol-based forming material G A polyvinyl alcohol resin having a polymerization degree of 2500 and a saponification degree of 96.0 mol% (trade name: JM-2500, manufactured by Nippon Vinegar Poval Co., Ltd.) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
- Polyvinyl alcohol-based forming material I 100 parts of acetoacetyl group-modified PVA (polymerization degree 1200, acetoacetyl modification degree 4.6%, saponification degree 99.0 mol%, manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd., trade name “Gosefimer Z200”)) and methylol 5 parts of melamine (manufactured by DIC, trade name “Watersol: S-695”) was dissolved in pure water to prepare an aqueous solution having a solid content of 4% by weight.
- Polyvinyl alcohol-based forming material J 100 parts of acetoacetyl group-modified PVA (polymerization degree 1200, acetoacetyl modification degree 4.6%, saponification degree 99.0 mol%, manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd., trade name “Gosefimer Z200”)) and methylol 20 parts of melamine (manufactured by DIC, trade name “Watersol: S-695”) was dissolved in pure water to prepare an aqueous solution having a solid content of 4% by weight.
- Polyvinyl alcohol forming material K A carbonyl group-modified polyvinyl alcohol resin (trade name “DC-17”, manufactured by Nippon Vinegar Poval Co., Ltd.) was dissolved in pure water to prepare an aqueous solution having a solid content of 4% by weight.
- Polyvinyl alcohol-based forming material L 100 parts of carbonyl group-modified polyvinyl alcohol resin (product name “DC-17”, manufactured by Nippon Vineyard Pover Co., Ltd.) and 10 parts of dihydrazine (adipic acid dihydrazide) are dissolved in pure water, and the solid content concentration is 4% by weight. An aqueous solution of was prepared.
- Polyvinyl alcohol-based forming material M A polyvinyl alcohol resin having a polymerization degree of 2000 and a saponification degree of 99.4 mol% (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “NH-20”) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
- Polyvinyl alcohol-based forming material N A polyvinyl alcohol resin having a polymerization degree of 1700 and a saponification degree of 97.0 mol% (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “AH-17”) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
- Polyvinyl alcohol-based forming material O A polyvinyl alcohol resin having a polymerization degree of 1700 and a saponification degree of 99.0 mol% (trade name “PVA117” manufactured by Kuraray Co., Ltd.) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight.
- Polyvinyl alcohol-based forming material P A polyvinyl alcohol resin having a degree of polymerization of 4000 and a degree of saponification of 99.0 mol% (trade name: JC-40, manufactured by Nippon Acetate / Poval) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
- Polyvinyl alcohol-based forming material Q A polyvinyl alcohol resin having a polymerization degree of 1700 and a saponification degree of 96.0 mol% (trade name: JM-17, manufactured by Nihon Acetate / Poval) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
- Polyvinyl alcohol-based forming material R A polyvinyl alcohol resin having a polymerization degree of 1400 and a saponification degree of 88.0 mol% (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “GM-14”) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
- Polyvinyl alcohol-based forming material S A polyvinyl alcohol resin having a polymerization degree of 1300 and a saponification degree of 93.0 mol% (trade name “PVA613” manufactured by Kuraray Co., Ltd.) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight.
- Polyvinyl alcohol forming material T A polyvinyl alcohol resin having a polymerization degree of 1700 and a saponification degree of 94.5 mol% (trade name “PVA617” manufactured by Kuraray Co., Ltd.) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight.
- Polyvinyl alcohol-based forming material U A polyvinyl alcohol resin having a degree of polymerization of 3300 and a degree of saponification of 94.0 mol% (manufactured by Nihon Acetate / Poval, trade name: JM-33) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
- Polyvinyl alcohol-based forming material V A polyvinyl alcohol resin having a polymerization degree of 500 and a saponification degree of 94.5 mol% (trade name: JT-05, manufactured by Nihon Acetate / Poval) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
- cross-linking agent 100 parts by weight of the solid content of the acrylic polymer solution is a cross-linking agent mainly composed of a compound having an isocyanate group of 0.5 part (trade name “Coronate L” manufactured by Nippon Polyurethane Co., Ltd.). And 0.075 parts of ⁇ -glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KMB-403”) as a silane coupling agent in this order, was prepared.
- the pressure-sensitive adhesive solution was applied to the surface of a release sheet (separator) made of a polyethylene terephthalate film (thickness 38 ⁇ m) subjected to a release treatment so that the thickness after drying was 25 ⁇ m and dried to form a pressure-sensitive adhesive layer. Formed.
- Example 1 Manufacturing a single protective polarizing film with a transparent resin layer>
- the thickness after drying the above-mentioned forming material A adjusted to 25 ° C. with a wire bar coater on the surface of the polarizer of the piece protective polarizing film A (polarizer surface not provided with a transparent protective film) is 1 ⁇ m. After coating, it was dried with hot air at 60 ° C. for 1 minute to produce a piece protective polarizing film with a transparent resin layer.
- Example 2 Comparative Examples 1 to 7
- 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 measurement sample may be a powder of the raw material itself, or may be a PVA film obtained by applying an aqueous PVA solution (solid content 4%) to a PET film so that the dry film thickness is several ⁇ m and drying.
- the measurement sample was aged for 24 hours in an environment of 23 ° C. and 50% RH, and 3 mg of the obtained sample was put into a DSC sample pan to measure DSC. The measurement conditions are shown below.
- ⁇ Pot life of transparent resin layer forming material The viscosity (cps) of the forming material (aqueous solution) was measured at 23 ° C. liquid temperature and air temperature using a rheometer RS1 (manufactured by Haake) and model 222-1267 as a coaxial cylinder.
- the viscosity X immediately after preparing the forming material (aqueous solution) and the viscosity Y after 6 hours from the preparation were measured. On the basis of the viscosity X, the case where the viscosity Y was 2 times or less was evaluated as “ ⁇ ”, and the case where it exceeded 2 times was evaluated as “x”.
- 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.
- B 1 to 100 pieces.
- C 101 or more.
- the obtained piece protective polarizing film 10 was cut into a size of 50 mm ⁇ 150 mm (the direction of the absorption axis was 50 mm).
- the sample 10 was used by bonding the test surface protective film 6 to the transparent protective film 2 side.
- two glass support bases 21 having a width of 25 mm and a height of 5 mm are arranged on a glass plate 20 with an inner space of 15 mm. It was installed in parallel so that The longitudinal direction of the two glass supports and the direction perpendicular to the absorption axis of the polarizer 1 in the cut sample 10 are parallel to each other, and both sides of the sample 11 are evenly placed on the two glass supports. Sample 10 was placed so as to hang. In the sample 10, the surface protective film 6 was disposed on the upper side.
- a load of 100 g is applied to the central portion of the sample 10 (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 surface of the polarizer 1 was scratched by repeating a load load of 10 reciprocations at a distance of 100 mm in the orthogonal direction. The load was applied at one place. It was visually confirmed whether or not nano slits were generated.
- the thickness of the polarizer of Comparative Examples 2 and 4 exceeded 10 ⁇ m, the shrinkage stress inside the polarizer was large, so the film was broken when nano slits were generated in the rock and roll test. Therefore, it could not be evaluated.
- FIG. 7 shows the following index for confirming the crack of light leakage (nano slit a) in the guitar pick test and the rock and roll 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 the photograph of the microscope of a film surface. In FIG. 7A, no light leakage crack due to the nano slit a is confirmed. The state as shown in FIG. 7A is before heating of the guitar pick test of the comparative example, before heating of the rock and roll test of the example, and after heating of the rock and roll test of the example (because of the expansion suppression effect, the nano slit Does not fall out). On the other hand, FIG.
- FIG. 7B 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. 7B corresponds to after heating of the guitar pick test of the comparative example and after heating of the rock and roll test of the comparative example.
- the sample in which the nano slit was 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. .
- ⁇ Confirmation of penetration crack heat shock test> The obtained polarizing film with a pressure-sensitive adhesive layer was cut into 50 mm ⁇ 150 mm (absorption axis direction is 50 mm) and 150 mm ⁇ 50 mm (absorption axis direction is 150 mm), and crossed Nicols on both sides of 0.5 mm-thick alkali-free glass. A sample was made by laminating in the direction. The sample was subjected to a heat shock of ⁇ 40 to 85 ° C. for 30 minutes ⁇ 100 times in each environment, and then taken out to visually check whether a through-crack (number) was generated in the polarizing film with the adhesive layer. Confirmed. This test was performed five times. Evaluation was performed according to the following. ⁇ : No through crack. X: There is a through crack.
- FIG. 8 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 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.
- the optical characteristics represented by the single transmittance T and the polarization degree P are expressed 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 34 Using a long film as a single protective polarizing film, coating a polyvinyl alcohol-based forming material using a micro gravure coater, long film as the release sheet (separator) and the following surface protective film Example 1 is the same as Example 1 except that the above are 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 thing of the width to do was prepared as a set.
- the piece protection with a transparent resin layer continuously supplied from a set of wound pieces of a piece protection polarizing film with a transparent resin layer 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 35-37 Each is the same as Example 34 except that the piece-protecting polarizing film with a transparent resin layer was produced in the same manner as in Examples 2, 3, and 4, respectively.
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Abstract
Description
前記偏光子は、ポリビニルアルコール系樹脂を含有し、厚みが10μm以下であり、かつ、単体透過率T及び偏光度Pによって表される光学特性が、下記式
P>-(100.929T-42.4-1)×100(ただし、T<42.3)、又は、
P≧99.9(ただし、T≧42.3)の条件を満足するように構成されたものであり、
前記偏光子の他の片面に、ポリビニルアルコール系樹脂を含有する形成材の形成物であって、厚み0.2μm以上の透明樹脂層を有することを特徴とする片保護偏光フィルム、に関する。 That is, the present invention is a piece protective polarizing film having a transparent protective film only on one side of the polarizer,
The polarizer contains a polyvinyl alcohol-based resin, has a thickness of 10 μm or less, and 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
P ≧ 99.9 (provided that T ≧ 42.3) is satisfied,
The present invention relates to a single-protective polarizing film, which is a formed material formed of a polyvinyl alcohol-based resin on the other surface of the polarizer and has a transparent resin layer having a thickness of 0.2 μm or more.
本発明では、厚み10μm以下の偏光子を用いる。偏光子の厚みは薄型化および貫通クラックの発生を抑える観点から8μm以下であるのが好ましく、さらには7μm以下、さらには6μm以下であるのが好ましい。一方、偏光子の厚みは2μm以上、さらには3μm以上であるのが好ましい。このような薄型の偏光子は、厚みムラが少なく、視認性が優れており、また寸法変化が少ないため熱衝撃に対する耐久性に優れる。 <Polarizer>
In the present invention, a polarizer having a thickness of 10 μm or less is used. The thickness of the polarizer is preferably 8 μm or less, more preferably 7 μm or less, and further preferably 6 μm or less from the viewpoint of reducing the thickness and preventing the occurrence of through cracks. On the other hand, the thickness of the polarizer is preferably 2 μm or more, and more preferably 3 μm or more. Such a thin polarizer has less thickness unevenness, excellent visibility, and less dimensional change, and therefore excellent durability against thermal shock.
特許第4751486号明細書、
特許第4751481号明細書、
特許第4815544号明細書、
特許第5048120号明細書、
国際公開第2014/077599号パンフレット、
国際公開第2014/077636号パンフレット、
等に記載されている薄型偏光子またはこれらに記載の製造方法から得られる薄型偏光子を挙げることができる。 As a thin polarizer, typically,
Patent No. 4751486,
Japanese Patent No. 4751481,
Patent No. 4815544,
Patent No. 5048120,
International Publication No. 2014/077599 pamphlet,
International Publication No. 2014/077636 Pamphlet,
And the thin polarizers obtained from the production methods described therein.
P>-(100.929T-42.4-1)×100(ただし、T<42.3)又は、
P≧99.9(ただし、T≧42.3)の条件を満足するように構成されている。前記条件を満足するように構成された偏光子は、一義的には、大型表示素子を用いた液晶テレビ用のディスプレイとして求められる性能を有する。具体的にはコントラスト比1000:1以上かつ最大輝度500cd/m2以上である。他の用途としては、例えば有機EL表示装置の視認側に貼り合される。 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.
前記透明保護フィルムを構成する材料としては、透明性、機械的強度、熱安定性、水分遮断性、等方性などに優れるものが好ましい。例えば、ポリエチレンテレフタレートやポリエチレンナフタレートなどのポリエステル系ポリマー、ジアセチルセルロースやトリアセチルセルロースなどのセルロース系ポリマー、ポリメチルメタクリレートなどのアクリル系ポリマー、ポリスチレンやアクリロニトリル・スチレン共重合体(AS樹脂)などのスチレン系ポリマー、ポリカーボネート系ポリマー等が挙げられる。また、ポリエチレン、ポリプロピレン、シクロ系ないしはノルボルネン構造を有するポリオレフィン、エチレン・プロピレン共重合体の如きポリオレフィン系ポリマー、塩化ビニル系ポリマー、ナイロンや芳香族ポリアミドなどのアミド系ポリマー、イミド系ポリマー、スルホン系ポリマー、ポリエーテルスルホン系ポリマー、ポリエーテルエーテルケトン系ポリマー、ポリフェニレンスルフィド系ポリマー、ビニルアルコール系ポリマー、塩化ビニリデン系ポリマー、ビニルブチラール系ポリマー、アリレート系ポリマー、ポリオキシメチレン系ポリマー、エポキシ系ポリマー、または上記ポリマーのブレンド物なども上記透明保護フィルムを形成するポリマーの例として挙げられる。 <Transparent protective film>
As the material constituting the transparent protective film, a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is preferable. For example, 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) And polymers based on polycarbonate and polycarbonate. In addition, 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 Examples of the polymer that forms the transparent protective film include polymer blends.
前記透明保護フィルムと偏光子は接着剤層、粘着剤層、下塗り層(プライマー層)などの介在層を介して積層される。この際、介在層により両者を空気間隙なく積層することが望ましい。 <Intervening layer>
The transparent 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.
透明樹脂層は、ポリビニルアルコール系樹脂を含有する形成材から形成される。透明樹脂層を形成するポリビニルアルコール系樹脂は、「ポリビニルアルコール系樹脂」である限り、偏光子が含有するポリビニルアルコール系樹脂と同一でも異なってもいてもよい。 <Transparent resin layer>
The transparent resin layer is formed from a forming material containing a polyvinyl alcohol-based resin. 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”.
粘着剤層の形成には、適宜な粘着剤を用いることができ、その種類について特に制限はない。粘着剤としては、ゴム系粘着剤、アクリル系粘着剤、シリコーン系粘着剤、ウレタン系粘着剤、ビニルアルキルエーテル系粘着剤、ポリビニルアルコール系粘着剤、ポリビニルピロリドン系粘着剤、ポリアクリルアミド系粘着剤、セルロース系粘着剤などがあげられる。 <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.
片保護偏光フィルム、粘着剤層付偏光フィルムには、表面保護フィルムを設けることができる。表面保護フィルムは、通常、基材フィルムおよび粘着剤層を有し、当該粘着剤層を介して偏光子を保護する。 <Surface protection film>
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.
本発明の片保護偏光フィルム、粘着剤層付偏光フィルムは、実用に際して他の光学層と積層した光学フィルムとして用いることができる。その光学層については特に限定はないが、例えば反射板や半透過板、位相差板(1/2や1/4などの波長板を含む)、視角補償フィルムなどの液晶表示装置などの形成に用いられることのある光学層を1層または2層以上用いることができる。特に、本発明の片保護偏光フィルムに更に反射板または半透過反射板が積層されてなる反射型偏光フィルムまたは半透過型偏光フィルム、偏光フィルムに更に位相差板が積層されてなる楕円偏光フィルムまたは円偏光フィルム、偏光フィルムに更に視角補償フィルムが積層されてなる広視野角偏光フィルム、あるいは偏光フィルムに更に輝度向上フィルムが積層されてなる偏光フィルムが好ましい。 <Other optical layers>
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. For example, for forming 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. In particular, 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.
上記の画像表示装置は、本発明の粘着剤層付偏光フィルムの巻回体(ロール)から繰り出され、前記セパレータにより搬送された前記粘着剤層付偏光フィルムを、前記粘着剤層を介して画像表示パネルの表面に連続的に貼り合せる工程を含む連続製造方法(ロール・トゥ・パネル方式)にて製造されることが好ましい。本発明の粘着剤層付偏光フィルムは非常に薄いフィルムであるため、シート状に切断(枚葉切断)したうえで画像表示パネルに1枚ずつ貼り合せる方式(「シート・トゥ・パネル方式」ともいう。)によると、シートの搬送や表示パネルへの貼合せ時のハンドリングが難しく、それらの過程で粘着剤層付偏光フィルム(シート)が大きな機械的衝撃(例えば、吸着による撓み等)を受けるリスクが高くなる。このようなリスクを低減するには、例えば基材フィルムの厚みが50μm以上の厚めの表面保護フィルムを用いる等の対策が別途必要となる。一方、ロール・トゥ・パネル方式によれば、粘着剤層付偏光フィルムがシート状に切断(枚葉切断)されることなく、連続状のセパレータによりロールから画像表示パネルまで安定的に搬送され、そのまま画像表示パネルに貼り合わされるため、厚めの表面保護フィルムを用いることなく、上記リスクを大幅に低減することができる。その結果、透明樹脂層形成前のナノスリットの発生による欠陥だけでなく、透明樹脂層形成後におけるナノスリットの発生による欠陥も効果的に抑制された画像表示装置を高速連続生産することができる。 <Continuous Manufacturing Method for Image Display Device>
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. Since 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 μm or more. On the other hand, according to the roll-to-panel method, 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, it is possible to continuously produce an image display device in which not only defects due to the generation of nanoslits before the formation of the transparent resin layer but also defects due to the generation of nanoslits after the formation of the transparent resin layer are effectively suppressed.
液晶表示装置の連続製造システム100は、図9に示すように、液晶表示パネルPを搬送する一連の搬送部X、第1偏光フィルム供給部101a、第1貼合部201a、第2偏光フィルム供給部101b、及び第2貼合部201bを含む。
なお、第1粘着剤層付偏光フィルムの巻回体(第1ロール)20a及び第2粘着剤層付偏光フィルムの巻回体(第2ロール)20bとしては、長手方向に吸収軸を有し、かつ図2(A)に記載の態様のものを用いる。 FIG. 9 is a schematic view showing an example of a continuous manufacturing system of a liquid crystal display device adopting a roll-to-panel method.
As shown in FIG. 9, the
In addition, 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.
搬送部Xは、液晶表示パネルPを搬送する。搬送部Xは、複数の搬送ローラおよび吸着プレート等を有して構成される。搬送部Xは、第1貼合部201aと第2貼合部201bとの間に、液晶表示パネルPの搬送方向に対して液晶表示パネルPの長辺と短辺との配置関係を入れ替える配置入替部(例えば、液晶表示パネルPを90°水平回転させる)300を含む。これにより、液晶表示パネルPに対して第1粘着剤層付偏光フィルム21a及び第2粘着剤層付偏光フィルム21bをクロスニコルの関係で貼り合せることができる。 (Transport section)
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
第1偏光フィルム供給部101aは、第1ロール20aから繰り出され、セパレータ5aにより搬送された第1粘着剤層付偏光フィルム(表面保護フィルム付)21aを第1貼合部201aに連続的に供給する。第1偏光フィルム供給部101aは、第1繰出部151a、第1切断部152a、第1剥離部153a、第1巻取部154a、および複数の搬送ローラ部、ダンサーロール等のアキュムレート部等を有する。 (First polarizing film supply unit)
The first polarizing
第1貼合部201aは、搬送部Xによって搬送された液晶表示パネルPに、第1剥離部153aによって剥離された第1粘着剤層付偏光フィルム21aを、第1粘着剤層付偏光フィルム21aの粘着剤層を介して連続的に貼り合わせる(第1貼合工程)。第1貼合部81は、一対の貼合ローラを有して構成され、貼合ローラの少なくとも一方が駆動ローラで構成される。 (1st bonding part)
The
第2偏光フィルム供給部101bは、第2ロール20bから繰り出され、セパレータ5bにより搬送された第2粘着剤層付偏光フィルム(表面保護フィルム付)21bを第2貼合部201bに連続的に供給する。第2偏光フィルム供給部101bは、第2繰出部151b、第2切断部152b、第2剥離部153b、第2巻取部154b、および複数の搬送ローラ部、ダンサーロール等のアキュムレート部等を有する。なお、第2繰出部151b、第2切断部152b、第2剥離部153b、第2巻取部154bは、それぞれ第1繰出部151a、第1切断部152a、第1剥離部153a、第1巻取部154aと同様の構成および機能を有する。 (Second polarizing film supply unit)
The 2nd polarizing
第2貼合部201bは、搬送部Xによって搬送された液晶表示パネルPに、第2剥離部153bによって剥離された第2粘着剤層付偏光フィルム21bを、第2粘着剤層付偏光フィルム21bの粘着剤層を介して連続的に貼り合わせる(第2貼合工程)。第2貼合部201bは、一対の貼合ローラを有して構成され、貼合ローラの少なくとも一方が駆動ローラで構成される。 (2nd bonding part)
The
(偏光子A0の作製)
吸水率0.75%、Tg75℃の非晶質のイソフタル酸共重合ポリエチレンテレフタレート(IPA共重合PET)フィルム(厚み:100μm)基材の片面に、コロナ処理を施し、このコロナ処理面に、ポリビニルアルコール(重合度4200、ケン化度99.2モル%)およびアセトアセチル変性PVA(重合度1200、アセトアセチル変性度4.6%、ケン化度99.0モル%以上、日本合成化学工業社製、商品名「ゴーセファイマーZ200」)を9:1の比で含む水溶液を25℃で塗布および乾燥して、厚み11μmのPVA系樹脂層を形成し、積層体を作製した。
得られた積層体を、120℃のオーブン内で周速の異なるロール間で縦方向(長手方向)に2.0倍に自由端一軸延伸した(空中補助延伸処理)。
次いで、積層体を、液温30℃の不溶化浴(水100重量部に対して、ホウ酸を4重量部配合して得られたホウ酸水溶液)に30秒間浸漬させた(不溶化処理)。
次いで、液温30℃の染色浴に、偏光板が所定の透過率となるようにヨウ素濃度、浸漬時間を調整しながら浸漬させた。本実施例では、水100重量部に対して、ヨウ素を0.2重量部配合し、ヨウ化カリウムを1.0重量部配合して得られたヨウ素水溶液に60秒間浸漬させた(染色処理)。
次いで、液温30℃の架橋浴(水100重量部に対して、ヨウ化カリウムを3重量部配合し、ホウ酸を3重量部配合して得られたホウ酸水溶液)に30秒間浸漬させた(架橋処理)。
その後、積層体を、液温70℃のホウ酸水溶液(水100重量部に対して、ホウ酸を4重量部配合し、ヨウ化カリウムを5重量部配合して得られた水溶液)に浸漬させながら、周速の異なるロール間で縦方向(長手方向)に総延伸倍率が5.5倍となるように一軸延伸を行った(水中延伸処理)。
その後、積層体を液温30℃の洗浄浴(水100重量部に対して、ヨウ化カリウムを4重量部配合して得られた水溶液)に浸漬させた(洗浄処理)。
以上により、厚み5μmの偏光子を含む光学フィルム積層体を得た。 <Strip protection polarizing film A>
(Preparation of polarizer A0)
One side of an amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA copolymerized PET) film (thickness: 100 μm) 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. An 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 μm, 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).
Next, 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).
Subsequently, it was immersed in a dyeing bath having a liquid temperature of 30 ° C. while adjusting the iodine concentration and the immersion time so that the polarizing plate had a predetermined transmittance. In this example, 0.2 parts by weight of iodine was blended with 100 parts by weight of water, and immersed in an aqueous iodine solution obtained by blending 1.0 part by weight of potassium iodide (dyeing treatment). .
Subsequently, it was immersed for 30 seconds in a crosslinking bath having a liquid temperature of 30 ° C. (a 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. However, 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).
Thereafter, 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).
As a result, an optical film laminate including a polarizer having a thickness of 5 μm was obtained.
上記の偏光子A0の作製において、製造条件を表1に示すように変えたこと以外は偏光子A0の作製と同様にして、偏光子A1~A8を作製した。偏光子A1~A8の厚み、光学特性(単体透過率、偏光度)、ホウ酸濃度を表1に示す。 (Production of polarizers A0 to A8)
Polarizers A1 to A8 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 A8.
透明保護フィルム:厚み40μmのラクトン環構造を有する(メタ)アクリル樹脂フィルムの易接着処理面にコロナ処理を施して用いた。 (Preparation of transparent protective film)
Transparent protective film: A (meth) acrylic resin film having a lactone ring structure having a thickness of 40 μm was subjected to corona treatment on the easy adhesion treated surface.
N-ヒドロキシエチルアクリルアミド(HEAA)40重量部とアクリロイルモルホリン(ACMO)60重量部と光開始剤「IRGACURE 819」(BASF社製)3重量部を混合し、紫外線硬化型接着剤を調製した。 (Preparation of adhesive to be applied to transparent protective film)
An ultraviolet curable adhesive was prepared by mixing 40 parts by weight of N-hydroxyethylacrylamide (HEAA), 60 parts by weight of acryloylmorpholine (ACMO), and 3 parts by weight of a photoinitiator “IRGACURE 819” (manufactured by BASF).
上記光学フィルム積層体の偏光子A0~A8の表面に、上記紫外線硬化型接着剤を硬化後の接着剤層の厚みが0.5μmとなるように塗布しながら、上記透明保護フィルムを貼合せたのち、活性エネルギー線として、紫外線を照射し、接着剤を硬化させた。紫外線照射は、ガリウム封入メタルハライドランプ、照射装置:Fusion UV Systems,Inc社製のLight HAMMER10、バルブ:Vバルブ、ピーク照度:1600mW/cm2、積算照射量1000/mJ/cm2(波長380~440nm)を使用し、紫外線の照度は、Solatell社製のSola-Checkシステムを使用して測定した。次いで、非晶性PET基材を剥離し、薄型偏光子を用いた片保護偏光フィルムA0~A8を作製した。得られた片保護偏光フィルムA0~A8の光学特性(単体透過率、偏光度)を表2に示す。 (Preparation of single protective polarizing film A)
The transparent protective film was bonded to the surfaces of the polarizers A0 to A8 of the optical film laminate while applying the ultraviolet curable adhesive so that the thickness of the adhesive layer after curing was 0.5 μm. After that, ultraviolet rays were applied as active energy rays to cure the adhesive. Ultraviolet irradiation is performed using a gallium-encapsulated metal halide lamp, an irradiation device: Fusion UV Systems, Inc.
(偏光子B(厚さ23μmの偏光子)の作製)
平均重合度2400、ケン化度99.9モル%の厚み75μmのポリビニルアルコールフィルムを、30℃の温水中に60秒間浸漬し膨潤させた。次いで、ヨウ素/ヨウ化カリウム(重量比=0.5/8)の濃度0.3%の水溶液に浸漬し、3.5倍まで延伸させながらフィルムを染色した。その後、65℃のホウ酸エステル水溶液中で、トータルの延伸倍率が6倍となるように延伸を行った。延伸後に、40℃のオーブンにて3分間乾燥を行い、PVA系偏光子(厚み23μm)を得た。 <Strip protection polarizing film B>
(Preparation of polarizer B (23 μm 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 75 μm was immersed in warm water at 30 ° C. for 60 seconds to swell. Next, the film was dyed while being immersed in an aqueous solution of 0.3% concentration of iodine / potassium iodide (weight ratio = 0.5 / 8) and stretched to 3.5 times. Then, it extended | stretched so that the total draw ratio might be 6 times in 65 degreeC borate ester aqueous solution. After extending | stretching, it dried for 3 minutes in 40 degreeC oven, and obtained the PVA-type polarizer (23 micrometers in thickness).
上記PVA系偏光子の片面に、片保護偏光フィルムAと同様にして、上記の紫外線硬化型接着剤を介して、上記透明保護フィルムを貼り合わせた。得られた片保護偏光フィルムBの光学特性は、透過率42.8%、偏光度99.99%であった。 (Preparation of single protective polarizing film B)
The transparent protective film was bonded to one side of the PVA polarizer in the same manner as the single protective polarizing film A via the ultraviolet curable adhesive. The optical properties of the obtained piece-protecting polarizing film B were a transmittance of 42.8% and a degree of polarization of 99.99%.
(偏光子Cの作製)
吸水率0.75%、Tg75℃の非晶質のイソフタル酸共重合ポリエチレンテレフタレート(IPA共重合PET)フィルム(厚み:130μm)基材の片面に、コロナ処理を施し、このコロナ処理面に、ポリビニルアルコール(重合度4200、ケン化度99.2モル%)およびアセトアセチル変性PVA(重合度1200、アセトアセチル変性度4.6%、ケン化度99.0モル%以上、日本合成化学工業社製、商品名「ゴーセファイマーZ200」)を9:1の比で含む水溶液を25℃で塗布および乾燥して、厚み11μmのPVA系樹脂層を形成し、積層体を作製した。
得られた積層体を、同時二軸延伸機を用いて、110℃で、第1の方向(MD)に30%収縮させると同時に、第2の方向(TD)に5.0倍に空中延伸した(延伸処理)。
次いで、積層体を、25℃のヨウ素水溶液(ヨウ素濃度:0.2重量%、ヨウ化カリウム濃度:1.4重量%)に40秒間浸漬させた(染色処理)。
染色後の積層体を、60℃のホウ酸水溶液(ホウ酸濃度:5重量%、ヨウ化カリウム濃度:5重量%)に80秒間浸漬させた(架橋処理)。
架橋処理後、積層体を、25℃のヨウ化カリウム水溶液(ヨウ化カリウム濃度:5重量%)に20秒間浸漬させた(洗浄処理)。
以上により、厚み3μmの偏光子を含む光学フィルム積層体を得た。 <Single protective polarizing film C>
(Preparation of polarizer C)
One side of an amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA copolymerized PET) film (thickness: 130 μm) 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. An 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 μm, 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).
Next, 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).
After the 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).
As a result, an optical film laminate including a polarizer having a thickness of 3 μm was obtained.
積層体の偏光子側にビニルアルコール系接着剤を介して保護フィルム(厚み:40μm、富士フイルム社製、商品名「Z-TAC ZRD40SL」)を貼り合わせた。次いで、非晶性PET基材を剥離し、薄型偏光子を用いた片保護偏光フィルムCを作製した。得られた片保護偏光フィルムCの光学特性は、透過率38.4%、偏光度99.99%であった。 (Production of single-protective polarizing film)
A protective film (thickness: 40 μm, manufactured by Fuji Film, trade name “Z-TAC ZRD40SL”) was bonded to the polarizer side of the laminate through a vinyl alcohol adhesive. Subsequently, the amorphous PET base material was peeled off to produce a piece protective polarizing film C using a thin polarizer. The optical properties of the obtained piece-protecting polarizing film C were a transmittance of 38.4% and a degree of polarization of 99.99%.
(偏光子D(厚さ12μmの偏光子)の作製)
平均重合度2400、ケン化度99.9モル%の厚み30μmのポリビニルアルコールフィルムを、30℃の温水中に60秒間浸漬し膨潤させた。次いで、ヨウ素/ヨウ化カリウム(重量比=0.5/8)の濃度0.3%の水溶液に浸漬し、3.5倍まで延伸させながらフィルムを染色した。その後、65℃のホウ酸エステル水溶液中で、総延伸倍率が6倍となるように延伸を行った。延伸後に、40℃のオーブンにて3分間乾燥を行い、PVA系偏光子を得た。得られた偏光子の厚みは12μmであった。 <Preparation of single protective polarizing film D>
(Preparation of polarizer D (12 μm 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 μm was immersed in warm water at 30 ° C. for 60 seconds to swell. Next, the film was dyed while being immersed in an aqueous solution of 0.3% concentration of iodine / potassium iodide (weight ratio = 0.5 / 8) and stretched to 3.5 times. Then, it extended | stretched so that the total draw ratio might be 6 time in 65 degreeC borate ester aqueous solution. After stretching, drying was performed in an oven at 40 ° C. for 3 minutes to obtain a PVA polarizer. The thickness of the obtained polarizer was 12 μm.
上記PVA系偏光子の片面に、片保護偏光フィルムAと同様にして、上記の紫外線硬化型接着剤を介して、上記透明保護フィルムを貼り合わせた。得られた片保護偏光フィルムDの光学特性は、透過率42.8%、偏光度99.99%であった。 (Preparation of single protective polarizing film D)
The transparent protective film was bonded to one side of the PVA polarizer in the same manner as the single protective polarizing film A via the ultraviolet curable adhesive. The optical properties of the obtained piece-protecting polarizing film D were a transmittance of 42.8% and a degree of polarization of 99.99%.
(ポリビニルアルコール系形成材A)
重合度2500、ケン化度99.0モル%のポリビニルアルコール樹脂(日本酢ビ・ポバール社製、商品名:JC-25)を純水に溶解し、固形分濃度4重量%の水溶液を調製した。 <Forming material for transparent resin layer>
(Polyvinyl alcohol-based forming material A)
A polyvinyl alcohol resin having a polymerization degree of 2500 and a saponification degree of 99.0 mol% (trade name: JC-25, manufactured by Nihon Acetate / Poval) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
重合度2500、ケン化度99.7モル%のポリビニルアルコール樹脂(日本酢ビ・ポバール社製、商品名:JC-25H)を純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol-based forming material B)
A polyvinyl alcohol resin having a degree of polymerization of 2500 and a degree of saponification of 99.7 mol% (trade name: JC-25H, manufactured by Nippon Vinegar Poval Co., Ltd.) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
重合度1700、ケン化度99.0モル%のポリビニルアルコール樹脂(日本酢ビ・ポバール社製、商品名:JC-17)を純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol-based forming material C)
A polyvinyl alcohol resin having a polymerization degree of 1700 and a saponification degree of 99.0 mol% (trade name: JC-17, manufactured by Nihon Acetate / Poval) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
重合度1000、ケン化度99.0モル%のポリビニルアルコール樹脂(日本酢ビ・ポバール社製、商品名:JC-10)を純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol-based forming material D)
A polyvinyl alcohol resin having a polymerization degree of 1000 and a saponification degree of 99.0 mol% (trade name: JC-10, manufactured by Nippon Vinegar Pover Co., Ltd.) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
重合度500、ケン化度99.0モル%のポリビニルアルコール樹脂(日本酢ビ・ポバール社製、商品名:JC-05)を純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol-based forming material E)
A polyvinyl alcohol resin having a degree of polymerization of 500 and a saponification degree of 99.0 mol% (trade name: JC-05, manufactured by Nihon Acetate / Poval) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
重合度2500、ケン化度98.0モル%のポリビニルアルコール樹脂(日本酢ビ・ポバール社製、商品名:JF-2500)を純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol-based forming material F)
A polyvinyl alcohol resin having a degree of polymerization of 2500 and a degree of saponification of 98.0 mol% (trade name: JF-2500, manufactured by Nippon Acetate / Poval) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
重合度2500、ケン化度96.0モル%のポリビニルアルコール樹脂(日本酢ビ・ポバール社製、商品名:JM-2500)を純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol-based forming material G)
A polyvinyl alcohol resin having a polymerization degree of 2500 and a saponification degree of 96.0 mol% (trade name: JM-2500, manufactured by Nippon Vinegar Poval Co., Ltd.) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
アセトアセチル基変性PVA(重合度1200、アセトアセチル変性度4.6%、ケン化度99.0モル%、日本合成化学工業社製、商品名「ゴーセファイマーZ200」))を純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol forming material H)
Acetacetyl group-modified PVA (degree of polymerization 1200, degree of acetoacetyl modification 4.6%, degree of saponification 99.0 mol%, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “Gosefimer Z200”) was dissolved in pure water An aqueous solution having a solid content concentration of 4% by weight was prepared.
アセトアセチル基変性PVA(重合度1200、アセトアセチル変性度4.6%、ケン化度99.0モル%、日本合成化学工業社製、商品名「ゴーセファイマーZ200」))100部と、メチロールメラミン(DIC社製、商品名「ウォーターゾル:S-695」)5部とを純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol-based forming material I)
100 parts of acetoacetyl group-modified PVA (polymerization degree 1200, acetoacetyl modification degree 4.6%, saponification degree 99.0 mol%, manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd., trade name “Gosefimer Z200”)) and
アセトアセチル基変性PVA(重合度1200、アセトアセチル変性度4.6%、ケン化度99.0モル%、日本合成化学工業社製、商品名「ゴーセファイマーZ200」))100部と、メチロールメラミン(DIC社製、商品名「ウォーターゾル:S-695」)20部とを純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol-based forming material J)
100 parts of acetoacetyl group-modified PVA (polymerization degree 1200, acetoacetyl modification degree 4.6%, saponification degree 99.0 mol%, manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd., trade name “Gosefimer Z200”)) and
カルボニル基変性ポリビニルアルコール樹脂(日本酢ビ・ポバール社製、商品名「DC-17」))を純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol forming material K)
A carbonyl group-modified polyvinyl alcohol resin (trade name “DC-17”, manufactured by Nippon Vinegar Poval Co., Ltd.) was dissolved in pure water to prepare an aqueous solution having a solid content of 4% by weight.
カルボニル基変性ポリビニルアルコール樹脂(日本酢ビ・ポバール社製、商品名「DC-17」))100部と、ジヒドラジン(アジピン酸ジヒドラジド)10部を純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol-based forming material L)
100 parts of carbonyl group-modified polyvinyl alcohol resin (product name “DC-17”, manufactured by Nippon Vineyard Pover Co., Ltd.) and 10 parts of dihydrazine (adipic acid dihydrazide) are dissolved in pure water, and the solid content concentration is 4% by weight. An aqueous solution of was prepared.
重合度2000、ケン化度99.4モル%のポリビニルアルコール樹脂(日本合成化学工業社製、商品名「NH-20」)を純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol-based forming material M)
A polyvinyl alcohol resin having a polymerization degree of 2000 and a saponification degree of 99.4 mol% (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “NH-20”) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
重合度1700、ケン化度97.0モル%のポリビニルアルコール樹脂(日本合成化学工業社製、商品名「AH-17」)を純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol-based forming material N)
A polyvinyl alcohol resin having a polymerization degree of 1700 and a saponification degree of 97.0 mol% (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “AH-17”) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
重合度1700、ケン化度99.0モル%のポリビニルアルコール樹脂(クラレ社製、商品名「PVA117」)を純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol-based forming material O)
A polyvinyl alcohol resin having a polymerization degree of 1700 and a saponification degree of 99.0 mol% (trade name “PVA117” manufactured by Kuraray Co., Ltd.) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight.
重合度4000、ケン化度99.0モル%のポリビニルアルコール樹脂(日本酢ビ・ポバール社製、商品名:JC-40)を純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol-based forming material P)
A polyvinyl alcohol resin having a degree of polymerization of 4000 and a degree of saponification of 99.0 mol% (trade name: JC-40, manufactured by Nippon Acetate / Poval) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
重合度1700、ケン化度96.0モル%のポリビニルアルコール樹脂(日本酢ビ・ポバール社製、商品名:JM-17)を純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol-based forming material Q)
A polyvinyl alcohol resin having a polymerization degree of 1700 and a saponification degree of 96.0 mol% (trade name: JM-17, manufactured by Nihon Acetate / Poval) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
重合度1400、ケン化度88.0モル%のポリビニルアルコール樹脂(日本合成化学工業社製、商品名「GM-14」)を純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol-based forming material R)
A polyvinyl alcohol resin having a polymerization degree of 1400 and a saponification degree of 88.0 mol% (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “GM-14”) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
重合度1300、ケン化度93.0モル%のポリビニルアルコール樹脂(クラレ社製、商品名「PVA613」)を純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol-based forming material S)
A polyvinyl alcohol resin having a polymerization degree of 1300 and a saponification degree of 93.0 mol% (trade name “PVA613” manufactured by Kuraray Co., Ltd.) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight.
重合度1700、ケン化度94.5モル%のポリビニルアルコール樹脂(クラレ社製、商品名「PVA617」)を純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol forming material T)
A polyvinyl alcohol resin having a polymerization degree of 1700 and a saponification degree of 94.5 mol% (trade name “PVA617” manufactured by Kuraray Co., Ltd.) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight.
重合度3300、ケン化度94.0モル%のポリビニルアルコール樹脂(日本酢ビ・ポバール社製、商品名:JM-33)を純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol-based forming material U)
A polyvinyl alcohol resin having a degree of polymerization of 3300 and a degree of saponification of 94.0 mol% (manufactured by Nihon Acetate / Poval, trade name: JM-33) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
重合度500、ケン化度94.5モル%のポリビニルアルコール樹脂(日本酢ビ・ポバール社製、商品名:JT-05)を純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol-based forming material V)
A polyvinyl alcohol resin having a polymerization degree of 500 and a saponification degree of 94.5 mol% (trade name: JT-05, manufactured by Nihon Acetate / Poval) was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight. .
冷却管、窒素導入管、温度計及び撹拌装置を備えた反応容器に、アクリル酸ブチル100部、アクリル酸3部、アクリル酸2-ヒドロキシエチル0.1部および2,2´-アゾビスイソブチロニトリル0.3部を酢酸エチルと共に加えて溶液を調製した。次いで、この溶液に窒素ガスを吹き込みながら撹拌して、55℃で8時間反応させて、重量平均分子量220万のアクリル系ポリマーを含有する溶液を得た。さらに、このアクリル系ポリマーを含有する溶液に、酢酸エチルを加えて固形分濃度を30%に調整したアクリル系ポリマー溶液を得た。 <Formation of adhesive layer>
In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, 100 parts of butyl acrylate, 3 parts of acrylic acid, 0.1 part of 2-hydroxyethyl acrylate and 2,2′-azobisisobutyrate A solution was prepared by adding 0.3 parts of ronitrile with ethyl acetate. Next, the solution was stirred while blowing nitrogen gas and reacted at 55 ° C. for 8 hours to obtain a solution containing an acrylic polymer having a weight average molecular weight of 2.2 million. Furthermore, the acrylic polymer solution which added ethyl acetate to the solution containing this acrylic polymer and adjusted solid content concentration to 30% was obtained.
<透明樹脂層付の片保護偏光フィルムを作製>
上記片保護偏光フィルムAの偏光子の面(透明保護フィルムが設けられていない偏光子面)に、25℃に調整した上記形成材Aをワイヤーバーコーターで乾燥後の厚みが1μmになるように塗布した後、60℃で1分間熱風乾燥して、透明樹脂層付の片保護偏光フィルムを作製した。 Example 1
<Manufacturing a single protective polarizing film with a transparent resin layer>
The thickness after drying the above-mentioned forming material A adjusted to 25 ° C. with a wire bar coater on the surface of the polarizer of the piece protective polarizing film A (polarizer surface not provided with a transparent protective film) is 1 μm. After coating, it was dried with hot air at 60 ° C. for 1 minute to produce a piece protective polarizing film with a transparent resin layer.
次いで、片保護偏光フィルムに形成した透明樹脂層に、上記離型シート(セパレータ)の剥離処理面に形成した粘着剤層を貼り合わせて、粘着剤層付偏光フィルムを作製した。 <Preparation of polarizing film with adhesive layer>
Next, the pressure-sensitive adhesive layer formed on the release treatment surface of the release sheet (separator) was bonded to the transparent resin layer formed on the piece protective polarizing film to prepare a polarizing film with a pressure-sensitive adhesive layer.
実施例1において、片保護偏光フィルムの種類、透明樹脂層の厚み、形成材として用いたポリビニルアルコール系樹脂の種類、架橋剤の配合(架橋剤の配合部は、ポリビニルアルコール系樹脂100部に対する値である)の有無を表2に示すように変えたこと以外は、実施例1と同様にして、片保護偏光フィルム、透明樹脂層付の片保護偏光フィルムおよび粘着剤層付偏光フィルムを作製した。 Examples 2 to 33, Comparative Examples 1 to 7
In Example 1, the kind of the piece-protecting polarizing film, the thickness of the transparent resin layer, the kind of the polyvinyl alcohol resin used as the forming material, the blending of the crosslinking agent (the blending part of the crosslinking agent is a value relative to 100 parts of the polyvinyl alcohol resin) Except that the presence / absence of) was changed as shown in Table 2, a piece protective polarizing film, a piece protective polarizing film with a transparent resin layer, and a polarizing film with a pressure-sensitive adhesive layer were produced in the same manner as in Example 1. .
得られた片保護偏光フィルムの単体透過率Tおよび偏光度Pを、積分球付き分光透過率測定器(村上色彩技術研究所のDot-3c)を用いて測定した。
なお、偏光度Pは、2枚の同じ偏光フィルムを両者の透過軸が平行となるように重ね合わせた場合の透過率(平行透過率:Tp)および、両者の透過軸が直交するように重ね合わせた場合の透過率(直交透過率:Tc)を以下の式に適用することにより求められるものである。偏光度P(%)={(Tp-Tc)/(Tp+Tc)}1/2×100
各透過率は、グランテラープリズム偏光子を通して得られた完全偏光を100%として、JIS Z8701の2度視野(C光源)により視感度補整したY値で示したものである。 <Single transmittance T and polarization degree P of polarizer>
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 | required by applying the transmittance | permeability (orthogonal transmittance | permeability: Tc) at the time of combining to the following formula | equation. 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.
実施例および比較例で得られた偏光子について、フーリエ変換赤外分光光度計(FTIR)(Perkin Elmer社製、商品名「SPECTRUM2000」)を用いて、偏光を測定光とする全反射減衰分光(ATR)測定によりホウ酸ピーク(665cm-1)の強度および参照ピーク(2941cm-1)の強度を測定した。得られたホウ酸ピーク強度および参照ピーク強度からホウ酸量指数を下記式により算出し、さらに、算出したホウ酸量指数から下記式によりホウ酸含有量(重量%)を決定した。
(ホウ酸量指数)=(ホウ酸ピーク665cm-1の強度)/(参照ピーク2941cm-1の強度)
(ホウ酸含有量(重量%))=(ホウ酸量指数)×5.54+4.1 <Measurement of boric acid content in polarizer>
Using the Fourier transform infrared spectrophotometer (FTIR) (manufactured by Perkin Elmer, trade name “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.
(Boric acid amount index) = (Intensity of boric acid peak 665 cm −1 ) / (Intensity of reference peak 2941 cm −1 )
(Boric acid content (% by weight)) = (Boric acid content index) × 5.54 + 4.1
DSC装置(セイコーインスツル社製、EXSTAR DSC6000)を用いて、昇温速度10℃/minで結晶融解熱量(mj/mg)を測定した。
測定サンプルは原料そのものの紛体でも良いし、PVA水溶液(固形分4%)をPETフィルムにドライ膜厚が数μmになるように塗工し、乾燥させて得られるPVAフィルムでも良い。測定サンプルは23℃50%RH環境下で24時間エイジングし、得られたサンプル3mgをDSCのサンプルパンに投入しDSCを測定した。測定条件を以下に示す。
1stRun
・-30℃で3分間ホールドし、その後10℃/minで300℃まで昇温
・300℃から-30℃まで30℃/minで降温
2ndRun
・-30℃で3分間ホールドし、その後10℃/minで300℃まで昇温
・300℃から-30℃まで30℃/minで降温
測定により得られたデータの2ndRunの昇温過程において、190℃から230℃までに観測される吸熱ピークを結晶の融解熱量とし、その面積から結晶融解熱量(mj/mg)を算出した。 <Measurement of heat of crystal melting of transparent resin layer>
Using a DSC apparatus (EXSTAR DSC6000, manufactured by Seiko Instruments Inc.), the heat of crystal melting (mj / mg) was measured at a temperature elevation rate of 10 ° C./min.
The measurement sample may be a powder of the raw material itself, or may be a PVA film obtained by applying an aqueous PVA solution (
1stRun
-Hold at -30 ° C for 3 minutes, then increase the temperature to 300 ° C at 10 ° C / min.-Decrease the temperature from 300 ° C to -30 ° C at 30 ° C / min. 2ndRun
Hold at −30 ° C. for 3 minutes, then raise the temperature to 300 ° C. at 10 ° C./min. • Decrease the temperature from 300 ° C. to −30 ° C. at 30 ° C./min. The endothermic peak observed from ℃ to 230 ℃ was taken as the heat of fusion of the crystal, and the heat of crystal fusion (mj / mg) was calculated from the area.
形成材(水溶液)の粘度(cps)を、レオメーターRS1(Haake社製)、共軸円筒として型式222-1267を用いて、23℃の液温及び気温にて測定した。
形成材(水溶液)を調製した直後の粘度Xおよび調製後6時間を経過した際の粘度Yを測定した。前記粘度Xを基準として、粘度Yが2倍以下である場合を「〇」、2倍を超える場合を「×」と評価した。 <Pot life of transparent resin layer forming material>
The viscosity (cps) of the forming material (aqueous solution) was measured at 23 ° C. liquid temperature and air temperature using a rheometer RS1 (manufactured by Haake) and model 222-1267 as a coaxial cylinder.
The viscosity X immediately after preparing the forming material (aqueous solution) and the viscosity Y after 6 hours from the preparation were measured. On the basis of the viscosity X, the case where the viscosity Y was 2 times or less was evaluated as “◯”, and the case where it exceeded 2 times was evaluated as “x”.
得られた粘着剤層付偏光フィルムを、50mm×150mmのサイズ(吸収軸方向が50mm)に裁断したものをサンプル11とした。サンプル11は、透明保護フィルム2の側に、下記方法で作製した表面保護フィルム6を貼り合わせて用いた。 <Inhibition of nano slit generation: Guitar pick test>
190℃におけるメルトフローレートが2.0g/10minである密度0.924g/cm3の低密度ポリエチレンから成る基材成形材料を共押出用インフレーション成形機に供給した。
同時に230℃におけるメルトフローレートが10.0g/10minである密度0.86g/cm3のプロピレン-ブテン共重合体(質量比でプロピレン:ブテン=85:15、アタクチック構造)から成る粘着成形材料とをダイス温度が220℃であるインフレーション成形機に供給して共押出成形を行った。
これにより、厚み33μmの基材層と厚み5μmの粘着剤層とから成る表面保護フィルムを製造した。 (Surface protection film for testing)
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.
At the same time, a pressure-sensitive adhesive molding material comprising a propylene-butene copolymer having a melt flow rate at 230 ° C. of 10.0 g / 10 min and a density of 0.86 g / cm 3 (propylene: butene = 85: 15 by mass ratio). Was supplied to an inflation molding machine having a die temperature of 220 ° C. to perform coextrusion molding.
As a result, a surface protective film consisting of a 33 μm thick base material layer and a 5 μm thick adhesive layer was produced.
次いで、サンプル11を80℃の環境下に1時間放置した後に、下記の基準により、サンプル11の光抜けのクラックの有無を確認した。
A:発生なし。
B:1~100個。
C:101個以上。 Next, as shown in the conceptual diagram of FIG. 5A and the cross-sectional view of FIG. 5B, the release sheet (separator) is peeled from the sample, and the
Next, after the
A: No occurrence.
B: 1 to 100 pieces.
C: 101 or more.
この試験に際しては、実施例および比較例において、片保護偏光フィルムを作製した後、下記方法により、透明樹脂層を形成する前の片保護偏光フィルム10の偏光子1にスクラッチを入れた。その後に、透明樹脂層付の片保護偏光フィルム11を作製した。
そして、当該透明樹脂層付の片保護偏光フィルム11を80℃の環境下に1時間放置した後に、下記の基準により、サンプル11の光抜けのクラックの有無を確認した。
A:発生なし。
B:1~100個。
C:101~200個。
D:201個以上。 <Inhibition of nano slit expansion: Rock and roll test>
In this test, after producing a piece protective polarizing film in Examples and Comparative Examples, the
And after leaving the piece
A: No occurrence.
B: 1 to 100 pieces.
C: 101-200.
D: 201 or more.
得られた片保護偏光フィルム10を、50mm×150mm(吸収軸の方向が50mm)のサイズに裁断した。サンプル10は、透明保護フィルム2の側に、上記の試験用の表面保護フィルム6を貼り合わせて用いた。 ≪How to put a scratch≫
The obtained piece protective
次いで、サンプル10(表面保護フィルム6側)の中央部に対して、ギターピック(HISTORY社製、型番「HP2H(HARD)」)により荷重100gを掛けて、サンプル11における偏光子1の吸収軸に直交する方向に100mmの距離に10往復の荷重負荷を繰り返して、偏光子1の表面にスクラッチを付けた。前記荷重負荷は、1箇所で行った。ナノスリットが発生しているか否かは目視で確認した。
比較例2、4の偏光子の厚さが10μmを超えるものは、偏光子内部の収縮応力が大きいため、ロックンロール試験のナノスリット発生時にフィルムが破断した。そのため評価できなかった。 As shown in the conceptual diagram of FIG. 6 (A) and the cross-sectional view of FIG. 6 (B), two glass support bases 21 having a width of 25 mm and a height of 5 mm are arranged on a
Next, a load of 100 g is applied to the central portion of the sample 10 (surface
When the thickness of the polarizer of Comparative Examples 2 and 4 exceeded 10 μm, the shrinkage stress inside the polarizer was large, so the film was broken when nano slits were generated in the rock and roll test. Therefore, it could not be evaluated.
得られた粘着剤層付偏光フィルムを、50mm×150mm(吸収軸方向が50mm)と150mm×50mm(吸収軸方向が150mm)に裁断し、0.5mm厚の無アルカリガラスの両面にクロスニコルの方向に貼り合せてサンプルを作成した。当該サンプルを、-40~85℃のヒートショックを各30分間×100回の環境下に投入した後に、取り出して粘着剤層付偏光フィルムに貫通クラック(本数)が発生しているか否かを目視にて確認した。この試験を5回行った。評価は下記に従って行った。
〇:貫通クラックなし。
×:貫通クラックあり。 <Confirmation of penetration crack: heat shock test>
The obtained polarizing film with a pressure-sensitive adhesive layer was cut into 50 mm × 150 mm (absorption axis direction is 50 mm) and 150 mm × 50 mm (absorption axis direction is 150 mm), and crossed Nicols on both sides of 0.5 mm-thick alkali-free glass. A sample was made by laminating in the direction. The sample was subjected to a heat shock of −40 to 85 ° C. for 30 minutes × 100 times in each environment, and then taken out to visually check whether a through-crack (number) was generated in the polarizing film with the adhesive layer. Confirmed. This test was performed five times. Evaluation was performed according to the following.
○: No through crack.
X: There is a through crack.
得られた片保護偏光フィルムを25mm×50mmのサイズ(吸収軸方向が50mm)に裁断した。当該片保護偏光フィルム(サンプル)を、85℃/85%RHの恒温恒湿機に150時間投入した。投入前と投入後の片保護偏光フィルムの偏光度を、積分球付き分光透過率測定器(村上色彩技術研究所のDot-3c)を用いて測定し、
偏光度の変化率(%)=(1-(投入後の偏光度/投入前の偏光度))、を求めた。
なお、偏光度Pは、2枚の同じ偏光フィルムを両者の透過軸が平行となるように重ね合わせた場合の透過率(平行透過率:Tp)および、両者の透過軸が直交するように重ね合わせた場合の透過率(直交透過率:Tc)を以下の式に適用することにより求められるものである。偏光度P(%)={(Tp-Tc)/(Tp+Tc)}1/2×100
各透過率は、グランテラープリズム偏光子を通して得られた完全偏光を100%として、JIS Z8701の2度視野(C光源)により視感度補整したY値で示したものである。
評価は下記に従って行った。
◎:偏光度の変化率が0.50%未満。
〇:偏光度の変化率が0.50%以上1.00%未満。
△:偏光度の変化率が1.00%以上2.00%未満。
×:偏光度の変化率が2.00%以上5.00%未満。
××:偏光度の変化率が5.00%以上。 <Heat and heat resistance: Change rate of polarization degree (optical reliability test)>
The obtained piece-protecting polarizing film was cut into a size of 25 mm × 50 mm (absorption axis direction was 50 mm). The piece protective polarizing film (sample) was put into a constant temperature and humidity machine of 85 ° C./85% RH for 150 hours. Measure the degree of polarization of the single-protective polarizing film before and after loading using a spectral transmittance meter with integrating sphere (Dot-3c from Murakami Color Research Laboratory)
Change rate of polarization degree (%) = (1− (polarization degree after injection / polarization degree before injection)).
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 | required by applying the transmittance | permeability (orthogonal transmittance | permeability: Tc) at the time of combining to the following formula | equation. 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.
Evaluation was performed according to the following.
A: Change rate of polarization degree is less than 0.50%.
A: The change rate of the degree of polarization is 0.50% or more and less than 1.00%.
(Triangle | delta): The change rate of a polarization degree is 1.00% or more and less than 2.00%.
X: Change rate of polarization degree is 2.00% or more and less than 5.00%.
XX: Change rate of polarization degree is 5.00% or more.
得られた片保護偏光フィルムを25mm×50mmのサイズ(吸収軸方向が50mm)に裁断した。当該片保護偏光フィルム(サンプル)を、当該片保護偏光フィルムを60℃の純水に6時間浸漬した後に、純水中から取り出し乾いた布で拭き取った後、偏光フィルムを撮像し、画像を二値化することで、色抜けしていない偏光フィルムの面積を測定した。次式で表される残存面積率が70%以上であれば、耐水性が良好であると判断できる。
残存面積率(%)=投入後面積/投入前面積 <Water resistance: warm water test>
The obtained piece-protecting polarizing film was cut into a size of 25 mm × 50 mm (absorption axis direction was 50 mm). After the piece protective polarizing film (sample) is immersed in pure water at 60 ° C. for 6 hours, the piece protective polarizing film is removed from the pure water and wiped with a dry cloth, the polarizing film is imaged, and two images are taken. By measuring the value, the area of the polarizing film that did not lose color was measured. If the remaining area ratio represented by the following formula is 70% or more, it can be determined that the water resistance is good.
Residual area ratio (%) = area after loading / area before loading
片保護偏光フィルムとして長尺状のものを用いたこと、ポリビニルアルコール系形成材をマイクログラビアコーターを用いて塗工したこと、上記の離型シート(セパレータ)及び下記の表面保護フィルムとして長尺状のものを用いたこと以外は、実施例1と同様である。これにより、透明樹脂層側にセパレータ及び透明保護フィルム側に表面保護フィルムが積層された透明樹脂層付片保護偏光フィルム(図2(A)に記載された態様)の巻回体を作製した。なお、透明樹脂層付片保護偏光フィルムの巻回体は、透明樹脂層付片保護偏光フィルムの連続搬送により切断を進行させるスリット加工によって、32インチ無アルカリガラスの短辺及び長辺に各々対応する幅のものをセットとして準備した。 Example 34
Using a long film as a single protective polarizing film, coating a polyvinyl alcohol-based forming material using a micro gravure coater, long film as the release sheet (separator) and the following surface protective film Example 1 is the same as Example 1 except that the above are used. This produced the wound body of the piece protection polarizing film with a transparent resin layer (a mode described in Drawing 2 (A)) by which the separator and the surface protection film were laminated on the transparent resin layer side at the transparent resin layer side. In addition, 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 thing of the width to do was prepared as a set.
帯電防止処理層付きポリエチレンテレフタレートフィルム(商品名:ダイアホイルT100G38、三菱樹脂社製、厚さ38μm)の帯電防止処理面とは反対の面にアクリル系粘着剤を厚さが15μmとなるように塗布形成し、表面保護フィルムを得た。 (Surface protection film for roll-to-panel)
An acrylic adhesive is applied to the surface opposite to the antistatic surface of the polyethylene terephthalate film (trade name: Diafoil T100G38, manufactured by Mitsubishi Plastics, Inc., thickness 38 μm) with an antistatic layer so that the thickness is 15 μm. The surface protection film was obtained.
各々、実施例2、3、4と同様の製法にて、透明樹脂層付片保護偏光フィルムを作製したこと以外は、実施例34と同様である。 Examples 35-37
Each is the same as Example 34 except that the piece-protecting polarizing film with a transparent resin layer was produced in the same manner as in Examples 2, 3, and 4, respectively.
透明樹脂層付片保護偏光フィルムが両面に貼り合わされた無アルカリガラス100枚を80℃のオーブンに24時間投入し、その後目視にてナノスリットの発生の有無を確認した。実施例34~37のいずれにおいても、ナノスリットによる欠陥(光抜け)の発生は見られなかった。 <Confirmation of nanoslit generation: heating test>
100 pieces of non-alkali glass having a transparent protective resin-coated piece-protecting polarizing film bonded on both sides was placed in an oven at 80 ° C. for 24 hours, and then the presence or absence of nanoslits was visually confirmed. In any of Examples 34 to 37, no defect (light loss) due to the nano slit was observed.
2 透明保護フィルム
3 透明樹脂層(ポリビニルアルコール系樹脂が主成分)
4 粘着剤層
5、5a、5b セパレータ
6、6a、6b 表面保護フィルム
10 片保護偏光フィルム
11 片保護偏光フィルム(透明樹脂層付)
12 粘着剤層付偏光フィルム
20a、20b 粘着剤層付偏光フィルムの巻回体(ロール)
21a、21b 粘着剤層付偏光フィルム(表面保護フィルム付)
100 画像表示装置の連続製造システム
101a、101b 偏光フィルム供給部
151a、151b 繰出部
152a、152b 切断部
153a、153b 剥離部
154a、154b 巻取部
201a、201b 貼合部
300 配置入替部
P 画像表示パネル
X 画像表示パネルの搬送部
DESCRIPTION OF
4
12 Polarizing film with pressure-
21a, 21b Polarizing film with adhesive layer (with surface protective film)
DESCRIPTION OF
Claims (14)
- 偏光子の片面にのみ透明保護フィルムを有する片保護偏光フィルムであって、
前記偏光子は、ポリビニルアルコール系樹脂を含有し、厚みが10μm以下であり、かつ、単体透過率T及び偏光度Pによって表される光学特性が、下記式
P>-(100.929T-42.4-1)×100(ただし、T<42.3)、又は、
P≧99.9(ただし、T≧42.3)の条件を満足するように構成されたものであり、
かつ、前記偏光子の他の片面に、ポリビニルアルコール系樹脂を含有する形成材の形成物であって、厚み0.2μm以上の透明樹脂層を有することを特徴とする片保護偏光フィルム。 A single protective polarizing film having a transparent protective film only on one side of the polarizer,
The polarizer contains a polyvinyl alcohol-based resin, has a thickness of 10 μm or less, and 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
P ≧ 99.9 (provided that T ≧ 42.3) is satisfied,
And the other side of the said polarizer is the formation material of the forming material containing polyvinyl alcohol-type resin, Comprising: It has a transparent resin layer with a thickness of 0.2 micrometer or more, The piece protection polarizing film characterized by the above-mentioned. - 前記透明樹脂層が、結晶融解熱量30mj/mg以上であることを特徴とする請求項1記載の片保護偏光フィルム。 The piece protective polarizing film according to claim 1, wherein the transparent resin layer has a heat of crystal melting of 30 mj / mg or more.
- 前記透明樹脂層は、厚みが3μm未満であることを特徴とする請求項1または2記載の片保護偏光フィルム。 The piece-protecting polarizing film according to claim 1 or 2, wherein the transparent resin layer has a thickness of less than 3 µm.
- 前記ポリビニルアルコール系樹脂は、ケン化度が99.0%以上、平均重合度が1000以上であることを特徴とする請求項1~3のいずれかに記載の片保護偏光フィルム。 4. The piece protective polarizing film according to claim 1, wherein the polyvinyl alcohol-based resin has a saponification degree of 99.0% or more and an average polymerization degree of 1000 or more.
- 前記形成材は、硬化性成分を含有していないことを特徴とする請求項1~4のいずれかに記載の片保護偏光フィルム。 The piece protective polarizing film according to any one of claims 1 to 4, wherein the forming material does not contain a curable component.
- 前記ポリビニルアルコール系樹脂は、ポリビニルアルコール樹脂であることを特徴とする請求項1~5のいずれかに記載の片保護偏光フィルム。 6. The piece protective polarizing film according to claim 1, wherein the polyvinyl alcohol-based resin is a polyvinyl alcohol resin.
- 前記偏光子は、偏光子全量に対してホウ酸を25重量%以下で含有することを特徴とする請求項1~6のいずれかに記載の片保護偏光フィルム。 The piece protective polarizing film according to any one of claims 1 to 6, wherein the polarizer contains boric acid in an amount of 25% by weight or less based on the total amount of the polarizer.
- 請求項1~7のいずれかに記載の片保護偏光フィルム、および粘着剤層を有することを特徴とする粘着剤層付偏光フィルム。 A polarizing film with a pressure-sensitive adhesive layer, comprising the piece protective polarizing film according to any one of claims 1 to 7 and a pressure-sensitive adhesive layer.
- 前記片保護偏光フィルムの透明樹脂層に、前記粘着剤層が設けられていることを特徴とする請求項8記載の粘着剤層付偏光フィルム。 The polarizing film with a pressure-sensitive adhesive layer according to claim 8, wherein the pressure-sensitive adhesive layer is provided on the transparent resin layer of the piece protective polarizing film.
- 前記片保護偏光フィルムの透明保護フィルムに、前記粘着剤層が設けられていることを特徴とする請求項8記載の粘着剤層付偏光フィルム。 The polarizing film with a pressure-sensitive adhesive layer according to claim 8, wherein the pressure-sensitive adhesive layer is provided on the transparent protective film of the piece protective polarizing film.
- 前記粘着剤層にセパレータが設けられていることを特徴とする請求項8~10のいずれかに記載の粘着剤層付偏光フィルム。 The polarizing film with a pressure-sensitive adhesive layer according to any one of claims 8 to 10, wherein a separator is provided on the pressure-sensitive adhesive layer.
- 巻回体であることを特徴とする請求項11記載の粘着剤層付偏光フィルム。 The polarizing film with an adhesive layer according to claim 11, wherein the polarizing film is a wound body.
- 請求項1~7のいずれかに記載の片保護偏光フィルム、または請求項8~10のいずれかに記載の粘着剤層付偏光フィルムを有する画像表示装置。 An image display device comprising the piece protective polarizing film according to any one of claims 1 to 7 or the polarizing film with an adhesive layer according to any one of claims 8 to 10.
- 請求項12記載の前記粘着剤層付偏光フィルムの巻回体から繰り出され、前記セパレータにより搬送された前記粘着剤層付偏光フィルムを、前記粘着剤層を介して画像表示パネルの表面に連続的に貼り合せる工程を含む画像表示装置の連続製造方法。 The said polarizing film with an adhesive layer unwound from the winding body of the said polarizing film with an adhesive layer of Claim 12, and was conveyed by the said separator is continuously on the surface of an image display panel through the said adhesive layer. A method for continuously manufacturing an image display device, including a step of bonding to a substrate.
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CN201580053067.4A CN107076909B (en) | 2014-09-30 | 2015-09-29 | Unilateral side protection polarizing coating, the polarizing coating with adhesive phase, image display device and its method for continuous production |
KR1020177008777A KR101844935B1 (en) | 2014-09-30 | 2015-09-29 | Polarizing film protected on one side, polarizing film with pressure-sensitive adhesive layer, image display device, and continuous production process therefor |
SG11201706375PA SG11201706375PA (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 |
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