WO2007145081A1 - Polarizer protective film, polarizing plate, and image display device - Google Patents

Polarizer protective film, polarizing plate, and image display device Download PDF

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Publication number
WO2007145081A1
WO2007145081A1 PCT/JP2007/061067 JP2007061067W WO2007145081A1 WO 2007145081 A1 WO2007145081 A1 WO 2007145081A1 JP 2007061067 W JP2007061067 W JP 2007061067W WO 2007145081 A1 WO2007145081 A1 WO 2007145081A1
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WIPO (PCT)
Prior art keywords
polarizing plate
polarizer
weight
layer
film
Prior art date
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PCT/JP2007/061067
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French (fr)
Japanese (ja)
Inventor
Mie Nakata
Yuuki Nakano
Original Assignee
Nitto Denko Corporation
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Publication of WO2007145081A1 publication Critical patent/WO2007145081A1/en

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G—PHYSICS
    • G02—OPTICS
    • 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
    • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
    • G02F2201/50—Protective arrangements

Definitions

  • Polarizer protective film polarizing plate, and image display device
  • the present invention relates to a polarizer protective film, a polarizing plate, and an image display device such as a liquid crystal display device, an organic EL display device, and a PDP, including at least the sentence.
  • a polarizing plate used in an image display device is typically a triacetyl cellulose in a polarizer obtained by dyeing polybutyl alcohol (PVA) film with dichroic iodine or a dichroic dye. Manufactured by attaching a polarizer protective film such as (TAC) film.
  • PVA polybutyl alcohol
  • TAC polarizer protective film
  • the polarizer protective film is likely to curl. For this reason, curling is likely to occur even in a polarizing plate obtained by laminating a polarizer protective film on both sides of the polarizer.
  • Curling in the polarizing plate causes various problems. For example, there is a problem that the liquid crystal cell cannot be smoothly bonded, a problem that the liquid crystal cell is easily peeled even if it is bonded, and a problem that the appearance is deteriorated.
  • the various problems described above become more prominent as the polarizing plate becomes larger. Therefore, several technical capabilities S have been proposed for obtaining a polarizing plate that suppresses curling as much as possible.
  • a polarizing plate provided with an adhesive layer and a separator is provided with a polarizing plate by strictly controlling the moisture content of the polarizing plate before and after the lamination of the adhesive layer and the separator.
  • a technique for suppressing the occurrence of curling in a plate has been proposed (see Patent Document 2).
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2004-184809
  • Patent Document 2 JP 2005-326531 A
  • the present invention has been made to solve the above-described conventional problems.
  • the purpose of the present invention is to (1) simply provide a polarizer protective film in which the occurrence of curling is suppressed at a high level.
  • (3) Using such a polarizing plate The object is to provide a high-quality image display device.
  • the polarizer protective film of the present invention has a cellulose resin as a main component and a moisture content of 3
  • the cellulosic resin is triacetyl cellulose.
  • a polarizing plate is provided.
  • the polarizing plate of the present invention is a polarizing plate having protective layers on both sides of the polarizer, and at least one of the protective layers is a cellulose resin layer, and the cellulose resin layer is the polarizer of the present invention. It is formed using a protective film.
  • the cellulose resin layer is a triacetyl cellulose layer.
  • the cellulose resin layer is provided only on one surface side of the polarizer.
  • the polarizer has a layer containing a (meth) acrylic resin as a main component on the side opposite to the side having the cellulose-based resin layer.
  • At least one of the protective layers on both sides of the polarizer is laminated with the polarizer via an adhesive layer formed from a polyvinyl alcohol-based adhesive.
  • both protective layers on both sides of the polarizer are It is laminated with the polarizer through an adhesive layer formed from a livinyl alcohol adhesive.
  • the polyvinyl alcohol-based adhesive contains a polyvinyl alcohol-based resin and a crosslinking agent.
  • the polybulualcohol-based adhesive contains a polybulualcohol-based resin, a crosslinking agent, and a metal compound colloid having an average particle size of:! To lOOnm.
  • the metal compound colloid is blended at a ratio of 200 parts by weight or less with respect to 100 parts by weight of the polybulal alcohol resin.
  • an adhesive layer is further provided as at least one of the outermost layers.
  • an image display device is provided.
  • the image display device of the present invention includes at least one polarizing plate of the present invention.
  • a polarizer protective film in which curling is suppressed at a high level without requiring a complicated manufacturing procedure.
  • a polarizing plate that is suppressed from being curled at a high level and has an excellent appearance that does not easily peel off even when bonded to a liquid crystal cell. It is possible to provide a high-quality image display device using such a polarizing plate.
  • FIG. 1 is a cross-sectional view showing an example of a polarizing plate of the present invention.
  • FIG. 2 is a cross-sectional view showing an example of a polarizing plate of the present invention.
  • FIG. 3 is a schematic cross-sectional view of a liquid crystal display device according to a preferred embodiment of the present invention.
  • the polarizer protective film of the present invention contains a cellulose resin as a main component.
  • the cellulose resin include diacetyl cellulose and triacetyl cellulose, and triacetyl cellulose is preferable in terms of transparency and adhesiveness.
  • the polarizer protective film of the present invention may contain any appropriate other component as long as the effects of the present invention are not impaired.
  • the polarizer protective film of the present invention preferably contains 90% by weight or more of a cellulose resin, more preferably 95% by weight or more, still more preferably 98% by weight or more, and particularly preferably 100% by weight.
  • the thickness of the polarizer protective film of the present invention is preferably 20 ⁇ ! ⁇ 100 zm, more preferably 30 ⁇ m to 80 ⁇ m.
  • the thickness of the polarizer protective film is 20 ⁇ m or more, it has appropriate strength and rigidity, and handling properties are good at the time of secondary care such as laminating and printing.
  • the phase difference generated by the stress at the time of cutting the bow can be easily controlled, and the film can be manufactured stably and easily. If the thickness of the polarizer protective film is 100 ⁇ or less, In addition to easy rumming, line speed, productivity, and control become easier.
  • the polarizer protective film of the present invention has a water content of 3.1 wt% to 4.0 wt%.
  • an effect that the occurrence of curling can be remarkably suppressed can be exhibited by a technical means of adjusting the water content of a film mainly composed of a cellulose-based resin within such a specific range.
  • the water content of the polarizer protective film of the present invention is preferably 3.2 wt% to 3.9 wt%, more preferably 3.3 wt% to 3.8 wt%.
  • any appropriate means can be adopted as means for adjusting the water content within the above specific range.
  • the polarizer protective film is immersed in water under appropriate conditions and then dried under appropriate conditions so that the water content is adjusted to be within the specific range described above.
  • the polarizer protective film of the present invention is preferably transparent and uncolored.
  • the thickness direction retardation value Rth is preferably 90 nm to +90 nm, more preferably 80 nm to +80 nm, and particularly preferably 70 nm to +70 nm.
  • the polarizer protective film of the present invention contains a cellulose-based resin as a main component and adjusts the water content within a specific range of 3.1 wt% to 4.0 wt%.
  • a polarizer protective film in which the occurrence of curling is suppressed at a high level is obtained.
  • a polybulal alcohol-based resin film dyed with a dichroic substance typically iodine or a dichroic dye
  • the degree of polymerization of the polybulal alcohol-based resin constituting the polybulal alcohol-based resin film is preferably 100 to 5000, and more preferably 1400 to 4000.
  • the polyvinyl alcohol-based resin film constituting the polarizer can be formed by any appropriate method (for example, a casting method in which a solution in which a resin is dissolved in water or an organic solvent is cast, a casting method, an extrusion method). .
  • the thickness of the polarizer can be appropriately set according to the purpose and application of the LCD in which the polarizing plate is used, but is typically 5 to 80 ⁇ m.
  • any appropriate method may be employed depending on the purpose, materials used, conditions, and the like.
  • a method is employed in which the polyvinyl alcohol-based resin film is subjected to a series of manufacturing steps including swelling, dyeing, crosslinking, stretching, washing, and drying steps. In each of the treatment steps except the drying step, the treatment is performed by immersing the polybulal alcohol-based resin film in a bath containing the solution used in each step.
  • the order, number of times, and presence / absence of each treatment of swelling, dyeing, crosslinking, stretching, washing with water, and drying can be appropriately set according to the purpose, materials used, conditions and the like.
  • a specific process that allows several processes to be performed simultaneously in one process may be omitted.
  • the stretching process may be performed after the dyeing process or before the dyeing process, or may be performed simultaneously with the swelling process, the dyeing process, and the crosslinking process.
  • it can be suitably employed to perform the crosslinking treatment before and after the stretching treatment.
  • the water washing process may be performed only after a specific process that may be performed after all the processes.
  • the swelling step is typically carried out by immersing the polybulal alcohol-based resin film in a treatment bath (swelling bath) filled with water.
  • a treatment bath shallowing bath
  • dirt on the surface of the polyvinyl alcohol resin film and an anti-blocking agent can be washed, and unevenness such as uneven dyeing can be prevented by swelling the polyvinyl alcohol resin film.
  • Glycerin, potassium iodide, or the like can be appropriately added to the swelling bath.
  • the temperature of the swelling bath is typically about 20 to 60 ° C, and the immersion time in the swelling bath is typically about 0.:! To 10 minutes.
  • the dyeing step is typically performed by immersing the polybulal alcohol-based resin film in a treatment bath (dye bath) containing a dichroic substance such as iodine.
  • a dichroic substance such as iodine.
  • water is generally used, but an appropriate amount of an organic solvent compatible with water may be added.
  • the dichroic substance is typically used at a ratio of 0.1 to 1.0 part by weight with respect to 100 parts by weight of the solvent.
  • the dye bath solution preferably further contains an auxiliary agent such as iodide. This is because the dyeing efficiency is improved.
  • the auxiliary agent is preferably used in a ratio of 0.02 to 20 parts by weight, more preferably 2 to 10 parts by weight with respect to 100 parts by weight of the solvent.
  • iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide , Lead iodide, copper iodide, barium iodide, calcium iodide, yowi tin and titanium iodide.
  • the temperature of the dyeing bath is typically about 20 to 70 ° C, and the immersion time in the dyeing bath is typically about:! To about 20 minutes.
  • the crosslinking step is typically performed by immersing the dyed polybulal alcohol resin film in a treatment bath (crosslinking bath) containing a crosslinking agent.
  • a crosslinking agent can be adopted as the crosslinking agent.
  • Specific examples of the crosslinking agent include boron compounds such as boric acid and borax, darioxal, dartalaldehyde and the like. These can be used alone or in combination.
  • a solvent used for the solution of the crosslinking bath water is generally used, but an appropriate amount of an organic solvent having compatibility with water may be added.
  • the crosslinking agent is typically used at a ratio of:! To 10 parts by weight with respect to 100 parts by weight of the solvent.
  • the solution of the crosslinking bath preferably further contains an auxiliary agent such as iodide. This is because uniform characteristics are easily obtained in the surface.
  • the concentration of the auxiliaries is preferably 0.05 to 15% by weight, more preferably 0.5 to 8% by weight. Specific examples of iodide are the same as those in the dyeing process.
  • the temperature of the crosslinking bath is typically about 20 to 70 ° C, preferably 40 to 60 ° C.
  • the immersion time in the crosslinking bath is typically about 1 second to 15 minutes, preferably 5 seconds to 10 minutes.
  • the stretching step may be performed at any stage as described above. Specifically, it may be carried out after the crosslinking treatment, which may be carried out after the dyeing treatment or before the dyeing treatment, or may be carried out simultaneously with the swelling treatment, the dyeing treatment and the crosslinking treatment.
  • the cumulative draw ratio of the polybulualcohol-based resin film needs to be 5 times or more, preferably 5 to 7 times, and more preferably 5 to 6.5 times. If the cumulative draw ratio is less than 5 times, it may be difficult to obtain a polarizing plate with a high degree of polarization. When the cumulative draw ratio exceeds 7 times, the polybulualcohol-based resin film (polarizer) may be easily broken.
  • Arbitrary appropriate methods may be employ
  • the drawing bath solution may be water or an organic solvent (e.g. A solution in which various metal salts, iodine, boron or zinc compounds are added to a solvent such as ethanol) is preferably used.
  • the water washing step is typically performed by immersing the polybutyl alcohol-based resin film subjected to the above-described various treatments in a treatment bath (water washing bath). Unnecessary residues of the polybutyl alcohol resin film can be washed away by the water washing process.
  • the washing bath may be an aqueous solution of iodide (eg, potassium iodide or sodium iodide) which may be pure water.
  • the concentration of the aqueous iodide solution is preferably 0.:! To 10% by mass.
  • An auxiliary agent such as zinc sulfate or zinc chloride may be added to the iodide aqueous solution.
  • the temperature of the washing bath is preferably 10 to 60 ° C, more preferably 30 to 40 ° C.
  • the immersion time is typically 1 second to 1 minute.
  • the water washing process can be performed only once or multiple times as necessary. In the case of carrying out a plurality of times, the kind and concentration of the additive contained in the washing bath used for each treatment can be appropriately adjusted.
  • the water washing step includes a step of immersing the polymer film in a potassium iodide aqueous solution (0 ⁇ :! to 10% by mass, 10 to 60 ° C.) for 1 second to 1 minute, and a step of rinsing with pure water. .
  • any appropriate drying method for example, natural drying, air drying, heat drying
  • the drying temperature is typically 20 to 80 ° C.
  • the drying time is typically:! To 10 minutes.
  • a polarizer is obtained.
  • the polarizing plate of the present invention has protective layers on both sides of the polarizer, and at least one of the protective layers is a cellulose resin layer. That is, a cellulose resin layer may be provided on both sides of the polarizer, or a cellulose resin layer may be provided only on one side. In the case where the cellulose resin layer is provided only on one surface side, other protective layers other than the cellulose resin layer are provided on the other surface side.
  • One of the preferred embodiments of the polarizing plate of the present invention is such that a cellulose resin layer 33 is laminated on one surface of a polarizer 31 with an adhesive layer 32 interposed therebetween, as shown in FIG.
  • the cellulose resin layer 33 ′ is laminated on the other surface of the polarizer 31 via the adhesive layer 32 ′.
  • Another preferred embodiment of the polarizing plate of the present invention is as shown in FIG.
  • the cellulose resin layer 33 is laminated on one surface of the polarizer 31 via the adhesive layer 32, and the other surface of the polarizer 31 via the adhesive layer 34 and the easy adhesion layer 35.
  • the other protective layer 36 is laminated.
  • the cellulose-based resin layer is formed using the polarizer protective film of the present invention.
  • the cellulose-based resin layer is a resin layer containing a cellulose-based resin as a main component, and examples thereof include a resin layer mainly composed of diacetyl cellulose or triacetyl cellulose, and triacetyl cellulose is transparent and adhesive. Preferable in terms of sex.
  • the cellulose-based resin layer may contain any appropriate other component as long as the effects of the present invention are not impaired.
  • the cellulose resin layer preferably contains 90% by weight or more of the cellulose resin, more preferably 95% by weight or more, further preferably 98% by weight or more, and particularly preferably 100% by weight. It is particularly preferable that the cellulose resin layer is a triacetyl cell mouth layer.
  • the cellulose resin layer has a thickness of preferably 20 ⁇ m to 100 ⁇ m, more preferably 30 ⁇ m to 80 ⁇ m.
  • the polarizing plate of the present invention has protective layers on both sides of the polarizer, and at least one of the protective layers is a cellulose resin layer.
  • the cellulose resin layer is formed using the polarizer protective film of the present invention having a water content of 3.1 wt% to 4.0 wt%. That is, the polarizing plate of the present invention is formed by bonding the polarizer protective film of the present invention to at least one of the polarizers.
  • the occurrence of curling in the polarizing plate is remarkable due to the technical means of adjusting the moisture content of the polarizer protective film to be bonded to the polarizer within such a specific range. The effect of being able to be suppressed is manifested.
  • the water content is less than 3.1% by weight or more than 4.0% by weight, curling may occur significantly in the polarizing plate.
  • any appropriate protective layer can be adopted as long as the effects of the present invention are not impaired.
  • the material which is the main component of such a protective layer include polyester-based, polyvinyl alcohol-based, polycarbonate-based, polyamide-based, polyimide-based, polyether sulfone.
  • transparent resins such as polyethylene, polysulfone, polystyrene, polynorbornene, polyolefin, talyl, and acetate.
  • thermosetting resins such as acrylic, urethane, acrylurethane, epoxy, and silicone, and ultraviolet curable resins.
  • a glassy polymer such as a siloxane-based polymer is also included.
  • polymer films described in JP-A-2001-343529 can also be used.
  • the material of the film include a resin containing a thermoplastic resin having a substituted or unsubstituted imide group in the side chain, and a thermoplastic resin having a substituted or unsubstituted phenyl group and a nitrile group in the side chain.
  • the composition can be used, for example, a resin composition having an alternating copolymer composed of isobutene and N-methylmaleimide and an acrylonitrile / styrene copolymer.
  • the polymer film can be, for example, an extruded product of the resin composition.
  • the other protective layers are preferably transparent and have no color.
  • the retardation value in the thickness direction is preferably from 1 to 90 nm, more preferably from 1 to 80 nm, and most preferably from 70 to +70 nm.
  • the other protective layer is a layer containing a (meth) acrylic resin as a main component.
  • Each of the (meth) acrylic resins may be composed of one kind of resin, or may be composed of two or more kinds of resins.
  • the (meth) acrylic resin preferably has a Tg (glass transition temperature) of 115 ° C or higher, more preferably 120 ° C or higher, still more preferably 125 ° C or higher, and particularly preferably 130 ° C. ° C or higher.
  • Tg glass transition temperature
  • the upper limit of Tg of the (meth) acrylic resin is not particularly limited, but is preferably 170 ° C or less from the viewpoint of moldability and the like.
  • the (meth) acrylic resin is not particularly limited, and examples thereof include poly (meth) acrylic acid esters such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, and methyl methacrylate.
  • poly (meth) acrylic acid C alkyl such as poly (meth) acrylic acid methyl ester as a main component (50 to: 100% by weight, preferably 7
  • Another example is a methyl methacrylate-based resin containing methyl methacrylate as a main component (50 to 100% by weight, preferably 70 to 100% by weight).
  • (meth) acrylic resin examples include, for example, a ring structure in a molecule described in Ataripet VH and Ataripet VRL20A manufactured by Mitsubishi Rayon Co., Ltd., and JP-A-2004-70296.
  • (meth) acrylic resin a rataton ring structure described in JP-A-2000-230016, JP-A-2001-151814, JP-A-2005-146084, etc.
  • a (meth) acrylic resin having a structure or a (meth) acrylic resin having a dartaric anhydride structure described in JP-A-2005-314534 may be used.
  • the layer containing the (meth) acrylic resin as a main component the content of the (meth) acrylic resin is preferably 50 to 99 weight 0/0, more preferably 60 to 98 weight 0/0, More preferably, it is 70 to 97% by weight. If the content of the (meth) acrylic resin is less than 50% by weight, the high heat resistance and high transparency inherent in the (meth) acrylic resin may not be sufficiently reflected. If it exceeds%, the mechanical strength may be inferior.
  • the other protective layer may contain any appropriate other component.
  • an ultraviolet absorber for example, an ultraviolet absorber, a general compounding agent, such as a stabilizer, a lubricant, an additive, a plasticizer, an impact assistant, a retardation reducing agent, an antibacterial agent, an antibacterial agent, an antibacterial agent.
  • a general compounding agent such as a stabilizer, a lubricant, an additive, a plasticizer, an impact assistant, a retardation reducing agent, an antibacterial agent, an antibacterial agent, an antibacterial agent.
  • a general compounding agent such as a stabilizer, a lubricant, an additive, a plasticizer, an impact assistant, a retardation reducing agent, an antibacterial agent, an antibacterial agent, an antibacterial agent.
  • a general compounding agent such as a stabilizer, a lubricant, an additive, a plasticizer, an impact assistant, a retardation reducing agent, an antibacterial agent, an antibacterial agent, an antibacterial agent.
  • examples include mold.
  • the other protective layer contains a retardation reducing agent.
  • the phase difference reducing agent include acrylonitrile-styrene copolymer.
  • styrene-containing polymers are preferred.
  • the addition amount of the retardation reducing agent is preferably 30% by weight or less, more preferably 25% by weight or less, and still more preferably 20% by weight or less, with respect to the total amount of resin in the other resin layers. is there. If added beyond this range, visible light is scattered or the transparency is impaired, so the properties of the polarizer as a protective layer may be lacking.
  • the thickness of the other protective layer any appropriate thickness can be adopted as long as the above preferred thickness direction retardation can be obtained.
  • the thickness of the other protective layer is preferably 20 to 200 ⁇ , more preferably 25 to 180 zm, and further preferably 30 to 140 ⁇ m.
  • the thickness of the other protective layer is 20 ⁇ m or more, it has appropriate strength and rigidity, and handling properties are good in the secondary care such as laminating and printing.
  • the phase difference generated by the stress at the time of take-up can be easily controlled, and the finoleum can be manufactured stably and easily. If the thickness of the other protective layer is 200 zm or less, film removal is facilitated, and line speed, productivity, and controllability are also facilitated.
  • the other protective layer may be a film stretched by longitudinal stretching and / or lateral stretching. By being stretched by longitudinal stretching and / or lateral stretching, it becomes possible to impart excellent optical properties, and it is also excellent in mechanical strength, and productivity and reworkability can be improved. .
  • the stretching may be stretching by only longitudinal stretching (free-end uniaxial stretching) or stretching by only lateral stretching (fixed-end uniaxial stretching), but the longitudinal stretching ratio is 1.:! To 3.0. It is preferable to perform sequential stretching or simultaneous biaxial stretching with a magnification of 1.times.
  • stretching by only longitudinal stretching (free end uniaxial stretching) and stretching by only transverse stretching (fixed end uniaxial stretching) the film strength increases only in the stretching direction, and the strength does not increase in the direction perpendicular to the stretching direction.
  • the film as a whole may not have sufficient film strength.
  • the longitudinal draw ratio is more preferably 1.2 to 2.5 times, and still more preferably 1.3 to 2.0 times.
  • the transverse stretching ratio is more preferably 1.2 to 2.5 times, and still more preferably 1.4 to 2.5 times.
  • the draw ratio may be too low and there may be little effect of stretching. If the longitudinal draw ratio and transverse draw ratio exceed 3.0, Due to the problem of the smoothness of the end face of the rumm, the stretch breakage is likely to occur.
  • the stretching temperature is preferably Tg to (Tg + 30 ° C) of the film to be stretched. If the stretching temperature is lower than Tg, the film may be broken. If the stretching temperature exceeds (Tg + 30 ° C), the film may start to melt, making it difficult to pass the paper.
  • the other protective layer may be produced by any appropriate method.
  • a film obtained by melt extrusion may be used as the other protective layer.
  • a method of forming a film by melt extrusion specifically, a resin composition as a raw material is supplied to an extruder connected to a T-die, and after melt-kneading, it is extruded, cooled by water, and taken out.
  • a method of forming can be exemplified.
  • the screw type of the extruder may be uniaxial or biaxial, and additives such as plasticizers or antioxidants may be added.
  • the temperature of melt extrusion can be set as appropriate, but when the glass transition temperature of the resin composition as the raw material is Tg (° C), (Tg + 80) ° C to (Tg + 180) ° C is preferred (Tg + 100) ° C to (Tg + 150) ° C is more preferred. If the extrusion molding temperature is too low, there is a possibility that molding cannot be performed due to the poor fluidity of the resin. If the extrusion molding temperature is too high, the resin viscosity will be low, and there may be a problem in production stability such as uneven thickness of the molded product.
  • the other protective layer has a YI force at a thickness of 80 ⁇ , preferably 1 ⁇ 3 or less, more preferably 1.27 or less, more preferably 1.25 or less, more preferably 1.23 or less, particularly Preferably it is 1. 20 or less. If the YI at a thickness of 80 / im exceeds 1.3, excellent optical transparency may not be exhibited.
  • YI uses, for example, a high-speed integrating sphere type spectral transmittance measuring device (trade name: DOT-3C: manufactured by Murakami Color Research Laboratory), and tristimulus values of colors obtained by measurement ( ⁇ , ⁇ , ⁇ ) From the following equation.
  • the other protective layer has a b value (hue scale according to Hunter's color system) at a thickness of 80 xm, preferably less than 1.5, and more preferably 1.0 or less. When the b value is 1.5 or more, excellent optical transparency may not be exhibited due to coloring of the film.
  • the b value can be measured, for example, by cutting the sample into 3cm squares and using a high-speed integrating sphere type spectral transmittance measuring machine (trade name DOT-3C: manufactured by Murakami Color Research Laboratory). . In addition, the hue can be evaluated by b value according to Hunter's color system.
  • the other protective layer has an in-plane retardation And of preferably 3. Onm or less, more preferably 1. Onm or less. If the in-plane retardation And exceeds 3. Onm, excellent optical characteristics may not be exhibited.
  • the other protective layer has a thickness direction retardation Rth force of preferably 5. Onm or less, and more preferably 3. Onm or less. When the thickness direction retardation Rth exceeds 5. Onm, excellent optical characteristics may not be exhibited.
  • moisture permeability preferably 100 g / m 2 '24hr or less, more preferably 60gZm 2' is 24hr or less. If the moisture permeability exceeds 100 g / m 2 '24 hr, the moisture resistance may be poor.
  • the other protective layer preferably also has excellent mechanical strength.
  • Tensile strength, in the MD direction preferably 65NZmm 2 or more, more preferably 70N / mm 2 or more, preferably in the al 75N / mm 2 or more, particularly preferably 80 N / mm 2 or more, Oite in TD , preferably 45N / mm 2 or more, more preferably 50 N / mm 2 or more, more preferably 55N / mm 2 or more, and particularly preferably 60N / mm 2 or more.
  • the tensile elongation is preferably 6.5% or more, more preferably 7.0% or more, further preferably 7.5% or more, particularly preferably 8.0% or more in the MD direction, and in the TD direction.
  • It is preferably 5.0% or more, more preferably 5.5% or more, still more preferably 6.0% or more, and particularly preferably 6.5% or more. If the tensile strength or tensile elongation is outside the above range, there is a risk that excellent mechanical strength will not be exhibited.
  • the other protective layer has a lower haze that represents optical transparency, and is preferably as low as possible. Preferably it is 5% or less, more preferably 3% or less, even more preferably 1.5% or less, and particularly preferably. Is less than 1%.
  • the haze is 5% or less, a good tally feeling can be visually given to the film, and when the haze is 1.5% or less, the visibility and the daylighting property can be obtained even when used as a daylighting member such as a window. Both can be obtained, and even when used as a front plate of a display device, the display contents can be visually recognized well, so the industrial utility value is high.
  • the polarizer protective film of the present invention and the above-mentioned other protective layers are used for, for example, building lighting members such as windows and carport roofing materials, vehicle lighting members such as windows, etc.
  • Agricultural daylighting materials such as greenhouses, lighting members, front filter etc. It can be used in layers, and has been traditionally covered with (meth) acrylic resin films.
  • Household appliance casings, vehicle interior parts, interior building materials, wallpaper, decorative boards, entrance doors, window frames, widths It can also be used by being laminated on wood or the like.
  • the polarizing plate of the present invention at least one of the protective layers on both sides of the polarizer is laminated with the polarizer via an adhesive layer formed from a polyvinyl alcohol-based adhesive. It is preferable. More preferably, both of the protective layers on both sides of the polarizer are laminated with the polarizer via an adhesive layer formed from a polybulal alcohol adhesive.
  • the polarizing plate of this invention it is preferable to have an adhesive layer between the said polarizer and the said cellulose resin layer. Moreover, when using the said other protective layer, it is preferable to have an adhesive bond layer between the said polarizer and said other protective layer.
  • the adhesive layer is a layer formed from a polybulal alcohol-based adhesive.
  • the polyvinyl alcohol-based adhesive contains a polyvinyl alcohol-based resin and a crosslinking agent.
  • the polyvinyl alcohol-based resin is not particularly limited.
  • the polyvinyl alcohol resin obtained by saponifying polyvinyl acetate; a derivative thereof; and a monomer co-polymerizable with butyl acetate. And saponified products of copolymers; modified polyvinyl alcohols obtained by polyacetalization, polyacetalization, urethane conversion, etherification, grafting, phosphate esterification, and the like.
  • Examples of the monomer include unsaturated carboxylic acids such as (anhydrous) maleic acid, fumaric acid, crotonic acid, itaconic acid, and (meth) acrylic acid and esters thereof; ⁇ -olefins such as ethylene and propylene, ( (Meth) aryl sulfonic acid (soda), sulfonic acid soda (monoanorequinolemaleate), disnolephonic acid soda anorequinolemaleate, ⁇ -methylo-noraretalinoreamide, acrylamidoalkyl sulfonic acid alkali salt, ⁇ ⁇ -Bulpyrrolidone, ⁇ _ Examples include bulurpyrrolidone derivatives. These polybulal alcohol resins can be used only for one type, or can be used in combination with two or more types.
  • the above polybulal alcohol resin preferably has an average degree of polymerization of 100 to 3000, more preferably 500 to 3000, and an average degree of polymerization of preferably 85 to 100 monolayer. 0/0, more preferably f or 90: 100 Monore 0/0.
  • a polyvinyl alcohol-based resin having a acetoacetyl group can be used as the polyvinyl alcohol-based resin.
  • a polyvinyl alcohol-based resin having a acetoacetyl group is a polyvinyl alcohol-based adhesive having a highly reactive functional group, which is preferable in terms of improving the durability of the polarizing plate.
  • a polybulualcohol-based resin containing a acetoacetyl group is obtained by reacting a polybulualcohol-based resin with diketene by a known method.
  • a polybutyl alcohol resin is dispersed in a solvent such as acetic acid and diketene is added thereto, and the polybutyl alcohol resin is dissolved in a solvent such as dimethylformamide or dioxane in advance. And a method of adding diketene to this.
  • the method of making polyketol alcohol contact diketene gas or liquid diketene directly is mentioned.
  • the degree of modification of the acetoacetyl group of the polybutyl alcohol resin having a acetoacetyl group is not particularly limited as long as it is 0.1 mol% or more. If it is less than 1 mol%, the adhesive layer has insufficient water resistance, which is inappropriate.
  • Asetasechiru group modification degree is preferably 0.1:! ⁇ 40 mol 0/0, more preferably 1 to 20 mol 0/0.
  • Asetasechiru group modification degree decreases the number of reaction sites with a crosslinking agent exceeds 40 mole 0/0, a small effect of improving the water resistance.
  • the degree of modification of the acetoacetyl group is a value measured by NMR.
  • crosslinking agent those used for polyvinyl alcohol adhesives can be used without particular limitation.
  • a compound having at least two functional groups having reactivity with the polybulal alcohol resin can be used.
  • ethylene diamine, triethylene diamine, hexamethylene diamine, etc., ananolylene diamine having two amino groups and an amino group hexamethylene diamine is particularly preferred
  • ethylene glycol diglycidyl ether polyethylene glycol diglycidyl ether, glycerin di or triglycidyl ether, 1,6-hexanediol diglycidyl ether, tri Chi trimethylolpropane triglycidyl ether, Jigurish
  • the blending amount of the crosslinking agent is preferably 0.:! To 35 parts by weight, and more preferably 10 to 25 parts by weight with respect to 100 parts by weight of the polybulal alcohol resin.
  • a crosslinking agent can be blended in a range of more than 30 parts by weight and not more than 46 parts by weight with respect to 100 parts by weight of the polybutyl alcohol resin.
  • the polyvinyl alcohol-based adhesive preferably further contains a metal compound colloid.
  • the metal compound colloid is one in which fine particles are dispersed in a dispersion basket, and is electrostatically stabilized due to mutual repulsion of the same kind of charge of the fine particles, and has permanent stability.
  • the average particle diameter of the metal compound colloid is 1 to:! OOnm, preferably 1 to 50nm. If the average particle diameter of the metal compound colloid is in the above range, the metal compound can be dispersed substantially uniformly in the adhesive layer, the adhesion between the polarizer and the protective layer can be ensured, and the resulting polarizing plate can be obtained. Can reduce nick defects. The range of the average particle diameter does not adversely affect the polarization characteristics even if transmitted light is scattered by the metal compound in the adhesive layer formed to be considerably smaller than the visible wavelength range.
  • any appropriate colloid may be used as the metal compound colloid.
  • metal compound colloid aluminum Colloids of metal oxides such as sodium, silica, zirconia, titania; colloids of metal salts such as aluminum silicate, magnesium silicate, calcium carbonate, zinc carbonate, barium carbonate, calcium phosphate; celite, talc, clay, kaolin, etc. Mineral colloids; and the like.
  • the metal compound colloid is present in the state of a colloidal solution dispersed in a dispersion medium.
  • a dispersion medium water is preferable.
  • other dispersers such as alcohols can be used.
  • any appropriate concentration can be adopted as long as the object of the present invention can be achieved. For example::! To 50% by weight is preferred, and:! To 30% by weight is more preferred.
  • a stabilizer containing an acid such as nitric acid, hydrochloric acid, or acetic acid can be used.
  • the metal compound colloid is electrostatically stabilized and can be classified into those having a positive charge and those having a negative charge.
  • the metal compound colloid is a non-conductive material. Positive charge and negative charge are distinguished by the charge state of the colloidal surface charge in the solution after the preparation of the adhesive.
  • the charge of the metal compound colloid can be confirmed, for example, by measuring the zeta potential with a zeta potential measuring machine.
  • the surface charge of a metal compound colloid generally varies with pH. Therefore, the surface charge of the metal compound colloid in the present invention is influenced by the pH of the prepared adhesive solution.
  • the pH of the adhesive solution is preferably in the range of 2 to 6, more preferably 2.5 to 5, more preferably 3 to 5, particularly preferably 3.5 to 4.5.
  • a metal compound colloid having a positive charge has a greater effect of suppressing the occurrence of nicks than a metal compound colloid having a negative charge.
  • positively charged metal compound colloids include alumina colloids and titania colloids. Among these, alumina colloid is particularly preferable.
  • the metal compound colloid is preferably blended at a ratio of 200 parts by weight or less (converted value of solid content) with respect to 100 parts by weight of the polybutyl alcohol resin.
  • the compounding ratio of the metal compound colloid is 10 to 200 parts by weight is more preferred with respect to 100 parts by weight of the alcoholic resin. 20 to 175 parts by weight is more preferred. 30 to 150 parts by weight is particularly preferred.
  • the mixing ratio of the metal compound colloid is preferably set to the lower limit of the above range.
  • the adhesive that can be used in the present invention is, for example, a resin solution containing a polybulal alcohol-based resin, and is usually used as an aqueous solution. Any appropriate concentration can be adopted as the solid content concentration in the resin solution. In consideration of coating property and storage stability, the content is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight. Any appropriate viscosity can be adopted as the viscosity of the resin solution. For example: the range of:! ⁇ 50mPa's is preferred. The nick generated during the production of the polarizing plate tends to increase as the viscosity of the resin solution decreases.
  • the adhesive containing the polyvinyl alcohol-based resin the cross-linking agent, and the metal compound colloid. Therefore, even at a low viscosity in the range of 1 to 20 mPa's, the occurrence of nicks can be suppressed, and the occurrence of nicks can be suppressed regardless of the viscosity of the resin solution.
  • Polyvinyl alcohol-based resins containing a acetoacetyl group cannot increase the degree of polymerization compared to general polybutyl alcohol-based resins, and have been used with the low viscosity as described above. By containing the slag, the occurrence of nicks caused by the low viscosity of the resin solution can be suppressed.
  • any appropriate method can be adopted as a method of preparing the resin solution.
  • the metal compound colloid is usually mixed with a polybutyl alcohol resin and the crosslinking agent, and the concentration is appropriately adjusted. Is added to prepare a resin solution.
  • a polyvinyl alcohol resin containing an acetoacetyl group is used as the polyvinyl alcohol resin, or if the amount of the crosslinking agent is large, the polybut alcohol alcohol resin is considered in view of the stability of the solution.
  • the metal compound colloid can be mixed, and then the cross-linking agent can be mixed in consideration of the timing of use of the resulting resin solution. Tree that is adhesive
  • the concentration of the fat solution can be appropriately adjusted after preparing the resin solution.
  • the polyvinyl alcohol-based adhesive further includes coupling agents such as silane coupling agents and titanium coupling agents, various tackifiers, UV absorbers, antioxidants, heat stabilizers, and water resistance. Stabilizers such as decomposition stabilizers can also be blended.
  • the polarizer protective film of the present invention is provided on the side where the polarizer is provided, or on the side provided with the polarizer of the protective layer when the other protective layer is used, in order to improve adhesion.
  • Adhesive treatment can be applied.
  • Examples of the easy adhesion treatment include surface treatment such as corona treatment, plasma treatment, low-pressure UV treatment, and saponification treatment.
  • An easy-adhesion layer is preferably formed between the protective layer and the adhesive layer in order to improve adhesion.
  • Examples of the easy-adhesion layer include a silicone layer having a reactive functional group.
  • the material of the silicone layer having a reactive functional group is not particularly limited.
  • a titanium-based catalyst or tin-based catalyst for efficiently reacting the above silanol it is possible to strengthen the adhesive force.
  • other additives may be added to the silicone having the reactive functional group. Specifically, terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins and other tackifiers, UV absorbers, antioxidants, heat stabilizers and other stabilizers may be used.
  • the silicone layer having a reactive functional group is formed by coating and drying by a known technique.
  • the thickness of the silicone layer is preferably 1 to 100 nm, more preferably 10 to 80 nm after drying.
  • silicone with reactive functional groups may be diluted with a solvent.
  • the dilution solvent is not particularly limited, and examples thereof include alcohols. Dilution concentration is special The amount is preferably, but not limited to: !! to 5% by weight, more preferably 1 to 3% by weight.
  • the adhesive layer is preferably formed by applying the adhesive.
  • the adhesive may be applied to either the polarizer protective film or the polarizer.
  • the adhesive may be applied to either the polarizer protective film or the polarizer. In doing so, it may go to either one of the other protective layers and the polarizer or to both.
  • a drying step is performed to form an adhesive layer composed of a coated and dried layer. This can also be bonded after forming the adhesive layer.
  • the polarizer and the polarizer protective film can be bonded together using a roll laminator or the like. The heat drying temperature and drying time are appropriately determined according to the type of adhesive.
  • the thickness of the adhesive layer is preferably 0.01 to 10 zm, more preferably 0.03 to 5xm.
  • the thickness of the adhesive layer is designed to be larger than the average particle size of the metal compound colloid.
  • the polarizing plate of the present invention may have an adhesive layer as at least one of the outermost layers (such a polarizing plate may be referred to as an adhesive polarizing plate).
  • an adhesive polarizing plate may be referred to as an adhesive polarizing plate.
  • other side of the polarizer protective film of the present invention where the polarizer is not bonded, or when the other protective layer is used, on the side where the polarizer of the protective layer is not bonded An adhesive layer for adhering to other members such as an optical film and a liquid crystal cell can be provided.
  • the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited.
  • an acrylic polymer, silicone-based polymer, polyester, polyurethane, polyamide, polyether, fluorine-based or rubber-based polymer is used as a base polymer.
  • those having excellent optical transparency such as an acrylic pressure-sensitive adhesive, exhibiting appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and having excellent weather resistance, heat resistance and the like can be preferably used.
  • an acrylic adhesive made of an acrylic polymer having 4 to 12 carbon atoms is preferred.
  • the pressure-sensitive adhesive layer includes, for example, natural and synthetic resins, in particular, tackifier resins, fillers and pigments made of glass fibers, glass beads, metal powders, other inorganic powders, and coloring.
  • An additive to be added to the pressure-sensitive adhesive layer such as an agent and an antioxidant may be contained.
  • An adhesive layer containing fine particles and exhibiting light diffusibility may also be used.
  • the pressure-sensitive adhesive layer can be attached by an appropriate method.
  • an adhesive solution of about 10 to 40% by weight in which a base polymer or a composition thereof is dissolved or dispersed in a solvent composed of a single solvent or a mixture of appropriate solvents such as toluene and ethyl acetate is prepared.
  • the pressure-sensitive adhesive layer may be provided on one side or both sides of the polarizing plate as a superimposed layer of different compositions or types. Moreover, when providing in both surfaces, it can also be set as adhesive layers with a different composition, a kind, thickness, etc. in the front and back of a polarizing plate.
  • the thickness of the pressure-sensitive adhesive layer can be appropriately determined according to the purpose of use and adhesive force, and is preferably 1 to 40 ⁇ m, more preferably 5 to 30 ⁇ m, and particularly preferably 10 ⁇ 25 ⁇ m. If it is thinner than 1 / m, the durability will be poor, and if it is thicker than 40 ⁇ , it will be liable to float or peel off due to foaming, resulting in poor appearance.
  • an anchor layer may be provided between the layers.
  • the anchor layer is preferably an anchor layer selected from polyurethane, polyester, and polymers containing amino groups in the molecule, particularly preferably polymers containing amino groups in the molecule. Is done. Polymers containing amino groups in the molecule are good because they exhibit interactions such as amino group strength in the molecule, carboxyl groups in the adhesive, polar groups in the conductive polymer, and ionic interactions. Secure adhesion.
  • polymers containing an amino group in the molecule include polyethyleneimine, polyallylamine, polybulamine, polybulurpyridine, polybulurpyrrolidine, and dimethylaminoethyl represented by a copolymerization monomer of the aforementioned acrylic adhesive. Contains amino groups such as attalylate Examples thereof include a monomer polymer.
  • an antistatic agent may be added.
  • Antistatic agents for imparting antistatic properties include ionic surfactants, conductive polymer systems such as polyaniline, polythiophene, polypyrrole, and polyquinoxaline, and metal oxide systems such as tin oxide, antimony oxide, and indium oxide.
  • a conductive polymer system is preferably used.
  • water-soluble conductive polymers such as polyaniline and polythiophene or water-dispersible conductive polymers are particularly preferably used. This is because when a water-soluble conductive polymer or a water-dispersible conductive polymer is used as a material for forming the antistatic layer, it is possible to suppress deterioration of the optical film substrate due to the organic solvent during the coating process.
  • the polarizer, polarizer protective film, and the like forming the polarizing plate described above, and the pressure-sensitive adhesive layer each include a salicylic acid ester compound, a benzophenol compound, and a benzotriazole compound.
  • the compound may be one having UV absorbing ability by a method such as a method of treating with a UV absorber such as a cyanoacrylate compound or a nickel complex compound.
  • a cellulose resin layer is provided on at least one surface side of a polarizer, and the water content of the cellulose resin layer is 3.1 wt% to 4.0 wt%.
  • the polarizing plate of the present invention is not limited to be provided on either the viewing side or the backlight side of the liquid crystal cell, or on both sides.
  • the image display device of the present invention includes at least one polarizing plate of the present invention.
  • a liquid crystal display device will be described as an example, but it goes without saying that the present invention can be applied to any display device that requires a polarizing plate.
  • a self-luminous display device such as ED (Field Emission Display) can be mentioned.
  • FIG. 3 is a schematic cross-sectional view of a liquid crystal display device according to a preferred embodiment of the present invention.
  • a transmissive liquid crystal display device will be described, but it goes without saying that the present invention is also applied to a reflective liquid crystal display device and the like.
  • the liquid crystal display device 100 includes a liquid crystal cell 10, a retardation film 20 and 20 'disposed with the liquid crystal cell 10 interposed therebetween, and a polarizing plate 30 disposed on the outside of the retardation films 20 and 20'. 30 ', a light guide plate 40, a light source 50, and a reflector 60.
  • the polarizing plates 30 and 30 ′ are arranged so that their polarization axes are orthogonal to each other.
  • the liquid crystal cell 10 includes a pair of glass substrates 11 and 11 ′ and a liquid crystal layer 12 as a display medium disposed between the substrates.
  • One substrate 11 is provided with a switching element (typically a TFT) for controlling the electro-optical characteristics of the liquid crystal, and a scanning line for supplying a gate signal to the switching element and a signal line for supplying a source signal. (Both not shown).
  • the other glass substrate 11 ′ is provided with a color layer constituting a color filter and a light shielding layer (black matrix layer) (both not shown).
  • a space (cell gap) between the substrates 11 and 11 ′ is controlled by a spacer 13.
  • the polarizing plate of the present invention described above is employed as at least one of the polarizing plates 30 and 30 ′.
  • such a liquid crystal display device 100 arranges IJ in such a state that the liquid crystal molecules of the liquid crystal layer 12 shift the polarization axis by 90 degrees when no voltage is applied. In such a state, incident light that is transmitted through only one direction of light by the polarizing plate is twisted 90 degrees by the liquid crystal molecule. As described above, since the polarizing plates are arranged so that their polarization axes are orthogonal to each other, the light (polarized light) reaching the other polarizing plate is transmitted through the polarizing plate. Therefore, when no voltage is applied, the liquid crystal display device 100 performs white display (normally white method).
  • the moisture content of the film was determined by loss on drying. That is, the weight of the film (10 cm ⁇ 10 cm) obtained in the example and the comparative example was measured, and then the weight after drying for 2 hours in an oven at 120 ° C. was measured. Rate.
  • the obtained polarizing plate was cut into a size of lOcm ⁇ 10 cm, placed on the plane so that the convex side was on the lower side, and the distance of the portion farthest from the plane of the polarizing plate was defined as the curl amount.
  • a polarizing plate was cut out so as to have a size of 1000 mm ⁇ 1000 mm, and a sampnore was produced. Under a fluorescent lamp, another polarizing plate (confirmed that there is no defect) was provided on the black light, and the above-mentioned Sampnore polarizing plate was placed thereon. The two polarizing plates were installed so that their absorption axes were orthogonal to each other, and in this state, the number of locations where light escaped (knic defects) was counted visually.
  • a mixture of methyl methacrylate (2 parts by weight), methacrylic acid (9 parts by weight) and potassium persulfate (0.005 parts by weight) was continuously added at 70 ° C. over 90 minutes, and maintained for another 90 minutes.
  • the shell layer was polymerized.
  • the polymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to obtain core-shell type acrylic elastic particles (B).
  • the average particle diameter of the rubber polymer part of the Atalinole elastic particles measured with an electron microscope was 140 nm.
  • the obtained acrylic resin composition (C) was vacuum-dried at 80 ° C for 8 hours, then dissolved in methyl ethyl ketone to a solid content concentration of 30% by weight, and filtered using a 1 xm cut filter. I went over.
  • This solution is cast on a PE T film through a T die with a lip gap of 0.5 mm using a gear pump, and heat-treated for 30 minutes in each of three stages of 60 ° C, 120 ° C, and 170 ° C in a hot air oven. And a (meth) acrylic resin film having a thickness of 100 / im was obtained.
  • Polybutyl alcohol-based adhesive solution prepared by adjusting an aqueous solution containing 20 parts by weight of methylol melamine to 100 parts by weight of a poly (butyl alcohol resin) modified with acetoacetyl group (degree of acetylation 13%) to a concentration of 0.5% by weight (A) was prepared.
  • Asetasechiru group-modified poly Bulle alcohol resin 100 parts by weight (average polymerization degree: 12 00, saponification degree: 98.5 Monore 0/0, Asetasechiru degree: 5 mol 0/0) with respect Mechirorumera Min 50 parts by weight was dissolved in pure water under a temperature condition of 30 ° C. to prepare an aqueous solution adjusted to a solid content concentration of 3.7% by weight.
  • An aqueous adhesive solution (B) was prepared by adding 18 parts by weight of an aqueous colloidal alumina solution (average particle size: 15 nm, solid content concentration: 10% by weight, positive charge) to 100 parts by weight of the aqueous solution.
  • the viscosity of the aqueous adhesive solution (B) was 9.6 mPa's.
  • the pH of the aqueous adhesive solution (B) was in the range of 4 to 4.5.
  • an aqueous adhesive solution (C) was prepared in the same manner as in Production Example 4 except that the alumina colloid aqueous solution was not used.
  • a saponified 40 ⁇ m-thick triacetyl cellulose film (manufactured by Konica Minoltabuto Co., Ltd., trade name: KC4UY) was prepared and immersed in a 60 ° C. water bath for 30 seconds and washed with water. Thereafter, drying was carried out at a drying temperature of 30 ° C. for 10 seconds to obtain a triacetyl cellulose film (1) having a moisture content of 3.3% by weight.
  • a triacetylcellulose film (2) having a water content of 3.8% by weight was obtained in the same manner as in Example 1 except that air drying was performed for 30 seconds.
  • Example 2 The same procedure as in Example 1 was performed except that drying was performed at a drying temperature of 30 ° C for 30 seconds. A triacetylcellulose film (CI) having a content of 3.0% by weight was obtained.
  • CI triacetylcellulose film
  • a triacetyl cellulose film (C2) having a water content of 2.8% by weight was obtained by performing the same procedure as in Example 1 except that drying was performed at a drying temperature of 40 ° C. for 10 seconds.
  • a triacetylcellulose film (C3) having a water content of 2.4% by weight was obtained in the same manner as in Example 1 except that drying was performed at a drying temperature of 40 ° C. for 30 seconds.
  • a triacetyl cellulose film (C4) having a water content of 1.9% by weight was obtained in the same manner as in Example 1 except that drying was performed at a drying temperature of 60 ° C. for 10 seconds.
  • a triacetylcellulose film (C5) having a water content of 1.5% by weight was obtained in the same manner as in Example 1 except that drying was performed at a drying temperature of 60 ° C. for 30 seconds.
  • a triacetylcellulose film (C6) having a water content of 1.3% by weight was obtained in the same manner as in Example 1 except that drying was performed at a drying temperature of 80 ° C. for 10 seconds.
  • a triacetylcellulose film (C7) having a water content of 1.4% by weight was obtained in the same manner as in Example 1 except that drying was performed at a drying temperature of 80 ° C. for 30 seconds.
  • a triacetyl cellulose film (C8) having a water content of 4.5% by weight was obtained by carrying out in the same manner as in Example 1 except that drying was not performed.
  • Triacetyl cellulose film (1) Z polarizer A polarizing plate (1A) comprising a Z (meth) acrylic resin film was prepared. Specifically, the triacetyl cellulose film (1) was obtained on one side of the polarizer obtained in Production Example 1 and the (meth) acrylic resin film was obtained on the other side of the polarizer in Production Example 3. The resulting polybulualcohol-based adhesive aqueous solution (A) was attached to obtain a polarizing plate (1A). Polyvinyl alcohol adhesive water-soluble Liquid (A) was applied to triacetyl cellulose film (1) and (meth) acrylic resin film, respectively, and dried at 70 ° C. for 10 minutes to obtain polarizing plate (1A). The curl amount of the obtained polarizing plate (1A) was measured and found to be 1 mm. The results are shown in Table 1.
  • a polarizing plate (2A) was produced in the same manner as in Example 3 except that the triacetylcellulose film (2) was used instead of the triacetyl cellulose film (1).
  • the curl amount of the obtained polarizing plate (2A) was measured and found to be 3 mm. The results are shown in Table 1.
  • An array and a polarizing plate (C1A) were prepared in the same manner as in Example 3 except that the triacetylcellulose film (C1) was used instead of the triacetylcellulose film (1).
  • the curling amount of the obtained polarizing plate (C1A) was measured to be _8 mm. The results are shown in Table 1.
  • a polarizing plate (C2A) was produced in the same manner as in Example 3 except that the triacetylcellulose film (C2) was used instead of the triacetyl cellulose film (1).
  • the curl amount of the obtained polarizing plate (C2A) was measured and found to be 10 mm. The results are shown in Table 1.
  • a polarizing plate (C3A) was produced in the same manner as in Example 3 except that a triacetylcellulose film (C3) was used instead of the triacetylcellulose film (1).
  • the curl amount of the obtained polarizing plate (C3A) was measured and found to be 18 mm. The results are shown in Table 1.
  • An array and a polarizing plate (C4A) were prepared in the same manner as in Example 3 except that the triacetylcellulose film (C4) was used instead of the triacetyl cellulose film (1).
  • the curl amount of the obtained polarizing plate (C4A) was measured to be _15 mm. The results are shown in Table 1.
  • An array and a polarizing plate (C5A) were prepared in the same manner as in Example 3 except that the triacetylcellulose film (C5) was used instead of the triacetyl cellulose film (1).
  • the curl amount of the obtained polarizing plate (C5A) was measured to be _15 mm. The results are shown in Table 1.
  • a polarizing plate (C6A) was produced in the same manner as in Example 3 except that a triacetylcellulose film (C6) was used instead of the triacetylcellulose film (1).
  • the curl amount of the obtained polarizing plate (C6A) was measured and found to be 16 mm. The results are shown in Table 1.
  • An array and a polarizing plate (C7A) were produced in the same manner as in Example 3 except that the triacetylcellulose film (C7) was used instead of the triacetyl cellulose film (1).
  • the curl amount of the obtained polarizing plate (C7A) was measured to be _14 mm. The results are shown in Table 1.
  • An array and a polarizing plate (C8A) were prepared in the same manner as in Example 3 except that the triacetylcellulose film (C8) was used instead of the triacetyl cellulose film (1).
  • the curl amount of the obtained polarizing plate (C8A) was measured and found to be 10 mm. The results are shown in Table 1.
  • the occurrence of curling can be remarkably suppressed.
  • the water content of the triacetyl cellulose film is less than 3.1% by weight or more than 4.0% by weight (Comparative Examples 9 to 16)
  • a polarizing plate (1A) having a composition of triacetyl cellulose film (1) / polarizer / (meth) acrylic resin film was produced. Specifically, the triacetyl cellulose film (1) was obtained on one side of the polarizer obtained in Production Example 1, and the (meth) acrylic resin film was obtained on the other side of the polarizer in Production Example 4. The resulting polybulualcohol-based adhesive aqueous solution (B) was bonded to obtain a polarizing plate (1B). Polyvinyl alcohol adhesive aqueous solution (B) was applied to triacetyl cellulose film (1) and (meth) acrylic resin film, respectively, and dried at 70 ° C for 10 minutes to obtain polarizing plate (1B). It was. The curl amount of the obtained polarizing plate (1B) was measured to be _lmm. When the number of knick defects in the obtained polarizing plate (1B) was measured, it was 0. The results are shown in Table 2.
  • An array and a polarizing plate (2B) were prepared in the same manner as in Example 5 except that the triacetyl cellulose film (2) was used instead of the triacetyl cellulose film (1).
  • the curl amount of the obtained polarizing plate (2B) was measured and found to be 3 mm.
  • the number of knick defects in the obtained polarizing plate (2B) was measured and found to be 0. The results are shown in Table 2.
  • Example 5 the polyvinyl alcohol-based adhesive aqueous solution (C) obtained in Production Example 5 was used in place of the polybulualcohol-based adhesive aqueous solution (B) obtained in Production Example 4. Was carried out in the same manner as in Example 5 to produce a polarizing plate (3B).
  • the curl amount of the obtained polarizing plate (3B) was measured and found to be 3 mm.
  • the number of knick defects in the obtained polarizing plate (3B) was measured and found to be 32.
  • Table 2 The results are shown in Table 2.
  • Example 6 except that the polyvinyl alcohol-based adhesive aqueous solution (C) obtained in Production Example 5 was used in place of the polyvinyl alcohol-based adhesive aqueous solution (B) obtained in Production Example 4. Was carried out in the same manner as in Example 6 to produce a polarizing plate (4B).
  • the curl amount of the obtained polarizing plate (4B) was measured and found to be Omm.
  • the number of knick defects in the obtained polarizing plate (4B) was measured and found to be 29. The results are shown in Table 2.
  • Triacetyl cellulose film (C1) instead of triacetyl cellulose film (1)
  • a polarizing plate (C1B) was produced in the same manner as in Example 5 except that was used.
  • the curl amount of the obtained polarizing plate (C1B) was measured and found to be 8 mm.
  • the number of knack defects of the obtained polarizing plate (C1B) was measured and found to be 0.
  • the results are shown in Table 2.
  • An array and a polarizing plate (C2B) were prepared in the same manner as in Example 5 except that the triacetylcellulose film (C2) was used instead of the triacetyl cellulose film (1).
  • the curl amount of the obtained polarizing plate (C2B) was measured to be _10 mm.
  • the number of knack defects of the obtained polarizing plate (C2B) was measured and found to be 0. The results are shown in Table 2.
  • An array and a polarizing plate (C3B) were prepared in the same manner as in Example 5 except that the triacetylcellulose film (C3) was used instead of the triacetyl cellulose film (1).
  • the curling amount of the obtained polarizing plate (C3B) was measured to be _18 mm.
  • the number of knack defects of the obtained polarizing plate (C3B) was measured and found to be 0. The results are shown in Table 2.
  • a triacetyl cellulose film (C4) was used in place of the triacetyl cellulose film (1), and the polyvinyl alcohol adhesive solution (C) obtained in Production Example 5 was used instead of the polybutyl alcohol adhesive solution (B).
  • a polarizer and a polarizing plate (C4B) were produced in the same manner as in Example 5 except that the above was used.
  • the curl amount of the obtained polarizing plate (C4B) was measured and found to be -15 mm.
  • the number of knick defects in the obtained polarizing plate (C4B) was measured and found to be 28. The results are shown in Table 2.
  • An array and a polarizing plate (C5B) were prepared in the same manner as in Example 5 except that the triacetylcellulose film (C5) was used instead of the triacetyl cellulose film (1).
  • the curl amount of the obtained polarizing plate (C5B) was measured to be _15 mm.
  • the number of knack defects of the obtained polarizing plate (C5B) was measured and found to be 0. The results are shown in Table 2.
  • An array and a polarizing plate (C6B) were prepared in the same manner as in Example 5 except that the triacetylcellulose film (C6) was used instead of the triacetyl cellulose film (1). Obtained polarizing plate The curl amount of (C6B) was measured and found to be 16 mm. The number of knack defects of the obtained polarizing plate (C6B) was measured to be 2. The results are shown in Table 2.
  • An array and a polarizing plate (C7B) were prepared in the same manner as in Example 5 except that the triacetylcellulose film (C7) was used instead of the triacetyl cellulose film (1).
  • the curl amount of the obtained polarizing plate (C7B) was measured to be _14 mm.
  • the number of knack defects of the obtained polarizing plate (C7B) was measured, it was 1.
  • the results are shown in Table 2.
  • An array and a polarizing plate (C8B) were prepared in the same manner as in Example 5 except that the triacetylcellulose film (C8) was used instead of the triacetyl cellulose film (1).
  • the curl amount of the obtained polarizing plate (C8B) was measured and found to be 10 mm.
  • the number of knack defects of the obtained polarizing plate (C8B) was measured and found to be 1. The results are shown in Table 2.
  • Comparative Example 20 except that the polyvinyl alcohol-based adhesive aqueous solution (B) obtained in Production Example 4 was used in place of the polybutyl alcohol-based adhesive aqueous solution (C) obtained in Production Example 5.
  • a polarizing plate (C9B) was produced.
  • the curl amount of the obtained polarizing plate (C9B) was measured and found to be 15 mm.
  • the number of knick defects in the obtained polarizing plate (C9B) was measured and found to be 0.
  • Table 2 The results are shown in Table 2.
  • the polarizer protective film and polarizing plate of the present invention can be suitably used for various image display devices (liquid crystal display devices, organic EL display devices, PDPs, etc.).

Abstract

This invention simply provides a polarizer protective film, which can suppress the occurrence of curling on a high level, simply provides a polarizing plate, which can suppress the occurrence of curling on a high level, is less likely to cause separation in the state of being laminated onto a liquid crystal cell and has excellent appearance, and provides a high-definition image display device using the polarizing plate. The polarizer protective film is composed mainly of a cellulosic resin and has a water content of 3.1% by weight to 4.0% by weight. The polarizing plate comprises a protective layer provided on both sides of a polarizer. At least one of the protective layers is a cellulosic resin layer, and the cellulosic resin layer is formed using the polarizer protective film.

Description

明 細 書  Specification
偏光子保護フィルム、偏光板、および画像表示装置  Polarizer protective film, polarizing plate, and image display device
技術分野  Technical field
[0001] 本発明は、偏光子保護フィルム、偏光板、および、その偏光板を少なくとも 文含む 、液晶表示装置、有機 EL表示装置、 PDP等の画像表示装置に関する。  TECHNICAL FIELD [0001] The present invention relates to a polarizer protective film, a polarizing plate, and an image display device such as a liquid crystal display device, an organic EL display device, and a PDP, including at least the sentence.
背景技術  Background art
[0002] 画像表示装置に用いる偏光板は、代表的には、ポリビュルアルコール（PVA)フィ ルムに 2色性を有するヨウ素または 2色性染料で染色して得られる偏光子に、トリァセ チルセルロース (TAC)フィルム等の偏光子保護フィルムを貼り合わせて製造される。  [0002] A polarizing plate used in an image display device is typically a triacetyl cellulose in a polarizer obtained by dyeing polybutyl alcohol (PVA) film with dichroic iodine or a dichroic dye. Manufactured by attaching a polarizer protective film such as (TAC) film.
[0003] 偏光子保護フィルムは、カールが発生しやすい。このため、偏光子保護フィルムを 偏光子の両面側に貼り合わせて得られる偏光板においてもカールが発生しやすくな る。  [0003] The polarizer protective film is likely to curl. For this reason, curling is likely to occur even in a polarizing plate obtained by laminating a polarizer protective film on both sides of the polarizer.
[0004] 偏光板におけるカールの発生は、様々な問題を引き起こす。例えば、液晶セルへ の貼り合わせがスムーズに行えないという問題や、液晶セルに貼り合わせても剥離し やすいという問題や外観が悪くなるという問題がある。上記のような様々な問題は、偏 光板が大型化されるに従って、一層顕著なものとなる。そこで、カールの発生をでき るだけ抑制した偏光板を得るための技術力 Sいくつか提案されている。  [0004] Curling in the polarizing plate causes various problems. For example, there is a problem that the liquid crystal cell cannot be smoothly bonded, a problem that the liquid crystal cell is easily peeled even if it is bonded, and a problem that the appearance is deteriorated. The various problems described above become more prominent as the polarizing plate becomes larger. Therefore, several technical capabilities S have been proposed for obtaining a polarizing plate that suppresses curling as much as possible.
[0005] 偏光子の両面に、カールの向きが逆方向の偏光子保護フィルムをそれぞれ貼り合 わせることで、偏光板におけるカールの発生を抑制する技術が提案されている（特許 文献 1参照）。しかし、偏光板の製造に際して、偏光子の両面に貼り合わせる 2つの 偏光子保護フィルムの互いのカールの向きに留意する必要があり、製造工程が煩雑 になるおそれがある。  [0005] A technique for suppressing the occurrence of curling in a polarizing plate has been proposed by bonding a polarizer protective film with opposite curl directions on both sides of a polarizer (see Patent Document 1). . However, when manufacturing the polarizing plate, it is necessary to pay attention to the direction of the curls of the two polarizer protective films to be bonded to both sides of the polarizer, which may complicate the manufacturing process.
[0006] 粘着剤層およびセパレータが設けられた粘着剤付き偏光板にぉレ、て、粘着剤層お よびセパレータの積層前と積層後の偏光板の水分率を厳密に制御することによって 、偏光板におけるカールの発生を抑制する技術が提案されている（特許文献 2参照） 。しかし、粘着剤層およびセパレータの積層前と積層後の両方の偏光板の水分率を 厳密に制御しなければならず、製造工程が煩雑になるおそれがある。 特許文献 1：特開 2004— 184809号公報 [0006] A polarizing plate provided with an adhesive layer and a separator is provided with a polarizing plate by strictly controlling the moisture content of the polarizing plate before and after the lamination of the adhesive layer and the separator. A technique for suppressing the occurrence of curling in a plate has been proposed (see Patent Document 2). However, it is necessary to strictly control the moisture content of the polarizing plate both before and after the pressure-sensitive adhesive layer and separator are laminated, and the manufacturing process may be complicated. Patent Document 1: Japanese Patent Application Laid-Open No. 2004-184809
特許文献 2 :特開 2005— 326531号公報  Patent Document 2: JP 2005-326531 A
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0007] 本発明は上記従来の課題を解決するためになされたものであり、その目的とすると ころは、（1)カールの発生が高いレベルで抑制された偏光子保護フィルムを簡便に 提供すること、（2)カールの発生が高いレベルで抑制され、液晶セルに貼り合わせて も剥離しにくぐ外観に優れた偏光板を簡便に提供すること、（3)そのような偏光板を 用いた高品位の画像表示装置を提供すること、にある。 [0007] The present invention has been made to solve the above-described conventional problems. The purpose of the present invention is to (1) simply provide a polarizer protective film in which the occurrence of curling is suppressed at a high level. (2) To easily provide a polarizing plate that is suppressed at a high level of curling and has an excellent appearance that is difficult to peel off even when bonded to a liquid crystal cell. (3) Using such a polarizing plate The object is to provide a high-quality image display device.
課題を解決するための手段  Means for solving the problem
[0008] 本発明の偏光子保護フィルムは、セルロース系樹脂を主成分とし、水分含有率が 3[0008] The polarizer protective film of the present invention has a cellulose resin as a main component and a moisture content of 3
. 1重量％〜4. 0重量％である。 1% to 4.0% by weight.
[0009] 好ましい実施形態においては、上記セルロース系樹脂がトリァセチルセルロースで ある。 [0009] In a preferred embodiment, the cellulosic resin is triacetyl cellulose.
[0010] 本発明の別の局面によれば偏光板が提供される。本発明の偏光板は、偏光子の両 面側に保護層を有し、該保護層の少なくとも一方がセルロース系樹脂層である偏光 板であって、該セルロース系樹脂層が本発明の偏光子保護フィルムを用いて形成さ れる。  [0010] According to another aspect of the present invention, a polarizing plate is provided. The polarizing plate of the present invention is a polarizing plate having protective layers on both sides of the polarizer, and at least one of the protective layers is a cellulose resin layer, and the cellulose resin layer is the polarizer of the present invention. It is formed using a protective film.
好ましい実施形態においては、上記セルロース系樹脂層がトリァセチルセルロース 層である。  In a preferred embodiment, the cellulose resin layer is a triacetyl cellulose layer.
好ましい実施形態においては、偏光子の一方の面側のみにセルロース系樹脂層を 有する。  In a preferred embodiment, the cellulose resin layer is provided only on one surface side of the polarizer.
好ましい実施形態においては、偏光子のセルロース系樹脂層を有する面側と反対 の面側に (メタ）アクリル系樹脂を主成分として含む層を有する。  In a preferred embodiment, the polarizer has a layer containing a (meth) acrylic resin as a main component on the side opposite to the side having the cellulose-based resin layer.
[0011] 好ましい実施形態においては、上記偏光子の両面側に有する保護層の少なくとも 一方が、ポリビニルアルコール系接着剤から形成される接着剤層を介して該偏光子 と積層している。  [0011] In a preferred embodiment, at least one of the protective layers on both sides of the polarizer is laminated with the polarizer via an adhesive layer formed from a polyvinyl alcohol-based adhesive.
好ましい実施形態においては、上記偏光子の両面側に有する保護層の両方が、ポ リビニルアルコール系接着剤から形成される接着剤層を介して該偏光子と積層して いる。 In a preferred embodiment, both protective layers on both sides of the polarizer are It is laminated with the polarizer through an adhesive layer formed from a livinyl alcohol adhesive.
好ましい実施形態においては、上記ポリビエルアルコール系接着剤は、ポリビニル アルコール系樹脂と架橋剤を含有する。  In a preferred embodiment, the polyvinyl alcohol-based adhesive contains a polyvinyl alcohol-based resin and a crosslinking agent.
好ましい実施形態においては、上記ポリビュルアルコール系接着剤は、ポリビュル アルコール系樹脂、架橋剤、および平均粒子径が:!〜 lOOnmの金属化合物コロイド を含有する。  In a preferred embodiment, the polybulualcohol-based adhesive contains a polybulualcohol-based resin, a crosslinking agent, and a metal compound colloid having an average particle size of:! To lOOnm.
好ましい実施形態においては、上記金属化合物コロイドは、上記ポリビュルアルコ ール系樹脂 100重量部に対して、 200重量部以下の割合で配合される。  In a preferred embodiment, the metal compound colloid is blended at a ratio of 200 parts by weight or less with respect to 100 parts by weight of the polybulal alcohol resin.
[0012] 好ましい実施形態においては、最外層の少なくとも一方として粘着剤層をさらに有 する。 In a preferred embodiment, an adhesive layer is further provided as at least one of the outermost layers.
[0013] 本発明の別の局面によれば、画像表示装置が提供される。本発明の画像表示装 置は、本発明の偏光板を少なくとも 1枚含む。  [0013] According to another aspect of the present invention, an image display device is provided. The image display device of the present invention includes at least one polarizing plate of the present invention.
発明の効果  The invention's effect
[0014] 本発明によれば、複雑な製造手順を必要とすることなぐカールの発生が高いレべ ルで抑制された偏光子保護フィルムを簡便に提供することができる。さらに、カール の発生が高いレベルで抑制され、液晶セルに貼り合わせても剥離しにくぐ外観に優 れた偏光板を簡便に提供することができる。カロえて、そのような偏光板を用いた高品 位の画像表示装置を提供することができる。  [0014] According to the present invention, it is possible to simply provide a polarizer protective film in which curling is suppressed at a high level without requiring a complicated manufacturing procedure. In addition, it is possible to simply provide a polarizing plate that is suppressed from being curled at a high level and has an excellent appearance that does not easily peel off even when bonded to a liquid crystal cell. It is possible to provide a high-quality image display device using such a polarizing plate.
図面の簡単な説明  Brief Description of Drawings
[0015] [図 1]本発明の偏光板の一例を示す断面図である。  FIG. 1 is a cross-sectional view showing an example of a polarizing plate of the present invention.
[図 2]本発明の偏光板の一例を示す断面図である。  FIG. 2 is a cross-sectional view showing an example of a polarizing plate of the present invention.
[図 3]本発明の好ましい実施形態による液晶表示装置の概略断面図である。  FIG. 3 is a schematic cross-sectional view of a liquid crystal display device according to a preferred embodiment of the present invention.
符号の説明  Explanation of symbols
[0016] 10 液晶セル [0016] 10 liquid crystal cell
11 , 11' ガラス基板  11, 11 'glass substrate
12 液晶層  12 Liquid crystal layer
13 スぺーサー 20、 20' 位相差フィルム 13 Spacer 20, 20 'retardation film
30、 30' 偏光板  30, 30 'polarizing plate
31 偏光子  31 Polarizer
32、 32' 接着剤層  32, 32 'adhesive layer
33、 33' セルロース系樹脂層  33, 33 'Cellulosic resin layer
34 接着剤層  34 Adhesive layer
35 易接着層  35 Easy adhesion layer
36 その他の保護層  36 Other protective layers
40 導光板  40 Light guide plate
50 光源  50 light sources
60 リフレタター  60 Reflector
100 液晶表示装置  100 liquid crystal display
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0017] 以下、本発明の好ましい実施形態について説明するが、本発明はこれらの実施形 態には限定されない。  [0017] Preferred embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.
〔偏光子保護フィルム〕  [Polarizer protective film]
本発明の偏光子保護フィルムは、セルロース系樹脂を主成分とする。セルロース系 樹脂としては、例えば、ジァセチルセルロースゃトリアセチルセルロースが挙げられ、 トリァセチルセルロースが透明性、接着性の点で好ましい。本発明の偏光子保護フィ ルムは、本発明の効果を損なわない範囲で任意の適切なその他の成分を含んでい ても良い。本発明の偏光子保護フィルムは、セルロース系樹脂を好ましくは 90重量 %以上含み、より好ましくは 95重量％以上含み、さらに好ましくは 98重量％以上含 み、特に好ましくは 100重量％含む。  The polarizer protective film of the present invention contains a cellulose resin as a main component. Examples of the cellulose resin include diacetyl cellulose and triacetyl cellulose, and triacetyl cellulose is preferable in terms of transparency and adhesiveness. The polarizer protective film of the present invention may contain any appropriate other component as long as the effects of the present invention are not impaired. The polarizer protective film of the present invention preferably contains 90% by weight or more of a cellulose resin, more preferably 95% by weight or more, still more preferably 98% by weight or more, and particularly preferably 100% by weight.
[0018] 本発明の偏光子保護フィルムの厚みは、好ましくは 20 μ π！〜 100 z m、より好ましく は 30 μ m〜80 μ mである。偏光子保護フィルムの厚みが 20 μ m以上であると、適度 な強度、剛性を有し、ラミネートや印刷等の二次カ卩ェ時に取扱性が良好となる。また 弓 1取り時の応力により発生する位相差も制御が容易で、安定かつ容易にフィルム製 造を行うことが可能である。偏光子保護フィルムの厚みが 100 μ ΐη以下であると、フィ ルム卷き取りが容易になるほか、ライン速度、生産性、そしてコントロール性が容易に なる。 [0018] The thickness of the polarizer protective film of the present invention is preferably 20 μπ! ˜100 zm, more preferably 30 μm to 80 μm. When the thickness of the polarizer protective film is 20 μm or more, it has appropriate strength and rigidity, and handling properties are good at the time of secondary care such as laminating and printing. In addition, the phase difference generated by the stress at the time of cutting the bow can be easily controlled, and the film can be manufactured stably and easily. If the thickness of the polarizer protective film is 100 μΐη or less, In addition to easy rumming, line speed, productivity, and control become easier.
[0019] 本発明の偏光子保護フィルムは、水分含有率が 3. 1重量％〜4. 0重量％である。  [0019] The polarizer protective film of the present invention has a water content of 3.1 wt% to 4.0 wt%.
本発明においては、セルロース系樹脂を主成分とするフィルムの水分含有量をこのよ うな特定の範囲内に調整するという技術手段によって、カールの発生が顕著に抑制 できるという効果が発現できる。水分含有率が 3. 1重量％より少ない場合や 4. 0重 量％より多い場合には、カールが顕著に発生するおそれがある。本発明の偏光子保 護フィルムの水分含有率は、好ましくは 3. 2重量％〜3. 9重量％であり、より好ましく は 3. 3重量％〜3. 8重量％である。  In the present invention, an effect that the occurrence of curling can be remarkably suppressed can be exhibited by a technical means of adjusting the water content of a film mainly composed of a cellulose-based resin within such a specific range. When the water content is less than 3.1% by weight or more than 4.0% by weight, curling may occur remarkably. The water content of the polarizer protective film of the present invention is preferably 3.2 wt% to 3.9 wt%, more preferably 3.3 wt% to 3.8 wt%.
[0020] 本発明の偏光子保護フィルムにおいて水分含有率を上記の特定の範囲内に調整 する手段としては、任意の適切な手段が採用され得る。例えば、偏光子保護フィルム を適切な条件下で水に浸漬したのち、適切な条件下で乾燥させて、水分含有率が上 記の特定の範囲内になるように調整する。  [0020] In the polarizer protective film of the present invention, any appropriate means can be adopted as means for adjusting the water content within the above specific range. For example, the polarizer protective film is immersed in water under appropriate conditions and then dried under appropriate conditions so that the water content is adjusted to be within the specific range described above.
[0021] 本発明の偏光子保護フィルムは、透明で、色付きが無いことが好ましい。具体的に は、厚み方向の位相差値 Rthが、好ましくは 90nm〜 + 90nmであり、より好ましく は 80nm〜 + 80nmであり、特に好ましくは 70nm〜 + 70nmである。  [0021] The polarizer protective film of the present invention is preferably transparent and uncolored. Specifically, the thickness direction retardation value Rth is preferably 90 nm to +90 nm, more preferably 80 nm to +80 nm, and particularly preferably 70 nm to +70 nm.
本発明の偏光子保護フィルムは、上記のように、セルロース系樹脂を主成分とする とともに、水分含有率を 3. 1重量％〜4. 0重量％という特定の範囲内に調整すること により、カールの発生が高いレベルで抑制された偏光子保護フィルムとなる。  As described above, the polarizer protective film of the present invention contains a cellulose-based resin as a main component and adjusts the water content within a specific range of 3.1 wt% to 4.0 wt%. A polarizer protective film in which the occurrence of curling is suppressed at a high level is obtained.
[0022] 〔偏光子〕  [0022] [Polarizer]
本発明の偏光板に用い得る偏光子は、ポリビュルアルコール系樹脂フィルムを二 色性物質 (代表的には、ヨウ素、二色性染料)で染色して一軸延伸したものが用いら れ得る。ポリビュルアルコール系樹脂フィルムを構成するポリビュルアルコール系樹 月旨の重合度は、好ましくは 100〜5000、さらに好ましくは 1400〜4000である。偏光 子を構成するポリビニルアルコール系樹脂フィルムは、任意の適切な方法 (例えば、 樹脂を水または有機溶媒に溶解した溶液を流延成膜する流延法、キャスト法、押出 法）で成形され得る。偏光子の厚みは、偏光板が用いられる LCDの目的や用途に応 じて適宜設定され得るが、代表的には 5〜80 μ mである。 [0023] 偏光子の製造方法としては、 目的、使用材料および条件等に応じて任意の適切な 方法が採用され得る。代表的には、上記ポリビニルアルコール系樹脂フィルムを、膨 潤、染色、架橋、延伸、水洗、および乾燥工程からなる一連の製造工程に供する方 法が採用される。乾燥工程を除く各処理工程においては、それぞれの工程に用いら れる溶液を含む浴中にポリビュルアルコール系樹脂フィルムを浸漬することにより処 理を行う。膨潤、染色、架橋、延伸、水洗、および乾燥の各処理の順番、回数および 実施の有無は、 目的、使用材料および条件等に応じて適宜設定され得る。例えば、 レ、くつかの処理を 1つの工程で同時に行ってもよぐ特定の処理を省略してもよい。よ り詳細には、例えば延伸処理は、染色処理の後に行ってもよぐ染色処理の前に行 つてもよく、膨潤処理、染色処理および架橋処理と同時に行ってもよレ、。また例えば、 架橋処理を延伸処理の前後に行うことが、好適に採用され得る。また例えば、水洗処 理は、すべての処理の後に行ってもよぐ特定の処理の後のみに行ってもよい。 As the polarizer that can be used in the polarizing plate of the present invention, a polybulal alcohol-based resin film dyed with a dichroic substance (typically iodine or a dichroic dye) and uniaxially stretched may be used. The degree of polymerization of the polybulal alcohol-based resin constituting the polybulal alcohol-based resin film is preferably 100 to 5000, and more preferably 1400 to 4000. The polyvinyl alcohol-based resin film constituting the polarizer can be formed by any appropriate method (for example, a casting method in which a solution in which a resin is dissolved in water or an organic solvent is cast, a casting method, an extrusion method). . The thickness of the polarizer can be appropriately set according to the purpose and application of the LCD in which the polarizing plate is used, but is typically 5 to 80 μm. [0023] As a method for producing a polarizer, any appropriate method may be employed depending on the purpose, materials used, conditions, and the like. Typically, a method is employed in which the polyvinyl alcohol-based resin film is subjected to a series of manufacturing steps including swelling, dyeing, crosslinking, stretching, washing, and drying steps. In each of the treatment steps except the drying step, the treatment is performed by immersing the polybulal alcohol-based resin film in a bath containing the solution used in each step. The order, number of times, and presence / absence of each treatment of swelling, dyeing, crosslinking, stretching, washing with water, and drying can be appropriately set according to the purpose, materials used, conditions and the like. For example, a specific process that allows several processes to be performed simultaneously in one process may be omitted. More specifically, for example, the stretching process may be performed after the dyeing process or before the dyeing process, or may be performed simultaneously with the swelling process, the dyeing process, and the crosslinking process. Further, for example, it can be suitably employed to perform the crosslinking treatment before and after the stretching treatment. Further, for example, the water washing process may be performed only after a specific process that may be performed after all the processes.
[0024] 膨潤工程は、代表的には、上記ポリビュルアルコール系樹脂フィルムを水で満たし た処理浴 (膨潤浴）中に浸漬することにより行われる。この処理により、ポリビエルアル コール系樹脂フィルム表面の汚れやブロッキング防止剤を洗浄するとともに、ポリビニ ルアルコール系樹脂フィルムを膨潤させることで染色ムラ等の不均一性を防止し得る [0024] The swelling step is typically carried out by immersing the polybulal alcohol-based resin film in a treatment bath (swelling bath) filled with water. By this treatment, dirt on the surface of the polyvinyl alcohol resin film and an anti-blocking agent can be washed, and unevenness such as uneven dyeing can be prevented by swelling the polyvinyl alcohol resin film.
。膨潤浴には、グリセリンやヨウ化カリウム等が適宜添加され得る。膨潤浴の温度は、 代表的には 20〜60°C程度であり、膨潤浴への浸漬時間は、代表的には 0. ：!〜 10 分程度である。 . Glycerin, potassium iodide, or the like can be appropriately added to the swelling bath. The temperature of the swelling bath is typically about 20 to 60 ° C, and the immersion time in the swelling bath is typically about 0.:! To 10 minutes.
[0025] 染色工程は、代表的には、上記ポリビュルアルコール系樹脂フィルムを、ヨウ素等 の二色性物質を含む処理浴 (染色浴）中に浸漬することにより行われる。染色浴の溶 液に用レ、られる溶媒は、水が一般的に使用されるが、水と相溶性を有する有機溶媒 が適量添加されていてもよい。二色性物質は、溶媒 100重量部に対して、代表的に は 0. 1〜： 1. 0重量部の割合で用いられる。二色性物質としてヨウ素を用いる場合に は、染色浴の溶液は、ヨウ化物等の助剤をさらに含有することが好ましい。染色効率 が改善されるからである。助剤は、溶媒 100重量部に対して、好ましくは 0. 02〜20 重量部、さらに好ましくは 2〜： 10重量部の割合で用いられる。ヨウ化物の具体例とし ては、ヨウ化カリウム、ヨウ化リチウム、ヨウ化ナトリウム、ヨウ化亜鉛、ヨウ化アルミユウ ム、ヨウ化鉛、ヨウ化銅、ヨウ化バリウム、ヨウ化カルシウム、ヨウィヒ錫、ヨウ化チタンが 挙げられる。染色浴の温度は、代表的には 20〜70°C程度であり、染色浴への浸漬 時間は、代表的には：!〜 20分程度である。 [0025] The dyeing step is typically performed by immersing the polybulal alcohol-based resin film in a treatment bath (dye bath) containing a dichroic substance such as iodine. As the solvent used for the dye bath solution, water is generally used, but an appropriate amount of an organic solvent compatible with water may be added. The dichroic substance is typically used at a ratio of 0.1 to 1.0 part by weight with respect to 100 parts by weight of the solvent. When iodine is used as the dichroic substance, the dye bath solution preferably further contains an auxiliary agent such as iodide. This is because the dyeing efficiency is improved. The auxiliary agent is preferably used in a ratio of 0.02 to 20 parts by weight, more preferably 2 to 10 parts by weight with respect to 100 parts by weight of the solvent. Specific examples of iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide , Lead iodide, copper iodide, barium iodide, calcium iodide, yowi tin and titanium iodide. The temperature of the dyeing bath is typically about 20 to 70 ° C, and the immersion time in the dyeing bath is typically about:! To about 20 minutes.
[0026] 架橋工程は、代表的には、上記染色処理されたポリビュルアルコール系樹脂フィル ムを、架橋剤を含む処理浴 (架橋浴）中に浸漬することにより行われる。架橋剤として は、任意の適切な架橋剤が採用され得る。架橋剤の具体例としては、ホウ酸、ホウ砂 等のホウ素化合物、ダリオキザール、ダルタルアルデヒド等が挙げられる。これらは、 単独で、または組み合わせて使用され得る。架橋浴の溶液に用いられる溶媒は、水 が一般的に使用されるが、水と相溶性を有する有機溶媒が適量添加されていてもよ レ、。架橋剤は、溶媒 100重量部に対して、代表的には:!〜 10重量部の割合で用いら れる。架橋剤の濃度力 重量部未満の場合には、十分な光学特性を得ることができ ない場合が多い。架橋剤の濃度が 10重量部を超える場合には、延伸時にフィルムに 発生する延伸力が大きくなり、得られる偏光板が収縮してしまう場合がある。架橋浴 の溶液は、ヨウ化物等の助剤をさらに含有することが好ましい。面内に均一な特性が 得られやすいからである。助剤の濃度は、好ましくは 0. 05〜： 15重量％、さらに好ま しくは 0. 5〜8重量％である。ヨウ化物の具体例は、染色工程の場合と同様である。 架橋浴の温度は、代表的には 20〜70°C程度、好ましくは 40〜60°Cである。架橋浴 への浸漬時間は、代表的には 1秒〜 15分程度、好ましくは 5秒〜 10分である。  [0026] The crosslinking step is typically performed by immersing the dyed polybulal alcohol resin film in a treatment bath (crosslinking bath) containing a crosslinking agent. Any appropriate crosslinking agent can be adopted as the crosslinking agent. Specific examples of the crosslinking agent include boron compounds such as boric acid and borax, darioxal, dartalaldehyde and the like. These can be used alone or in combination. As a solvent used for the solution of the crosslinking bath, water is generally used, but an appropriate amount of an organic solvent having compatibility with water may be added. The crosslinking agent is typically used at a ratio of:! To 10 parts by weight with respect to 100 parts by weight of the solvent. If the concentration of the crosslinking agent is less than parts by weight, sufficient optical properties cannot often be obtained. When the concentration of the crosslinking agent exceeds 10 parts by weight, the stretching force generated in the film during stretching increases, and the resulting polarizing plate may shrink. The solution of the crosslinking bath preferably further contains an auxiliary agent such as iodide. This is because uniform characteristics are easily obtained in the surface. The concentration of the auxiliaries is preferably 0.05 to 15% by weight, more preferably 0.5 to 8% by weight. Specific examples of iodide are the same as those in the dyeing process. The temperature of the crosslinking bath is typically about 20 to 70 ° C, preferably 40 to 60 ° C. The immersion time in the crosslinking bath is typically about 1 second to 15 minutes, preferably 5 seconds to 10 minutes.
[0027] 延伸工程は、上記のように、いずれの段階で行ってもよい。具体的には、染色処理 の後に行ってもよぐ染色処理の前に行ってもよぐ膨潤処理、染色処理および架橋 処理と同時に行ってもよぐ架橋処理の後に行ってもよい。ポリビュルアルコール系 樹脂フィルムの累積延伸倍率は、 5倍以上にすることが必要であり、好ましくは 5〜7 倍、さらに好ましくは 5〜6. 5倍である。累積延伸倍率が 5倍未満である場合には、高 偏光度の偏光板を得ることが困難となる場合がある。累積延伸倍率が 7倍を超える場 合には、ポリビュルアルコール系樹脂フィルム (偏光子）が破断しやすくなる場合があ る。延伸の具体的な方法としては、任意の適切な方法が採用され得る。例えば、湿式 延伸法を採用した場合には、ポリビュルアルコール系樹脂フィルムを、処理浴 (延伸 浴）中で所定の倍率に延伸する。延伸浴の溶液としては、水または有機溶媒 (例えば 、エタノール)などの溶媒中に、各種金属塩、ヨウ素、ホウ素または亜鉛の化合物を添 加した溶液が好適に用いられる。 [0027] The stretching step may be performed at any stage as described above. Specifically, it may be carried out after the crosslinking treatment, which may be carried out after the dyeing treatment or before the dyeing treatment, or may be carried out simultaneously with the swelling treatment, the dyeing treatment and the crosslinking treatment. The cumulative draw ratio of the polybulualcohol-based resin film needs to be 5 times or more, preferably 5 to 7 times, and more preferably 5 to 6.5 times. If the cumulative draw ratio is less than 5 times, it may be difficult to obtain a polarizing plate with a high degree of polarization. When the cumulative draw ratio exceeds 7 times, the polybulualcohol-based resin film (polarizer) may be easily broken. Arbitrary appropriate methods may be employ | adopted as a specific method of extending | stretching. For example, when the wet stretching method is adopted, the polybulualcohol-based resin film is stretched at a predetermined magnification in a treatment bath (stretching bath). The drawing bath solution may be water or an organic solvent (e.g. A solution in which various metal salts, iodine, boron or zinc compounds are added to a solvent such as ethanol) is preferably used.
[0028] 水洗工程は、代表的には、上記各種処理を施されたポリビュルアルコール系樹脂 フィルムを、処理浴 (水洗浴）中に浸漬することにより行われる。水洗工程により、ポリ ビュルアルコール系樹脂フィルムの不要残存物を洗い流すことができる。水洗浴は、 純水であってもよぐヨウ化物（例えば、ヨウ化カリウム、ヨウ化ナトリウム）の水溶液であ つてもよい。ヨウ化物水溶液の濃度は、好ましくは 0.：!〜 10質量％である。ヨウ化物 水溶液には、硫酸亜鉛、塩化亜鉛などの助剤を添加してもよい。水洗浴の温度は、 好ましくは 10〜60°C、さらに好ましくは 30〜40°Cである。浸漬時間は、代表的には 1秒〜 1分である。水洗工程は 1回だけ行ってもよぐ必要に応じて複数回行ってもよ レ、。複数回実施する場合、各処理に用いられる水洗浴に含まれる添加剤の種類や 濃度は適宜調整され得る。例えば、水洗工程は、ポリマーフィルムをヨウ化カリウム水 溶液（0·：!〜 10質量％、 10〜60°C)に 1秒〜 1分浸漬する工程と、純水ですすぐェ 程とを含む。  [0028] The water washing step is typically performed by immersing the polybutyl alcohol-based resin film subjected to the above-described various treatments in a treatment bath (water washing bath). Unnecessary residues of the polybutyl alcohol resin film can be washed away by the water washing process. The washing bath may be an aqueous solution of iodide (eg, potassium iodide or sodium iodide) which may be pure water. The concentration of the aqueous iodide solution is preferably 0.:! To 10% by mass. An auxiliary agent such as zinc sulfate or zinc chloride may be added to the iodide aqueous solution. The temperature of the washing bath is preferably 10 to 60 ° C, more preferably 30 to 40 ° C. The immersion time is typically 1 second to 1 minute. The water washing process can be performed only once or multiple times as necessary. In the case of carrying out a plurality of times, the kind and concentration of the additive contained in the washing bath used for each treatment can be appropriately adjusted. For example, the water washing step includes a step of immersing the polymer film in a potassium iodide aqueous solution (0 · :! to 10% by mass, 10 to 60 ° C.) for 1 second to 1 minute, and a step of rinsing with pure water. .
[0029] 乾燥工程としては、任意の適切な乾燥方法 (例えば、 自然乾燥、送風乾燥、加熱乾 燥）が採用され得る。例えば、加熱乾燥の場合には、乾燥温度は代表的には 20〜8 0°Cであり、乾燥時間は代表的には：!〜 10分である。以上のようにして、偏光子が得 られる。  [0029] Any appropriate drying method (for example, natural drying, air drying, heat drying) may be employed as the drying step. For example, in the case of heat drying, the drying temperature is typically 20 to 80 ° C., and the drying time is typically:! To 10 minutes. As described above, a polarizer is obtained.
[0030] 〔偏光板〕  [Polarizing plate]
本発明の偏光板は、偏光子の両面側に保護層を有し、該保護層の少なくとも一方 がセルロース系樹脂層である。すなわち、偏光子の両方の面側にセルロース系樹脂 層を有していても良いし、一方の面側のみにセルロース系樹脂層を有していても良 レ、。一方の面側のみにセルロース系樹脂層を有している場合には、他方の面側にセ ルロース系樹脂層以外のその他の保護層を有している。  The polarizing plate of the present invention has protective layers on both sides of the polarizer, and at least one of the protective layers is a cellulose resin layer. That is, a cellulose resin layer may be provided on both sides of the polarizer, or a cellulose resin layer may be provided only on one side. In the case where the cellulose resin layer is provided only on one surface side, other protective layers other than the cellulose resin layer are provided on the other surface side.
[0031] 本発明の偏光板の好ましい実施形態の 1つは、図 1に示すように、偏光子 31の一 方の面に、接着剤層 32を介してセルロース系樹脂層 33が積層されてなり、偏光子 3 1のもう一方の面に、接着剤層 32'を介してセルロース系樹脂層 33'が積層されてな る形態である。本発明の偏光板の好ましい実施形態の別の 1つは、図 2に示すように 、偏光子 31の一方の面に、接着剤層 32を介してセルロース系樹脂層 33が積層され てなり、偏光子 31のもう一方の面に、接着剤層 34および易接着層 35を介してその他 の保護層 36が積層されてなる形態である。 [0031] One of the preferred embodiments of the polarizing plate of the present invention is such that a cellulose resin layer 33 is laminated on one surface of a polarizer 31 with an adhesive layer 32 interposed therebetween, as shown in FIG. Thus, the cellulose resin layer 33 ′ is laminated on the other surface of the polarizer 31 via the adhesive layer 32 ′. Another preferred embodiment of the polarizing plate of the present invention is as shown in FIG. The cellulose resin layer 33 is laminated on one surface of the polarizer 31 via the adhesive layer 32, and the other surface of the polarizer 31 via the adhesive layer 34 and the easy adhesion layer 35. The other protective layer 36 is laminated.
[0032] 上記セルロース系樹脂層は、本発明の偏光子保護フィルムを用いて形成される。  [0032] The cellulose-based resin layer is formed using the polarizer protective film of the present invention.
上記セルロース系樹脂層は、セルロース系樹脂を主成分として含む樹脂層であり、 例えば、ジァセチルセルロースゃトリアセチルセルロースを主成分とする樹脂層が挙 げられ、トリァセチルセルロースが透明性、接着性の点で好ましレ、。上記セルロース 系樹脂層は、本発明の効果を損なわない範囲で任意の適切なその他の成分を含ん でいても良い。上記セルロース系樹脂層は、セルロース系樹脂を好ましくは 90重量 %以上含み、より好ましくは 95重量％以上含み、さらに好ましくは 98重量％以上含 み、特に好ましくは 100重量％含む。上記セルロース系樹脂層がトリァセチルセル口 ース層であることが特に好ましレ、。  The cellulose-based resin layer is a resin layer containing a cellulose-based resin as a main component, and examples thereof include a resin layer mainly composed of diacetyl cellulose or triacetyl cellulose, and triacetyl cellulose is transparent and adhesive. Preferable in terms of sex. The cellulose-based resin layer may contain any appropriate other component as long as the effects of the present invention are not impaired. The cellulose resin layer preferably contains 90% by weight or more of the cellulose resin, more preferably 95% by weight or more, further preferably 98% by weight or more, and particularly preferably 100% by weight. It is particularly preferable that the cellulose resin layer is a triacetyl cell mouth layer.
[0033] 上記セルロース系樹脂層の厚みは、好ましくは 20 μ m〜100 μ m、より好ましくは 3 0 μ m〜80 μ mである。  [0033] The cellulose resin layer has a thickness of preferably 20 μm to 100 μm, more preferably 30 μm to 80 μm.
[0034] 本発明の偏光板は、上記のように、偏光子の両面側に保護層を有し、該保護層の 少なくとも一方がセルロース系樹脂層である。上記セルロース系樹脂層は、水分含有 率が 3. 1重量％〜4. 0重量％である上記本発明の偏光子保護フィルムを用いて形 成される。すなわち、本発明の偏光板は、上記本発明の偏光子保護フィルムを偏光 子の少なくとも一方に貼り合わせて形成される。本発明においては、偏光板の作製の 際に、偏光子に貼り合わせる偏光子保護フィルムの水分含有量をこのような特定の 範囲内に調整するという技術手段によって、偏光板におけるカールの発生が顕著に 抑制できるという効果が発現できる。水分含有率が 3. 1重量％より少ない場合や 4. 0重量％より多い場合には、偏光板においてカールが顕著に発生するおそれがある  [0034] As described above, the polarizing plate of the present invention has protective layers on both sides of the polarizer, and at least one of the protective layers is a cellulose resin layer. The cellulose resin layer is formed using the polarizer protective film of the present invention having a water content of 3.1 wt% to 4.0 wt%. That is, the polarizing plate of the present invention is formed by bonding the polarizer protective film of the present invention to at least one of the polarizers. In the present invention, during the production of the polarizing plate, the occurrence of curling in the polarizing plate is remarkable due to the technical means of adjusting the moisture content of the polarizer protective film to be bonded to the polarizer within such a specific range. The effect of being able to be suppressed is manifested. When the water content is less than 3.1% by weight or more than 4.0% by weight, curling may occur significantly in the polarizing plate.
[0035] 本発明の偏光板に用い得るその他の保護層としては、本発明の効果を損なわない 限り、任意の適切な保護層を採用し得る。 As the other protective layer that can be used in the polarizing plate of the present invention, any appropriate protective layer can be adopted as long as the effects of the present invention are not impaired.
[0036] このような保護層の主成分となる材料の具体例としては、ポリエステル系、ポリビニ ノレアルコール系、ポリカーボネート系、ポリアミド系、ポリイミド系、ポリエーテルスルホ ン系、ポリスルホン系、ポリスチレン系、ポリノルボルネン系、ポリオレフイン系、アタリ ル系、アセテート系等の透明樹脂等が挙げられる。また、アクリル系、ウレタン系、ァク リルウレタン系、エポキシ系、シリコーン系等の熱硬化型樹脂または紫外線硬化型榭 脂等も挙げられる。この他にも、例えば、シロキサン系ポリマー等のガラス質系ポリマ 一も挙げられる。また、特開 2001— 343529号公報（WO01Z37007)に記載のポ リマーフィルムも使用できる。このフィルムの材料としては、例えば、側鎖に置換また は非置換のイミド基を有する熱可塑性樹脂と、側鎖に置換または非置換のフエニル 基ならびに二トリル基を有する熱可塑性樹脂を含有する樹脂組成物が使用でき、例 えば、イソブテンと N メチルマレイミドからなる交互共重合体と、アクリロニトリル .ス チレン共重合体とを有する樹脂組成物が挙げられる。上記ポリマーフィルムは、例え ば、上記樹脂組成物の押出成形物であり得る。 [0036] Specific examples of the material which is the main component of such a protective layer include polyester-based, polyvinyl alcohol-based, polycarbonate-based, polyamide-based, polyimide-based, polyether sulfone. Examples thereof include transparent resins such as polyethylene, polysulfone, polystyrene, polynorbornene, polyolefin, talyl, and acetate. Further, examples thereof include thermosetting resins such as acrylic, urethane, acrylurethane, epoxy, and silicone, and ultraviolet curable resins. In addition to this, for example, a glassy polymer such as a siloxane-based polymer is also included. In addition, polymer films described in JP-A-2001-343529 (WO01Z37007) can also be used. Examples of the material of the film include a resin containing a thermoplastic resin having a substituted or unsubstituted imide group in the side chain, and a thermoplastic resin having a substituted or unsubstituted phenyl group and a nitrile group in the side chain. The composition can be used, for example, a resin composition having an alternating copolymer composed of isobutene and N-methylmaleimide and an acrylonitrile / styrene copolymer. The polymer film can be, for example, an extruded product of the resin composition.
[0037] 上記その他の保護層は、透明で、色付きが無いことが好ましい。具体的には、厚み 方向の位相差値が、好ましくは一 90nm〜 + 90nmであり、さらに好ましくは一 80nm 〜 + 80nmであり、最も好ましくは 70nm〜 + 70nmである。  [0037] The other protective layers are preferably transparent and have no color. Specifically, the retardation value in the thickness direction is preferably from 1 to 90 nm, more preferably from 1 to 80 nm, and most preferably from 70 to +70 nm.
[0038] 上記その他の保護層としては、（メタ）アクリル系樹脂を主成分として含む層であるこ とが好ましい態様の 1つである。  [0038] It is one of the preferred embodiments that the other protective layer is a layer containing a (meth) acrylic resin as a main component.
[0039] 上記 (メタ）アクリル系樹脂は、それぞれ、 1種の樹脂からなるものでも良いし、 2種以 上の樹脂からなるものでも良い。  [0039] Each of the (meth) acrylic resins may be composed of one kind of resin, or may be composed of two or more kinds of resins.
[0040] 上記 (メタ）アクリル系樹脂としては、 Tg (ガラス転移温度）が 115°C以上のものが好 ましぐより好ましくは 120°C以上、さらに好ましくは 125°C以上、特に好ましくは 130 °C以上である。 Tg (ガラス転移温度）が 115°C以上である（メタ）アクリル系樹脂を主 成分として含むことにより、例えば、最終的に偏光板に組み入れた場合に、耐久性に 優れたものとなり易い。  [0040] The (meth) acrylic resin preferably has a Tg (glass transition temperature) of 115 ° C or higher, more preferably 120 ° C or higher, still more preferably 125 ° C or higher, and particularly preferably 130 ° C. ° C or higher. By including a (meth) acrylic resin having a Tg (glass transition temperature) of 115 ° C or higher as a main component, for example, when it is finally incorporated into a polarizing plate, it tends to be excellent in durability.
[0041] 上記 (メタ）アクリル系樹脂の Tgの上限値は特に限定されないが、成形性等の点か ら、好ましくは 170°C以下である。  [0041] The upper limit of Tg of the (meth) acrylic resin is not particularly limited, but is preferably 170 ° C or less from the viewpoint of moldability and the like.
[0042] 上記 (メタ）アクリル系樹脂としては、特に限定されないが、例えば、ポリメタクリル酸 メチルなどのポリ（メタ）アクリル酸エステル、メタクリル酸メチル—（メタ）アクリル酸共重 合体、メタクリル酸メチル—（メタ）アクリル酸エステル共重合体、メタクリル酸メチル— アクリル酸エステル （メタ）アクリル酸共重合体、（メタ）アクリル酸メチルースチレン 共重合体 (MS樹脂など）、脂環族炭化水素基を有する重合体 (例えば、メタクリル酸 メチルーメタクリル酸シクロへキシル共重合体、メタクリル酸メチルー（メタ）アクリル酸 ノルボルニル共重合体など）などが挙げられる。好ましくは、ポリ（メタ）アクリル酸メチ ルなどのポリ（メタ）アクリル酸 C アルキルを主成分（50〜： 100重量％、好ましくは 7 [0042] The (meth) acrylic resin is not particularly limited, and examples thereof include poly (meth) acrylic acid esters such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, and methyl methacrylate. — (Meth) acrylic acid ester copolymer, methyl methacrylate— Acrylic ester (meth) acrylic acid copolymer, (meth) acrylic acid methyl-styrene copolymer (MS resin, etc.), polymer having alicyclic hydrocarbon group (for example, methyl methacrylate-cyclomethacrylate) Xyl copolymer, methyl methacrylate- (meth) acrylic acid norbornyl copolymer, etc.). Preferably, poly (meth) acrylic acid C alkyl such as poly (meth) acrylic acid methyl ester as a main component (50 to: 100% by weight, preferably 7
1 -6  1 -6
0〜： 100重量％)とする（メタ）アクリル酸 C アルキル系樹脂が挙げられ、より好まし  0 ~: 100% by weight) (meth) acrylic acid C alkyl resin, more preferred
1 - 6  1-6
くは、メタクリル酸メチルを主成分（50〜： 100重量％、好ましくは 70〜： 100重量％)と するメタクリル酸メチル系樹脂が挙げられる。  Another example is a methyl methacrylate-based resin containing methyl methacrylate as a main component (50 to 100% by weight, preferably 70 to 100% by weight).
[0043] 上記 (メタ）アクリル系樹脂の具体例としては、例えば、三菱レイヨン社製のアタリぺ ット VHやアタリペット VRL20A、特開 2004— 70296号公報に記載の分子内に環構 造を有する (メタ）アクリル系樹脂、分子内架橋や分子内環化反応により得られる高 T g (メタ）アクリル系樹脂が挙げられる。  [0043] Specific examples of the (meth) acrylic resin include, for example, a ring structure in a molecule described in Ataripet VH and Ataripet VRL20A manufactured by Mitsubishi Rayon Co., Ltd., and JP-A-2004-70296. (Meth) acrylic resins having high T g (meth) acrylic resins obtained by intramolecular crosslinking or intramolecular cyclization reactions.
[0044] 本発明においては、上記 (メタ）アクリル系樹脂として、特開 2000— 230016号公 報、特開 2001— 151814号公報、特開 2005— 146084号公報などに記載の、ラタ トン環構造を有する（メタ）アクリル系樹脂や、特開 2005— 314534号公報などに記 載の、ダルタル酸無水物構造を有する (メタ）アクリル系樹脂を用いても良い。  In the present invention, as the above (meth) acrylic resin, a rataton ring structure described in JP-A-2000-230016, JP-A-2001-151814, JP-A-2005-146084, etc. A (meth) acrylic resin having a structure or a (meth) acrylic resin having a dartaric anhydride structure described in JP-A-2005-314534 may be used.
[0045] (メタ）アクリル系樹脂を主成分として含む層中の、 （メタ）アクリル系樹脂の含有量は 、好ましくは 50〜99重量0 /0、より好ましくは 60〜98重量0 /0、さらに好ましくは 70〜9 7重量％である。 （メタ）アクリル系樹脂の含有量が 50重量％未満の場合には、（メタ） アクリル系樹脂が本来有する高耐熱性、高透明性が十分に反映できなレ、おそれがあ り、 99重量％を超える場合には、機械的強度に劣るおそれがある。 [0045] the layer containing the (meth) acrylic resin as a main component, the content of the (meth) acrylic resin is preferably 50 to 99 weight 0/0, more preferably 60 to 98 weight 0/0, More preferably, it is 70 to 97% by weight. If the content of the (meth) acrylic resin is less than 50% by weight, the high heat resistance and high transparency inherent in the (meth) acrylic resin may not be sufficiently reflected. If it exceeds%, the mechanical strength may be inferior.
[0046] 上記その他の保護層中には、任意の適切なその他の成分が含まれていても良い。  [0046] The other protective layer may contain any appropriate other component.
具体的には、例えば、紫外線吸収剤、一般的な配合剤、例えば、安定剤、滑剤、加 ェ助剤、可塑剤、耐衝撃助剤、位相差低減剤、艷消し剤、抗菌剤、防かび等が挙げ られる。  Specifically, for example, an ultraviolet absorber, a general compounding agent, such as a stabilizer, a lubricant, an additive, a plasticizer, an impact assistant, a retardation reducing agent, an antibacterial agent, an antibacterial agent, an antibacterial agent. Examples include mold.
[0047] 偏光子の保護層の光学特性として、正面および厚み方向の位相差の大きさが問題 となる。そのため、上記その他の保護層中には、位相差低減剤が含まれていることが 好ましい。位相差低減剤としては、例えば、アクリロニトリル—スチレン系共重合体な ど、スチレン含有ポリマーが好ましい。位相差低減剤の添加量としては、その他の樹 脂層中の樹脂の総量に対し、 30重量％以下であることが好ましぐより好ましくは 25 重量％以下、さらに好ましくは 20重量％以下である。この範囲を超えて添加した場合 、可視光線を散乱させたり、透明性を損なったりするため、偏光子の保護層としての 特性に欠けてしまうおそれがある。 [0047] As the optical characteristics of the protective layer of the polarizer, the magnitude of the retardation in the front and thickness directions becomes a problem. Therefore, it is preferable that the other protective layer contains a retardation reducing agent. Examples of the phase difference reducing agent include acrylonitrile-styrene copolymer. However, styrene-containing polymers are preferred. The addition amount of the retardation reducing agent is preferably 30% by weight or less, more preferably 25% by weight or less, and still more preferably 20% by weight or less, with respect to the total amount of resin in the other resin layers. is there. If added beyond this range, visible light is scattered or the transparency is impaired, so the properties of the polarizer as a protective layer may be lacking.
[0048] 上記その他の保護層の厚みとしては、上記の好ましい厚み方向の位相差が得られ る限りにおいて、任意の適切な厚みが採用され得る。具体的には、その他の保護層 の厚みは、好ましくは 20〜200 μ πιであり、より好ましくは 25〜： 180 z mであり、さら に好ましくは 30〜： 140 μ mである。その他の保護層の厚みが 20 μ m以上であると、 適度な強度、剛性を有し、ラミネートや印刷等の二次カ卩ェ時に取扱性が良好となる。 また引取り時の応力により発生する位相差も制御が容易で、安定かつ容易にフィノレ ム製造を行うことが可能である。その他の保護層の厚みが 200 z m以下であると、フ イルム卷き取りが容易になるほか、ライン速度、生産性、そしてコントロール性が容易 になる。 [0048] As the thickness of the other protective layer, any appropriate thickness can be adopted as long as the above preferred thickness direction retardation can be obtained. Specifically, the thickness of the other protective layer is preferably 20 to 200 μπι, more preferably 25 to 180 zm, and further preferably 30 to 140 μm. When the thickness of the other protective layer is 20 μm or more, it has appropriate strength and rigidity, and handling properties are good in the secondary care such as laminating and printing. In addition, the phase difference generated by the stress at the time of take-up can be easily controlled, and the finoleum can be manufactured stably and easily. If the thickness of the other protective layer is 200 zm or less, film removal is facilitated, and line speed, productivity, and controllability are also facilitated.
[0049] 上記その他の保護層は、縦延伸および/または横延伸によって延伸されたフィル ムであっても良レ、。縦延伸および/または横延伸によって延伸されてなることにより、 優れた光学的特性を付与することが可能となり、また、機械的強度にも優れ、生産性 ゃリワーク性が向上することも可能となる。  [0049] The other protective layer may be a film stretched by longitudinal stretching and / or lateral stretching. By being stretched by longitudinal stretching and / or lateral stretching, it becomes possible to impart excellent optical properties, and it is also excellent in mechanical strength, and productivity and reworkability can be improved. .
[0050] 上記延伸は、縦延伸のみによる延伸（自由端一軸延伸）でも良いし、横延伸のみに よる延伸（固定端一軸延伸）でも良いが、縦延伸倍率が 1.：!〜 3. 0倍、横延伸倍率 が 1.：!〜 3. 0倍の、逐次延伸または同時二軸延伸であることが好ましい。縦延伸の みによる延伸（自由端一軸延伸）や横延伸のみによる延伸（固定端一軸延伸）では、 延伸方向にのみフィルム強度が上がり、延伸方向に対して直角方向には強度がアツ プせず、フィルム全体として十分なフィルム強度が得られないおそれがある。上記縦 延伸倍率は、より好ましくは 1. 2〜2. 5倍、さらに好ましくは 1. 3〜2. 0倍である。上 記横延伸倍率は、より好ましくは 1. 2〜2. 5倍、さらに好ましくは 1. 4〜2. 5倍である 。縦延伸倍率、横延伸倍率が 1. 1倍未満の場合、延伸倍率が低すぎて、延伸の効 果がほとんどないおそれがある。縦延伸倍率、横延伸倍率が 3. 0倍を超えると、フィ ルム端面の平滑性の問題により、延伸切れが生じやすい。 [0050] The stretching may be stretching by only longitudinal stretching (free-end uniaxial stretching) or stretching by only lateral stretching (fixed-end uniaxial stretching), but the longitudinal stretching ratio is 1.:! To 3.0. It is preferable to perform sequential stretching or simultaneous biaxial stretching with a magnification of 1.times. In stretching by only longitudinal stretching (free end uniaxial stretching) and stretching by only transverse stretching (fixed end uniaxial stretching), the film strength increases only in the stretching direction, and the strength does not increase in the direction perpendicular to the stretching direction. The film as a whole may not have sufficient film strength. The longitudinal draw ratio is more preferably 1.2 to 2.5 times, and still more preferably 1.3 to 2.0 times. The transverse stretching ratio is more preferably 1.2 to 2.5 times, and still more preferably 1.4 to 2.5 times. When the longitudinal draw ratio and the transverse draw ratio are less than 1.1 times, the draw ratio may be too low and there may be little effect of stretching. If the longitudinal draw ratio and transverse draw ratio exceed 3.0, Due to the problem of the smoothness of the end face of the rumm, the stretch breakage is likely to occur.
[0051] 上記延伸温度は、延伸させるフィルムの Tg〜（Tg + 30°C)が好ましレ、。上記延伸 温度が Tgより低いと、フィルムが破断してしまうおそれがある。上記延伸温度が (Tg + 30°C)を超えると、フィルムが溶融し始めて通紙が困難になるおそれがある。  [0051] The stretching temperature is preferably Tg to (Tg + 30 ° C) of the film to be stretched. If the stretching temperature is lower than Tg, the film may be broken. If the stretching temperature exceeds (Tg + 30 ° C), the film may start to melt, making it difficult to pass the paper.
[0052] 上記その他の保護層は、任意の適切な方法で製造し得る。例えば、溶融押出しに よって得られるフィルムを上記その他の保護層として用いても良い。溶融押出しによ つてフィルムを成形する方法としては、具体的には、 Tダイに連結した押出し機に原 料となる樹脂組成物を供給し、溶融混練後、押出し、水冷して引き取り、フィルムを成 形する方法を例示できる。押出し機のスクリュータイプは単軸または 2軸であってもよ ぐ可塑剤または酸化防止剤などの添加剤を添加してもよい。溶融押出しの温度は 適宜設定できるが、原料となる樹脂組成物のガラス転移温度を Tg (°C)とした場合、（ Tg + 80) °C〜（Tg+ 180) °Cが好ましぐ（Tg+ 100) °C〜（Tg+ 150) °Cがより好ま しい。押出し成形温度が低すぎると、樹脂の流動性がなぐ成形できなくなるおそれ 力 Sある。押出し成形温度が高すぎると、樹脂粘度が低くなり、成形物の厚み不均一等 の生産安定性に問題が生じるおそれがある。  [0052] The other protective layer may be produced by any appropriate method. For example, a film obtained by melt extrusion may be used as the other protective layer. As a method of forming a film by melt extrusion, specifically, a resin composition as a raw material is supplied to an extruder connected to a T-die, and after melt-kneading, it is extruded, cooled by water, and taken out. A method of forming can be exemplified. The screw type of the extruder may be uniaxial or biaxial, and additives such as plasticizers or antioxidants may be added. The temperature of melt extrusion can be set as appropriate, but when the glass transition temperature of the resin composition as the raw material is Tg (° C), (Tg + 80) ° C to (Tg + 180) ° C is preferred (Tg + 100) ° C to (Tg + 150) ° C is more preferred. If the extrusion molding temperature is too low, there is a possibility that molding cannot be performed due to the poor fluidity of the resin. If the extrusion molding temperature is too high, the resin viscosity will be low, and there may be a problem in production stability such as uneven thickness of the molded product.
[0053] 上記その他の保護層は、厚み 80 μ ΐηにおける YI力 好ましくは 1 · 3以下、より好ま しくは 1. 27以下、さらに好ましくは 1. 25以下、さらに好ましくは 1. 23以下、特に好 ましくは 1. 20以下である。厚み 80 /i mにおける YIが 1. 3を超えると、優れた光学的 透明性が発揮されないおそれがある。なお、 YIは、例えば、高速積分球式分光透過 率測定機 (商品名 DOT— 3C：村上色彩技術研究所製)を用レ、、測定で得られる色 の三刺激値 (Χ、 Υ、 Ζ)より、次式によって求めることができる。  [0053] The other protective layer has a YI force at a thickness of 80 μΐη, preferably 1 · 3 or less, more preferably 1.27 or less, more preferably 1.25 or less, more preferably 1.23 or less, particularly Preferably it is 1. 20 or less. If the YI at a thickness of 80 / im exceeds 1.3, excellent optical transparency may not be exhibited. YI uses, for example, a high-speed integrating sphere type spectral transmittance measuring device (trade name: DOT-3C: manufactured by Murakami Color Research Laboratory), and tristimulus values of colors obtained by measurement (Χ, Υ, Ζ ) From the following equation.
YI= [ (1. 28X- 1. 06Z) /Y] X 100  YI = [(1. 28X- 1. 06Z) / Y] X 100
[0054] 上記その他の保護層は、厚み 80 x mにおける b値 (ハンターの表色系に準じた色 相の尺度）が、好ましくは 1. 5未満、より好ましくは 1. 0以下である。 b値が 1. 5以上 の場合、フィルムの着色により、優れた光学的透明性が発揮されないおそれがある。 なお、 b値は、例えば、サンプルを 3cm角に裁断し、高速積分球式分光透過率測定 機 (商品名 DOT— 3C：村上色彩技術研究所製)を用いて色相を測定することができ る。また、色相をハンターの表色系に準じて b値にて評価することができる。 [0055] 上記その他の保護層は、面内位相差 A ndが、好ましくは 3. Onm以下、より好ましく は 1. Onm以下である。上記面内位相差 A ndが 3. Onmを超えると、優れた光学的 特性が発揮されなレ、おそれがある。 [0054] The other protective layer has a b value (hue scale according to Hunter's color system) at a thickness of 80 xm, preferably less than 1.5, and more preferably 1.0 or less. When the b value is 1.5 or more, excellent optical transparency may not be exhibited due to coloring of the film. The b value can be measured, for example, by cutting the sample into 3cm squares and using a high-speed integrating sphere type spectral transmittance measuring machine (trade name DOT-3C: manufactured by Murakami Color Research Laboratory). . In addition, the hue can be evaluated by b value according to Hunter's color system. [0055] The other protective layer has an in-plane retardation And of preferably 3. Onm or less, more preferably 1. Onm or less. If the in-plane retardation And exceeds 3. Onm, excellent optical characteristics may not be exhibited.
[0056] 上記その他の保護層は、厚み方向位相差 Rth力 好ましくは 5. Onm以下、より好 ましくは 3. Onm以下である。上記厚み方向位相差 Rthが 5. Onmを超えると、優れた 光学的特性が発揮されなレ、おそれがある。 [0056] The other protective layer has a thickness direction retardation Rth force of preferably 5. Onm or less, and more preferably 3. Onm or less. When the thickness direction retardation Rth exceeds 5. Onm, excellent optical characteristics may not be exhibited.
[0057] 上記その他の保護層は、透湿度が、好ましくは 100g/m2' 24hr以下、より好ましく は 60gZm2' 24hr以下である。上記透湿度が 100g/m2' 24hrを超えると、耐湿性 に劣るおそれがある。 [0057] These and other protective layer, moisture permeability, preferably 100 g / m 2 '24hr or less, more preferably 60gZm 2' is 24hr or less. If the moisture permeability exceeds 100 g / m 2 '24 hr, the moisture resistance may be poor.
[0058] 上記その他の保護層は、好ましくは、優れた機械的強度をも有する。引張強度は、 MD方向において、好ましくは 65NZmm2以上、より好ましくは 70N/mm2以上、さ らに好ましくは 75N/mm2以上、特に好ましくは 80N/mm2以上であり、 TD方向に おいて、好ましくは 45N/mm2以上、より好ましくは 50N/mm2以上であり、さらに 好ましくは 55N/mm2以上、特に好ましくは 60N/mm2以上である。引張伸びは、 MD方向において、好ましくは 6. 5%以上、より好ましくは 7. 0%以上、さらに好まし くは 7. 5%以上、特に好ましくは 8. 0%以上であり、 TD方向において、好ましくは 5. 0%以上、より好ましくは 5. 5%以上、さらに好ましくは 6. 0%以上、特に好ましくは 6 . 5%以上である。引張強度あるいは引張伸びが上記範囲を外れる場合は、優れた 機械的強度が発揮されなレ、おそれがある。 [0058] The other protective layer preferably also has excellent mechanical strength. Tensile strength, in the MD direction, preferably 65NZmm 2 or more, more preferably 70N / mm 2 or more, preferably in the al 75N / mm 2 or more, particularly preferably 80 N / mm 2 or more, Oite in TD , preferably 45N / mm 2 or more, more preferably 50 N / mm 2 or more, more preferably 55N / mm 2 or more, and particularly preferably 60N / mm 2 or more. The tensile elongation is preferably 6.5% or more, more preferably 7.0% or more, further preferably 7.5% or more, particularly preferably 8.0% or more in the MD direction, and in the TD direction. It is preferably 5.0% or more, more preferably 5.5% or more, still more preferably 6.0% or more, and particularly preferably 6.5% or more. If the tensile strength or tensile elongation is outside the above range, there is a risk that excellent mechanical strength will not be exhibited.
[0059] 上記その他の保護層は、光学的透明性を表すヘイズが、低ければ低いほど良ぐ 好ましくは 5%以下、より好ましくは 3%以下、さらに好ましくは 1. 5%以下、特に好ま しくは 1%以下である。ヘイズが 5%以下であると、フィルムに良好なタリヤー感を視覚 的に与えることができ、さらに 1. 5%以下とすると、窓等の採光部材として使用した時 でも、視認性と採光性がともに得られるため、また、表示装置の前面板として使用した 時でも、表示内容が良好に視認できるため、工業的利用価値が高い。  [0059] The other protective layer has a lower haze that represents optical transparency, and is preferably as low as possible. Preferably it is 5% or less, more preferably 3% or less, even more preferably 1.5% or less, and particularly preferably. Is less than 1%. When the haze is 5% or less, a good tally feeling can be visually given to the film, and when the haze is 1.5% or less, the visibility and the daylighting property can be obtained even when used as a daylighting member such as a window. Both can be obtained, and even when used as a front plate of a display device, the display contents can be visually recognized well, so the industrial utility value is high.
[0060] 本発明の偏光子保護フィルムや上記その他の保護層は、偏光子保護の用途以外 にも、例えば、窓やカーポート屋根材等の建築用採光部材、窓等の車輛用採光部材 、温室等の農業用採光部材、照明部材、前面フィルタ一等のディスプレイ部材等に 積層して用いることができ、また、従来から (メタ）アクリル系樹脂フィルムが被覆されて いた家電の筐体、車輛内装部材、内装用建築材料、壁紙、化粧板、玄関ドア、窓枠 、巾木等にも積層して用いることができる。 [0060] The polarizer protective film of the present invention and the above-mentioned other protective layers are used for, for example, building lighting members such as windows and carport roofing materials, vehicle lighting members such as windows, etc. Agricultural daylighting materials such as greenhouses, lighting members, front filter etc. It can be used in layers, and has been traditionally covered with (meth) acrylic resin films. Household appliance casings, vehicle interior parts, interior building materials, wallpaper, decorative boards, entrance doors, window frames, widths It can also be used by being laminated on wood or the like.
[0061] 本発明の偏光板においては、上記偏光子の両面側に有する保護層の少なくとも一 方が、ポリビニルアルコール系接着剤から形成される接着剤層を介して該偏光子と 積層していることが好ましい。また、上記偏光子の両面側に有する保護層の両方が、 ポリビュルアルコール系接着剤から形成される接着剤層を介して該偏光子と積層し ていることがより好ましい。  [0061] In the polarizing plate of the present invention, at least one of the protective layers on both sides of the polarizer is laminated with the polarizer via an adhesive layer formed from a polyvinyl alcohol-based adhesive. It is preferable. More preferably, both of the protective layers on both sides of the polarizer are laminated with the polarizer via an adhesive layer formed from a polybulal alcohol adhesive.
本発明の偏光板においては、上記偏光子と上記セルロース系樹脂層との間に接着 剤層を有することが好ましい。また、上記その他の保護層を用いる場合、上記偏光子 と上記その他の保護層との間に接着剤層を有することが好ましい。  In the polarizing plate of this invention, it is preferable to have an adhesive layer between the said polarizer and the said cellulose resin layer. Moreover, when using the said other protective layer, it is preferable to have an adhesive bond layer between the said polarizer and said other protective layer.
[0062] 上記接着剤層は、ポリビュルアルコール系接着剤から形成される層であることが好 ましレ、。ポリビニルアルコール系接着剤は、ポリビニルアルコール系樹脂と架橋剤を 含有する。  [0062] Preferably, the adhesive layer is a layer formed from a polybulal alcohol-based adhesive. The polyvinyl alcohol-based adhesive contains a polyvinyl alcohol-based resin and a crosslinking agent.
[0063] 上記ポリビニルアルコール系樹脂は、特に限定されないが、例えば、ポリ酢酸ビニ ルをケン化して得られたポリビュルアルコール；その誘導体；更に酢酸ビュルと共重 合性を有する単量体との共重合体のケン化物；ポリビュルアルコールをァセタール化 、ウレタンィ匕、エーテル化、グラフト化、リン酸エステル化等した変性ポリビエルアルコ ール；などが挙げられる。前記単量体としては、（無水）マレイン酸、フマール酸、クロ トン酸、ィタコン酸、（メタ）アクリル酸等の不飽和カルボン酸及びそのエステル類；ェ チレン、プロピレン等の α—ォレフイン、 （メタ）ァリルスルホン酸（ソーダ）、スルホン酸 ソーダ（モノアノレキノレマレート）、ジスノレホン酸ソーダァノレキノレマレート、 Ν—メチロー ノレアタリノレアミド、アクリルアミドアルキルスルホン酸アルカリ塩、 Ν—ビュルピロリドン、 Ν_ビュルピロリドン誘導体等が挙げられる。これらポリビュルアルコール系樹脂は 1 種のみ用レ、ても良レ、し 2種以上を併用しても良レ、。 [0063] The polyvinyl alcohol-based resin is not particularly limited. For example, the polyvinyl alcohol resin obtained by saponifying polyvinyl acetate; a derivative thereof; and a monomer co-polymerizable with butyl acetate. And saponified products of copolymers; modified polyvinyl alcohols obtained by polyacetalization, polyacetalization, urethane conversion, etherification, grafting, phosphate esterification, and the like. Examples of the monomer include unsaturated carboxylic acids such as (anhydrous) maleic acid, fumaric acid, crotonic acid, itaconic acid, and (meth) acrylic acid and esters thereof; α -olefins such as ethylene and propylene, ( (Meth) aryl sulfonic acid (soda), sulfonic acid soda (monoanorequinolemaleate), disnolephonic acid soda anorequinolemaleate, Ν-methylo-noraretalinoreamide, acrylamidoalkyl sulfonic acid alkali salt, ビ ュ -Bulpyrrolidone, Ν_ Examples include bulurpyrrolidone derivatives. These polybulal alcohol resins can be used only for one type, or can be used in combination with two or more types.
[0064] 上記ポリビュルアルコール系樹脂は、接着性の点からは、平均重合度が好ましくは 100〜3000、より好ましくは 500〜3000であり、平均ケンィ匕度カ好ましくは 85〜： 10 0モノレ0 /0、より好ましく fま 90〜： 100モノレ0 /0である。 [0065] 上記ポリビニルアルコール系樹脂としては、ァセトァセチル基を有するポリビエルァ ルコール系樹脂を用いることができる。ァセトァセチル基を有するポリビニルアルコー ル系樹脂は、反応性の高い官能基を有するポリビニルアルコール系接着剤であり、 偏光板の耐久性が向上する点で好ましレ、。 [0064] From the viewpoint of adhesiveness, the above polybulal alcohol resin preferably has an average degree of polymerization of 100 to 3000, more preferably 500 to 3000, and an average degree of polymerization of preferably 85 to 100 monolayer. 0/0, more preferably f or 90: 100 Monore 0/0. [0065] As the polyvinyl alcohol-based resin, a polyvinyl alcohol-based resin having a acetoacetyl group can be used. A polyvinyl alcohol-based resin having a acetoacetyl group is a polyvinyl alcohol-based adhesive having a highly reactive functional group, which is preferable in terms of improving the durability of the polarizing plate.
[0066] ァセトァセチル基を含有するポリビュルアルコール系樹脂は、ポリビュルアルコール 系樹脂とジケテンとを公知の方法で反応して得られる。例えば、ポリビュルアルコー ル系樹脂を酢酸等の溶媒中に分散させておき、これにジケテンを添加する方法、ポリ ビュルアルコール系樹脂をジメチルホルムアミドまたはジォキサン等の溶媒にあらか じめ溶解しておき、これにジケテンを添加する方法等が挙げられる。また、ポリビュル アルコールにジケテンガスまたは液状ジケテンを直接接触させる方法が挙げられる。 [0066] A polybulualcohol-based resin containing a acetoacetyl group is obtained by reacting a polybulualcohol-based resin with diketene by a known method. For example, a polybutyl alcohol resin is dispersed in a solvent such as acetic acid and diketene is added thereto, and the polybutyl alcohol resin is dissolved in a solvent such as dimethylformamide or dioxane in advance. And a method of adding diketene to this. Moreover, the method of making polyketol alcohol contact diketene gas or liquid diketene directly is mentioned.
[0067] ァセトァセチル基を有するポリビュルアルコール系樹脂のァセトァセチル基変性度 は、 0. 1モル％以上であれば特に制限はない。 0. 1モル％未満では接着剤層の耐 水性が不十分であり不適当である。ァセトァセチル基変性度は、好ましくは 0. ：!〜 40 モル0 /0、さらに好ましくは 1〜20モル0 /0である。ァセトァセチル基変性度が 40モル0 /0 を超えると架橋剤との反応点が少なくなり、耐水性の向上効果が小さい。ァセトァセ チル基変性度は NMRにより測定した値である。 [0067] The degree of modification of the acetoacetyl group of the polybutyl alcohol resin having a acetoacetyl group is not particularly limited as long as it is 0.1 mol% or more. If it is less than 1 mol%, the adhesive layer has insufficient water resistance, which is inappropriate. Asetasechiru group modification degree is preferably 0.1:! ~ 40 mol 0/0, more preferably 1 to 20 mol 0/0. Asetasechiru group modification degree decreases the number of reaction sites with a crosslinking agent exceeds 40 mole 0/0, a small effect of improving the water resistance. The degree of modification of the acetoacetyl group is a value measured by NMR.
[0068] 上記架橋剤としては、ポリビニルアルコール系接着剤に用いられているものを特に 制限なく使用できる。  [0068] As the crosslinking agent, those used for polyvinyl alcohol adhesives can be used without particular limitation.
架橋剤は、ポリビュルアルコール系樹脂と反応性を有する官能基を少なくとも 2つ有 する化合物を使用できる。例えば、エチレンジァミン、トリエチレンァミン、へキサメチ レンジァミン等のァノレキレン基とアミノ基を 2個有するァノレキレンジァミン類（なかでも へキサメチレンジァミンが好ましい）；トリレンジイソシァネート、水素化トリレンジイソシ ァネート、トリメチレンプロパントリレンジイソシァネートァダクト、トリフエニルメタントリイ ソシァネート、メチレンビス（4—フエニルメタントリイソシァネート、イソホロンジイソシァ ネートおよびこれらのケトォキシムブロック物またはフエノールブロック物等のイソシァ ネート類；エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシ ジルエーテル、グリセリンジまたはトリグリシジルエーテル、 1 , 6—へキサンジオール ジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ジグリシジルァ 二リン、ジグリシジルァミン等のエポキシ類；ホルムアルデヒド、ァセトアルデヒド、プロ ピオンアルデヒド、ブチルアルデヒド等のモノアルデヒド類；グリオキザール、マロンジ アルデヒド、スクシンジアルデヒド、グルタルジアルデヒド、マレインジアルデヒド、フタ ルジアルデヒド等のジアルデヒド類；メチロール尿素、メチロールメラミン、アルキル化 メチロール尿素、アルキル化メチロール化メラミン、ァセトグアナミン、ベンゾグァナミ ンとホルムアルデヒドとの縮合物等のアミノ一ホルムアルデヒド樹脂；更にナトリウム、 カリウム、マグネシウム、カルシウム、ァノレミニゥム、鉄、ニッケル等の二価金属、又は 三価金属の塩及びその酸化物；などが挙げられる。架橋剤としては、メラミン系架橋 剤が好ましぐ特にメチロールメラミンが好適である。 As the cross-linking agent, a compound having at least two functional groups having reactivity with the polybulal alcohol resin can be used. For example, ethylene diamine, triethylene diamine, hexamethylene diamine, etc., ananolylene diamine having two amino groups and an amino group (hexamethylene diamine is particularly preferred); tolylene diisocyanate, hydrogen Tolylene diisocyanate, trimethylene propane tolylene diisocyanate adduct, triphenylmethane triisocyanate, methylene bis (4-phenylmethane triisocyanate, isophorone diisocyanate and their ketoxime block or phenol block Isocyanates; ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin di or triglycidyl ether, 1,6-hexanediol diglycidyl ether, tri Chi trimethylolpropane triglycidyl ether, Jigurishijirua Epoxys such as diphosphorus and diglycidylamine; monoaldehydes such as formaldehyde, acetoaldehyde, propionaldehyde, butyraldehyde; glyoxal, malondialdehyde, succinaldehyde, glutardialdehyde, maledialdehyde, phthaldialdehyde Dialdehydes such as: methylol urea, methylol melamine, alkylated methylol urea, alkylated methylolated melamine, acetoguanamine, amino monoformaldehyde resins such as condensates of benzoguanamine and formaldehyde; , Divalent metals such as iron and nickel, or trivalent metal salts and oxides thereof. As the crosslinking agent, melamine-based crosslinking agents are preferred, and methylol melamine is particularly preferred.
[0069] 上記架橋剤の配合量は、ポリビュルアルコール系樹脂 100重量部に対して、好まし くは 0.：!〜 35重量部、より好ましくは 10〜25重量部である。一方、耐久性をより向上 させるには、ポリビュルアルコール系樹脂 100重量部に対して、架橋剤を 30重量部 を超え 46重量部以下の範囲で配合することができる。特に、ァセトァセチル基を含有 するポリビュルアルコール系樹脂を用いる場合には、架橋剤の使用量を 30重量部を 超えて用いるのが好ましい。架橋剤を 30重量部を超え 46重量部以下の範囲で配合 することにより、耐水性が向上する。  [0069] The blending amount of the crosslinking agent is preferably 0.:! To 35 parts by weight, and more preferably 10 to 25 parts by weight with respect to 100 parts by weight of the polybulal alcohol resin. On the other hand, in order to further improve the durability, a crosslinking agent can be blended in a range of more than 30 parts by weight and not more than 46 parts by weight with respect to 100 parts by weight of the polybutyl alcohol resin. In particular, in the case of using a polybutyl alcohol-based resin containing a acetoacetyl group, it is preferable to use the crosslinking agent in an amount exceeding 30 parts by weight. Addition of a crosslinking agent in the range of more than 30 parts by weight and less than 46 parts by weight improves water resistance.
[0070] 上記ポリビニルアルコール系接着剤は、さらに、金属化合物コロイドを含有すること が好ましい。金属化合物コロイドは、微粒子が分散煤中に分散しているものであり、 微粒子の同種電荷の相互反発に起因して静電的に安定化し、永続的に安定性を有 するものである。  [0070] The polyvinyl alcohol-based adhesive preferably further contains a metal compound colloid. The metal compound colloid is one in which fine particles are dispersed in a dispersion basket, and is electrostatically stabilized due to mutual repulsion of the same kind of charge of the fine particles, and has permanent stability.
[0071] 上記金属化合物コロイド（微粒子）の平均粒子径は 1〜： !OOnmであり、好ましくは 1 〜50nmである。金属化合物コロイドの平均粒子径が上記範囲であれば、接着剤層 中において、金属化合物を略均一に分散させることができ、偏光子と保護層の接着 性を確保し、かつ得られる偏光板のクニック欠陥を抑えることができる。上記平均粒 子径の範囲は、可視光線の波長領域よりもかなり小さぐ形成される接着剤層中にお いて、金属化合物によって透過光が散乱したとしても、偏光特性には悪影響を及ぼさ ない。  [0071] The average particle diameter of the metal compound colloid (fine particles) is 1 to:! OOnm, preferably 1 to 50nm. If the average particle diameter of the metal compound colloid is in the above range, the metal compound can be dispersed substantially uniformly in the adhesive layer, the adhesion between the polarizer and the protective layer can be ensured, and the resulting polarizing plate can be obtained. Can reduce nick defects. The range of the average particle diameter does not adversely affect the polarization characteristics even if transmitted light is scattered by the metal compound in the adhesive layer formed to be considerably smaller than the visible wavelength range.
[0072] 上記金属化合物コロイドとしては、任意の適切なコロイドを用い得る。例えば、アルミ ナ、シリカ、ジルコニァ、チタニア等の金属酸化物のコロイド；ケィ酸アルミニウム、ケィ 酸マグネシウム、炭酸カルシウム、炭酸亜鉛、炭酸バリウム、リン酸カルシウム等の金 属塩のコロイド；セライト、タルク、クレイ、カオリン等の鉱物のコロイド；などが挙げられ る。 [0072] Any appropriate colloid may be used as the metal compound colloid. For example, aluminum Colloids of metal oxides such as sodium, silica, zirconia, titania; colloids of metal salts such as aluminum silicate, magnesium silicate, calcium carbonate, zinc carbonate, barium carbonate, calcium phosphate; celite, talc, clay, kaolin, etc. Mineral colloids; and the like.
[0073] 上記金属化合物コロイドは、分散媒に分散してコロイド溶液の状態で存在している 。分散媒としては、水が好ましい。水の他に、アルコール類等の他の分散煤を用いる ことちできる。  [0073] The metal compound colloid is present in the state of a colloidal solution dispersed in a dispersion medium. As the dispersion medium, water is preferable. In addition to water, other dispersers such as alcohols can be used.
[0074] コロイド溶液中の上記金属化合物コロイドの固形分濃度としては、本発明の目的を 達成し得る範囲で任意の適切な濃度を採用し得る。例えば、：!〜 50重量％が好まし く、：!〜 30重量％がより好ましい。  [0074] As the solid content concentration of the metal compound colloid in the colloid solution, any appropriate concentration can be adopted as long as the object of the present invention can be achieved. For example::! To 50% by weight is preferred, and:! To 30% by weight is more preferred.
[0075] 上記金属化合物コロイドは、安定剤として硝酸、塩酸、酢酸などの酸を含有するも のを用いることができる。  [0075] As the metal compound colloid, a stabilizer containing an acid such as nitric acid, hydrochloric acid, or acetic acid can be used.
[0076] 上記金属化合物コロイドは、静電的に安定化しており、正電荷を有するものと、負 電荷を有するものに分けられるが、金属化合物コロイドは非導電性の材料である。正 電荷と負電荷とは、接着剤調製後の溶液におけるコロイド表面電荷の荷電状態によ り区別される。金属化合物コロイドの電荷は、例えば、ゼータ電位測定機により、ゼー タ電位を測定することにより確認できる。金属化合物コロイドの表面電荷は、一般に、 pHにより変化する。従って、本発明における金属化合物コロイドの表面電荷は、調 製された接着剤溶液の pHにより影響される。接着剤溶液の pHは、好ましくは 2〜6、 より好ましくは 2. 5〜5、さらに好ましくは 3〜5、特に好ましくは 3. 5〜4. 5の範囲で ある。本発明においては、正電荷を有する金属化合物コロイドが、負電荷を有する金 属化合物コロイドに比べて、クニックの発生を抑える効果が大きい。正電荷を有する 金属化合物コロイドとしては、アルミナコロイド、チタ二アコロイド等が挙げられる。これ らの中でも、特に、アルミナコロイドが好適である。  [0076] The metal compound colloid is electrostatically stabilized and can be classified into those having a positive charge and those having a negative charge. The metal compound colloid is a non-conductive material. Positive charge and negative charge are distinguished by the charge state of the colloidal surface charge in the solution after the preparation of the adhesive. The charge of the metal compound colloid can be confirmed, for example, by measuring the zeta potential with a zeta potential measuring machine. The surface charge of a metal compound colloid generally varies with pH. Therefore, the surface charge of the metal compound colloid in the present invention is influenced by the pH of the prepared adhesive solution. The pH of the adhesive solution is preferably in the range of 2 to 6, more preferably 2.5 to 5, more preferably 3 to 5, particularly preferably 3.5 to 4.5. In the present invention, a metal compound colloid having a positive charge has a greater effect of suppressing the occurrence of nicks than a metal compound colloid having a negative charge. Examples of positively charged metal compound colloids include alumina colloids and titania colloids. Among these, alumina colloid is particularly preferable.
[0077] 上記金属化合物コロイドは、好ましくは、ポリビュルアルコール系樹脂 100重量部に 対して、 200重量部以下の割合（固形分の換算値)で配合される。また金属化合物コ ロイドの配合割合を上記範囲とすることで、偏光子と保護層との接着性を確保しなが ら、クニックの発生を抑えることができる。金属化合物コロイドの配合割合は、ポリビニ ルアルコール系樹脂 100重量部に対して、 10〜200重量部がより好ましぐ 20〜17 5重量部がさらに好ましぐ 30〜： 150重量部が特に好ましい。金属化合物コロイドの 配合割合が、ポリビエルアルコール系樹脂 100重量部に対して、 200重量部を超え ると、接着剤中における、ポリビュルアルコール系樹脂の割合が小さくなり、接着性の 点から好ましくないおそれがある。なお、有効にクニックを抑えるには、金属化合物コ ロイドの配合割合は、上記範囲の下限値とするのが好ましい。 [0077] The metal compound colloid is preferably blended at a ratio of 200 parts by weight or less (converted value of solid content) with respect to 100 parts by weight of the polybutyl alcohol resin. In addition, by setting the blending ratio of the metal compound colloid within the above range, it is possible to suppress the occurrence of nicks while ensuring the adhesion between the polarizer and the protective layer. The compounding ratio of the metal compound colloid is 10 to 200 parts by weight is more preferred with respect to 100 parts by weight of the alcoholic resin. 20 to 175 parts by weight is more preferred. 30 to 150 parts by weight is particularly preferred. When the compounding ratio of the metal compound colloid exceeds 200 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol-based resin, the ratio of the polybulal alcohol-based resin in the adhesive is reduced, which is preferable from the viewpoint of adhesiveness. There is a risk of not. In order to effectively suppress nicks, the mixing ratio of the metal compound colloid is preferably set to the lower limit of the above range.
[0078] 本発明において用いられ得る接着剤は、例えば、ポリビュルアルコール系樹脂を含 有する樹脂溶液であり、通常、水溶液として用いられる。樹脂溶液中の固形分濃度と しては、任意の適切な濃度を採用し得る。塗工性や放置安定性等を考慮すれば、好 ましくは 0. 1〜： 15重量％、より好ましくは 0. 5〜： 10重量％である。上記樹脂溶液の 粘度としては、任意の適切な粘度を採用し得る。例えば、：!〜 50mPa ' sの範囲が好 ましい。偏光板の作製にあたって生じるクニックは、樹脂溶液の粘度が下がるに従つ て、クニックの発生も多くなる傾向があるが、上記ポリビニルアルコール系樹脂、架橋 剤、および金属化合物コロイドを含有する接着剤によれば、 l〜20mPa ' sの範囲に あるような低粘度においても、クニックの発生を抑えることができ、樹脂溶液の粘度に 拘らず、クニックの発生を抑えることができる。ァセトァセチル基を含有するポリビエル アルコール系樹脂は、一般的なポリビュルアルコール系樹脂に比べて、重合度を高 くすることができず、上記のような低粘度で用いられていた力 上記金属化合物コロイ ドを含有することで、樹脂溶液の低粘度によって生じるクニックの発生を抑えることが できる。 [0078] The adhesive that can be used in the present invention is, for example, a resin solution containing a polybulal alcohol-based resin, and is usually used as an aqueous solution. Any appropriate concentration can be adopted as the solid content concentration in the resin solution. In consideration of coating property and storage stability, the content is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight. Any appropriate viscosity can be adopted as the viscosity of the resin solution. For example: the range of:! ~ 50mPa's is preferred. The nick generated during the production of the polarizing plate tends to increase as the viscosity of the resin solution decreases. However, in the adhesive containing the polyvinyl alcohol-based resin, the cross-linking agent, and the metal compound colloid. Therefore, even at a low viscosity in the range of 1 to 20 mPa's, the occurrence of nicks can be suppressed, and the occurrence of nicks can be suppressed regardless of the viscosity of the resin solution. Polyvinyl alcohol-based resins containing a acetoacetyl group cannot increase the degree of polymerization compared to general polybutyl alcohol-based resins, and have been used with the low viscosity as described above. By containing the slag, the occurrence of nicks caused by the low viscosity of the resin solution can be suppressed.
[0079] 上記樹脂溶液の調製法としては、任意の適切な方法を採用し得る。上記ポリビニル アルコール系樹脂、架橋剤、および金属化合物コロイドを含有する接着剤の場合は 、通常は、ポリビュルアルコール系樹脂および架橋剤を混合し、適宜に濃度を調整し たものに、金属化合物コロイドを配合することで、樹脂溶液が調製される。また、ポリビ ニルアルコール系樹脂として、ァセトァセチル基を含有するポリビュルアルコール系 樹脂を用いたり、架橋剤の配合量が多いような場合には、溶液の安定性を考慮して、 ポリビュルアルコール系樹脂と金属化合物コロイドを混合した後に、架橋剤を、得ら れる樹脂溶液の使用時期等を考慮しながら、混合することができる。接着剤である樹 脂溶液の濃度は、樹脂溶液を調製した後に適宜に調整することもできる。 [0079] Any appropriate method can be adopted as a method of preparing the resin solution. In the case of the adhesive containing the polyvinyl alcohol resin, the crosslinking agent, and the metal compound colloid, the metal compound colloid is usually mixed with a polybutyl alcohol resin and the crosslinking agent, and the concentration is appropriately adjusted. Is added to prepare a resin solution. In addition, if a polyvinyl alcohol resin containing an acetoacetyl group is used as the polyvinyl alcohol resin, or if the amount of the crosslinking agent is large, the polybut alcohol alcohol resin is considered in view of the stability of the solution. And the metal compound colloid can be mixed, and then the cross-linking agent can be mixed in consideration of the timing of use of the resulting resin solution. Tree that is adhesive The concentration of the fat solution can be appropriately adjusted after preparing the resin solution.
[0080] なお、上記ポリビエルアルコール系接着剤には、さらにシランカップリング剤、チタン カップリング剤などのカップリング剤、各種粘着付与剤、紫外線吸収剤、酸化防止剤 、耐熱安定剤、耐加水分解安定剤などの安定剤等を配合することもできる。  [0080] The polyvinyl alcohol-based adhesive further includes coupling agents such as silane coupling agents and titanium coupling agents, various tackifiers, UV absorbers, antioxidants, heat stabilizers, and water resistance. Stabilizers such as decomposition stabilizers can also be blended.
[0081] 本発明の偏光子保護フィルムの偏光子が設けられた側や、上記その他の保護層を 用いる場合の該保護層の偏光子が設けられた側には、接着性向上のために易接着 処理を施すことができる。易接着処理としては、コロナ処理、プラズマ処理、低圧 UV 処理、ケン化処理等の表面処理が挙げられる。  [0081] The polarizer protective film of the present invention is provided on the side where the polarizer is provided, or on the side provided with the polarizer of the protective layer when the other protective layer is used, in order to improve adhesion. Adhesive treatment can be applied. Examples of the easy adhesion treatment include surface treatment such as corona treatment, plasma treatment, low-pressure UV treatment, and saponification treatment.
[0082] 本発明の偏光子保護フィルムの偏光子が設けられた側や、上記その他の保護層を 用いる場合の該保護層の偏光子が設けられた側であって、該偏光子保護フィルムと 上記接着剤層との間ゃ該保護層と上記接着剤層との間には、接着性向上のために 、易接着層を形成することが好ましい。  [0082] The side of the polarizer protective film of the present invention where the polarizer is provided, or the side of the protective layer where the polarizer is provided in the case of using the other protective layer, and the polarizer protective film An easy-adhesion layer is preferably formed between the protective layer and the adhesive layer in order to improve adhesion.
[0083] 上記易接着層としては、例えば、反応性官能基を有するシリコーン層が挙げられる 。反応性官能基を有するシリコーン層の材料は、特に制限されないが、例えば、イソ シァネート基含有のアルコキシシラノール類、アミノ基含有アルコキシシラノール類、 メルカプト基含有アルコキシシラノール類、カルボキシ含有アルコキシシラノール類、 エポキシ基含有アルコキシシラノール類、ビニル型不飽和基含有アルコキシシラノー ル類、ハロゲン基含有アルコキシラノール類、イソシァネート基含有アルコキシシラノ ール類が挙げられ、アミノ系シラノールが好ましい。さらに上記シラノールを効率よく 反応させるためのチタン系触媒や錫系触媒を添加することにより、接着力を強固にす ること力 Sできる。また上記反応性官能基を有するシリコーンに他の添加剤を加えても よい。具体的にはさらにはテルペン樹脂、フエノール樹脂、テルペン-フエノール樹脂 、ロジン樹脂、キシレン樹脂などの粘着付与剤、紫外線吸収剤、酸化防止剤、耐熱 安定剤などの安定剤等を用いても良い。  [0083] Examples of the easy-adhesion layer include a silicone layer having a reactive functional group. The material of the silicone layer having a reactive functional group is not particularly limited. For example, an isocyanate group-containing alkoxysilanol, an amino group-containing alkoxysilanol, a mercapto group-containing alkoxysilanol, a carboxy-containing alkoxysilanol, an epoxy group -Containing alkoxysilanols, vinyl unsaturated group-containing alkoxysilanols, halogen group-containing alkoxylanols, isocyanate group-containing alkoxysilanols, and amino silanols are preferred. Furthermore, by adding a titanium-based catalyst or tin-based catalyst for efficiently reacting the above silanol, it is possible to strengthen the adhesive force. Further, other additives may be added to the silicone having the reactive functional group. Specifically, terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins and other tackifiers, UV absorbers, antioxidants, heat stabilizers and other stabilizers may be used.
[0084] 上記反応性官能基を有するシリコーン層は公知の技術により塗工、乾燥して形成さ れる。シリコーン層の厚みは、乾燥後で、好ましくは 1〜： 100nm、さらに好ましくは 10 〜80nmである。塗工の際、反応性官能基を有するシリコーンを溶剤で希釈してもよ レ、。希釈溶剤は特に制限はされないが、アルコール類があげられる。希釈濃度は特 に制限されないが、好ましくは:!〜 5重量％、より好ましくは 1〜3重量％である。 [0084] The silicone layer having a reactive functional group is formed by coating and drying by a known technique. The thickness of the silicone layer is preferably 1 to 100 nm, more preferably 10 to 80 nm after drying. During coating, silicone with reactive functional groups may be diluted with a solvent. The dilution solvent is not particularly limited, and examples thereof include alcohols. Dilution concentration is special The amount is preferably, but not limited to: !! to 5% by weight, more preferably 1 to 3% by weight.
[0085] 上記接着剤層の形成は、好ましくは、上記接着剤の塗布によって行う。上記接着剤 の塗布は、偏光子保護フィルムと偏光子の接着にあたっては、偏光子保護フィルムと 偏光子のいずれか一方に行っても両者に行っても良ぐその他の保護層と偏光子の 接着にあたっては、その他の保護層と偏光子のいずれか一方に行っても両者に行つ ても良い。偏光子保護フィルムやその他の保護層と偏光子とを貼り合せた後には、乾 燥工程を施し、塗布乾燥層からなる接着剤層を形成する。接着剤層を形成した後に これを貼り合わせることもできる。偏光子と偏光子保護フィルムの貼り合わせは、ロー ルラミネーター等により行うことができる。加熱乾燥温度、乾燥時間は接着剤の種類 に応じて適宜決定される。 [0085] The adhesive layer is preferably formed by applying the adhesive. The adhesive may be applied to either the polarizer protective film or the polarizer. The adhesive may be applied to either the polarizer protective film or the polarizer. In doing so, it may go to either one of the other protective layers and the polarizer or to both. After the polarizer protective film or other protective layer is bonded to the polarizer, a drying step is performed to form an adhesive layer composed of a coated and dried layer. This can also be bonded after forming the adhesive layer. The polarizer and the polarizer protective film can be bonded together using a roll laminator or the like. The heat drying temperature and drying time are appropriately determined according to the type of adhesive.
[0086] 接着剤層の厚みは、好ましくは 0. 01〜： 10 z m、さらに好ましくは 0. 03〜5 x mで ある。接着剤が金属化合物コロイドを含有するときは、接着剤層の厚みは、金属化合 物コロイドの平均粒子径よりも大きくなるように設計する。 [0086] The thickness of the adhesive layer is preferably 0.01 to 10 zm, more preferably 0.03 to 5xm. When the adhesive contains a metal compound colloid, the thickness of the adhesive layer is designed to be larger than the average particle size of the metal compound colloid.
[0087] 本発明の偏光板は、最外層の少なくとも一方として粘着剤層を有していても良い（こ のような偏光板を粘着型偏光板と称することがある)。特に好ましい形態として、本発 明の偏光子保護フィルムの偏光子が接着されていない側や、上記その他の保護層 を用いる場合には該保護層の偏光子が接着されていない側に、他の光学フィルムや 液晶セル等の他部材と接着するための粘着剤層を設けることができる。  [0087] The polarizing plate of the present invention may have an adhesive layer as at least one of the outermost layers (such a polarizing plate may be referred to as an adhesive polarizing plate). As a particularly preferred form, other side of the polarizer protective film of the present invention where the polarizer is not bonded, or when the other protective layer is used, on the side where the polarizer of the protective layer is not bonded, An adhesive layer for adhering to other members such as an optical film and a liquid crystal cell can be provided.
[0088] 上記粘着剤層を形成する粘着剤は、特に限定されないが、例えばアクリル系重合 体、シリコーン系ポリマー、ポリエステル、ポリウレタン、ポリアミド、ポリエーテル、フッ 素系やゴム系などのポリマーをベースポリマーとするものを適宜に選択して用いること ができる。特に、アクリル系粘着剤の如く光学的透明性に優れ、適度な濡れ性と凝集 性と接着性の粘着特性を示して、耐候性や耐熱性などに優れるものが好ましく用い 得る。特に、炭素数が 4〜： 12のアクリル系ポリマーよりなるアクリル系粘着剤が好まし レ、。  [0088] The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited. For example, an acrylic polymer, silicone-based polymer, polyester, polyurethane, polyamide, polyether, fluorine-based or rubber-based polymer is used as a base polymer. Can be appropriately selected and used. In particular, those having excellent optical transparency such as an acrylic pressure-sensitive adhesive, exhibiting appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and having excellent weather resistance, heat resistance and the like can be preferably used. In particular, an acrylic adhesive made of an acrylic polymer having 4 to 12 carbon atoms is preferred.
[0089] また上記に加えて、吸湿による発泡現象や剥がれ現象の防止、熱膨張差等による 光学特性の低下や液晶セルの反り防止、ひレ、ては高品質で耐久性に優れる液晶表 示装置の形成性などの点より、吸湿率が低くて耐熱性に優れる粘着剤層が好ましい [0090] 上記粘着剤層は、例えば天然物や合成物の樹脂類、特に、粘着性付与樹脂や、 ガラス繊維、ガラスビーズ、金属粉、その他の無機粉末等からなる充填剤や顔料、着 色剤、酸化防止剤などの粘着剤層に添加されることの添加剤を含有していてもよい。 [0089] In addition to the above, prevention of foaming and peeling phenomenon due to moisture absorption, deterioration of optical properties due to thermal expansion difference, prevention of warpage of liquid crystal cell, fin, and high quality and excellent durability An adhesive layer having a low moisture absorption and excellent heat resistance is preferable from the viewpoint of device formability. [0090] The pressure-sensitive adhesive layer includes, for example, natural and synthetic resins, in particular, tackifier resins, fillers and pigments made of glass fibers, glass beads, metal powders, other inorganic powders, and coloring. An additive to be added to the pressure-sensitive adhesive layer such as an agent and an antioxidant may be contained.
[0091] また微粒子を含有して光拡散性を示す粘着剤層などであってもよい。 [0091] An adhesive layer containing fine particles and exhibiting light diffusibility may also be used.
[0092] 上記粘着剤層の付設は、適宜な方式で行いうる。その例としては、例えばトルエン や酢酸ェチル等の適宜な溶剤の単独物又は混合物からなる溶媒にベースポリマー またはその組成物を溶解又は分散させた 10〜40重量％程度の粘着剤溶液を調製 し、それを流延方式や塗工方式等の適宜な展開方式で偏光板上または光学フィル ム上に直接付設する方式、あるいは前記に準じセパレータ上に粘着剤層を形成して それを偏光子保護フィルム面に移着する方式などがあげられる。 [0092] The pressure-sensitive adhesive layer can be attached by an appropriate method. For example, an adhesive solution of about 10 to 40% by weight in which a base polymer or a composition thereof is dissolved or dispersed in a solvent composed of a single solvent or a mixture of appropriate solvents such as toluene and ethyl acetate is prepared. A method in which it is attached directly on a polarizing plate or an optical film by an appropriate development method such as a casting method or a coating method, or an adhesive layer is formed on a separator according to the above, and this is applied to a polarizer protective film. The method of transferring to the surface is given.
[0093] 粘着剤層は、異なる組成又は種類等のものの重畳層として偏光板の片面又は両面 に設けることもできる。また両面に設ける場合に、偏光板の表裏において異なる組成 や種類や厚さ等の粘着剤層とすることもできる。 [0093] The pressure-sensitive adhesive layer may be provided on one side or both sides of the polarizing plate as a superimposed layer of different compositions or types. Moreover, when providing in both surfaces, it can also be set as adhesive layers with a different composition, a kind, thickness, etc. in the front and back of a polarizing plate.
[0094] 粘着剤層の厚さは、使用目的や接着力などに応じて適宜に決定でき、好ましくは 1 〜40 μ mであり、より好ましくは 5〜30 μ mであり、特に好ましくは 10〜25 μ mである 。 1 / mより薄いと耐久性が悪くなり、また、 40 μ ΐηより厚くなると発泡などによる浮き や剥がれが生じやすく外観不良となる。  [0094] The thickness of the pressure-sensitive adhesive layer can be appropriately determined according to the purpose of use and adhesive force, and is preferably 1 to 40 μm, more preferably 5 to 30 μm, and particularly preferably 10 ~ 25 μm. If it is thinner than 1 / m, the durability will be poor, and if it is thicker than 40 μΐη, it will be liable to float or peel off due to foaming, resulting in poor appearance.
[0095] 上記偏光子保護フィルムやその他の保護層と上記粘着剤層との間の密着性を向 上させるために、その層間にアンカー層を設けることも可能である。  [0095] In order to improve the adhesion between the polarizer protective film or other protective layer and the pressure-sensitive adhesive layer, an anchor layer may be provided between the layers.
[0096] 上記アンカー層としては、好ましくは、ポリウレタン、ポリエステル、分子中にアミノ基 を含むポリマー類から選ばれるアンカー層が用いられ、特に好ましくは分子中にアミ ノ基を含んだポリマー類が使用される。分子中にアミノ基を含んだポリマーは、分子 中のアミノ基力 粘着剤中のカルボキシル基や、導電性ポリマー中の極性基と反応も しくはイオン性相互作用などの相互作用を示すため、良好な密着性が確保される。  [0096] The anchor layer is preferably an anchor layer selected from polyurethane, polyester, and polymers containing amino groups in the molecule, particularly preferably polymers containing amino groups in the molecule. Is done. Polymers containing amino groups in the molecule are good because they exhibit interactions such as amino group strength in the molecule, carboxyl groups in the adhesive, polar groups in the conductive polymer, and ionic interactions. Secure adhesion.
[0097] 分子中にアミノ基を含むポリマー類としては、例えば、ポリエチレンィミン、ポリアリル ァミン、ポリビュルァミン、ポリビュルピリジン、ポリビュルピロリジン、前述アクリル系粘 着剤の共重合モノマーで示したジメチルアミノエチルアタリレート等の含ァミノ基含有 モノマーの重合体などを挙げることができる。 [0097] Examples of the polymers containing an amino group in the molecule include polyethyleneimine, polyallylamine, polybulamine, polybulurpyridine, polybulurpyrrolidine, and dimethylaminoethyl represented by a copolymerization monomer of the aforementioned acrylic adhesive. Contains amino groups such as attalylate Examples thereof include a monomer polymer.
[0098] 上記アンカー層に帯電防止性を付与するために、帯電防止剤を添加することもでき る。帯電防止性付与のための帯電防止剤としては、イオン性界面活性剤系、ポリア二 リン、ポリチォフェン、ポリピロール、ポリキノキサリン等の導電ポリマー系、酸化スズ、 酸化アンチモン、酸化インジウム等の金属酸化物系などが挙げられるが、特に光学 特性、外観、帯電防止効果、および帯電防止効果の熱時、加湿時での安定性という 観点から、導電性ポリマー系が好ましく使用される。この中でも、ポリア二リン、ポリチ ォフェンなどの水溶性導電性ポリマー、もしくは水分散性導電性ポリマーが特に好ま しく使用される。これは、帯電防止層の形成材料として水溶性導電性ポリマーや水分 散性導電性ポリマーを用いた場合、塗布工程に際して有機溶剤による光学フィルム 基材の変質を抑える事が出来るためである。  [0098] In order to impart antistatic properties to the anchor layer, an antistatic agent may be added. Antistatic agents for imparting antistatic properties include ionic surfactants, conductive polymer systems such as polyaniline, polythiophene, polypyrrole, and polyquinoxaline, and metal oxide systems such as tin oxide, antimony oxide, and indium oxide. In particular, from the viewpoint of optical properties, appearance, antistatic effect, and stability of the antistatic effect when heated and humidified, a conductive polymer system is preferably used. Among these, water-soluble conductive polymers such as polyaniline and polythiophene or water-dispersible conductive polymers are particularly preferably used. This is because when a water-soluble conductive polymer or a water-dispersible conductive polymer is used as a material for forming the antistatic layer, it is possible to suppress deterioration of the optical film substrate due to the organic solvent during the coating process.
[0099] なお本発明において、上記した偏光板を形成する偏光子や偏光子保護フィルム等 、また粘着剤層などの各層には、例えばサリチル酸エステル系化合物やべンゾフエノ ール系化合物、ベンゾトリアゾール系化合物ゃシァノアクリレート系化合物、ニッケル 錯塩系化合物等の紫外線吸収剤で処理する方式などの方式により紫外線吸収能を もたせたものなどであってもよい。  [0099] In the present invention, the polarizer, polarizer protective film, and the like forming the polarizing plate described above, and the pressure-sensitive adhesive layer, for example, each include a salicylic acid ester compound, a benzophenol compound, and a benzotriazole compound. The compound may be one having UV absorbing ability by a method such as a method of treating with a UV absorber such as a cyanoacrylate compound or a nickel complex compound.
[0100] 本発明の偏光板は、偏光子の少なくとも一方の面側にセルロース系樹脂層を設け るとともに、該セルロース系樹脂層の水分含有率を 3. 1重量％〜4. 0重量％の範囲 内に調整することによって、カールの発生が高いレベルで抑制され、液晶セルに貼り 合わせても剥離しにくぐ外観に優れた偏光板となる。  [0100] In the polarizing plate of the present invention, a cellulose resin layer is provided on at least one surface side of a polarizer, and the water content of the cellulose resin layer is 3.1 wt% to 4.0 wt%. By adjusting within the range, the occurrence of curling is suppressed at a high level, and the polarizing plate has an excellent appearance that is difficult to peel off even when bonded to a liquid crystal cell.
[0101] 本発明の偏光板は、液晶セルの視認側、バックライト側のどちらか片側に設けても、 両側に設けてもよぐ限定されない。  [0101] The polarizing plate of the present invention is not limited to be provided on either the viewing side or the backlight side of the liquid crystal cell, or on both sides.
[0102] 〔画像表示装置〕  [0102] [Image display device]
次に、本発明の画像表示装置について説明する。本発明の画像表示装置は本発 明の偏光板を少なくとも 1枚含む。ここでは一例として液晶表示装置について説明す るが、本発明が偏光板を必要とするあらゆる表示装置に適用され得ることはいうまで もなレ、。本発明の偏光板が適用可能な画像表示装置の具体例としては、エレクト口ノレ ED : Field Emission Display)のような自発光型表示装置が挙げられる。図 3は、 本発明の好ましい実施形態による液晶表示装置の概略断面図である。図示例では 透過型液晶表示装置について説明するが、本発明が反射型液晶表示装置等にも適 用されることはいうまでもない。 Next, the image display apparatus of the present invention will be described. The image display device of the present invention includes at least one polarizing plate of the present invention. Here, a liquid crystal display device will be described as an example, but it goes without saying that the present invention can be applied to any display device that requires a polarizing plate. As a specific example of an image display device to which the polarizing plate of the present invention can be applied, A self-luminous display device such as ED (Field Emission Display) can be mentioned. FIG. 3 is a schematic cross-sectional view of a liquid crystal display device according to a preferred embodiment of the present invention. In the illustrated example, a transmissive liquid crystal display device will be described, but it goes without saying that the present invention is also applied to a reflective liquid crystal display device and the like.
[0103] 液晶表示装置 100は、液晶セル 10と、液晶セル 10を挟んで配された位相差フィノレ ム 20、 20'と、位相差フィルム 20、 20'の外側に配された偏光板 30、 30'と、導光板 40と、光源 50と、リフレタター 60とを備える。偏光板 30、 30'は、その偏光軸が互い に直交するようにして配置されている。液晶セル 10は、一対のガラス基板 11、 11 'と 、該基板間に配された表示媒体としての液晶層 12とを有する。一方の基板 11には、 液晶の電気光学特性を制御するスイッチング素子（代表的には TFT)と、このスイツ チング素子にゲート信号を与える走査線およびソース信号を与える信号線とが設けら れている（いずれも図示せず)。他方のガラス基板 11 'には、カラーフィルターを構成 するカラー層と遮光層（ブラックマトリックス層）とが設けられている（いずれも図示せず )。基板 11、 11 'の間隔（セルギャップ）は、スぺーサー 13によって制御されている。 本発明の液晶表示装置においては、偏光板 30、 30'の少なくとも 1つとして、上記記 載の本発明の偏光板が採用される。 [0103] The liquid crystal display device 100 includes a liquid crystal cell 10, a retardation film 20 and 20 'disposed with the liquid crystal cell 10 interposed therebetween, and a polarizing plate 30 disposed on the outside of the retardation films 20 and 20'. 30 ', a light guide plate 40, a light source 50, and a reflector 60. The polarizing plates 30 and 30 ′ are arranged so that their polarization axes are orthogonal to each other. The liquid crystal cell 10 includes a pair of glass substrates 11 and 11 ′ and a liquid crystal layer 12 as a display medium disposed between the substrates. One substrate 11 is provided with a switching element (typically a TFT) for controlling the electro-optical characteristics of the liquid crystal, and a scanning line for supplying a gate signal to the switching element and a signal line for supplying a source signal. (Both not shown). The other glass substrate 11 ′ is provided with a color layer constituting a color filter and a light shielding layer (black matrix layer) (both not shown). A space (cell gap) between the substrates 11 and 11 ′ is controlled by a spacer 13. In the liquid crystal display device of the present invention, the polarizing plate of the present invention described above is employed as at least one of the polarizing plates 30 and 30 ′.
[0104] 例えば、 TN方式の場合には、このような液晶表示装置 100は、電圧無印加時には 液晶層 12の液晶分子が、偏光軸を 90度ずらすような状態で配歹 IJしている。そのよう な状態においては、偏光板によって一方向の光のみが透過した入射光は、液晶分 子によって 90度ねじられる。上記のように、偏光板はその偏光軸が互いに直交するよ うにして配置されているので、他方の偏光板に到達した光（偏光）は、当該偏光板を 透過する。したがって、電圧無印加時には、液晶表示装置 100は白表示を行う（ノー マリホワイト方式)。一方、このような液晶表示装置 100に電圧を印加すると、液晶層 1 2内の液晶分子の配列が変化する。その結果、他方の偏光板に到達した光 (偏光） は、当該偏光板を透過できず、黒表示となる。このような表示の切り替えを、ァクティ ブ素子を用いて画素ごとに行うことにより、画像が形成される。 [0104] For example, in the case of the TN mode, such a liquid crystal display device 100 arranges IJ in such a state that the liquid crystal molecules of the liquid crystal layer 12 shift the polarization axis by 90 degrees when no voltage is applied. In such a state, incident light that is transmitted through only one direction of light by the polarizing plate is twisted 90 degrees by the liquid crystal molecule. As described above, since the polarizing plates are arranged so that their polarization axes are orthogonal to each other, the light (polarized light) reaching the other polarizing plate is transmitted through the polarizing plate. Therefore, when no voltage is applied, the liquid crystal display device 100 performs white display (normally white method). On the other hand, when a voltage is applied to such a liquid crystal display device 100, the arrangement of liquid crystal molecules in the liquid crystal layer 12 changes. As a result, light (polarized light) that has reached the other polarizing plate cannot be transmitted through the polarizing plate, resulting in black display. An image is formed by switching such display for each pixel using an active element.
実施例  Example
[0105] 以下、実施例により本発明を具体的に説明するが、本発明はこれら実施例には限 定されない。なお、特に示さない限り、実施例中の部およびパーセントは重量基準で ある。 [0105] Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples. Not determined. Unless otherwise indicated, parts and percentages in the examples are based on weight.
[0106] 〈偏光子保護フィルムの水分含有率の測定〉  <Measurement of moisture content of polarizer protective film>
乾燥減量により、フィルムの水分含有率を求めた。すなわち、実施例および比較例 で得たフィルム（10cm X 10cm)の重量を測定し、次いで、 120°Cのオーブンで 2時 間乾燥した後の重量を測定し、乾燥による重量減少量を水分含有率とした。  The moisture content of the film was determined by loss on drying. That is, the weight of the film (10 cm × 10 cm) obtained in the example and the comparative example was measured, and then the weight after drying for 2 hours in an oven at 120 ° C. was measured. Rate.
[0107] 〈偏光板のカール量の測定〉 <Measurement of Curling Amount of Polarizing Plate>
得られた偏光板を、 lOcm X 10cmの大きさに切り出し、平面の上に凸側が下側に なるように置き、偏光板の平面から最も離れている部分の距離をカール量とした。  The obtained polarizing plate was cut into a size of lOcm × 10 cm, placed on the plane so that the convex side was on the lower side, and the distance of the portion farthest from the plane of the polarizing plate was defined as the curl amount.
[0108] 〈クニック欠陥数の測定〉 <Measurement of the number of knick defects>
偏光板を、 1000mm X 1000mmになるように切り出してサンプノレを作製した。蛍光 灯下、ブラックライト上に別の偏光板（予め欠陥のないことを確認）を設け、その上に 上記サンプノレの偏光板を置いた。 2枚の偏光板は、それぞれの吸収軸が直交するよ うに設置し、この状態で、 目視で、光抜けする箇所 (クニック欠陥）の個数をカウントし た。  A polarizing plate was cut out so as to have a size of 1000 mm × 1000 mm, and a sampnore was produced. Under a fluorescent lamp, another polarizing plate (confirmed that there is no defect) was provided on the black light, and the above-mentioned Sampnore polarizing plate was placed thereon. The two polarizing plates were installed so that their absorption axes were orthogonal to each other, and in this state, the number of locations where light escaped (knic defects) was counted visually.
[0109] 〔製造例 1：偏光子の製造〕  [Production Example 1: Production of polarizer]
厚さ 80 μ mのポリビニルアルコールフィルムを、 5重量％ (重量比：ヨウ素/ヨウ化力 リウム = 1/10)のヨウ素水溶液中で染色した。次いで、 3重量％のホウ酸および 2重 量％ヨウ化カリウムを含む水溶液に浸漬し、さらに 4重量％のホウ酸および 3重量％ のヨウ化カリウムを含む水溶液中で 5. 5倍まで延伸した後、 5重量％のヨウ化カリウム 水溶液に浸漬した。その後、 40°Cのオーブンで 3分間乾燥を行レ、、厚さ 30 μ ΐηの偏 光子を得た。  A polyvinyl alcohol film having a thickness of 80 μm was dyed in an aqueous iodine solution having a concentration of 5% by weight (weight ratio: iodine / ium iodide power = 1/10). Next, it was immersed in an aqueous solution containing 3% by weight boric acid and 2% by weight potassium iodide, and further stretched to 5.5 times in an aqueous solution containing 4% by weight boric acid and 3% by weight potassium iodide. Thereafter, it was immersed in an aqueous solution of 5% by weight potassium iodide. After that, drying was performed in an oven at 40 ° C for 3 minutes to obtain a polarizer having a thickness of 30 μΐη.
[0110] 〔製造例 2 : (メタ）アクリル系樹脂フィルムの製造〕  [0110] [Production Example 2: Production of (meth) acrylic resin film]
メタクリル酸メチル 20重量部、アクリルアミド 80重量部、過硫酸カリウム 0. 3重量部 、イオン交換水 1500重量部を反応器中に仕込み、反応器中を窒素ガスで置換しな がら、単量体が完全に重合体に転化するまで、 70°Cに保ち反応を進行させた。得ら れた水溶液を、メタクリル酸メチル /アクリルアミド共重合体系懸濁剤とした。さらに、 容量が 5リットルで、バッフルおよびファゥドラ型撹拌翼を備えたステンレス製オートク レーブに、上記懸濁剤 0. 05部をイオン交換水 165部に溶解した溶液を供給し、系 内を窒素ガスで置換しながら 400rpmで撹拌した。 20 parts by weight of methyl methacrylate, 80 parts by weight of acrylamide, 0.3 part by weight of potassium persulfate and 1500 parts by weight of ion-exchanged water were charged into the reactor, and the monomer was replaced while the reactor was replaced with nitrogen gas. The reaction was allowed to proceed at 70 ° C until it was completely converted to a polymer. The obtained aqueous solution was used as a methyl methacrylate / acrylamide copolymer suspending agent. In addition, a stainless steel autoclave with a capacity of 5 liters and equipped with baffles and fudra-type stirring blades. A solution in which 0.05 part of the suspending agent was dissolved in 165 parts of ion-exchanged water was supplied to the leve, and the system was stirred at 400 rpm while replacing the system with nitrogen gas.
次に、メタクリル酸 27重量部、メタクリル酸メチル 73重量部、 tードデシルメルカプタ ン 1. 2重量部、 2, 2'—ァゾビスイソプチロニトリル 0. 4重量部を仕込み組成とした混 合物質を、上記反応系を撹拌しながら添加した。添加した後、 70°Cまで昇温し、内温 が 70°Cに達した時点を重合開始時点として、 180分間保ち、重合を進行させた。 その後、通常の方法に従い、反応系の冷却、ポリマーの分離、洗浄、乾燥を行い、 ビーズ状の共重合体を得た。この共重合体の重合率は 97%であり、重量平均分子 量は 13万であった。得られた共重合体に添加剤（NaOCH )を 0. 2重量％配合し、  Next, 27 parts by weight of methacrylic acid, 73 parts by weight of methyl methacrylate, 1.2 parts by weight of tododecyl mercaptan, and 0.4 parts by weight of 2,2′-azobisisoptyronitrile were mixed. The combined materials were added while stirring the reaction system. After the addition, the temperature was raised to 70 ° C., and the time when the internal temperature reached 70 ° C. was set as the polymerization start time, and the polymerization was continued for 180 minutes. Thereafter, the reaction system was cooled, the polymer was separated, washed and dried according to the usual method to obtain a bead-shaped copolymer. The polymerization rate of this copolymer was 97%, and the weight average molecular weight was 130,000. Add 0.2% by weight of additive (NaOCH) to the resulting copolymer,
3  Three
2軸押出機 (TEX30 (日本製鋼社製、 L/D = 44. 5)を用いて、ホッパー部より窒素 を 10LZ分の量でパージしながら、スクリュー回転数 100rpm、原料供給量 5kg/h 、シリンダ温度 290°Cで分子内環化反応を行レ、、ペレット状のアクリル樹脂 (A)を得 た。  Using a twin screw extruder (TEX30 (manufactured by Nippon Steel Co., Ltd., L / D = 44.5)), while purging nitrogen from the hopper at an amount of 10LZ, the screw rotation speed is 100rpm, the feed rate is 5kg / h, An intramolecular cyclization reaction was performed at a cylinder temperature of 290 ° C. to obtain a pellet-shaped acrylic resin (A).
冷却器付きのガラス容器 (容量 5リットル）内に、初期調整溶液として、脱イオン水 12 0重量部、炭酸カリウム 0. 5重量部、スルホコハク酸ジォクチル 0. 5重量部、過硫酸 カリウム 0. 005重量部を仕込み、窒素雰囲気下で撹拌後、アクリル酸ブチル 53重量 部、スチレン 17重量部、メタクリル酸ァリル (架橋剤） 1重量部を仕込んだ。これら混合 物を 70°Cで 30分間反応させて、ゴム質重合体を得た。次いで、メタクリノレ酸メチル 2 1重量部、メタクリル酸 9重量部、過硫酸カリウム 0. 005重量部の混合物を引き続き 7 0°Cで 90分かけて連続的に添加し、更に 90分間保持して、シェル層を重合させた。 この重合体ラテックスを硫酸で凝固し、苛性ソーダで中和した後、洗浄、濾過、乾燥 して、コア'シェル型アクリル弾性体粒子（B)を得た。電子顕微鏡で測定したアタリノレ 弾性体粒子のゴム質重合体部分の平均粒子径は 140nmであった。  In a glass container with a condenser (capacity 5 liters), as an initial adjustment solution, 120 parts by weight of deionized water, 0.5 parts by weight of potassium carbonate, 0.5 parts by weight of dioctyl sulfosuccinate, potassium persulfate 0.005 After adding parts by weight and stirring in a nitrogen atmosphere, 53 parts by weight of butyl acrylate, 17 parts by weight of styrene, and 1 part by weight of aryl methacrylate (crosslinking agent) were added. These mixtures were reacted at 70 ° C. for 30 minutes to obtain a rubbery polymer. Next, a mixture of methyl methacrylate (2 parts by weight), methacrylic acid (9 parts by weight) and potassium persulfate (0.005 parts by weight) was continuously added at 70 ° C. over 90 minutes, and maintained for another 90 minutes. The shell layer was polymerized. The polymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to obtain core-shell type acrylic elastic particles (B). The average particle diameter of the rubber polymer part of the Atalinole elastic particles measured with an electron microscope was 140 nm.
アクリル樹脂 (A) 80重量部とアクリル弾性体粒子（B) 20重量部とを配合し、 2軸押 出機（日本製鋼社製 TEX30、 L/D = 44. 5)を用いて、スクリュー回転数 150rpm、 シリンダ温度 280°Cで混練し、ペレット状のアクリル樹脂組成物（C)を得た。  Mixing 80 parts by weight of acrylic resin (A) and 20 parts by weight of acrylic elastic particles (B), and using a twin screw extruder (TEX30, Nippon Steel Co., Ltd., L / D = 44.5), screw rotation The mixture was kneaded at several 150 rpm and a cylinder temperature of 280 ° C. to obtain a pellet-shaped acrylic resin composition (C).
得られたアクリル樹脂組成物（C)を 80°Cで 8時間真空乾燥した後、メチルェチルケ トンに固形分濃度 30重量％となるように溶解させ、 1 x mカットフィルターを用いて濾 過を行った。この溶液をギアポンプを用いてリップ間隙 0. 5mmの Tダイを通じて PE Tフィルム上にキャストし、熱風オーブンにて 60°C、 120°C、 170°Cの 3段階でそれぞ れ 30分間熱処理を行い、厚み 100 /i mの（メタ）アクリル系樹脂フィルムを得た。 The obtained acrylic resin composition (C) was vacuum-dried at 80 ° C for 8 hours, then dissolved in methyl ethyl ketone to a solid content concentration of 30% by weight, and filtered using a 1 xm cut filter. I went over. This solution is cast on a PE T film through a T die with a lip gap of 0.5 mm using a gear pump, and heat-treated for 30 minutes in each of three stages of 60 ° C, 120 ° C, and 170 ° C in a hot air oven. And a (meth) acrylic resin film having a thickness of 100 / im was obtained.
[0111] 〔製造例 3：ポリビニルアルコール系接着剤水溶液 (A)の調製〕 [Production Example 3: Preparation of polyvinyl alcohol-based adhesive aqueous solution (A)]
ァセトァセチル基変性したポリビュルアルコール樹脂 100重量部（ァセチル化度 13 %)に対してメチロールメラミン 20重量部を含む水溶液を、濃度 0. 5重量％になるよ うに調整したポリビュルアルコール系接着剤水溶液 (A)を調製した。  Polybutyl alcohol-based adhesive solution prepared by adjusting an aqueous solution containing 20 parts by weight of methylol melamine to 100 parts by weight of a poly (butyl alcohol resin) modified with acetoacetyl group (degree of acetylation 13%) to a concentration of 0.5% by weight (A) was prepared.
[0112] 〔製造例 4：ポリビニルアルコール系接着剤水溶液 (B)の調製〕 [Production Example 4: Preparation of polyvinyl alcohol adhesive aqueous solution (B)]
ァセトァセチル基変性したポリビュルアルコール樹脂 100重量部（平均重合度： 12 00、ケン化度： 98. 5モノレ0 /0、ァセトァセチル化度： 5モル0 /0)に対してメチロールメラ ミン 50重量部を、 30°Cの温度条件下に、純水に溶解し、固形分濃度 3. 7重量％に 調整した水溶液を調製した。上記水溶液 100重量部に対してアルミナコロイド水溶液 18重量部（平均粒子径： 15nm、固形分濃度： 10重量％、正電荷）を加えて接着剤 水溶液（B)を調製した。接着剤水溶液 (B)の粘度は、 9. 6mPa' sであった。また接 着剤水溶液（B)の pHは、 4〜4· 5の範囲であった。 Asetasechiru group-modified poly Bulle alcohol resin 100 parts by weight (average polymerization degree: 12 00, saponification degree: 98.5 Monore 0/0, Asetasechiru degree: 5 mol 0/0) with respect Mechirorumera Min 50 parts by weight Was dissolved in pure water under a temperature condition of 30 ° C. to prepare an aqueous solution adjusted to a solid content concentration of 3.7% by weight. An aqueous adhesive solution (B) was prepared by adding 18 parts by weight of an aqueous colloidal alumina solution (average particle size: 15 nm, solid content concentration: 10% by weight, positive charge) to 100 parts by weight of the aqueous solution. The viscosity of the aqueous adhesive solution (B) was 9.6 mPa's. The pH of the aqueous adhesive solution (B) was in the range of 4 to 4.5.
[0113] 〔製造例 5：ポリビニルアルコール系接着剤水溶液 (C)の調製〕 [Production Example 5: Preparation of aqueous solution of polyvinyl alcohol adhesive (C)]
製造例 4において、アルミナコロイド水溶液を使用しなかったこと以外は、製造例 4と 同様にして接着剤水溶液 (C)を調整した。  In Production Example 4, an aqueous adhesive solution (C) was prepared in the same manner as in Production Example 4 except that the alumina colloid aqueous solution was not used.
[0114] 〔実施例 1〕 [0114] [Example 1]
けん化処理された厚み 40 μ mのトリアセチルセルロースフィルム（コニ力ミノルタォ ブト株式会社製、商品名： KC4UY)を用意し、 60°Cの水浴に 30秒間浸漬して水洗 した。その後、乾燥温度 30°Cで 10秒間の乾燥を行ったところ、水分含有率が 3. 3重 量％のトリアセチルセルロースフィルム（1)が得られた。  A saponified 40 μm-thick triacetyl cellulose film (manufactured by Konica Minoltabuto Co., Ltd., trade name: KC4UY) was prepared and immersed in a 60 ° C. water bath for 30 seconds and washed with water. Thereafter, drying was carried out at a drying temperature of 30 ° C. for 10 seconds to obtain a triacetyl cellulose film (1) having a moisture content of 3.3% by weight.
[0115] 〔実施例 2〕 [0115] [Example 2]
風乾で 30秒間の乾燥を行った以外は実施例 1と同様に行ったところ、水分含有率 が 3. 8重量％のトリアセチルセルロースフィルム（2)が得られた。  A triacetylcellulose film (2) having a water content of 3.8% by weight was obtained in the same manner as in Example 1 except that air drying was performed for 30 seconds.
[0116] 〔比較例 1〕 [Comparative Example 1]
乾燥温度 30°Cで 30秒間の乾燥を行った以外は実施例 1と同様に行ったところ、水 分含有率が 3. 0重量％のトリアセチルセルロースフィルム（CI)が得られた。 The same procedure as in Example 1 was performed except that drying was performed at a drying temperature of 30 ° C for 30 seconds. A triacetylcellulose film (CI) having a content of 3.0% by weight was obtained.
[0117] 〔比較例 2〕 [Comparative Example 2]
乾燥温度 40°Cで 10秒間の乾燥を行つた以外は実施例 1と同様に行つたところ、水 分含有率が 2. 8重量％のトリアセチルセルロースフィルム（C2)が得られた。  A triacetyl cellulose film (C2) having a water content of 2.8% by weight was obtained by performing the same procedure as in Example 1 except that drying was performed at a drying temperature of 40 ° C. for 10 seconds.
[0118] 〔比較例 3〕 [Comparative Example 3]
乾燥温度 40°Cで 30秒間の乾燥を行った以外は実施例 1と同様に行ったところ、水 分含有率が 2. 4重量％のトリアセチルセルロースフィルム（C3)が得られた。  A triacetylcellulose film (C3) having a water content of 2.4% by weight was obtained in the same manner as in Example 1 except that drying was performed at a drying temperature of 40 ° C. for 30 seconds.
[0119] 〔比較例 4〕 [Comparative Example 4]
乾燥温度 60°Cで 10秒間の乾燥を行った以外は実施例 1と同様に行ったところ、水 分含有率が 1. 9重量％のトリアセチルセルロースフィルム（C4)が得られた。  A triacetyl cellulose film (C4) having a water content of 1.9% by weight was obtained in the same manner as in Example 1 except that drying was performed at a drying temperature of 60 ° C. for 10 seconds.
[0120] 〔比較例 5〕 [Comparative Example 5]
乾燥温度 60°Cで 30秒間の乾燥を行った以外は実施例 1と同様に行ったところ、水 分含有率が 1. 5重量％のトリアセチルセルロースフィルム（C5)が得られた。  A triacetylcellulose film (C5) having a water content of 1.5% by weight was obtained in the same manner as in Example 1 except that drying was performed at a drying temperature of 60 ° C. for 30 seconds.
[0121] 〔比較例 6〕 [Comparative Example 6]
乾燥温度 80°Cで 10秒間の乾燥を行つた以外は実施例 1と同様に行つたところ、水 分含有率が 1. 3重量％のトリアセチルセルロースフィルム（C6)が得られた。  A triacetylcellulose film (C6) having a water content of 1.3% by weight was obtained in the same manner as in Example 1 except that drying was performed at a drying temperature of 80 ° C. for 10 seconds.
[0122] 〔比較例 7〕 [Comparative Example 7]
乾燥温度 80°Cで 30秒間の乾燥を行った以外は実施例 1と同様に行ったところ、水 分含有率が 1. 4重量％のトリアセチルセルロースフィルム（C7)が得られた。  A triacetylcellulose film (C7) having a water content of 1.4% by weight was obtained in the same manner as in Example 1 except that drying was performed at a drying temperature of 80 ° C. for 30 seconds.
[0123] 〔比較例 8〕 [Comparative Example 8]
乾燥を行わなかった以外は実施例 1と同様に行ったところ、水分含有率が 4. 5重量 %のトリアセチルセルロースフィルム（C8)が得られた。  A triacetyl cellulose film (C8) having a water content of 4.5% by weight was obtained by carrying out in the same manner as in Example 1 except that drying was not performed.
[0124] 〔実施例 3〕 [Example 3]
トリァセチルセルロースフィルム（1) Z偏光子 Z (メタ）アクリル系樹脂フィルムの構 成からなる偏光板（1A)を作製した。具体的には、製造例 1で得られた偏光子の一方 の面にトリァセチルセルロースフィルム（1)を、偏光子の他方の面に（メタ）アクリル系 樹脂フィルムを、それぞれ製造例 3で得られたポリビュルアルコール系接着剤水溶液 (A)を用いて貼り合わせ、偏光板（1A)を得た。ポリビニルアルコール系接着剤水溶 液 (A)は、それぞれ、トリァセチルセルロースフィルム（1)、 （メタ）アクリル系樹脂フィ ルムに塗布し、 70°Cで 10分間乾燥させて偏光板（1A)を得た。得られた偏光板（1A )のカール量を測定すると、 lmmであった。結果を表 1に示す。 Triacetyl cellulose film (1) Z polarizer A polarizing plate (1A) comprising a Z (meth) acrylic resin film was prepared. Specifically, the triacetyl cellulose film (1) was obtained on one side of the polarizer obtained in Production Example 1 and the (meth) acrylic resin film was obtained on the other side of the polarizer in Production Example 3. The resulting polybulualcohol-based adhesive aqueous solution (A) was attached to obtain a polarizing plate (1A). Polyvinyl alcohol adhesive water-soluble Liquid (A) was applied to triacetyl cellulose film (1) and (meth) acrylic resin film, respectively, and dried at 70 ° C. for 10 minutes to obtain polarizing plate (1A). The curl amount of the obtained polarizing plate (1A) was measured and found to be 1 mm. The results are shown in Table 1.
[0125] 〔実施例 4〕 [Example 4]
トリァセチルセルロースフィルム（1)の代わりにトリアセチルセルロースフィルム（2)を 用いた以外は実施例 3と同様に行い、偏光板（2A)を作製した。得られた偏光板（2A )のカール量を測定すると、 3mmであった。結果を表 1に示す。  A polarizing plate (2A) was produced in the same manner as in Example 3 except that the triacetylcellulose film (2) was used instead of the triacetyl cellulose film (1). The curl amount of the obtained polarizing plate (2A) was measured and found to be 3 mm. The results are shown in Table 1.
[0126] 〔比較例 9〕 [Comparative Example 9]
トリァセチルセルロースフィルム（1)の代わりにトリァセチルセルロースフィルム（C1) を用いた以外は実施例 3と同様に行レ、、偏光板（C1A)を作製した。得られた偏光板 (C1A)のカール量を測定すると、 _ 8mmであった。結果を表 1に示す。  An array and a polarizing plate (C1A) were prepared in the same manner as in Example 3 except that the triacetylcellulose film (C1) was used instead of the triacetylcellulose film (1). The curling amount of the obtained polarizing plate (C1A) was measured to be _8 mm. The results are shown in Table 1.
[0127] 〔比較例 10〕 [Comparative Example 10]
トリァセチルセルロースフィルム（1)の代わりにトリアセチルセルロースフィルム（C2) を用いた以外は実施例 3と同様に行い、偏光板（C2A)を作製した。得られた偏光板 (C2A)のカール量を測定すると、 10mmであった。結果を表 1に示す。  A polarizing plate (C2A) was produced in the same manner as in Example 3 except that the triacetylcellulose film (C2) was used instead of the triacetyl cellulose film (1). The curl amount of the obtained polarizing plate (C2A) was measured and found to be 10 mm. The results are shown in Table 1.
[0128] 〔比較例 11〕 [Comparative Example 11]
トリァセチルセルロースフィルム（1)の代わりにトリアセチルセルロースフィルム（C3) を用いた以外は実施例 3と同様に行い、偏光板（C3A)を作製した。得られた偏光板 (C3A)のカール量を測定すると、 18mmであった。結果を表 1に示す。  A polarizing plate (C3A) was produced in the same manner as in Example 3 except that a triacetylcellulose film (C3) was used instead of the triacetylcellulose film (1). The curl amount of the obtained polarizing plate (C3A) was measured and found to be 18 mm. The results are shown in Table 1.
[0129] 〔比較例 12〕 [Comparative Example 12]
トリァセチルセルロースフィルム（1)の代わりにトリアセチルセルロースフィルム（C4) を用いた以外は実施例 3と同様に行レ、、偏光板（C4A)を作製した。得られた偏光板 (C4A)のカール量を測定すると、 _ 15mmであった。結果を表 1に示す。  An array and a polarizing plate (C4A) were prepared in the same manner as in Example 3 except that the triacetylcellulose film (C4) was used instead of the triacetyl cellulose film (1). The curl amount of the obtained polarizing plate (C4A) was measured to be _15 mm. The results are shown in Table 1.
[0130] 〔比較例 13〕 [Comparative Example 13]
トリァセチルセルロースフィルム（1)の代わりにトリアセチルセルロースフィルム（C5) を用いた以外は実施例 3と同様に行レ、、偏光板（C5A)を作製した。得られた偏光板 (C5A)のカール量を測定すると、 _ 15mmであった。結果を表 1に示す。  An array and a polarizing plate (C5A) were prepared in the same manner as in Example 3 except that the triacetylcellulose film (C5) was used instead of the triacetyl cellulose film (1). The curl amount of the obtained polarizing plate (C5A) was measured to be _15 mm. The results are shown in Table 1.
[0131] 〔比較例 14〕 トリァセチルセルロースフィルム（1)の代わりにトリアセチルセルロースフィルム（C6) を用いた以外は実施例 3と同様に行い、偏光板（C6A)を作製した。得られた偏光板 (C6A)のカール量を測定すると、 16mmであった。結果を表 1に示す。 [Comparative Example 14] A polarizing plate (C6A) was produced in the same manner as in Example 3 except that a triacetylcellulose film (C6) was used instead of the triacetylcellulose film (1). The curl amount of the obtained polarizing plate (C6A) was measured and found to be 16 mm. The results are shown in Table 1.
[0132] 〔比較例 15〕 [Comparative Example 15]
トリァセチルセルロースフィルム（1)の代わりにトリアセチルセルロースフィルム（C7) を用いた以外は実施例 3と同様に行レ、、偏光板（C7A)を作製した。得られた偏光板 (C7A)のカール量を測定すると、 _ 14mmであった。結果を表 1に示す。  An array and a polarizing plate (C7A) were produced in the same manner as in Example 3 except that the triacetylcellulose film (C7) was used instead of the triacetyl cellulose film (1). The curl amount of the obtained polarizing plate (C7A) was measured to be _14 mm. The results are shown in Table 1.
[0133] 〔比較例 16〕 [Comparative Example 16]
トリァセチルセルロースフィルム（1)の代わりにトリアセチルセルロースフィルム（C8) を用いた以外は実施例 3と同様に行レ、、偏光板（C8A)を作製した。得られた偏光板 (C8A)のカール量を測定すると、 10mmであった。結果を表 1に示す。  An array and a polarizing plate (C8A) were prepared in the same manner as in Example 3 except that the triacetylcellulose film (C8) was used instead of the triacetyl cellulose film (1). The curl amount of the obtained polarizing plate (C8A) was measured and found to be 10 mm. The results are shown in Table 1.
[0134] [表 1] [0134] [Table 1]
Figure imgf000032_0001
Figure imgf000032_0001
[0135] 表 1を見ると、トリァセチルセルロースフィルムの水分含有率を 3· 1重量0/。〜 4. 0重 量％という特定範囲内に調整した実施例 3 (トリァセチルセルロースフィルムの水分含 有率 = 3. 3重量％)、実施例 4 (トリァセチルセルロースフィルムの水分含有率 = 3. 8 重量％)では、カールの発生が顕著に抑制できていることが判る。一方、トリァセチル セルロースフィルムの水分含有率が 3. 1重量％より少ない場合や 4. 0重量％より多 い場合（比較例 9〜： 16)には、カールが顕著に発生していることが判る。 [0135] Looking at Table 1, the water content of the triacetyl cellulose film was 3.1 · 0 weight. Example 3 (moisture content of triacetylcellulose film = 3.3 wt%), Example 4 (water content of triacetylcellulose film = 3. 8 wt%), it can be seen that the occurrence of curling can be remarkably suppressed. On the other hand, when the water content of the triacetyl cellulose film is less than 3.1% by weight or more than 4.0% by weight (Comparative Examples 9 to 16), it can be seen that the curl is remarkably generated. .
[0136] 〔実施例 5〕 トリァセチルセルロースフィルム（1) /偏光子/ (メタ）アクリル系樹脂フィルムの構 成からなる偏光板（1A)を作製した。具体的には、製造例 1で得られた偏光子の一方 の面にトリァセチルセルロースフィルム（1)を、偏光子の他方の面に（メタ）アクリル系 樹脂フィルムを、それぞれ製造例 4で得られたポリビュルアルコール系接着剤水溶液 (B)を用いて貼り合わせ、偏光板（1B)を得た。ポリビニルアルコール系接着剤水溶 液（B)は、それぞれ、トリァセチルセルロースフィルム（1)、 （メタ）アクリル系樹脂フィ ルムに塗布し、 70°Cで 10分間乾燥させて偏光板（1B)を得た。得られた偏光板（1B )のカール量を測定すると、 _ lmmであった。得られた偏光板（1B)のクニック欠陥 数を測定すると、 0であった。結果を表 2に示す。 [Example 5] A polarizing plate (1A) having a composition of triacetyl cellulose film (1) / polarizer / (meth) acrylic resin film was produced. Specifically, the triacetyl cellulose film (1) was obtained on one side of the polarizer obtained in Production Example 1, and the (meth) acrylic resin film was obtained on the other side of the polarizer in Production Example 4. The resulting polybulualcohol-based adhesive aqueous solution (B) was bonded to obtain a polarizing plate (1B). Polyvinyl alcohol adhesive aqueous solution (B) was applied to triacetyl cellulose film (1) and (meth) acrylic resin film, respectively, and dried at 70 ° C for 10 minutes to obtain polarizing plate (1B). It was. The curl amount of the obtained polarizing plate (1B) was measured to be _lmm. When the number of knick defects in the obtained polarizing plate (1B) was measured, it was 0. The results are shown in Table 2.
[0137] 〔実施例 6〕 [Example 6]
トリァセチルセルロースフィルム（1)の代わりにトリアセチルセルロースフィルム（2)を 用いた以外は実施例 5と同様に行レ、、偏光板（2B)を作製した。得られた偏光板（2B )のカール量を測定すると、 3mmであった。得られた偏光板（2B)のクニック欠陥数を 測定すると、 0であった。結果を表 2に示す。  An array and a polarizing plate (2B) were prepared in the same manner as in Example 5 except that the triacetyl cellulose film (2) was used instead of the triacetyl cellulose film (1). The curl amount of the obtained polarizing plate (2B) was measured and found to be 3 mm. The number of knick defects in the obtained polarizing plate (2B) was measured and found to be 0. The results are shown in Table 2.
[0138] 〔実施例 7〕 [Example 7]
実施例 5におレ、て、製造例 4で得られたポリビュルアルコール系接着剤水溶液（B) に代えて製造例 5で得られたポリビニルアルコール系接着剤水溶液（C)を用いた以 外は実施例 5と同様に行い、偏光板（3B)を作製した。得られた偏光板（3B)のカー ル量を測定すると、 3mmであった。得られた偏光板（3B)のクニック欠陥数を測定す ると、 32であった。結果を表 2に示す。  In Example 5, the polyvinyl alcohol-based adhesive aqueous solution (C) obtained in Production Example 5 was used in place of the polybulualcohol-based adhesive aqueous solution (B) obtained in Production Example 4. Was carried out in the same manner as in Example 5 to produce a polarizing plate (3B). The curl amount of the obtained polarizing plate (3B) was measured and found to be 3 mm. The number of knick defects in the obtained polarizing plate (3B) was measured and found to be 32. The results are shown in Table 2.
[0139] 〔実施例 8〕 [Example 8]
実施例 6におレ、て、製造例 4で得られたポリビニルアルコール系接着剤水溶液（B) に代えて製造例 5で得られたポリビュルアルコール系接着剤水溶液（C)を用いた以 外は実施例 6と同様に行い、偏光板 (4B)を作製した。得られた偏光板 (4B)のカー ル量を測定すると、 Ommであった。得られた偏光板 (4B)のクニック欠陥数を測定す ると、 29であった。結果を表 2に示す。  In Example 6, except that the polyvinyl alcohol-based adhesive aqueous solution (C) obtained in Production Example 5 was used in place of the polyvinyl alcohol-based adhesive aqueous solution (B) obtained in Production Example 4. Was carried out in the same manner as in Example 6 to produce a polarizing plate (4B). The curl amount of the obtained polarizing plate (4B) was measured and found to be Omm. The number of knick defects in the obtained polarizing plate (4B) was measured and found to be 29. The results are shown in Table 2.
[0140] 〔比較例 17〕 [Comparative Example 17]
トリァセチルセルロースフィルム（1)の代わりにトリァセチルセルロースフィルム（C1) を用いた以外は実施例 5と同様に行い、偏光板（C1B)を作製した。得られた偏光板 (C1B)のカール量を測定すると、 8mmであった。得られた偏光板（C1B)のクニッ ク欠陥数を測定すると、 0であった。結果を表 2に示す。 Triacetyl cellulose film (C1) instead of triacetyl cellulose film (1) A polarizing plate (C1B) was produced in the same manner as in Example 5 except that was used. The curl amount of the obtained polarizing plate (C1B) was measured and found to be 8 mm. The number of knack defects of the obtained polarizing plate (C1B) was measured and found to be 0. The results are shown in Table 2.
[0141] 〔比較例 18〕  [0141] [Comparative Example 18]
トリァセチルセルロースフィルム（1)の代わりにトリアセチルセルロースフィルム（C2) を用いた以外は実施例 5と同様に行レ、、偏光板（C2B)を作製した。得られた偏光板 (C2B)のカール量を測定すると、 _ 10mmであった。得られた偏光板（C2B)のクニ ック欠陥数を測定すると、 0であった。結果を表 2に示す。  An array and a polarizing plate (C2B) were prepared in the same manner as in Example 5 except that the triacetylcellulose film (C2) was used instead of the triacetyl cellulose film (1). The curl amount of the obtained polarizing plate (C2B) was measured to be _10 mm. The number of knack defects of the obtained polarizing plate (C2B) was measured and found to be 0. The results are shown in Table 2.
[0142] 〔比較例 19〕  [0142] [Comparative Example 19]
トリァセチルセルロースフィルム（1)の代わりにトリアセチルセルロースフィルム（C3) を用いた以外は実施例 5と同様に行レ、、偏光板（C3B)を作製した。得られた偏光板 (C3B)のカール量を測定すると、 _ 18mmであった。得られた偏光板（C3B)のクニ ック欠陥数を測定すると、 0であった。結果を表 2に示す。  An array and a polarizing plate (C3B) were prepared in the same manner as in Example 5 except that the triacetylcellulose film (C3) was used instead of the triacetyl cellulose film (1). The curling amount of the obtained polarizing plate (C3B) was measured to be _18 mm. The number of knack defects of the obtained polarizing plate (C3B) was measured and found to be 0. The results are shown in Table 2.
[0143] 〔比較例 20〕  [Comparative Example 20]
トリァセチルセルロースフィルム（1)の代わりにトリアセチルセルロースフィルム（C4) を用い、ポリビュルアルコール系接着剤水溶液（B)の代わりに製造例 5で得られたポ リビニルアルコール系接着剤水溶液（C)を用いた以外は実施例 5と同様に行レ、、偏 光板（C4B)を作製した。得られた偏光板（C4B)のカール量を測定すると、 - 15mm であった。得られた偏光板（C4B)のクニック欠陥数を測定すると、 28であった。結果 を表 2に示す。  A triacetyl cellulose film (C4) was used in place of the triacetyl cellulose film (1), and the polyvinyl alcohol adhesive solution (C) obtained in Production Example 5 was used instead of the polybutyl alcohol adhesive solution (B). A polarizer and a polarizing plate (C4B) were produced in the same manner as in Example 5 except that the above was used. The curl amount of the obtained polarizing plate (C4B) was measured and found to be -15 mm. The number of knick defects in the obtained polarizing plate (C4B) was measured and found to be 28. The results are shown in Table 2.
[0144] 〔比較例 21〕  [Comparative Example 21]
トリァセチルセルロースフィルム（1)の代わりにトリアセチルセルロースフィルム（C5) を用いた以外は実施例 5と同様に行レ、、偏光板（C5B)を作製した。得られた偏光板 (C5B)のカール量を測定すると、 _ 15mmであった。得られた偏光板（C5B)のクニ ック欠陥数を測定すると、 0であった。結果を表 2に示す。  An array and a polarizing plate (C5B) were prepared in the same manner as in Example 5 except that the triacetylcellulose film (C5) was used instead of the triacetyl cellulose film (1). The curl amount of the obtained polarizing plate (C5B) was measured to be _15 mm. The number of knack defects of the obtained polarizing plate (C5B) was measured and found to be 0. The results are shown in Table 2.
[0145] 〔比較例 22〕  [Comparative Example 22]
トリァセチルセルロースフィルム（1)の代わりにトリアセチルセルロースフィルム（C6) を用いた以外は実施例 5と同様に行レ、、偏光板（C6B)を作製した。得られた偏光板 (C6B)のカール量を測定すると、 16mmであった。得られた偏光板（C6B)のクニ ック欠陥数を測定すると、 2であった。結果を表 2に示す。 An array and a polarizing plate (C6B) were prepared in the same manner as in Example 5 except that the triacetylcellulose film (C6) was used instead of the triacetyl cellulose film (1). Obtained polarizing plate The curl amount of (C6B) was measured and found to be 16 mm. The number of knack defects of the obtained polarizing plate (C6B) was measured to be 2. The results are shown in Table 2.
[0146] 〔比較例 23〕  [Comparative Example 23]
トリァセチルセルロースフィルム（1)の代わりにトリアセチルセルロースフィルム（C7) を用いた以外は実施例 5と同様に行レ、、偏光板（C7B)を作製した。得られた偏光板 (C7B)のカール量を測定すると、 _ 14mmであった。得られた偏光板（C7B)のクニ ック欠陥数を測定すると、 1であった。結果を表 2に示す。  An array and a polarizing plate (C7B) were prepared in the same manner as in Example 5 except that the triacetylcellulose film (C7) was used instead of the triacetyl cellulose film (1). The curl amount of the obtained polarizing plate (C7B) was measured to be _14 mm. When the number of knack defects of the obtained polarizing plate (C7B) was measured, it was 1. The results are shown in Table 2.
[0147] 〔比較例 24〕  [Comparative Example 24]
トリァセチルセルロースフィルム（1)の代わりにトリアセチルセルロースフィルム（C8) を用いた以外は実施例 5と同様に行レ、、偏光板（C8B)を作製した。得られた偏光板 (C8B)のカール量を測定すると、 10mmであった。得られた偏光板（C8B)のクニッ ク欠陥数を測定すると、 1であった。結果を表 2に示す。  An array and a polarizing plate (C8B) were prepared in the same manner as in Example 5 except that the triacetylcellulose film (C8) was used instead of the triacetyl cellulose film (1). The curl amount of the obtained polarizing plate (C8B) was measured and found to be 10 mm. The number of knack defects of the obtained polarizing plate (C8B) was measured and found to be 1. The results are shown in Table 2.
[0148] 〔比較例 25〕  [Comparative Example 25]
比較例 20におレ、て、製造例 5で得られたポリビュルアルコール系接着剤水溶液（C )に代えて製造例 4で得られたポリビニルアルコール系接着剤水溶液（B)を用いた以 外は比較例 20と同様に行い、偏光板 (C9B)を作製した。得られた偏光板（C9B)の カール量を測定すると、 15mmであった。得られた偏光板（C9B)のクニック欠陥数 を測定すると、 0であった。結果を表 2に示す。  In Comparative Example 20, except that the polyvinyl alcohol-based adhesive aqueous solution (B) obtained in Production Example 4 was used in place of the polybutyl alcohol-based adhesive aqueous solution (C) obtained in Production Example 5. Was carried out in the same manner as in Comparative Example 20, and a polarizing plate (C9B) was produced. The curl amount of the obtained polarizing plate (C9B) was measured and found to be 15 mm. The number of knick defects in the obtained polarizing plate (C9B) was measured and found to be 0. The results are shown in Table 2.
[0149] [表 2] [0149] [Table 2]
m トリアセチル 力一 クニック m Triacetyl Rikiichi Knick
セノレ口—スフイノレム (mm)  Senole Mouth-Sufinolem (mm)
番号 水^^碑 m  Number Water ^^ Monument m
(*«%)  (* «%)
(C8B) (C8) 4. 5 10 1  (C8B) (C8) 4.5 5 10 1
mm 5 (IB) (1) 3. 8 3 0  mm 5 (IB) (1) 3. 8 3 0
(2B) (2) 3. 3 -1 0 (2B) (2) 3.3 3 -1 0
m 7 (3B) (1) 3. 8 3 32  m 7 (3B) (1) 3. 8 3 32
例 8 (4B) (2) 3. 3 0 29 Example 8 (4B) (2) 3. 3 0 29
i 7 (C1B) (C1) 3. 0 一 8 0  i 7 (C1B) (C1) 3. 0 1 8 0
ti Mi 8 (C2B) (C2) 2. 8 -10 0  ti Mi 8 (C2B) (C2) 2. 8 -10 0
(C3B) (C3) 2. 4 -18 0  (C3B) (C3) 2. 4 -18 0
(C4B) (C4) 1. 9 -15 28  (C4B) (C4) 1. 9 -15 28
(C5B) (C5) 1. 5 -15 0  (C5B) (C5) 1. 5 -15 0
1¾¾¾22 (C6B) (C6) 1. 3 -16 2  1¾¾¾22 (C6B) (C6) 1. 3 -16 2
(C7B) (C7) 1. 4 -14 1  (C7B) (C7) 1. 4 -14 1
i 25 (C9B) (C4) 1. 9 -15 0 産業上の利用可能性  i 25 (C9B) (C4) 1. 9 -15 0 Industrial applicability
本発明の偏光子保護フィルムおよび偏光板は、各種画像表示装置 (液晶表示装置 、有機 EL表示装置、 PDP等）に好適に用いることができる。  The polarizer protective film and polarizing plate of the present invention can be suitably used for various image display devices (liquid crystal display devices, organic EL display devices, PDPs, etc.).

Claims

請求の範囲 The scope of the claims
[I] セルロース系樹脂を主成分とし、水分含有率が 3. 1重量％〜4. 0重量％である、 偏光子保護フィルム。  [I] A polarizer protective film comprising a cellulose-based resin as a main component and having a moisture content of 3.1% by weight to 4.0% by weight.
[2] 前記セルロース系樹脂がトリァセチルセルロースである、請求項 1に記載の偏光子 保護フィルム。  [2] The polarizer protective film according to [1], wherein the cellulosic resin is triacetyl cellulose.
[3] 偏光子の両面側に保護層を有し、該保護層の少なくとも一方がセルロース系樹脂 層である偏光板であって、該セルロース系樹脂層が請求項 1に記載の偏光子保護フ イルムを用いて形成される、偏光板。  [3] The polarizing plate having a protective layer on both sides of the polarizer, wherein at least one of the protective layers is a cellulose resin layer, wherein the cellulose resin layer is the polarizer protective film according to claim 1. A polarizing plate formed using film.
[4] 前記セルロース系樹脂層がトリァセチルセルロース層である、請求項 3に記載の偏 光板。  [4] The polarizing plate according to [3], wherein the cellulose resin layer is a triacetyl cellulose layer.
[5] 偏光子の一方の面側のみにセルロース系樹脂層を有する、請求項 3または 4に記 載の偏光板。  [5] The polarizing plate according to claim 3 or 4, wherein the polarizing plate has a cellulose resin layer only on one surface side of the polarizer.
[6] 偏光子のセルロース系樹脂層を有する面側と反対の面側に (メタ）アクリル系樹脂を 主成分として含む層を有する、請求項 5に記載の偏光板。  [6] The polarizing plate according to claim 5, wherein the polarizing plate has a layer containing a (meth) acrylic resin as a main component on the side opposite to the side having the cellulose resin layer.
[7] 前記偏光子の両面側に有する保護層の少なくとも一方が、ポリビニルアルコール系 接着剤から形成される接着剤層を介して該偏光子と積層している、請求項 3から 6ま でのレ、ずれかに記載の偏光板。 [7] At least one of the protective layers on both sides of the polarizer is laminated with the polarizer via an adhesive layer formed of a polyvinyl alcohol-based adhesive. A polarizing plate according to any one of the above.
[8] 前記偏光子の両面側に有する保護層の両方が、ポリビュルアルコール系接着剤か ら形成される接着剤層を介して該偏光子と積層している、請求項 7までのいずれかに 記載の偏光板。 [8] The protective layer according to claim 7, wherein both of the protective layers on both sides of the polarizer are laminated with the polarizer via an adhesive layer formed from a polybulal alcohol adhesive. The polarizing plate as described in.
[9] 前記ポリビュルアルコール系接着剤は、ポリビュルアルコール系樹脂と架橋剤を含 有する、請求項 7または 8に記載の偏光板。  [9] The polarizing plate according to [7] or [8], wherein the polybulualcohol-based adhesive includes a polybulualcohol-based resin and a crosslinking agent.
[10] 前記ポリビュルアルコール系接着剤は、ポリビュルアルコール系樹脂、架橋剤、お よび平均粒子径が 1〜： !OOnmの金属化合物コロイドを含有する、請求項 7または 8に 記載の偏光板。 [10] The polarizing plate according to claim 7 or 8, wherein the polybulualcohol-based adhesive contains a polybulualcohol-based resin, a crosslinking agent, and a metal compound colloid having an average particle diameter of 1 to! OOnm. .
[II] 前記金属化合物コロイドは、前記ポリビュルアルコール系樹脂 100重量部に対して 、 200重量部以下の割合で配合される、請求項 10に記載の偏光板。  [II] The polarizing plate according to claim 10, wherein the metal compound colloid is blended at a ratio of 200 parts by weight or less with respect to 100 parts by weight of the polybutyl alcohol resin.
[12] 最外層の少なくとも一方として粘着剤層をさらに有する、請求項 3から 11までのい ずれかに記載の偏光板。 [12] The method according to any one of claims 3 to 11, further comprising an adhesive layer as at least one of the outermost layers. The polarizing plate as described in any one.
請求項 3から 12までのいずれかに記載の偏光板を少なくとも 1枚含む、画像表示装 置。  An image display device comprising at least one polarizing plate according to any one of claims 3 to 12.
PCT/JP2007/061067 2006-06-14 2007-05-31 Polarizer protective film, polarizing plate, and image display device WO2007145081A1 (en)

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JP2009139658A (en) * 2007-12-06 2009-06-25 Nitto Denko Corp Multilayer optical film
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JP2009139661A (en) * 2007-12-06 2009-06-25 Nitto Denko Corp Polarizing plate, optical film and image display device
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JP2011107686A (en) * 2009-10-22 2011-06-02 Sumitomo Chemical Co Ltd Optical laminate and method of manufacturing the same
US9507202B2 (en) 2012-05-24 2016-11-29 Fujifilm Corporation Polarization plate and liquid crystal display

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