WO2013161647A1 - Procédé pour la fabrication d'une plaque polarisante - Google Patents

Procédé pour la fabrication d'une plaque polarisante Download PDF

Info

Publication number
WO2013161647A1
WO2013161647A1 PCT/JP2013/061436 JP2013061436W WO2013161647A1 WO 2013161647 A1 WO2013161647 A1 WO 2013161647A1 JP 2013061436 W JP2013061436 W JP 2013061436W WO 2013161647 A1 WO2013161647 A1 WO 2013161647A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
cellulose ester
acid
polarizing plate
polarizing
Prior art date
Application number
PCT/JP2013/061436
Other languages
English (en)
Japanese (ja)
Inventor
睦美 笠原
Original Assignee
コニカミノルタ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by コニカミノルタ株式会社 filed Critical コニカミノルタ株式会社
Priority to CN201380021480.3A priority Critical patent/CN104254791A/zh
Priority to KR1020147029302A priority patent/KR101688288B1/ko
Priority to JP2014512492A priority patent/JP6086117B2/ja
Publication of WO2013161647A1 publication Critical patent/WO2013161647A1/fr

Links

Images

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/056—Forming hydrophilic coatings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose

Definitions

  • the present invention relates to a method for producing a polarizing plate. More specifically, the present invention relates to a method for manufacturing a thinned polarizing plate.
  • a method for producing a thin polarizing film by applying a hydrophilic polymer to a base material, stretching and dyeing, and then peeling the base material is disclosed (for example, see Patent Documents 1 and 2.)
  • a polarizing film obtained by stretching and dyeing a conventional polyvinyl alcohol film has a limit in thinning, and the thickness is more than 20 ⁇ m, whereas the thickness is less than 10 ⁇ m. It is said that an ultra-thin polarizing film can be obtained.
  • thermoplastic resin films such as cellulose ester, polyethylene terephthalate (PET), cycloolefin polymer (COP), and polycarbonate (PC) are known.
  • thermoplastic resin film a cellulose ester film is used more widely than other thermoplastic resin films because of its moderate moisture permeability, adhesion and drying with a polarizing film proceed smoothly.
  • a hydrophilic treatment is essential before the bonding step with the polarizing film, and the alkali saponification treatment is most widely used as the hydrophilic treatment.
  • Alkali saponification treatment uses a high-temperature, high-concentration alkaline aqueous solution, so that a part of the film dissolves into the alkali saponification solution by alkali saponification, and the strength of the film is lost. There was a point.
  • the high-temperature, high-concentration alkali saponification treatment loses the strength of the film, and the polarized light is thinned to 10 ⁇ m or less.
  • the polarized light is thinned to 10 ⁇ m or less.
  • the above-disclosed method is a technique for imparting hydrophilicity to a thick cellulose ester film, and it is desired to impart sufficient hydrophilicity to a desired thin film cellulose ester film of 40 ⁇ m or less.
  • Decrease in film strength (koshi) due to thermal decomposition of the film, generation of wrinkles and curls during polarizing plate production, and generation of bubbles due to curling and deformation during panel bonding, and further thermal decomposition of the film There is a problem that the haze is increased due to the decrease in the front contrast of the liquid crystal display device.
  • JP 2011-1000016 A Japanese Patent No. 4815544 JP 2000-356714 A JP 2002-82226 A
  • the present invention has been made in view of the above problems and situations, and its solution is to obtain excellent adhesion between the thin film polarizing film and the thin film protective film, Another object of the present invention is to provide a method for producing a thinned polarizing plate which does not generate bubbles due to curling or deformation during panel bonding, and does not increase haze and lower the front contrast in a liquid crystal display device associated therewith.
  • a polarizing film (A) comprising a hydrophilic polymer layer dyed with a dichroic substance, and a cellulose ester film (B )
  • the cellulose ester film (B) is hydrophilized by either plasma treatment or corona treatment, and has a specific surface freeness.
  • the manufacturing method of the polarizing plate which is a cellulose ester film having energy, there is no generation of wrinkles or curls at the time of manufacturing the polarizing plate, generation of bubbles due to curling or deformation at the time of panel bonding, an increase in haze, and a liquid crystal display device associated therewith It has been found that a thin-film polarizing plate without lowering the front contrast can be obtained.
  • the cellulose ester film (B) is hydrophilized by either plasma treatment or corona treatment, and the surface free energy before hydrophilization treatment of the cellulose ester film (B) is as follows:
  • ⁇ sh represents a hydrogen bond component of surface free energy
  • ⁇ sp represents a dipole component.
  • the polarizing film (A) has a thickness in the range of 0.5 to 10 ⁇ m, and the cellulose ester film (B) has a thickness in the range of 5 to 40 ⁇ m.
  • the cellulose ester film (B) is subjected to a plasma treatment or a corona treatment to obtain a ratio ( ⁇ sh / ⁇ sp) of a hydrogen bond component ( ⁇ sh) and a dipole component ( ⁇ sp) of surface free energy.
  • a plasma treatment or a corona treatment to obtain a ratio ( ⁇ sh / ⁇ sp) of a hydrogen bond component ( ⁇ sh) and a dipole component ( ⁇ sp) of surface free energy.
  • the ratio ( ⁇ sh / ⁇ sp) between the hydrogen bond component ( ⁇ sh) and the dipole component ( ⁇ sp) of the surface free energy indicates the size of the ratio of the hydrogen bond component in the surface free energy. It gets bigger as you go.
  • the strength of the plasma treatment can be reduced, and desired hydrophilicity can be achieved while maintaining film properties.
  • the plasma treatment since the plasma treatment has an effect of increasing the surface irregularities of the film, it can contribute to the improvement of the adhesion with the polarizing film surface by the anchor effect.
  • the amount of diffusing boric acid affects the adhesion, and the thinner the polarizing film, the more the boric acid content decreases, making it difficult to adhere. Accordingly, it is presumed that the combination of the thin polarizing film and the thin cellulose ester film is more likely to cause poor adhesion, and the generation of wrinkles and curls is promoted.
  • Sample film placed on glycerin State where glycerin is dropped on the sample film Cover glass placed on glycerin 1 is a schematic view showing an example of a plasma processing apparatus of a single frequency high frequency voltage application method useful for the present invention.
  • the polarizing plate production method of the present invention comprises a polarizing film (A) having a hydrophilic polymer layer dyed with a dichroic substance, and an adhesive agent on at least one surface of the polarizing film (A).
  • the cellulose ester film (B) may contain diacetyl cellulose having a total acyl group substitution degree in the range of 2.0 to 2.5.
  • the above formula (I) is satisfied.
  • the polarizing film (A) has a film thickness of 0.5 to 10 ⁇ m
  • the cellulose ester film (B) has a film thickness of 5 to 40 ⁇ m. It is preferable from the viewpoint of obtaining a difficult polarizing plate.
  • the film thickness of the cellulose ester film (B) is in the range of 5 to 20 ⁇ m.
  • a separator is bonded to the dyed surface of the polarizing film (A), the thermoplastic resin layer is peeled off while the separator is bonded, and the cellulose ester film (B) is hydrophilized on the peeled surface.
  • the manufacturing method of pasting the coated surfaces is preferable because it can suppress wrinkling and curling at the time of manufacturing the polarizing plate.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the polarizing plate produced by the method for producing a polarizing plate of the present invention is also referred to as “polarizing plate of the present invention” in the present specification.
  • polarizing film (A) In the polarizing film (A) according to the present invention, a hydrophilic polymer layer is laminated on a thermoplastic resin layer by a coating method, and preferably a stretching treatment is performed to form a stretched laminate, and then a dichroic substance is used.
  • the hydrophilic polymer layer is dyed to impart a polarizing function, and then the thermoplastic resin layer is peeled off to form a polarizing film (A). Therefore, the polarizing film (A) according to the present invention finally refers to the hydrophilic polymer layer, and since the thermoplastic resin layer is peeled off, the film thickness can be reduced to 10 ⁇ m or less. .
  • a preferred film thickness is in the range of 0.5 to 10 ⁇ m.
  • thermoplastic resin layer used in the present invention functions as a base material for forming a hydrophilic polymer layer.
  • a film similar to the protective film constituting the polarizing plate can be applied.
  • thermoplastic resin used in the present invention includes a crystalline thermoplastic resin in which polymers are regularly arranged, and an amorphous or amorphous state in which the polymers do not have a regular arrangement or only a small part.
  • crystalline thermoplastic resin in which polymers are regularly arranged
  • amorphous or amorphous state in which the polymers do not have a regular arrangement or only a small part.
  • a resin that is not in a crystalline state or a resin that does not reach a crystalline state regardless of whether it is a crystalline resin or an amorphous resin is referred to as an amorphous or amorphous resin.
  • an amorphous resin or an amorphous resin is used in distinction from an amorphous resin having a property of not forming a crystalline state.
  • the crystalline thermoplastic resin examples include olefin resins including polyethylene (PE) and polypropylene (PP), and ester resins including polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).
  • olefin resins including polyethylene (PE) and polypropylene (PP)
  • ester resins including polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • One of the characteristics of the crystalline thermoplastic resin is that it generally has a property that crystallization proceeds due to alignment of polymers by heating or stretching orientation. The physical properties of the resin vary depending on the degree of crystallization. On the other hand, for example, even with a crystalline thermoplastic resin such as polypropylene (PP) and polyethylene terephthalate (PET), crystallization can be suppressed by inhibiting the arrangement of the polymers caused by heat treatment or stretching orientation
  • polypropylene (PP) and polyethylene terephthalate (PET) whose crystallization is suppressed are called amorphous polypropylene and amorphous polyethylene terephthalate. These are collectively called amorphous olefin resin and amorphous ester type. It is called resin.
  • amorphous polypropylene (PP) in which crystallization is suppressed can be produced by using an atactic structure without stereoregularity.
  • PET polyethylene terephthalate
  • PET polyethylene terephthalate
  • a molecule that inhibits crystallization of polyethylene terephthalate (PET) by copolymerizing a modifying group such as isophthalic acid or 1,4-cyclohexanedimethanol as a polymerization monomer By copolymerization, amorphous polyethylene terephthalate (PET) with suppressed crystallization can be produced.
  • ester resins that are polycondensates of polycarboxylic acids (dicarboxylic acids) and polyhydric alcohols (diols)
  • examples of the crystalline ester resins used in the present invention include polyethylene terephthalate (PET), poly Examples include butylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), and polybutylene naphthalate (PBN).
  • PET polyethylene terephthalate
  • PBT butylene terephthalate
  • PTT polytrimethylene terephthalate
  • PEN polyethylene naphthalate
  • PBN polybutylene naphthalate
  • These crystalline ester resins have the property of being easily crystallized when formed into a film, but they are not rapidly crystallized and are stretchable when produced at a temperature that maintains an amorphous state. Therefore, it can be used as a thermoplastic resin. If the film is crystallized during film formation
  • the crystalline ester resin used in the present invention may contain a plasticizer or an elastomer in order to improve the workability and stretchability of the film.
  • the plasticizer include phthalates and polycondensates thereof, fatty acid esters such as adipic acid and polycondensates thereof, polyester plasticizers, epoxy plasticizers, styrene polymers, acrylic polymers, terphenyl compounds, and the like. Examples thereof include substituted derivatives thereof.
  • the elastomer include styrene, olefin, acrylic, vinyl chloride, urethane, ester, and nylon.
  • the thickness of the thermoplastic resin layer (before stretching) can be determined as appropriate, but is generally about 1 to 500 ⁇ m from the viewpoints of workability such as strength and handleability, and thin layer properties. 1 to 300 ⁇ m is particularly preferable, and 5 to 200 ⁇ m is more preferable. The thickness of the thermoplastic resin layer is particularly suitable when it is 5 to 150 ⁇ m. On the other hand, the thickness of the thermoplastic resin layer (after stretching) in the stretched laminate is about 1 to 400 ⁇ m, preferably 1 to 200 ⁇ m, preferably 5 to 100 ⁇ m from the viewpoint of workability such as strength and handleability. It is more preferable that The thickness of the thermoplastic resin layer in the stretched laminate is determined by the thickness of the thermoplastic resin layer (before stretching) and the stretch ratio.
  • the stretched laminate includes a hydrophilic polymer layer.
  • the hydrophilic polymer layer is a layer containing a hydrophilic polymer as a main component, and the hydrophilic polymer layer adsorbs a dichroic substance by a dyeing process described later. Thereby, the hydrophilic polymer layer functions as the polarizing film (A) in the polarizing plate of the present invention.
  • the hydrophilic polymer constituting the hydrophilic polymer layer is not particularly limited, but a polyvinyl alcohol material is preferably exemplified.
  • the polyvinyl alcohol-based material include polyvinyl alcohol and derivatives thereof.
  • polyvinyl alcohol derivatives include polyvinyl formal, polyvinyl acetal, etc., olefins such as ethylene and propylene, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, alkyl esters thereof, acrylamide, and the like. Can be mentioned.
  • the degree of polymerization of polyvinyl alcohol is preferably about 100 to 10,000, and more preferably 1,000 to 10,000. A saponification degree of about 80 to 100 mol% is generally used.
  • hydrophilic polymer examples include partially saponified ethylene / vinyl acetate copolymer, dehydrated polyvinyl alcohol and dehydrochlorinated polyvinyl chloride.
  • polyvinyl alcohol is preferably used as the hydrophilic polymer.
  • the hydrophilic polymer layer may contain additives such as a plasticizer and a surfactant in addition to the hydrophilic polymer described above.
  • the plasticizer include polyols and condensates thereof, and examples include glycerin, diglycerin, triglycerin, ethylene glycol, propylene glycol, and polyethylene glycol.
  • the amount of the plasticizer used is not particularly limited, but is preferably 20% by mass or less with respect to the total solid content (100% by mass) of the hydrophilic polymer layer.
  • the polarizing film (A) according to the present invention is formed by laminating a hydrophilic polymer layer on a thermoplastic resin layer to form a laminate, and further stretching to form a stretched laminate.
  • the stretching treatment may be carried out after or simultaneously with the dyeing treatment. However, if the drawing treatment is carried out before the dyeing treatment, it is possible to dye along the oriented hydrophilic polymer molecules, so that uniform polarization characteristics are imparted. This is also preferable.
  • a hydrophilic polymer layer is laminated on the thermoplastic resin layer by a coating method and then stretched in the TD direction (width direction) or MD direction (longitudinal direction). It is preferable to form a stretched laminate having a polarizing film through the step of performing.
  • the production method of the stretched laminate is not particularly limited, and can be suitably produced while referring to the conventionally known knowledge and the description in the Examples section described later.
  • An example of a method for producing a stretched laminate can be obtained, for example, by applying an aqueous solution containing a hydrophilic polymer to a thermoplastic resin layer, followed by drying and stretching.
  • a method for forming the stretched laminate the thermoplastic resin layer and the hydrophilic polymer layer are laminated directly or via a photocurable adhesive layer, so that the thermoplastic resin layer and the hydrophilic polymer layer are integrated.
  • a laminated body in a state of being converted is obtained.
  • thermoplastic resin layer used for the production of the stretched laminate may be subjected to a stretching treatment in advance before applying an aqueous solution containing a hydrophilic polymer.
  • the stretching treatment for forming the stretched laminate includes uniaxial stretching, biaxial stretching, oblique stretching, and the like.
  • Uniaxial stretching may be either longitudinal stretching performed in the MD direction of the laminate or transverse stretching performed in the TD direction of the laminate.
  • transverse stretching the film can be contracted in the longitudinal direction while stretching in the width direction.
  • the transverse stretching method include a fixed end uniaxial stretching method in which one end is fixed via a tenter, and a free end uniaxial stretching method in which one end is not fixed.
  • Examples of the longitudinal stretching method include an inter-roller stretching method, a compression stretching method, and a stretching method using a tenter.
  • the stretching process can be performed in multiple stages.
  • the temperature during the stretching treatment of the laminate is not particularly limited, but is preferably in the range of 130 to 200 ° C, more preferably in the range of 150 to 180 ° C.
  • the stretching process of the laminate may be performed such that the total stretch ratio in all directions is in the range of 1.1 to 10 times the original length of the laminate. It is preferably in the range of 2 to 6 times, more preferably 3 to 5 times.
  • An aqueous solution containing a hydrophilic polymer (a coating solution for forming a hydrophilic polymer) is prepared by appropriately heating a powder of a hydrophilic polymer (for example, polyvinyl alcohol) or a pulverized product or a cut product of a hydrophilic polymer film. It can be prepared by dissolving in water (hot water).
  • a method for applying the aqueous solution containing the hydrophilic polymer onto the thermoplastic resin layer include a wire bar coating method, a roller coating method such as reverse coating and gravure coating, a spin coating method, a screen coating method, and a fountain coating.
  • a method, a dipping method, a spray method, an ink jet method and the like can be appropriately selected and applied.
  • Drying is carried out after applying a coating solution for forming a hydrophilic polymer onto the thermoplastic resin layer, and the drying temperature is usually in the range of 50 to 200 ° C., preferably in the range of 80 to 150 ° C.
  • the drying time is usually about 5 to 30 minutes.
  • a laminate is formed in one step by supplying from a die or the like by a co-extrusion method of a thermoplastic resin layer forming material and an aqueous polymer layer forming material. Can do.
  • the material for forming the thermoplastic resin layer and the material for forming the hydrophilic polymer layer are respectively charged into the coextrusion machine so that the thicknesses of the thermoplastic resin layer and the hydrophilic polymer layer are within a desired range. It is preferable to control the coextrusion amount.
  • the stretched laminate obtained above is dyed with a dichroic substance, so that the dichroic substance is adsorbed on the hydrophilic polymer layer and functions as a polarizing film (A). .
  • the dyeing process is performed by adsorbing a dichroic substance to the hydrophilic polymer layer of the laminate.
  • the dyeing process is performed, for example, by immersing the laminate in a solution (dyeing solution) containing a dichroic substance.
  • a solution in which a dichroic substance is dissolved in a solvent can be used.
  • the solvent water is generally used, but an organic solvent compatible with water may be further added.
  • the specific configuration of the dichroic substance adsorbed on the hydrophilic polymer layer is not particularly limited, and examples thereof include iodine and organic dyes.
  • Organic dyes include, for example, Red BR, Red LR, Red R, Pink LB, Rubin BL, Bordeaux GS, Sky Blue LG, Lemon Yellow, Blue BR, Blue 2R, Navy RY, Green LG, Violet LB, Violet B, Black H, Black B, Black GSP, Yellow 3G, Yellow R, Orange LR, Orange 3R, Scarlet GL, Scarlet KGL, Congo Red, Brilliant Violet BK, Spura Blue G, Spura Blue GL, Spura Orange GL, Direct Sky Blue, Direct First orange S, first black, etc. are used.
  • iodide examples include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and iodide.
  • the addition ratio of these iodides is preferably 0.01 to 10% by mass, and more preferably 0.1 to 5% by mass in the dyeing solution.
  • the ratio (mass ratio) of iodine and potassium iodide is preferably in the range of 1: 5 to 1: 100, and in the range of 1: 6 to 1:80. More preferably, it is in a range of 1: 7 to 1:70.
  • the immersion time of the stretched laminate in the dyeing solution is not particularly limited, but usually it is preferably in the range of 15 seconds to 5 minutes, more preferably 1 to 3 minutes.
  • the temperature of the dyeing solution is preferably in the range of 10 to 60 ° C., more preferably in the range of 20 to 40 ° C.
  • the dichroic substance is fixed by sequentially immersing the laminate in a decolorizing solution containing potassium iodide and a crosslinking solution containing boric acid or a boron compound and potassium iodide. Then, when it dries with a dryer, a coating-type polarizing film (A) is obtained.
  • cellulose ester film (B) functioning as a protective film for the polarizing plate of the present invention will be described in detail.
  • the cellulose ester film (B) may be referred to as “protective film” or “polarizing plate protective film” in order to express its function. Further, it may be simply referred to as “cellulose ester film”.
  • the cellulose ester film (B) according to the present invention is hydrophilized by either plasma treatment or corona treatment, and the surface free energy before and after the hydrophilization treatment of the cellulose ester film (B) is within the following specific range. It is characterized by being.
  • the cellulose ester film (B) is a protective film hydrophilized by either plasma treatment or corona treatment, and the surface free energy of the cellulose ester film before hydrophilization is represented by the following formula (SI): And the surface free energy after the hydrophilic treatment of the cellulose ester film satisfies the following formula (SII).
  • (gamma) sh represents the hydrogen bond component of surface free energy
  • (gamma) sp represents a dipole component.
  • the ratio ( ⁇ sh / ⁇ sp) of the hydrogen bond component to the dipole component ( ⁇ sh / ⁇ sp) of the surface free energy before the hydrophilization treatment is preferably in the range of 0.28 to 1.0, more preferably 0.8. It is within the range of 30 to 0.50.
  • the ratio of the hydrogen bond component to the dipole component ( ⁇ sh / ⁇ sp) of the surface free energy before the hydrophilic treatment is smaller than 0.25, in order to obtain sufficient adhesion to the polarizing film, plasma treatment or corona It is necessary to carry out hydrophilic treatment such as treatment under strong conditions, in which case the film surface is subject to thermal damage, the physical properties and transparency of the film are significantly impaired, film strength is lowered, haze is increased, and accompanying this The front contrast in the liquid crystal display device is reduced.
  • the ratio ( ⁇ sh / ⁇ sp) of the hydrogen bond component to the dipole component of the surface free energy after the hydrophilic treatment ( ⁇ sh / ⁇ sp) is preferably 1.8 to 3.5 in order to obtain sufficient adhesion to the polarizing film. Within the range, more preferably within the range of 2.0 to 3.0.
  • Means to change the ratio of hydrogen bond component to dipole component ( ⁇ sh / ⁇ sp) of surface free energy include change of substitution degree of cellulose acetate, change of carbon number of substituent, change of additive structure and addition amount Can be mentioned. By using these factors in combination, the ratio of the surface free energy hydrogen bond component to the dipole component can be variously changed.
  • the ratio ( ⁇ sh / ⁇ sp) between the hydrogen bond component and dipole component of the surface free energy before or after the hydrophilization treatment is larger than the upper limit of the formulas (SI) and (SII), the hygroscopicity of the film increases.
  • the film strength (koshi) decreases, and wrinkles and curls are a problem.
  • the viewing angle and the color variation of the panel increase.
  • the surface free energy before the hydrophilic treatment of the cellulose ester film (B) satisfies the formula (SI) and the hydrophilic treatment of the cellulose ester film (B). It is necessary to control the selection of the material type of the cellulose ester film (B) and the hydrophilization surface treatment conditions so that the later surface free energy satisfies the formula (SII).
  • the surface free energy is obtained by using a reagent whose dipole component, dispersion component and hydrogen bond component of the surface free energy are known, and measuring the adhesion to the reagent.
  • the surface free energy of the cellulose ester film (B) was measured as follows.
  • Measuring device Solid-liquid interface analyzer (DropMaster 500, manufactured by Kyowa Interface Science Co., Ltd.)
  • Measuring method Droplet method Environment: Temperature 23 ° C, 55% RH
  • Three types of standard liquids pure water, nitromethane, methylene iodide and a solid to be measured (cellulose ester film (B)) were contacted with about 3 ⁇ l of the standard liquid dropped on the film to analyze the solid-liquid interface. Measurement is performed five times with an apparatus (DropMaster 500, manufactured by Kyowa Interface Science Co., Ltd.), and the average contact angle is obtained from the average of the measured values. The time to contact angle measurement is measured 60 seconds after the reagent is dropped.
  • the cellulose ester film (B) according to the present invention preferably contains a lower fatty acid ester of cellulose.
  • the lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms.
  • mixed fatty acid esters such as cellulose acetate butyrate can be used.
  • the lower fatty acid ester of cellulose that is particularly preferably used is diacetyl cellulose having an acetyl group substitution degree in the range of 2.1 to 2.5, and the use of the diacetyl cellulose can make the film hydrophilic. It is preferable in that the previous surface free energy satisfies the formula (SI) and the surface free energy after the hydrophilization treatment can be easily adjusted to satisfy the formula (SII).
  • the cellulose as a raw material of the cellulose ester according to the present invention is not particularly limited, and examples thereof include cotton linter, wood pulp, and kenaf. Moreover, the cellulose ester obtained from them can be mixed and used in arbitrary ratios, respectively.
  • the cellulose ester used in the present invention can be produced by a known method. Specifically, it can be synthesized with reference to the method described in JP-A-10-45804.
  • acetyl celluloses such as Daicel LM80, L20, L30, L40, and L50, Eastman Chemical Co. Ca398-3, Ca398-6, Ca398-10, Ca398-30, and Ca394-60S.
  • the cellulose ester has a number average molecular weight (Mn) of 125,000 or more and less than 180000, a weight average molecular weight (Mw) of 225,000 or more and less than 360,000, and Mw / Mn is in the range of 1.8 to 2.0. It is preferable to contain.
  • the number average molecular weight (Mn) and molecular weight distribution (Mw) of cellulose ester can be measured using high performance liquid chromatography.
  • the measurement conditions are as follows.
  • the surface free energy before the hydrophilization treatment satisfies the above formula (SI)
  • the surface free energy after the surface self-hydrophilization treatment after the hydrophilization treatment is the formula (
  • various additives plasticizers, ultraviolet absorbers, antioxidants, acid scavengers, fine particles, etc. depending on the application can be added.
  • the cellulose acetate film (B) according to the present invention is represented by the following general formula (X) from the viewpoint of controlling the surface free energy before and after the hydrophilization treatment and improving the physical characteristics and dimensional stability under environmental changes. It is preferable to contain an ester or sugar ester. In particular, it is preferable because it can improve a decrease in physical strength, which is a concern when the cellulose ester film (B) is thinned, and a deterioration in dimensional stability due to an increase in moisture permeability.
  • Formula (X) B- (GA) n -GB (In the formula, B represents an aliphatic or aromatic monocarboxylic acid residue. G represents an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or 4 to 4 carbon atoms. Represents an oxyalkylene glycol residue having 12.
  • A represents an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 1 or more.
  • the ester is a polyester containing a repeating unit obtained by reacting a dicarboxylic acid and a diol, A represents a carboxylic acid residue in the ester, and G represents an alcohol residue.
  • the dicarboxylic acid constituting the polyester is an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid or an alicyclic dicarboxylic acid, preferably an aromatic dicarboxylic acid.
  • the dicarboxylic acid may be one kind or a mixture of two or more kinds.
  • the diol constituting the polyester is an aromatic diol, an aliphatic diol or an alicyclic diol, preferably an aliphatic diol, and more preferably a diol having 1 to 4 carbon atoms.
  • the diol may be one type or a mixture of two or more types.
  • Both ends of the polyester molecule may or may not be sealed, but are sealed from the viewpoint of reducing the retardation value fluctuation of the cellulose ester film against fluctuations in temperature and humidity. Is preferred.
  • alkylene dicarboxylic acid constituting A in the general formula (X) examples include 1,2-ethanedicarboxylic acid (succinic acid), 1,3-propanedicarboxylic acid (glutaric acid), and 1,4-butanedicarboxylic acid.
  • Divalent groups derived from (adipic acid), 1,5-pentanedicarboxylic acid (pimelic acid), 1,8-octanedicarboxylic acid (sebacic acid) and the like are included.
  • alkenylene dicarboxylic acid constituting A include maleic acid and fumaric acid.
  • aryl dicarboxylic acid constituting A examples include 1,2-benzenedicarboxylic acid (phthalic acid), 1,3-benzenedicarboxylic acid, 1,4-benzenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and the like. Can be mentioned.
  • A may be one type or two or more types may be combined. Among them, A is preferably a combination of an alkylene dicarboxylic acid having 4 to 12 carbon atoms and an aryl dicarboxylic acid having 8 to 12 carbon atoms.
  • G in the general formula (X) is a divalent group derived from an alkylene glycol having 2 to 12 carbon atoms, a divalent group derived from an aryl glycol having 6 to 12 carbon atoms, or the number of carbon atoms Represents a divalent group derived from 4 to 12 oxyalkylene glycols.
  • Examples of the divalent group derived from an alkylene glycol having 2 to 12 carbon atoms in G include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1, 3-butanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol ( Neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylol) Heptane), 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanedio ,
  • divalent groups derived from aryl glycols having 6 to 12 carbon atoms in G include 1,2-dihydroxybenzene (catechol), 1,3-dihydroxybenzene (resorcinol), 1,4-dihydroxybenzene Divalent groups derived from (hydroquinone) and the like are included.
  • divalent group derived from oxyalkylene glycol having 4 to 12 carbon atoms in G are derived from diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol and the like. Divalent groups are included.
  • G may be one type or two or more types may be combined. Among these, G is preferably an alkylene glycol having 2 to 12 carbon atoms.
  • B in the general formula (X) is a monovalent group derived from an aromatic ring-containing monocarboxylic acid or an aliphatic monocarboxylic acid.
  • the aromatic ring-containing monocarboxylic acid in the monovalent group derived from the aromatic ring-containing monocarboxylic acid is a carboxylic acid containing an aromatic ring in the molecule, and not only those in which the aromatic ring is directly bonded to a carboxy group, Also included are those in which an aromatic ring is bonded to a carboxy group via an alkylene group or the like.
  • monovalent groups derived from aromatic ring-containing monocarboxylic acids include benzoic acid, para-tert-butyl benzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethyl benzoic acid, ethyl benzoic acid, and normal propyl benzoic acid. , Monovalent groups derived from aminobenzoic acid, acetoxybenzoic acid, phenylacetic acid, 3-phenylpropionic acid and the like.
  • Examples of monovalent groups derived from aliphatic monocarboxylic acids include monovalent groups derived from acetic acid, propionic acid, butanoic acid, caprylic acid, caproic acid, decanoic acid, dodecanoic acid, stearic acid, oleic acid and the like. Is included. Among these, a monovalent group derived from an alkyl monocarboxylic acid having 1 to 3 carbon atoms in the alkyl portion is preferable, and an acetyl group (a monovalent group derived from acetic acid) is more preferable.
  • the weight average molecular weight of the polyester is preferably in the range of 500 to 3000, and more preferably in the range of 600 to 2000.
  • the weight average molecular weight can be measured by gel permeation chromatography (GPC).
  • ester represented by the general formula (X) include compounds described in paragraphs [0123] to [0124] of JP-A-2009-192681, but are not limited thereto.
  • cellulose ester film (B) In order to control the surface free energy before and after the hydrophilic treatment of the cellulose ester film (B), it is preferable to contain a sugar ester.
  • Sugar ester is a sugar ester other than cellulose ester, and is a compound obtained by esterifying all or part of OH groups of sugars such as the following monosaccharide, disaccharide, trisaccharide or oligosaccharide.
  • sugars such as the following monosaccharide, disaccharide, trisaccharide or oligosaccharide.
  • examples of the sugar include glucose, galactose, mannose, fructose, xylose, arabinose, lactose, sucrose, nystose, 1F-fructosyl nystose, stachyose, maltitol, lactitol, lactulose, cellobiose, maltose, cellotriose, maltotriose, raffinose And kestose.
  • gentiobiose gentiotriose, gentiotetraose, xylotriose, galactosyl sucrose, and the like are also included.
  • compounds having a furanose structure and / or a pyranose structure are particularly preferable.
  • sucrose, kestose, nystose, 1F-fructosyl nystose, stachyose and the like are preferable, and sucrose is more preferable.
  • oligosaccharides maltooligosaccharides, isomaltooligosaccharides, fructooligosaccharides, galactooligosaccharides, and xylo-oligosaccharides can also be preferably used.
  • the monocarboxylic acid used for esterifying the sugar is not particularly limited, and known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid and the like can be used.
  • the carboxylic acid to be used may be one kind or a mixture of two or more kinds.
  • Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid , Saturated fatty acids such as tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid, Examples include unsaturated fatty acids such as undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid and oc
  • Examples of preferred alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, or derivatives thereof.
  • Examples of preferred aromatic monocarboxylic acids include benzoic acid, aromatic monocarboxylic acids having an alkyl group or alkoxy group introduced into the benzene ring of benzoic acid, cinnamic acid, benzylic acid, biphenylcarboxylic acid, naphthalenecarboxylic acid, tetralin
  • An aromatic monocarboxylic acid having two or more benzene rings such as carboxylic acid, or a derivative thereof can be mentioned, and more specifically, xylic acid, hemelic acid, mesitylene acid, planicylic acid, ⁇ -isojurylic acid, Julylic acid, mesitic acid, ⁇ -isoduric acid, cumic acid, ⁇ -toluic acid, hydroatropic acid
  • sugar ester is preferably a compound represented by the following general formula (Y).
  • R 1 ⁇ R 8 is a hydrogen atom, a substituted or unsubstituted alkylcarbonyl group having 2 to 22 carbon atoms or a substituted or unsubstituted arylcarbonyl group having 2 to 22 carbon atoms, R 1 ⁇ R 8 may be the same or different.
  • sugar ester represented by the general formula (Y) include exemplified compounds (1-1) to (1-23) described in paragraphs [0077] to [0078] of JP2012-230282A. However, it is not limited to these.
  • the average degree of substitution of R 1 to R 8 can be adjusted to the desired degree of substitution by adjusting the esterification reaction time or mixing compounds having different degrees of substitution.
  • the ester or sugar ester represented by the general formula (X) is preferably contained in the range of 1 to 30% by mass, more preferably in the range of 5 to 25% by mass relative to the cellulose ester. It is particularly preferable to contain 20% by mass.
  • the cellulose ester film (B) according to the present invention can contain a plasticizer as necessary, for example, to improve dimensional stability.
  • the plasticizer is not particularly limited, but is preferably a polycarboxylic acid ester plasticizer, a glycolate plasticizer, a phthalate ester plasticizer, a fatty acid ester plasticizer and a polyhydric alcohol ester plasticizer, a polyester It is selected from plasticizers, acrylic plasticizers and the like.
  • At least one is preferably a polyhydric alcohol ester plasticizer.
  • the polyhydric alcohol ester plasticizer is a plasticizer composed of an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule.
  • a divalent to 20-valent aliphatic polyhydric alcohol ester is preferred.
  • the polyhydric alcohol preferably used in the present invention is represented by the following general formula (a).
  • R1- (OH) n represents an n-valent organic group
  • n represents a positive integer of 2 or more
  • the OH group represents an alcoholic and / or phenolic hydroxy group.
  • Examples of preferable polyhydric alcohols include the following.
  • triethylene glycol triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable.
  • monocarboxylic acid used for polyhydric alcohol ester there is no restriction
  • the carboxylic acid used in the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.
  • polyhydric alcohol ester examples include compounds described in paragraphs [0087] to [0090] of JP-A-2009-192681, but are not limited thereto.
  • the glycolate plasticizer is not particularly limited, but alkylphthalylalkyl glycolates can be preferably used.
  • alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl Glycolate, ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl glycol Butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl glycolate, octyl phthalyl
  • phthalate ester plasticizer examples include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and dicyclohexyl terephthalate.
  • citrate plasticizer examples include acetyltrimethyl citrate, acetyltriethyl citrate, and acetyltributyl citrate.
  • fatty acid ester plasticizers examples include butyl oleate, methylacetyl ricinoleate, and dibutyl sebacate.
  • phosphate ester plasticizer examples include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, and the like.
  • the polyvalent carboxylic acid ester is composed of an ester of a divalent or higher, preferably 2-20 valent polycarboxylic acid and an alcohol.
  • the aliphatic polyvalent carboxylic acid is preferably divalent to 20-valent, and in the case of an aromatic polyvalent carboxylic acid or an alicyclic polyvalent carboxylic acid, it is preferably 3 to 20 valent.
  • the polyvalent carboxylic acid is represented by the following general formula (b).
  • R2 (COOH) m (OH) n
  • R2 is an (m + n) -valent organic group
  • m is a positive integer of 2 or more
  • n is an integer of 0 or more
  • COOH group is a carboxy group
  • OH The group represents an alcoholic or phenolic hydroxy group.
  • the molecular weight of the polyvalent carboxylic acid ester is not particularly limited, but is preferably in the range of 300 to 1000, more preferably in the range of 350 to 750. The larger one is preferable in terms of improving the retention, and the smaller one is preferable in terms of moisture permeability and compatibility with the cellulose ester.
  • the alcohol used for the polyvalent carboxylic acid ester may be one kind or a mixture of two or more kinds.
  • the acid value of the polyvalent carboxylic acid ester is preferably 1 mgKOH / g or less, and more preferably 0.2 mgKOH / g or less. It is preferable to set the acid value within the above range since the environmental fluctuation of the retardation value is also suppressed.
  • the acid value refers to the number of milligrams of potassium hydroxide necessary for neutralizing the acid (carboxy group present in the sample) contained in 1 g of the sample.
  • the acid value is measured according to JIS K0070.
  • Particularly preferred polyvalent carboxylic acid esters include triethyl citrate, tributyl citrate, acetyl triethyl citrate (ATEC), acetyl tributyl citrate (ATBC), benzoyl tributyl citrate, acetyl triphenyl citrate, acetyl tribenzyl citrate , Dibutyl tartrate, diacetyl dibutyl tartrate, tributyl trimellitic acid, tetrabutyl pyromellitic acid, and the like.
  • ATEC acetyl triethyl citrate
  • ATBC acetyl tributyl citrate
  • benzoyl tributyl citrate acetyl triphenyl citrate
  • acetyl tribenzyl citrate Dibutyl tartrate, diacetyl dibutyl tartrate, tributyl trimellitic acid, tetrabutyl pyrom
  • the amount of use is, for example, preferably in the range of 1 to 50% by mass, more preferably in the range of 5 to 35% by mass, with respect to the cellulose ester, and 5 to 25% by mass. It is especially preferable to make it contain in the range of%.
  • UV absorber The ultraviolet absorber is intended to improve durability by absorbing ultraviolet light having a wavelength of 400 nm or less, and the transmittance at a wavelength of 370 nm is particularly preferably 10% or less, more preferably 5% or less. Preferably it is 2% or less.
  • the ultraviolet absorber used is not particularly limited, and examples thereof include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, inorganic powders, and the like. Can be mentioned.
  • the UV absorbers preferably used in the present invention are benzotriazole UV absorbers, benzophenone UV absorbers, and triazine UV absorbers, particularly preferably benzotriazole UV absorbers and benzophenone UV absorbers. .
  • a discotic compound such as a compound having a 1,3,5-triazine ring is also preferably used as the ultraviolet absorber.
  • the polarizing plate protective film of the present invention may contain two or more kinds of ultraviolet absorbers.
  • a polymeric ultraviolet absorber can be preferably used, and in particular, a polymer type ultraviolet absorber described in JP-A-6-148430 is preferably used.
  • the method of adding the UV absorber can be added to the dope after dissolving the UV absorber in an alcohol such as methanol, ethanol or butanol, an organic solvent such as methylene chloride, methyl acetate, acetone or dioxolane or a mixed solvent thereof. Or you may add directly in dope composition.
  • an alcohol such as methanol, ethanol or butanol
  • an organic solvent such as methylene chloride, methyl acetate, acetone or dioxolane or a mixed solvent thereof.
  • inorganic powders that do not dissolve in organic solvents use a dissolver or sand mill in the organic solvent and cellulose ester to disperse them before adding them to the dope.
  • the amount of the UV absorber used is not uniform depending on the type of UV absorber, the operating conditions, etc., but when the dry film thickness of the polarizing plate protective film is 30 to 200 ⁇ m, it is 0.5 to 10 with respect to the cellulose ester. % By mass is preferable, and 0.6 to 4% by mass is more preferable.
  • Antioxidant are also referred to as deterioration inhibitors.
  • a liquid crystal image display device or the like is placed in a high humidity and high temperature state, the cellulose ester film may be deteriorated.
  • the antioxidant has a role of delaying or preventing the cellulose ester film from being decomposed by, for example, a residual solvent amount of halogen in the cellulose ester film or phosphoric acid of a phosphoric acid plasticizer. It is preferable to make it contain in a film (B).
  • a hindered phenol compound is preferably used.
  • 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate] triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)- 1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], oct Decyl-3- (3,5-di-t-butyl-4-hydroxyphenyl
  • 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] is preferred.
  • hydrazine-based metal deactivators such as N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine and tris (2,4-di- A phosphorus processing stabilizer such as t-butylphenyl) phosphite may be used in combination.
  • the amount of these compounds added is preferably in the range of 1 ppm to 1.0% by mass ratio with respect to the cellulose ester, and more preferably in the range of 10 to 1000 ppm.
  • Any useful acid scavenger can be used without limitation as long as it is a compound that reacts with an acid to inactivate the acid.
  • compounds having an epoxy group described in US Pat. No. 4,137,201 are particularly preferred.
  • Epoxy compounds as such acid scavengers are known in the art and are derived by condensation of diglycidyl ethers of various polyglycols, particularly about 8-40 moles of ethylene oxide per mole of polyglycol.
  • Glycol diglycidyl ether of glycerol, metal epoxy compounds (such as those conventionally used in and with vinyl chloride polymer compositions), epoxidized ether condensation products, diphenols of bisphenol A Glycidyl ether (ie, 4,4'-dihydroxydiphenyldimethylmethane), epoxidized unsaturated fatty acid ester (especially an ester of alkyl of about 2 to 2 carbon atoms of fatty acids of 2 to 22 carbon atoms such as butyl Epoxy steerer )), And epoxidized vegetable oils and other unsaturated natural oils (sometimes epoxidized natural, which can be represented and exemplified by compositions of various epoxidized long chain fatty acid triglycerides and the like (eg epoxidized soybean oil and the like) These are referred to as glycerides or unsaturated fatty acids, which generally contain 12 to 22 carbon atoms).
  • EPON 815C can also be preferably
  • acid scavengers that can be used other than the above include oxetane compounds, oxazoline compounds, organic earth salts of alkaline earth metals and acetylacetonate complexes, and paragraphs 68 to 105 of JP-A-5-194788. Is included.
  • the acid scavenger may be referred to as an acid scavenger, an acid scavenger, an acid catcher, etc., but in the present invention, they can be used without any difference due to their names.
  • Fine particles In order to impart slipperiness, it is preferable to add fine particles to the cellulose ester film (B) according to the present invention.
  • the primary average particle diameter of the fine particles is preferably 20 nm or less, more preferably in the range of 5 to 16 nm, and particularly preferably in the range of 5 to 12 nm.
  • These fine particles are preferably contained in the cellulose ester film by forming secondary particles having a particle size in the range of 0.1 to 5 ⁇ m, and the preferred average particle size is in the range of 0.1 to 2 ⁇ m, more preferably It is in the range of 0.2 to 0.6 ⁇ m.
  • irregularities having a height of about 0.1 to 1.0 ⁇ m are formed on the film surface, thereby providing appropriate slipperiness to the film surface.
  • the primary average particle size of the fine particles is measured by observing the particles with a transmission electron microscope (magnification 500,000 to 2,000,000 times), observing 100 particles, measuring the particle size, and using the average value, the primary value is measured. The average particle size was taken.
  • the apparent specific gravity of the fine particles is preferably 70 g / liter or more, more preferably 90 to 200 g / liter, and particularly preferably 100 to 200 g / liter.
  • a larger apparent specific gravity makes it possible to make a high-concentration dispersion, which improves haze and agglomerates, and is preferable when preparing a dope having a high solid content concentration as in the present invention.
  • the amount of fine particles added to the cellulose ester is preferably in the range of 0.01 to 5.0 parts by weight, more preferably in the range of 0.05 to 1.0 parts by weight, with respect to 100 parts by weight of the cellulose ester. A range of 0.5 parts by weight is most preferred. The larger the added amount, the better the dynamic friction coefficient, and the smaller the added amount, the less aggregates.
  • the cellulose ester film (B) according to the present invention can be preferably used regardless of whether it is a film produced by a solution casting method or a film produced by a melt casting method.
  • the cellulose ester film (B) according to the present invention is prepared by dissolving a cellulose ester and an additive in a solvent to prepare a dope, on an endless metal support that moves the dope indefinitely.
  • the step of casting, the step of drying the cast dope as a web, the step of peeling from the metal support, the step of stretching or maintaining the width, the step of further drying, and the step of winding up the finished film are performed.
  • the concentration of cellulose ester in the dope is preferably higher because the drying load after casting on the metal support can be reduced. However, if the concentration of cellulose ester is too high, the load during filtration increases and the filtration accuracy is poor. Become.
  • the concentration for achieving both of these is preferably in the range of 10 to 35% by mass, and more preferably in the range of 15 to 25% by mass.
  • the solvent used in the dope may be used alone or in combination of two or more, but it is preferable to use a mixture of a good solvent and a poor solvent of cellulose ester in terms of production efficiency, and there are many good solvents. This is preferable from the viewpoint of the solubility of the cellulose ester.
  • the preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent.
  • the good solvent used in the present invention is not particularly limited, and examples thereof include organic halogen compounds such as methylene chloride, dioxolanes, acetone, methyl acetate, and methyl acetoacetate. Particularly preferred is methylene chloride or methyl acetate.
  • the poor solvent used in the present invention is not particularly limited, but for example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone and the like are preferably used.
  • the dope preferably contains water in the range of 0.01 to 2% by mass.
  • the solvent used for dissolving the cellulose ester is used by collecting the solvent removed from the film by drying in the film-forming process and reusing it.
  • the recovery solvent may contain trace amounts of additives added to the cellulose ester, such as plasticizers, UV absorbers, polymers, monomer components, etc., but even if these are included, they are preferably reused. Can be purified and reused if necessary.
  • additives added to the cellulose ester such as plasticizers, UV absorbers, polymers, monomer components, etc., but even if these are included, they are preferably reused. Can be purified and reused if necessary.
  • a general method can be used as a method for dissolving the cellulose ester when preparing the dope. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure.
  • a method in which a cellulose ester is mixed with a poor solvent and wetted or swollen, and then a good solvent is added and dissolved is also preferably used.
  • Pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside.
  • a jacket type is preferable because temperature control is easy.
  • the heating temperature with the addition of the solvent is preferably higher from the viewpoint of the solubility of the cellulose ester, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates.
  • the preferable heating temperature is in the range of 45 to 120 ° C, more preferably in the range of 60 to 110 ° C, and still more preferably in the range of 70 to 105 ° C.
  • the pressure is adjusted so that the solvent does not boil at the set temperature.
  • a cooling dissolution method is also preferably used, whereby the cellulose ester can be dissolved in a solvent such as methyl acetate.
  • the cellulose ester solution is filtered using an appropriate filter medium such as filter paper.
  • an appropriate filter medium such as filter paper.
  • the filter medium it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters and the like, but there is a problem that the filter medium is likely to be clogged if the absolute filtration accuracy is too small.
  • a filter medium having an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium in the range of 0.001 to 0.008 mm is more preferable, and a filter medium in the range of 0.003 to 0.006 mm is more preferable.
  • the material of the filter medium there are no particular restrictions on the material of the filter medium, and ordinary filter media can be used. However, plastic filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel do not drop off fibers. preferable.
  • Bright spot foreign matter is when two polarizing plates are placed in a crossed Nicol state, an optical film or the like is placed between them, light is applied from the side of one polarizing plate, and observed from the side of the other polarizing plate
  • the number of bright spots having a diameter of 0.01 mm or more is preferably 200 / cm 2 or less.
  • it is 100 pieces / cm 2 or less, still more preferably 50 pieces / m 2 or less, still more preferably 0 to 10 pieces / cm 2 . Further, it is preferable that the number of bright spots of 0.01 mm or less is small.
  • the dope can be filtered by a normal method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and in a range where the solvent does not boil under pressure is the filtration pressure before and after filtration.
  • the increase in the difference (referred to as differential pressure) is small and preferable.
  • the preferred temperature is in the range of 45 to 120 ° C, more preferably in the range of 45 to 70 ° C, and still more preferably in the range of 45 to 55 ° C.
  • the filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.
  • the metal support in the casting process is preferably a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support.
  • the cast width can be in the range of 1-4m.
  • the surface temperature of the metal support in the casting step is ⁇ 50 ° C. to less than the boiling point of the solvent, and a higher temperature is preferable because the web drying speed can be increased. May deteriorate.
  • the support temperature is preferably in the range of 0 to 55 ° C, more preferably in the range of 25 to 50 ° C.
  • the method for controlling the temperature of the metal support is not particularly limited, but there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short. When warm air is used, wind at a temperature higher than the target temperature may be used.
  • the amount of residual solvent when peeling the web from the metal support is preferably in the range of 10 to 150% by mass, more preferably in the range of 20 to 40% by mass or 60%. It is in the range of ⁇ 130% by mass, particularly preferably in the range of 20-30% by mass or in the range of 70-120% by mass.
  • the amount of residual solvent is defined by the following formula.
  • Residual solvent amount (% by mass) ⁇ (MN) / N ⁇ ⁇ 100 Note that M is the mass of a sample collected during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.
  • the web is peeled off from the metal support, and further dried, and the residual solvent amount is preferably 1% by mass or less, more preferably 0.1% by mass or less, Particularly preferred is a range of 0 to 0.01% by mass.
  • a roller drying method (a method in which webs are alternately passed through a plurality of upper and lower rollers) and a tenter method for drying while transporting the web are employed.
  • the cellulose ester film (B) In order to produce the cellulose ester film (B) according to the present invention, it is particularly preferable to perform stretching in the width direction (lateral direction) by a tenter method in which both ends of the web are held with clips or the like. Peeling is preferably performed at a peeling tension of 300 N / m or less.
  • the means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roller, a microwave, or the like, but it is preferably performed with hot air in terms of simplicity.
  • the drying temperature in the web drying process is preferably increased stepwise in the range of 40 to 200 ° C.
  • the film thickness of the cellulose ester film (B) according to the present invention is preferably in the range of 5 to 40 ⁇ m, more preferably in the range of 5 to 20 ⁇ m from the viewpoint of obtaining a thin and light polarizing plate. More preferably, it is in the range of 10 to 20 ⁇ m.
  • the film thickness is in this range, the film physical properties can be maintained even if the plasma treatment or corona treatment, which is a hydrophilic treatment according to the present invention, is performed.
  • the polarizing film (A) having a film thickness of 10 ⁇ m or less, which is a subject of the present invention curling is also suppressed, and wrinkles are produced during polarizing plate production, and curling and deformation during panel bonding. Generation of bubbles can also be prevented.
  • the cellulose ester film having a width in the range of 1 to 4 m is used.
  • a width in the range of 1.4 to 4 m is preferably used, and a range of 1.6 to 3 m is particularly preferable. If it exceeds 4 m, conveyance becomes difficult.
  • the retardation value can be changed by lowering or increasing the tension in the longitudinal direction.
  • biaxial stretching or uniaxial stretching sequentially or simultaneously with respect to the longitudinal direction (film forming direction) of the film and the direction orthogonal to the longitudinal direction of the film, that is, the width direction.
  • the draw ratios in the biaxial directions orthogonal to each other are preferably finally in the range of 0.8 to 1.5 times in the casting direction and in the range of 1.1 to 2.5 times in the width direction, It is preferable to carry out in the range of 0.8 to 1.0 times in the casting direction and 1.2 to 2.0 times in the width direction.
  • the stretching temperature is preferably in the range of 120 to 200 ° C, more preferably in the range of 150 to 200 ° C, and even more preferably over 150 ° C and 190 ° C or less.
  • the residual solvent in the film is preferably in the range of 20 to 0%, more preferably in the range of 15 to 0%.
  • the residual solvent is stretched by 11% at 155 ° C., or the residual solvent is stretched by 2% at 155 ° C.
  • the residual solvent is preferably stretched at 11% at 160 ° C., or the residual solvent is preferably stretched at less than 1% at 160 ° C.
  • the method of stretching the web For example, a method in which a difference in peripheral speed is applied to a plurality of rollers, and the rollers are stretched in the longitudinal direction using the difference in peripheral speed between the rollers, and both ends of the web are fixed with clips and pins, and the interval between the clips and pins is increased in the traveling direction. And a method of stretching in the vertical direction, a method of stretching in the horizontal direction and stretching in the horizontal direction, a method of stretching in the vertical and horizontal directions and stretching in both the vertical and horizontal directions, and the like. Of course, these methods may be used in combination.
  • a tenter it may be a pin tenter or a clip tenter.
  • the slow axis or fast axis of the cellulose ester film (B) used in the present invention exists in the film plane, and ⁇ 1 is ⁇ 1 ° or more and + 1 ° or less when the angle formed with the film forming direction is ⁇ 1. Is more preferably ⁇ 0.5 ° or more and + 0.5 ° or less, and further preferably ⁇ 0.1 ° or more and + 0.1 ° or less.
  • This ⁇ 1 can be defined as an orientation angle, and ⁇ 1 can be measured using an automatic birefringence meter KOBRA-WPR (Oji Scientific Instruments).
  • KOBRA-WPR automatic birefringence meter
  • the moisture permeability of the cellulose ester film (B) according to the present invention is preferably 300 to 1800 g / m 2 ⁇ 24 h in terms of a film thickness of 80 ⁇ m when measured at a temperature of 40 ° C. and a humidity of 90% RH, more preferably 400 to 1500 g / m 2 ⁇ 24 h is preferable, and 40 to 1300 g / m 2 ⁇ 24 h is particularly preferable.
  • the moisture permeability can be measured according to the method described in JIS Z 0208.
  • the breaking elongation is preferably 5 to 80%, more preferably 10 to 50%. It is measured by a measuring method according to JIS-C-2151 and ASTM-D-882. Specifically, using a tensile tester, the sample is pulled at a speed of 200 mm / min, and the strength (value obtained by dividing the tensile load value by the cross-sectional area of the test piece) and the elongation when the sample is cut (ruptured) are obtained. . The tensile elongation is calculated by the following formula.
  • Elongation rate (%) (L-Lo) / Lo Lo: Sample length before test L: Sample length at break
  • the visible light transmittance is preferably 90% or more, and more preferably 93% or more.
  • the transmittance of visible light (615 nm) is measured with a spectrophotometer (U-3210, Hitachi, Ltd.) at 25 ° C. and 60% RH for a 13 mm ⁇ 40 mm sample.
  • the in-plane retardation value (Ro) and the retardation value (Rt) in the thickness direction of the cellulose ester film (B) according to the present invention are 0 ⁇ Ro and Rt ⁇ 70 nm when used as a polarizing film protective film. It is preferable. More preferably, the range is 0 ⁇ Ro ⁇ 30 nm and 0 ⁇ Rt ⁇ 50 nm, and more preferably the range is 0 ⁇ Ro ⁇ 10 nm and 0 ⁇ Rt ⁇ 30 nm.
  • the cellulose ester film (B) according to the present invention can also be used as a retardation film, in which case the range is 30 ⁇ Ro ⁇ 100 nm and 70 ⁇ Rt ⁇ 400 nm, more preferably 35 ⁇ Ro ⁇ . A range of 65 nm and a range of 90 ⁇ Rt ⁇ 180 nm.
  • the type of cellulose ester In order to provide these retardation values, it can be controlled by the type of cellulose ester, the additive, the type and amount of plasticizer, and the stretching treatment conditions.
  • the retardation values Ro and Rt can be obtained by the following equations.
  • d is the thickness (nm) of the film
  • the refractive index nx the maximum refractive index in the plane of the film, also referred to as the refractive index in the slow axis direction
  • ny with the slow axis in the film plane.
  • n z the refractive index of the film in the thickness direction.
  • Retardation values Ro and Rt can be measured using an automatic birefringence meter. For example, it can be obtained at a wavelength of 590 nm in an environment of 23 ° C. and 55% RH using KOBRA-WPR (Oji Scientific Instruments).
  • the cellulose ester film (B) after the hydrophilization treatment according to the present invention preferably has an internal haze value of 0.1 or less, more preferably 0.05 or less, and still more preferably 0.03 or less.
  • the internal haze is a haze generated by a scattering factor inside the film, and the internal is a portion of 5 ⁇ m or more from the film surface.
  • the improvement effect is the effect of the internal haze. The effect is greater.
  • the internal haze value can be adjusted to the above range by adjusting the plasma treatment or corona treatment conditions so that the surface free energy after the hydrophilization treatment according to the present invention satisfies the formula (SII).
  • the internal haze is measured with a haze meter by dropping a solvent having a refractive index of film refractive index ⁇ 0.05 on the film interface so that the haze on the film surface can be ignored as much as possible.
  • Haze meter (turbidity meter) (model: NDH 2000, manufactured by Nippon Denshoku Industries Co., Ltd.)
  • a 5V9W halogen bulb is used as the light source, and a silicon photocell (with a relative visibility filter) is used as the light receiving unit.
  • the present invention is characterized in that the value is 0.05 or less in the haze measurement of a film when a solvent having a refractive index of ⁇ 0.05 is used as the film interface in this apparatus. Measurement conforms to JIS K-7136.
  • the blank haze 1 of a measuring instrument other than a film is measured.
  • the haze 2 including the sample is measured by the following procedure. 4).
  • Glycerin (0.05 ml) is dropped onto the slide glass (see FIG. 1A). 5.
  • a sample film to be measured is placed thereon so that air bubbles do not enter (see FIG. 1B).
  • Glycerin (0.05 ml) is dropped on the sample film (see FIG. 1C). 7).
  • a cover glass is placed thereon (see FIG. 1D). 8).
  • the laminate prepared as described above from above, cover glass / glycerin / sample film / glycerin / slide glass) is set on a haze meter and haze 2 is measured.
  • (Haze 2) ⁇ (Haze 1) (Internal haze of the cellulose ester film (B) according to the present invention) is calculated.
  • cellulose ester film (B) For the cellulose ester film (B), a sample after conditioning for 5 hours or more at 23 ° C. and 55% RH is used, and all the above haze measurements are performed at 23 ° C. and 55% RH.
  • the glass and glycerin used for the measurement are as follows.
  • the cellulose ester film (B) of the present invention is characterized by being hydrophilized by either plasma treatment or corona treatment.
  • plasma treatment or corona treatment various conventionally known methods can be employed. In the present invention, it is particularly preferable to employ plasma treatment.
  • Examples of the plasma treatment applicable to the present invention include JP-A-11-133205, JP-A-2000-185362, JP-A-11-61406, JP-A-2000-147209, and JP-A-2000-121804. Can be mentioned.
  • a gas is supplied to the discharge space (between the counter electrodes) at atmospheric pressure or in the vicinity thereof, a high frequency voltage is applied to the discharge space, and the gas is excited to generate plasma.
  • Surface treatment is performed by exposing the cellulose ester film (B) to this excited plasma state gas. This includes cases where the surface of the cellulose ester film (B) is directly exposed to a gas in a plasma state, and cases where excited active species formed by plasma discharge are sprayed onto the surface of the cellulose ester film (B).
  • the high frequency voltage applied to the discharge space formed between the counter electrodes may be a high frequency of one frequency, or may be a high frequency of two or more frequencies.
  • the high frequency as used in this invention means what has a frequency of at least 0.5 kHz or more.
  • the frequency of the high frequency power source is preferably 50 kHz or more and 27 MHz or less.
  • the atmospheric pressure or the pressure in the vicinity thereof is about 20 to 110 kPa, and a range of 93 to 104 kPa is preferable in order to obtain a good effect described in the present invention.
  • the difference is that there are two high-frequency power supplies, a filter attached to it, and a high-frequency voltage is applied from both electrodes of the counter electrode.
  • one of the counter electrodes is a ground electrode, and the other is an application electrode.
  • a high-frequency power source is connected to the application electrode, and the ground is grounded to the ground electrode. Has been.
  • the plasma processing apparatus (atmospheric pressure plasma processing apparatus) of each of the 1-frequency high-frequency voltage application system and the 2-frequency high-frequency voltage application system will be described with reference to the drawings.
  • FIG. 2 is a schematic view showing an example of a plasma processing apparatus of a 1 frequency high frequency voltage application system useful for the present invention.
  • a counter electrode is formed by an application electrode (square tube electrode) 136 for applying a high-frequency voltage inside the plasma discharge vessel 130 and a roller-type ground electrode 135 around which the cellulose ester film F is wound. Any number of application electrodes 136 may be arranged.
  • the gas G is supplied from the gas supply port 152 of the plasma discharge vessel 10, passes through a mesh for uniformizing the gas G, passes between the application electrodes 136 and along the inner wall of the application electrode and the plasma discharge vessel 131, and The discharge space 13 is filled with the gas G.
  • a high frequency voltage is applied to the application electrode 136 by the high frequency power source 21, and the cellulose ester film F is exposed to the gas G excited in the discharge space 132, and a thin film is formed on the cellulose ester film F.
  • the frequency of the applied high frequency voltage is in the range of 50 kHz to 150 MHz. In the present invention, the frequency of the high frequency power source is preferably 50 kHz or more and 27 MHz or less.
  • the electrode is heated or cooled via the pipe from the electrode temperature adjusting means 160.
  • the temperature control medium an insulating material such as distilled water or oil is preferably used.
  • it is desired to uniformly adjust the temperature inside the electrode so that the temperature unevenness of the base material in the width direction or the longitudinal direction does not occur as much as possible.
  • FIG. 3 is a schematic view showing an example of a plasma processing apparatus of a two-frequency high-frequency voltage application system useful for the present invention.
  • the cellulose ester film F is subjected to plasma treatment between the counter electrodes (discharge space) 132 between the roller electrode (first electrode) 135 and the square tube electrode group (second electrode) 136. .
  • the roller electrode 135 In the discharge space 132 between the roller electrode 135 and the rectangular tube type electrode group 136, the roller electrode 135 is supplied with the high frequency voltage V1 from the first power source 141 and the frequency ⁇ 1, and the rectangular tube type electrode group (second electrode). A high frequency voltage V2 having a frequency ⁇ 2 is applied to 136 from the second power source 142.
  • a first filter 143 is installed between the roller electrode 135 and the first power supply 141 so that a current from the first power supply 141 flows toward the roller electrode 135, and the first filter is the first power supply 141. It is designed to make it difficult to pass current from the second power source and to easily pass current from the second power source 142.
  • a second filter 144 is installed between the square tube electrode group 136 and the second power source 142 so that a current from the second power source flows toward the second electrode. It is designed to make it difficult to pass the current from the second power source 142 and to easily pass the current from the first power source 141.
  • being difficult to pass means that it preferably passes only 20% or less of the current, more preferably 10% or less.
  • being easy to pass means preferably passing 80% or more of the current, more preferably 90% or more.
  • any filter having the above properties can be used without limitation.
  • a capacitor of several tens to several tens of thousands pF or a coil of about several ⁇ H can be used depending on the frequency of the second power source.
  • a coil of 10 ⁇ H or more is used according to the frequency of the first power supply, and it can be used as a filter by grounding through these coils or capacitors.
  • either the roller electrode 135 or the rectangular tube electrode group 136 may be the first electrode, and the first power source is connected to the first electrode, and the second power source is connected to the second electrode. Furthermore, the first power source only needs to have the capability of applying a higher frequency voltage (V1> V2) than the second power source. Moreover, the frequency should just have the capability which becomes (omega) 1 ⁇ (omega) 2.
  • the gas G generated by the gas supply device 151 of the gas supply means 150 is introduced into the plasma processing vessel 131 from the air supply port 152 while controlling the flow rate.
  • the discharge space 132 and the plasma processing vessel 131 are filled with the gas G.
  • the cellulose ester film F is unwound from an original winding (not shown) and conveyed, or is conveyed from the previous process, and air or the like that is entrained by a nip roller 165 via a guide roller 164 is blocked. It is transferred to and from the rectangular tube electrode group 136 while being wound while being in contact with the electrode 135. A voltage is applied from both the roller electrode 135 and the rectangular tube electrode group 136 to generate discharge plasma between the counter electrodes 132. The cellulose ester film F is exposed to plasma gas while being wound in contact with the roller electrode 135. The cellulose ester film F passes through the nip roller 166 and the guide roller 167, and is taken up by a winder (not shown) or transferred to the next step. The treated excitation discharge gas Gex is discharged from the exhaust port 153.
  • the medium whose temperature is adjusted by the electrode temperature adjusting means 160 is sent to both electrodes via the pipe 161 by the liquid feed pump P, and the electrodes Adjust the temperature from the inside.
  • Reference numerals 165 and 166 denote partition plates that partition the plasma processing vessel 131 from the outside.
  • the high-frequency voltage to be applied may be an intermittent pulse wave or a continuous sine wave. Either one may be adopted, but at least the second electrode side is preferable because the continuous sine wave is more precise and can perform a high-quality plasma treatment.
  • the frequency of the high frequency voltage applied to the first electrode is preferably in the range of 1 to 200 kHz, and the frequency of the high frequency voltage applied to the second electrode is preferably 800 kHz or more.
  • the power density at that time is preferably 1 to 50 W / cm 2 (where the denominator cm 2 is the area where discharge occurs), more preferably 1.2 to 30 W / cm 2 .
  • a first power source (high-frequency power source) and a second power source (high-frequency power source) can be selectively used as follows according to the frequency.
  • High frequency power supply code Manufacturer Frequency A1 Shinko Electric 3kHz A2 Shinko Electric 5kHz A3 Kasuga Electric 15kHz A4 Shinko Electric 50kHz A5 HEIDEN Laboratory 100kHz * A6 Pearl Industry 200kHz In addition, * mark is HEIDEN Laboratory impulse high frequency power supply (100 kHz in continuous mode).
  • High frequency power supply symbol Manufacturer Frequency B1 Pearl Industry 800kHz B2 Pearl Industry 2MHz B3 Pearl Industry 13.56MHz B4 Pearl Industry 27MHz B5 Pearl Industry 150MHz And the like, and any of them can be preferably used.
  • the discharge condition in the present invention is that a high frequency voltage is applied to the discharge space between the first electrode and the second electrode facing each other, and the high frequency voltage is derived from the voltage component of the first frequency ⁇ 1 and the first frequency ⁇ 1. It is preferable to have at least a component obtained by superimposing a high voltage component of the second frequency ⁇ 2.
  • the high frequency voltage is a component obtained by superimposing the voltage component of the first frequency ⁇ 1 and the voltage component of the second frequency ⁇ 2 higher than the first frequency ⁇ 1, and the waveform thereof is on the sine wave of the frequency ⁇ 1, It becomes a waveform of a sine wave of ⁇ 1 on which a sine wave of higher frequency ⁇ 2 is superimposed. It is not limited to a waveform in which a sine wave is superimposed, and both pulse waves may be used, one may be a sine wave and the other may be a pulse wave. Furthermore, it may have a third voltage component. However, in the present invention, as in the single-frequency high-frequency voltage application method, a continuous sine wave at least on the second electrode side can provide a denser and better quality film.
  • a high-frequency voltage is applied between the first electrode and the second electrode facing each other, and the high-frequency voltage superimposes the first high-frequency voltage V1 and the second high-frequency voltage V2.
  • V1 ⁇ IV> V2 or V1> IV ⁇ V2 is satisfied. More preferably, V1> IV> V2 is satisfied.
  • the discharge start voltage IV is about 3.7 kV / mm. Therefore, in the above relationship, the first high-frequency voltage is set as V1 ⁇ 3.7 kV / mm. By applying this, nitrogen gas can be excited to be in a plasma state.
  • nitrogen, helium, argon and other rare gases, air, carbon monoxide, ammonia, hydrogen, etc. can be used, and these may be used alone as a discharge gas, or may be used in combination.
  • the use of nitrogen gas is particularly preferable because high economic efficiency of the discharge gas can be obtained as compared with the case where a rare gas such as helium or argon is used.
  • the amount of the discharge gas is preferably in the range of 70 to 100% by volume with respect to the total amount of gas supplied to the discharge space.
  • corona treatment (also referred to as “corona discharge treatment”) is any conventionally known method, for example, Japanese Patent Publication Nos. 48-5043, 47-51905, and Japanese Patent Publication No. 47-28067. No. 49-83767, No. 51-41770, No. 51-131576, and the like.
  • a corona treatment machine used for corona treatment various commercially available corona treatment machines currently used as means for surface modification of plastic films and the like can be applied. Among them, a multi-knife electrode manufactured by SOFTAL is used.
  • the corona treatment machine has a number of electrodes, and air is sent between the electrodes, which can prevent the heating of the film and remove small molecules that appear on the film surface.
  • This is a particularly preferred corona treatment machine for the present invention because it is very high and enables high corona treatment.
  • the conditions for corona treatment vary depending on the type of film used, the type of pressure-sensitive adhesive, the type of corona treatment machine used, etc., but the energy density per treatment is about 20 to 400 W ⁇ min / m 2. preferable.
  • the treatment with low energy as much as possible can suppress the deterioration of the protective film to be treated, the bleeding of the filler in the protective film to the surface, and the like. If the single treatment is insufficient, the adhesive strength can be further improved by carrying out multiple treatments twice or more.
  • the polarizing plate of the present invention comprises the polarizing film (A) comprising a hydrophilic polymer layer dyed with a dichroic substance, and the cellulose ester via an adhesive on at least one surface of the polarizing film (A).
  • the film (B) is formed by laminating the hydrophilically treated surface.
  • thermoplastic resin layer and the hydrophilic polymer layer constituting the polarizing film (A) are not particularly limited.
  • the hydrophilic polymer layer and the hydrophilic surface of the cellulose ester film (B) were laminated without peeling off the thermoplastic resin layer, and the polarizing film (A) was exposed.
  • a polarizing plate protective film is preferably bonded to the surface from the viewpoint of preventing wrinkles and curling.
  • the cellulose ester film (B) may be bonded to the other surface of the polarizing film (A), or another polarizing plate protective film may be bonded.
  • cellulose ester films for example, Konica Minoltack KC8UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC4UE, KC8UE, KC8UY-HA, KC8UX-RHA, KC8UX-RHA, KC8UX KC4UXW-RHA-NC, manufactured by Konica Minolta Opto Co., Ltd.
  • cellulose ester films for example, Konica Minoltack KC8UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC4UE, KC8UE, KC8UY-HA, KC8UX-RHA, KC8UX-RHA, KC8UX KC4UXW-RHA-NC, manufactured by Konica Minolta Opto Co., Ltd.
  • polarizing plate protective film of 40 ⁇ m or less.
  • the polarizing plate protective film used on the surface side of the liquid crystal display device preferably has an antireflection layer, an antistatic layer, an antifouling layer, and a backcoat layer in addition to the antiglare layer or the clear hard coat layer.
  • an adhesive used for laminating a polarizing plate protective film and a polarizing film an adhesive having sufficient adhesiveness, transparent and not impairing a polarizing function is preferably used.
  • examples thereof include acrylic adhesives, epoxy adhesives, cyanoacrylate adhesives, polyurethane adhesives, polyvinyl alcohol adhesives such as polyvinyl alcohol and polyvinyl butyral.
  • a water paste such as a completely saponified polyvinyl alcohol aqueous solution is preferable.
  • the surface of the polarizing film (A) opposite to the dyed surface of the hydrophilic polymer layer and the cellulose ester film (B) were hydrophilized. Bonding to the surface is also preferable from the viewpoint of further improving the adhesion and preventing wrinkles and curling.
  • the polarizing film (A) according to the present invention is dyed with a dichroic substance from the surface side of the hydrophilic polymer layer, so that iodine which is a dichroic substance.
  • bonding the surface of the polarizing film (A) opposite to the dyed surface of the hydrophilic polymer layer and the surface of the cellulose ester film (B) subjected to the hydrophilic treatment is diffusion. Since the amount of boron ions to be increased is relatively increased, it is preferable because it has an effect of further improving the adhesiveness.
  • the manufacturing method which manufactures a polarizing plate through the process of bonding the surface to which the said hydrophilic treatment of B) was given is preferable.
  • the cellulose ester film (B) can be bonded to the surface opposite to the surface dyed with the dichroic material while maintaining the physical strength of the polarizing film. As a result, wrinkles and curling can be prevented.
  • the above separator means a so-called separate film, but is not particularly limited, but is preferably a biaxially stretched polyester film that is inexpensive and easy to handle.
  • the present invention The polarizing plate of the present invention can be used for liquid crystal display devices of various drive systems such as STN, TN, OCB, HAN, VA (MVA, PVA), IPS, OCB.
  • VA VA, PVA
  • liquid crystal display device for a small and medium-sized mobile device called a smartphone or a pad can obtain a liquid crystal display device with excellent visibility such as color unevenness and front contrast with little environmental fluctuation and reduced light leakage.
  • Example 1 Preparation of Stretched Laminate 1 Having Polarizing Film (A)> ⁇ Production of laminate> (Thermoplastic resin layer A) The following film was prepared and used as a thermoplastic resin layer A.
  • A-PET amorphous polyethylene terephthalate film (Novaclear manufactured by Mitsubishi Plastics, glass transition temperature 80 ° C.) having a film thickness of 200 ⁇ m and a length of 1000 m was used.
  • Hydrophilic polymer layer Polyvinyl alcohol powder (manufactured by Nippon Vinegar Bipovar Co., Ltd., average polymerization degree 2500, saponification degree 99.0 mol% or more, trade name: JC-25) as a hydrophilic polymer is dissolved in 95 ° C. hot water to obtain a concentration An 8% by mass aqueous polyvinyl alcohol solution was prepared. The obtained aqueous polyvinyl alcohol solution is coated on the thermoplastic resin layer A for lamination using a lip coater, dried at 80 ° C. for 20 minutes, and consists of the thermoplastic resin layer A and a hydrophilic polymer layer. The laminated body 1 was produced.
  • the hydrophilic polymer layer had a thickness of 12.0 ⁇ m.
  • the laminate was subjected to 5.3 times free end uniaxial stretching at 160 ° C. in the transport direction (MD direction).
  • the thickness of the hydrophilic polymer layer after stretching was 5.6 ⁇ m.
  • the stretched laminate was immersed in a 60 ° C. bath for 60 seconds, and immersed in an aqueous solution containing 0.05 parts by mass of iodine and 5 parts by mass of potassium iodide per 100 parts by mass of water at a temperature of 28 ° C. for 60 seconds. .
  • a boric acid aqueous solution containing 7.5 parts by mass of boric acid and 6 parts by mass of potassium iodide per 100 parts by mass of water at a temperature of 73 ° C. for 300 seconds.
  • ⁇ Fine particle additive solution CE-1 (Daicel Diacetyl Cellulose: L20: Degree of substitution of acetyl group: 2.41) was added to the dissolution tank containing methylene chloride and heated to completely dissolve, and then this was made by Azumi Filter Paper Co., Ltd. No. Azumi filter paper No. Filtered using 244. The fine particle dispersion was slowly added thereto while sufficiently stirring the filtered cellulose ester solution. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution.
  • Methylene chloride 99 parts by mass CE-1 4 parts by mass Fine particle dispersion 11 parts by mass CE-1 was used to prepare a main dope having the following composition.
  • CE-1 was charged into a pressure dissolution tank containing a solvent while stirring. This was heated, stirred and completely dissolved, and two additives shown in Table 1 were added and dissolved. This was designated as Azumi Filter Paper No.
  • the main dope was prepared by filtration using 244.
  • a cellulose ester film 101 having a film thickness of 40 ⁇ m and a length of 1000 m having a knurling of 1.5 m in width and 1 cm in width and 5 ⁇ m in height was produced.
  • Each additive was added in an amount of 7 parts by mass per 100 parts by mass of the cellulose ester.
  • TPP triphenyl phosphate
  • BDP biphenyl diphenyl phosphate
  • PETB pentaerythritol tetrabenzoate
  • EPEG ethyl phthalyl ethyl glycolate
  • B-4 polyhydric alcohol ester plasticizer
  • X-1, X-15 in general formula (X) Ester Represented Y-11: Sugar Ester Represented by General Formula (Y)
  • the cellulose ester was the same as the cellulose ester film 101 except that the cellulose ester used was CE-2 (Ca394-60S manufactured by Eastman Chemical Co., Ltd .: acetyl group substitution degree 2.43) and the film thickness was changed as shown in Table 1. A film 108 was produced.
  • cellulose ester film 109 was the same as the cellulose ester film 101 except that the cellulose ester used was CE-3 (Ca398-30, Eastman Chemical Co., Inc .: acetyl group substitution degree 2.48) and the film thickness was changed as shown in Table 1. A film 109 was produced.
  • ⁇ Preparation of cellulose ester film 110> The cellulose ester used was changed to CE-4 (50:50 mixture of Ca394-60S and Ca398-6 from Eastman Chemical Co .: acetyl group substitution degree 2.28) and the film thickness was changed as shown in Table 1. In the same manner as the film 101, a cellulose ester film 110 was produced.
  • a cellulose ester film 111 was produced in the same manner as the cellulose ester film 101 except that the cellulose ester used was CE-5 (LM80 from Daicel, acetyl group substitution degree 2.15) and the film thickness was changed as shown in Table 1. did.
  • a cellulose ester film 112 was produced in the same manner as the cellulose ester film 101 except that the cellulose ester used was CE-6 (Daicel LT35: acetyl group substitution degree 2.88) and the film thickness was changed as shown in Table 1. did.
  • cellulose ester film 113 ⁇ Preparation of cellulose ester film 113>
  • the cellulose ester used was CE-7 (CAP 141-20, Eastman Chemical Co., Ltd .: cellulose acetate propionate having an acetyl group substitution degree of 1.92, a propionyl group substitution degree of 0.74, and a total substitution degree of 2.66) and a membrane.
  • a cellulose ester film 113 was produced in the same manner as the cellulose ester film 101 except that the thickness was changed as shown in Table 1.
  • cellulose ester film 114 was produced in the same manner except for the above.
  • Alkali treatment step 2.5 mol / L-KOH 50 ° C. 120 seconds Water washing step Water 30 ° C. 60 seconds Neutralization step 10% by mass HCl aqueous solution 30 ° C. 10 seconds Water washing step Water 30 ° C. 60 seconds After alkali treatment, water washing, neutralization, water washing Followed by drying at 100 ° C.
  • the surface of the cellulose ester film (B) that has been subjected to the hydrophilic treatment is bonded to the hydrophilic polymer layer side of the stretched laminate 1 having the polarizing film (A) thus prepared, and then stretched laminate. 1 of the thermoplastic resin layer A was peeled off, and the surface of the cellulose ester film (B) that had been subjected to the hydrophilic treatment was bonded to the surface in combination of the same type to produce a long polarizing plate and wound up. .
  • Step 1 The cellulose ester films 101 to 114 were hydrophilized under the conditions shown in Tables 2 to 4.
  • Step 2 The stretched laminate 1 having the polarizing film (A) was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.
  • Step 3 Excess adhesive adhered to the stretched laminate 1 in Step 2 was lightly wiped off, and this was placed on the hydrophilically treated surface of the cellulose ester film (B) hydrophilized in Step 1.
  • Step 4 The films laminated in Step 3 were bonded at a pressure of 20 to 30 N / cm 2 and a conveyance speed of about 2 m / min.
  • Step 5 The sample prepared in Step 4 was dried for 2 minutes in a dryer at 80 ° C., and then the thermoplastic resin layer A of the stretched laminate 1 was peeled off.
  • the thermoplastic resin layer A could be easily peeled off.
  • Step 6 The surface of the cellulose ester film (B) subjected to the hydrophilic treatment was bonded to the peeled surface with the same kind of combination through a polyvinyl alcohol adhesive to produce polarizing plates 201 to 227. .
  • a liquid crystal panel for front contrast measurement was produced as follows, and the characteristics of the liquid crystal display device were evaluated.
  • the polarizing plates on both surfaces of the Sony 40-type display KLV-40V2500 previously bonded were peeled off, and the prepared polarizing plates 201 to 227 were bonded to both surfaces of the glass surface of the liquid crystal cell, respectively.
  • the direction of bonding of the polarizing plate was set so that the absorption axis was in the same direction as that of the polarizing plate bonded in advance, and each liquid crystal display device was produced.
  • each of the obtained polarizing plates 201 to 227 was cut out into a rectangular shape having a width of 30 cm and a length of 20 cm in the substantially central portion, and was placed on a horizontal substrate in an environment of 23 ° C. and relative humidity of 80%. After standing for a period of time, the curled shape of the polarizing plate was visually observed, and wrinkle / curl was evaluated according to the following criteria.
  • the obtained polarizing plate is allowed to stand for 24 hours in an environment with a relative humidity of 55% at 23 ° C., and then the adhesive surface is peeled off by hand, and the degree of material destruction and peelability is visually observed. evaluated.
  • the produced polarizing plate was bonded to the glass surface of the liquid crystal cell using an air adsorption polarizing plate bonding apparatus.
  • the following criteria evaluated the ease of bubble entry. After bonding, an autoclave (pressure defoaming) treatment was performed under the conditions of 45 ° C., 0.45 MPa, and 15 minutes. The bubbles were evaluated according to the following criteria.
  • the front contrast of each liquid crystal display device was measured.
  • the front contrast was measured by a front contrast measuring device (EZ-contrast) manufactured by ELDIM, and the light quantity during white display and black display was measured.
  • the measurement results were ranked according to superiority or inferiority according to the value of the front contrast as follows.
  • the polarizing plate of the present invention has an internal haze value, generation of wrinkles / curls, adhesion to the polarizing film, generation of bubbles during panel bonding, as compared with the comparative example. It can be seen that the front contrast is excellent. That is, based on this result, the above-mentioned means of the present invention has excellent adhesiveness with the polarizing film, generation of wrinkles and curls at the time of polarizing plate production, and generation of bubbles due to curling and deformation at the time of polarizing film panel bonding. Thus, it can be seen that a method for producing a thin polarizing plate without haze increase and accompanying decrease in front contrast in the liquid crystal display device can be provided.
  • Polarizers 301 and 302 were produced by the following process.
  • Step 1 A 100 ⁇ m-thick PET film was bonded as a separator to the hydrophilic polymer layer side of the stretched laminate 1 having the produced polarizing film (A) via an adhesive.
  • Step 2 Next, the thermoplastic resin layer A was peeled from the stretched laminate 1.
  • Step 3 The polarizing film (A) with a separator was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.
  • Step 4 Excess adhesive adhered to the polarizing film (A) with a separator in Step 3 is gently wiped off, and the hydrophilized cellulose ester films 105-3 and 107 prepared in Example 1 are made hydrophilic. The treated surface was placed on the polarizing film (A).
  • Step 5 The films laminated in Step 4 were bonded at a pressure of 20 to 30 N / cm 2 and a conveyance speed of about 2 m / min.
  • Step 6 The sample prepared in Step 5 was dried for 2 minutes in a dryer at 80 ° C., and then the separator was peeled from the polarizing plate on which the polarizing film (A) and the cellulose ester film were bonded.
  • Step 7 The polarizing plates 301 and 302 are prepared by bonding the surfaces of the cellulose ester films 105-3 and 107 that have been subjected to hydrophilic treatment to each other with a polyvinyl alcohol adhesive in the same type combination. did.
  • ⁇ There is no peeling at the interface between the cellulose ester film and the polarizing film, and the material (base material) breaks.
  • ⁇ The material (base material) breaks down, but the area peeled off at the interface between the cellulose ester film and the polarizing film.
  • X Peeled at the interface between the cellulose ester film and the polarizing film If the film is not peeled off at the interface, the adhesiveness is good.
  • a polarizing plate of the present invention By the method for producing a polarizing plate of the present invention, excellent adhesion to a polarizing film, no generation of wrinkles and curls at the time of polarizing plate production, no generation of bubbles due to curling and deformation at the time of polarizing film panel lamination, haze increase Further, it is possible to provide a thinned polarizing plate without lowering the front contrast in the liquid crystal display device associated therewith, and the polarizing plate is suitably included in the liquid crystal display device.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

Le problème à résoudre dans le cadre de la présente invention consiste à obtenir une excellente adhérence entre une couche mince formant film polarisant et une couche mince formant film protecteur et ainsi à fournir un procédé permettant de fabriquer une plaque polarisante à couches minces au moyen de laquelle l'adhérence avec le film polarisant est excellente, mais ne présentant aucun plissement ni aucune ondulation pendant la fabrication de la plaque polarisante, aucune génération de bulles d'air due à l'ondulation ou à la déformation lorsque les panneaux de film polarisant sont liés, ni aucune augmentation du flou ni réduction associée du contraste de surface avant du dispositif d'affichage à cristaux liquides. Le procédé pour la fabrication d'une plaque polarisante selon la présente invention est un procédé permettant de fabriquer une plaque polarisante, un film polarisant (A) possédant une couche polymère hydrophile teintée par une substance dichroïque et un film d'ester de cellulose (B) étant stratifiés par le biais d'un agent adhésif sur au moins une surface du film polarisant (A), le procédé étant caractérisé en ce que le film d'ester de cellulose (B) est soumis à une hydrophilisation soit par traitement plasmatique, soit par traitement corona, et l'énergie libre de surface avant et après le traitement d'hydrophilisation du film d'ester de cellulose (B) est une valeur se trouvant dans une plage prédéfinie .
PCT/JP2013/061436 2012-04-24 2013-04-18 Procédé pour la fabrication d'une plaque polarisante WO2013161647A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201380021480.3A CN104254791A (zh) 2012-04-24 2013-04-18 偏振片的制造方法
KR1020147029302A KR101688288B1 (ko) 2012-04-24 2013-04-18 편광판의 제조 방법
JP2014512492A JP6086117B2 (ja) 2012-04-24 2013-04-18 偏光板の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012098398 2012-04-24
JP2012-098398 2012-04-24

Publications (1)

Publication Number Publication Date
WO2013161647A1 true WO2013161647A1 (fr) 2013-10-31

Family

ID=49482969

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/061436 WO2013161647A1 (fr) 2012-04-24 2013-04-18 Procédé pour la fabrication d'une plaque polarisante

Country Status (4)

Country Link
JP (1) JP6086117B2 (fr)
KR (1) KR101688288B1 (fr)
CN (1) CN104254791A (fr)
WO (1) WO2013161647A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015111547A1 (fr) * 2014-01-23 2015-07-30 富士フイルム株式会社 Plaque polarisante et dispositif d'affichage d'image
WO2015147553A1 (fr) * 2014-03-26 2015-10-01 주식회사 엘지화학 Procédé de fabrication de polariseur ayant une région localement dépolarisée, et polariseur, plaque de polarisation et dispositif d'affichage d'image fabriqués par utilisation de ce dernier
WO2016039296A1 (fr) * 2014-09-09 2016-03-17 住友化学株式会社 Plaque polarisante et procédé de production de panneau à cristaux liquides
CN105467652A (zh) * 2014-09-30 2016-04-06 住友化学株式会社 偏振片、液晶显示装置和有机电致发光显示装置
JP2016071349A (ja) * 2014-09-30 2016-05-09 住友化学株式会社 偏光性積層フィルム及び偏光板の製造方法
JP2016224410A (ja) * 2015-05-29 2016-12-28 日本合成化学工業株式会社 ポリビニルアルコール系フィルム及び偏光膜、ならびにポリビニルアルコール系フィルムの製造方法
WO2017126361A1 (fr) * 2016-01-21 2017-07-27 横浜ゴム株式会社 Procédé de traitement de surface d'un élément, et procédé de fabrication d'élément stratifié
WO2021182758A1 (fr) * 2020-03-09 2021-09-16 삼성에스디아이 주식회사 Plaque de polarisation et dispositif d'affichage optique la comprenant
WO2022049910A1 (fr) * 2020-09-02 2022-03-10 日東電工株式会社 Plaque de polarisation, plaque de polarisation dotée de couche à différence de phase, et dispositif d'affichage électroluminescent organique

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000338329A (ja) * 1999-06-01 2000-12-08 Sanritsutsu:Kk 偏光板及びその製造方法
JP2001343521A (ja) * 2000-05-31 2001-12-14 Sumitomo Chem Co Ltd 偏光板及びその製造方法
WO2011007587A1 (fr) * 2009-07-15 2011-01-20 コニカミノルタオプト株式会社 Plaque de polarisation, procédé de fabrication de celle-ci, dispositif d'affichage à cristaux liquides l'utilisant
WO2011108350A1 (fr) * 2010-03-03 2011-09-09 コニカミノルタオプト株式会社 Procédé de fabrication d'une plaque de polarisation, plaque de polarisation fabriquée à l'aide de ce procédé, et dispositif d'affichage à cristaux liquides
JP2012073563A (ja) * 2010-09-03 2012-04-12 Nitto Denko Corp 薄型高機能偏光膜を含む光学フィルム積層体の製造方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4688116B2 (ja) 1999-04-15 2011-05-25 コニカミノルタホールディングス株式会社 偏光板用保護フィルム
JP2002082226A (ja) 2000-06-21 2002-03-22 Fuji Photo Film Co Ltd 光学補償シート、偏光板および液晶表示装置
JP2009098653A (ja) 2007-09-27 2009-05-07 Nitto Denko Corp 偏光板、光学フィルムおよび画像表示装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000338329A (ja) * 1999-06-01 2000-12-08 Sanritsutsu:Kk 偏光板及びその製造方法
JP2001343521A (ja) * 2000-05-31 2001-12-14 Sumitomo Chem Co Ltd 偏光板及びその製造方法
WO2011007587A1 (fr) * 2009-07-15 2011-01-20 コニカミノルタオプト株式会社 Plaque de polarisation, procédé de fabrication de celle-ci, dispositif d'affichage à cristaux liquides l'utilisant
WO2011108350A1 (fr) * 2010-03-03 2011-09-09 コニカミノルタオプト株式会社 Procédé de fabrication d'une plaque de polarisation, plaque de polarisation fabriquée à l'aide de ce procédé, et dispositif d'affichage à cristaux liquides
JP2012073563A (ja) * 2010-09-03 2012-04-12 Nitto Denko Corp 薄型高機能偏光膜を含む光学フィルム積層体の製造方法

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2015111547A1 (ja) * 2014-01-23 2017-03-23 富士フイルム株式会社 偏光板および画像表示装置
US10241251B2 (en) 2014-01-23 2019-03-26 Fujifilm Corporation Polarizing plate and image display device
WO2015111547A1 (fr) * 2014-01-23 2015-07-30 富士フイルム株式会社 Plaque polarisante et dispositif d'affichage d'image
KR101953171B1 (ko) * 2014-03-26 2019-02-28 주식회사 엘지화학 국지적으로 편광 해소 영역을 갖는 편광자 제조방법, 이를 이용하여 제조된 편광자, 편광판 및 화상표시장치
KR20150111871A (ko) * 2014-03-26 2015-10-06 주식회사 엘지화학 국지적으로 편광 해소 영역을 갖는 편광자 제조방법, 이를 이용하여 제조된 편광자, 편광판 및 화상표시장치
US10359553B2 (en) 2014-03-26 2019-07-23 Lg Chem, Ltd. Method for manufacturing polarizer having locally depolarized area, and polarizer, polarizing plate and image display device manufactured by using same
KR20160128980A (ko) * 2014-03-26 2016-11-08 주식회사 엘지화학 국지적으로 편광 해소 영역을 갖는 편광자 제조방법, 이를 이용하여 제조된 편광자, 편광판 및 화상표시장치
KR101964602B1 (ko) * 2014-03-26 2019-04-02 주식회사 엘지화학 국지적으로 편광 해소 영역을 갖는 편광자 제조방법, 이를 이용하여 제조된 편광자, 편광판 및 화상표시장치
WO2015147553A1 (fr) * 2014-03-26 2015-10-01 주식회사 엘지화학 Procédé de fabrication de polariseur ayant une région localement dépolarisée, et polariseur, plaque de polarisation et dispositif d'affichage d'image fabriqués par utilisation de ce dernier
JPWO2016039296A1 (ja) * 2014-09-09 2017-06-22 住友化学株式会社 偏光板、及び、液晶パネルの製造方法
WO2016039296A1 (fr) * 2014-09-09 2016-03-17 住友化学株式会社 Plaque polarisante et procédé de production de panneau à cristaux liquides
JP2016071349A (ja) * 2014-09-30 2016-05-09 住友化学株式会社 偏光性積層フィルム及び偏光板の製造方法
JP2020204777A (ja) * 2014-09-30 2020-12-24 住友化学株式会社 偏光フィルム
CN105467652A (zh) * 2014-09-30 2016-04-06 住友化学株式会社 偏振片、液晶显示装置和有机电致发光显示装置
JP2016224410A (ja) * 2015-05-29 2016-12-28 日本合成化学工業株式会社 ポリビニルアルコール系フィルム及び偏光膜、ならびにポリビニルアルコール系フィルムの製造方法
EP3406659A4 (fr) * 2016-01-21 2019-09-18 The Yokohama Rubber Co., Ltd. Procédé de traitement de surface d'un élément, et procédé de fabrication d'élément stratifié
WO2017126361A1 (fr) * 2016-01-21 2017-07-27 横浜ゴム株式会社 Procédé de traitement de surface d'un élément, et procédé de fabrication d'élément stratifié
US10737406B2 (en) 2016-01-21 2020-08-11 The Yokohama Rubber Co., Ltd. Member surface treatment method and method for producing multilayer member
CN108473701A (zh) * 2016-01-21 2018-08-31 横滨橡胶株式会社 构件的表面处理方法及叠层构件的制造方法
CN108473701B (zh) * 2016-01-21 2021-08-17 横滨橡胶株式会社 构件的表面处理方法及叠层构件的制造方法
WO2021182758A1 (fr) * 2020-03-09 2021-09-16 삼성에스디아이 주식회사 Plaque de polarisation et dispositif d'affichage optique la comprenant
WO2022049910A1 (fr) * 2020-09-02 2022-03-10 日東電工株式会社 Plaque de polarisation, plaque de polarisation dotée de couche à différence de phase, et dispositif d'affichage électroluminescent organique
JP2022042217A (ja) * 2020-09-02 2022-03-14 日東電工株式会社 偏光板、位相差層付偏光板および有機エレクトロルミネセンス表示装置
JP7411520B2 (ja) 2020-09-02 2024-01-11 日東電工株式会社 偏光板、位相差層付偏光板および有機エレクトロルミネセンス表示装置

Also Published As

Publication number Publication date
CN104254791A (zh) 2014-12-31
KR101688288B1 (ko) 2016-12-20
KR20140146132A (ko) 2014-12-24
JPWO2013161647A1 (ja) 2015-12-24
JP6086117B2 (ja) 2017-03-01

Similar Documents

Publication Publication Date Title
JP6086117B2 (ja) 偏光板の製造方法
JP5725011B2 (ja) 偏光板の製造方法、それを用いた偏光板、及び液晶表示装置
WO2011016279A1 (fr) Film d'acétate de cellulose, plaque polarisante et dispositif d'affichage à cristaux liquides
TWI391428B (zh) 延遲膜及使用彼之偏光板和顯示裝置
JP6015469B2 (ja) 光学フィルムのロール体、偏光板及び液晶表示装置
WO2011007587A1 (fr) Plaque de polarisation, procédé de fabrication de celle-ci, dispositif d'affichage à cristaux liquides l'utilisant
JP6202009B2 (ja) セルロースアシレートフィルムの製造方法
WO2013099727A1 (fr) Film à retard optique, méthode de production d'un film à retard optique, plaque polarisante et dispositif d'affichage à cristaux liquides
JP5821849B2 (ja) セルロースアセテートフィルムの製造方法
WO2011096036A1 (fr) Film optique
JP2013001042A (ja) セルロースエステルフィルムおよびその製造方法、並びにこれを用いた位相差フィルムおよび表示装置
TWI637850B (zh) 偏光板及液晶顯示裝置
JP2011248192A (ja) ロール状偏光板、枚葉状偏光板、及びそれを用いた液晶表示装置
JPWO2013133276A1 (ja) 偏光板およびこれを用いた表示装置
WO2011114764A1 (fr) Film de retardement et plaque de polarisation le comprenant
JP5962002B2 (ja) 偏光板およびこれを用いた表示装置
JP5637207B2 (ja) 位相差フィルム、位相差フィルムの製造方法
WO2012063559A1 (fr) Film primaire pour étirage oblique
TWI519830B (zh) A polarizing plate, a method for manufacturing the same, and a liquid crystal display device using the same
JPWO2012008242A1 (ja) 液晶表示装置
JP2017219767A (ja) 偏光板保護フィルム、偏光板及び液晶表示装置
JPWO2017013948A1 (ja) 偏光板及びそれを用いた液晶表示装置
JP5692237B2 (ja) 位相差フィルム、及びそれを用いた偏光板、液晶表示装置
JP2012103657A (ja) 液晶表示装置
JP5772680B2 (ja) セルロースアシレート積層フィルムおよびその製造方法、並びにそれを用いた偏光板および液晶表示装置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13781233

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014512492

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20147029302

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13781233

Country of ref document: EP

Kind code of ref document: A1