WO2012172696A1 - Plaque de polarisation et dispositif d'affichage à cristaux liquides - Google Patents

Plaque de polarisation et dispositif d'affichage à cristaux liquides Download PDF

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Publication number
WO2012172696A1
WO2012172696A1 PCT/JP2011/064489 JP2011064489W WO2012172696A1 WO 2012172696 A1 WO2012172696 A1 WO 2012172696A1 JP 2011064489 W JP2011064489 W JP 2011064489W WO 2012172696 A1 WO2012172696 A1 WO 2012172696A1
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WIPO (PCT)
Prior art keywords
film
protective film
resin
polarizing
polarizing plate
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PCT/JP2011/064489
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English (en)
Japanese (ja)
Inventor
立陽 ▲ジュ▼
昭彦 中谷
林　秀樹
松岡　祥樹
Original Assignee
住友化学株式会社
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Priority to PCT/JP2011/064489 priority Critical patent/WO2012172696A1/fr
Publication of WO2012172696A1 publication Critical patent/WO2012172696A1/fr

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G02B1/105—
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers

Definitions

  • the present invention relates to a polarizing plate used in a liquid crystal display device in which a protective film is laminated on a polarizing film, and a liquid crystal display device using the polarizing plate.
  • Liquid crystal display devices are used in various display devices by taking advantage of features such as low power consumption, low voltage operation, light weight and thinness.
  • the liquid crystal display device is composed of many materials such as a liquid crystal cell, a polarizing plate, a retardation film, a condensing sheet, a diffusion film, a light guide plate, and a light reflecting sheet. Therefore, improvements aimed at productivity, weight reduction, brightness improvement, etc. are actively performed by reducing the number of constituent films or reducing the thickness of the film or sheet.
  • liquid crystal display devices are required to have a product that can withstand severe durability conditions depending on the application.
  • a liquid crystal display device for a car navigation system may have a high temperature and humidity in a vehicle in which the liquid crystal display device is placed, and the temperature and humidity conditions are severe as compared with a monitor for a normal television or personal computer.
  • polarizing plates that are highly durable are also required.
  • the polarizing plate usually has a structure in which a transparent protective film is laminated on both sides or one side of a polarizing film made of a polyvinyl alcohol-based resin having a dichroic dye adsorbed and oriented.
  • the polarizing film is produced by a method in which a polyvinyl alcohol-based resin film is subjected to longitudinal uniaxial stretching and dyeing with a dichroic dye, then treated with boric acid to cause a crosslinking reaction, and then washed with water and dried.
  • dichroic dye iodine or a dichroic organic dye is used.
  • a protective film is laminated on both sides or one side of the polarizing film thus obtained to form a polarizing plate, which is used by being incorporated in a liquid crystal display device.
  • a cellulose acetate resin film typified by triacetyl cellulose is often used, and its thickness is usually in the range of about 30 to 120 ⁇ m.
  • an adhesive composed of an aqueous solution of a polyvinyl alcohol-based resin is often used for laminating the protective film.
  • a polarizing plate in which a protective film made of triacetyl cellulose is laminated on both sides or one side of a polarizing film on which a dichroic dye is adsorbed and oriented via an adhesive made of an aqueous solution of a polyvinyl alcohol-based resin, under wet heat conditions
  • a polarizing plate in which a protective film made of triacetyl cellulose is laminated on both sides or one side of a polarizing film on which a dichroic dye is adsorbed and oriented via an adhesive made of an aqueous solution of a polyvinyl alcohol-based resin, under wet heat conditions
  • a polarizing plate in which a protective film is laminated on both surfaces of a polarizing film, it is known that at least one of the protective films is composed of a thermoplastic norbornene resin having the function of a retardation film at the same time (for example, JPH08). -43812-A).
  • a protective film made of an amorphous polyolefin resin is laminated on one surface of a polarizing film made of a polyvinyl alcohol resin film on which iodine or a dichroic organic dye is adsorbed and oriented.
  • a polarizing plate in which a protective film made of a resin different from an amorphous polyolefin-based resin such as a resin is laminated is known (see, for example, JP2002-174729-A).
  • a protective film made of a cycloolefin resin is laminated on a polyvinyl alcohol polarizing film via an adhesive containing a urethane adhesive and a polyvinyl alcohol resin (for example, JP2004). -334168-A).
  • a polarizing plate is obtained by laminating a cycloolefin resin film having specific retardation characteristics on a polyvinyl alcohol polarizing film (see, for example, JP2007-65452-A).
  • amorphous polyolefin-based resins such as norbornene-based resins are resins that have been put into practical use in recent years and are more expensive than triacetyl cellulose. It was often used as a phase difference film.
  • an inexpensive resin material for the protective film of the polarizing plate For example, it is known to use a crystalline polyolefin resin, particularly a polypropylene resin as a protective film (for example, JP2009- 75471-A).
  • the present invention has been made in order to solve the above-mentioned problems, and the purpose thereof is to provide a protective film laminated on a polarizing film, which can realize improvement in moisture and heat resistance, cost reduction, and suppression of contrast reduction. It is to provide a polarizing plate.
  • the present invention includes the following.
  • a polarizing plate comprising a polarizing film and a transparent protective film disposed on one surface of the polarizing film, wherein the protective film is mainly composed of a polypropylene resin and has a haze value of 1% or less.
  • the polarizing plate is used by being arranged in the order of the protective film and the polarizing film from the side close to the liquid crystal cell.
  • the protective film is made of an unstretched resin film (hereinafter sometimes simply referred to as “unstretched film”) mainly composed of polypropylene resin, and has an in-plane retardation at a wavelength of 590 nm of less than 20 nm.
  • unstretched film mainly composed of polypropylene resin
  • the protective film is composed of a stretched resin film mainly composed of a polypropylene resin (hereinafter sometimes simply referred to as “stretched film”), and has an in-plane retardation at a wavelength of 590 nm of 400 nm or less.
  • stretched resin film mainly composed of a polypropylene resin (hereinafter sometimes simply referred to as “stretched film”), and has an in-plane retardation at a wavelength of 590 nm of 400 nm or less.
  • the polarizing plate as described in [1] or [2].
  • a liquid crystal display device in which a viewing side polarizing plate, a liquid crystal cell, a backlight side polarizing plate, and a backlight are arranged in this order, and at least one of the viewing side polarizing plate and the backlight side polarizing plate is a polarizing film And a protective film disposed on one surface of the polarizing film, the protective film is disposed in the order of the protective film and the polarizing film from the side close to the liquid crystal cell, and the protective film is a polypropylene resin. And a haze value of 1% or less.
  • the backlight side polarizing plate includes the polarizing film and a protective film disposed on one surface of the polarizing film, and the protective film and the polarizing film are arranged in this order from the side close to the liquid crystal cell.
  • the viewing side polarizing plate includes the polarizing film and a protective film disposed on one surface of the polarizing film, and the protective film and the polarizing film are arranged in this order from the side close to the liquid crystal cell.
  • Both the viewing side polarizing plate and the backlight side polarizing plate include the polarizing film and a protective film disposed on one surface of the polarizing film, and the protective film from the side close to the liquid crystal cell,
  • the protective film is mainly composed of a polypropylene resin, it has excellent heat resistance and can suppress a decrease in front contrast when used in a liquid crystal display device.
  • the polarizing plate of the present invention includes a polarizing film and a protective film disposed on one surface of the polarizing film, and the protective film is mainly composed of a polypropylene resin and has a haze value of 1% or less.
  • the polarizing plate of the present invention is used by disposing the protective film and the polarizing film in this order from the side close to the liquid crystal cell.
  • the polarizing film is obtained by adsorbing and orienting a dichroic dye on a polyvinyl alcohol-based resin film so as to obtain predetermined polarizing characteristics.
  • the dichroic dye iodine or a dichroic organic dye is used.
  • Specific examples of the polarizing film include an iodine polarizing film in which iodine is adsorbed and oriented on a polyvinyl alcohol resin film, and a dye polarizing film in which a dichroic organic dye is adsorbed and oriented on a polyvinyl alcohol resin film.
  • the polyvinyl alcohol resin is obtained by saponifying a polyvinyl acetate resin.
  • the polyvinyl acetate resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith.
  • examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, and unsaturated sulfonic acids.
  • the polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal modified with aldehydes, polyvinyl acetal, polyvinyl butyral, and the like can be used.
  • the polarizing plate is usually a humidity adjusting step for adjusting the moisture of the polyvinyl alcohol-based resin film, a step for uniaxially stretching the polyvinyl alcohol-based resin film, and the dichroic pigment by dyeing the polyvinyl alcohol-based resin film with a dichroic pigment.
  • the process of adsorbing, the process of treating the polyvinyl alcohol resin film on which the dichroic dye is adsorbed and oriented with a boric acid aqueous solution, the washing process of washing off the boric acid aqueous solution, and the dichroic dye are adsorbed and oriented by performing these steps. It is manufactured through a process of pasting a protective film on the uniaxially stretched polyvinyl alcohol resin film.
  • Uniaxial stretching may be performed before dyeing, may be performed during dyeing, or may be performed during boric acid treatment after dyeing. It is also possible to perform uniaxial stretching in these plural stages. For uniaxial stretching, rolls having different peripheral speeds may be uniaxially stretched or uniaxially stretched using a hot roll. Moreover, the dry-type extending
  • the thickness of the stretched and dyed polyvinyl alcohol polarizing film can be, for example, about 1 to 50 ⁇ m.
  • the protective film is formed of a resin mainly composed of a polypropylene resin.
  • this protective film can be composed of a polypropylene resin itself, or a resin composition containing a polypropylene resin as a main component and another resin that is compatible or uniformly dispersed therein.
  • a protective film can also be constructed. For example, constituting this protective film with a resin composition mainly composed of a polypropylene resin and containing 0.1 to 30% by weight of an alicyclic saturated hydrocarbon resin in order to lower the haze value of the film. It is valid.
  • the polypropylene resin constituting the protective film may be a resin substantially composed of a homopolymer of propylene, or other monomers copolymerizable with propylene.
  • the copolymer may be used. These may be used in combination.
  • the homopolymer of propylene is advantageous in that the film rigidity and yield strength can be further increased because the degree of crystallinity is higher than the copolymer of propylene and other copolymerizable comonomers. . Therefore, by using a resin substantially consisting of a propylene homopolymer as the polypropylene resin, it becomes possible to further improve the handleability in the protective film preparation step and the polarizing plate formation step.
  • the substantially homopolymer of propylene is a polymer having a propylene unit content of 100% by weight, in the range of about 0.6% by weight or less for the purpose of improving the productivity of the protective film.
  • a propylene / ethylene copolymer containing an ethylene unit is also included.
  • the polypropylene resin composed of a copolymer of propylene and another copolymerizable comonomer is preferably one in which propylene is the main component and one or two or more types of comonomer copolymerizable therewith are copolymerized in a small amount.
  • the polypropylene resin composed of such a copolymer can be a resin containing a comonomer unit in a range of, for example, 10% by weight or less, more preferably 7% by weight or less.
  • the comonomer unit content in the copolymer is at least more than 0.6% by weight, preferably 1% by weight or more, more preferably 3% by weight or more.
  • the content of the comonomer unit By setting the content of the comonomer unit to 1% by weight or more, processability and transparency can be significantly improved. On the other hand, when the content of the comonomer unit exceeds 10% by weight, the melting point of the polypropylene resin is lowered and the heat resistance tends to be lowered. In addition, when setting it as the copolymer of 2 or more types of comonomer, and propylene, it is preferable that the total content of the unit derived from all the comonomer contained in the copolymer is the said range.
  • the comonomer copolymerized with propylene can be, for example, an unsaturated hydrocarbon such as ethylene or an ⁇ -olefin having 4 to 20 carbon atoms.
  • an unsaturated hydrocarbon such as ethylene or an ⁇ -olefin having 4 to 20 carbon atoms.
  • Specific examples of the ⁇ -olefin include the following.
  • ⁇ -olefins having 4 to 12 carbon atoms are preferable.
  • the copolymer may be a random copolymer or a block copolymer.
  • Preferred copolymers include propylene / ethylene copolymers and propylene / 1-butene copolymers.
  • the ethylene unit content and the 1-butene unit content are, for example, those of “Polymer Analysis Handbook” (1995, published by Kinokuniya Shoten) Infrared (IR) spectrum measurement can be performed by the method described on page 616.
  • the copolymer is preferably a random copolymer of propylene and the unsaturated hydrocarbon, and a random copolymer of propylene and ethylene. More preferably, it is a coalescence.
  • the content of the ethylene unit in the propylene / ethylene random copolymer is preferably 1 to 10% by weight, and more preferably 3 to 7% by weight.
  • the stereoregularity of the polypropylene resin may be any of isotactic, syndiotactic and atactic, but syndiotactic or isotactic polypropylene resin is preferred from the viewpoint of improving the heat resistance of the protective film. Used.
  • the polypropylene resin used for the protective film has a melt flow rate (MFR) measured at a temperature of 230 ° C. and a load of 21.18 N in accordance with JIS K 7210, 0.1 to 200 g / 10 min, particularly 0.5. It is preferably in the range of ⁇ 50 g / 10 minutes.
  • the polypropylene resin may be a polymer or copolymer polymerized using a known polymerization catalyst
  • the polymerization catalyst include the following. (1) Ti—Mg-based catalyst comprising a solid catalyst component containing magnesium, titanium and halogen as essential components, (2) a catalyst system in which a solid catalyst component containing magnesium, titanium and halogen as essential components is combined with an organoaluminum compound and, if necessary, a third component such as an electron donating compound, (3) Metallocene catalysts.
  • Examples of the solid catalyst component of (1) above include catalyst systems described in JPS61-218606-A, JPS61-287904-A, JPH07-216017-A, and the like.
  • Preferred examples of the organoaluminum compound in the catalyst system of (2) above include triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride, tetraethyldialumoxane, and the like.
  • Preferable examples include cyclohexylethyldimethoxysilane, tert-butylpropyldimethoxysilane, tert-butylethyldimethoxysilane, dicyclopentyldimethoxysilane and the like.
  • Examples of the metallocene catalyst of (3) above include the catalyst systems described in Japanese Patent No. 2587251, Japanese Patent No. 2627669, Japanese Patent No. 2668732, and the like.
  • Polypropylene resins are, for example, solution polymerization methods using an inert solvent typified by hydrocarbon compounds such as hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, and liquid monomers as solvents. It can be produced by a bulk polymerization method to be used or a gas phase polymerization method in which a gaseous monomer is polymerized as it is. Polymerization by these methods may be carried out batchwise or continuously.
  • an inert solvent typified by hydrocarbon compounds such as hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, and liquid monomers as solvents. It can be produced by a bulk polymerization method to be used or a gas phase polymerization
  • Alicyclic saturated hydrocarbon resin The alicyclic saturated hydrocarbon resin blended with the polypropylene resin as necessary is a resin classified as a petroleum resin.
  • the petroleum resin is a thermoplastic resin obtained by polymerizing and solidifying a cracked oil fraction generated by thermal decomposition of petroleum, for example, an aliphatic petroleum resin using a C5 fraction as a raw material; a C9 fraction.
  • hydrogenated petroleum resins obtained by hydrogenating
  • an alicyclic saturated hydrocarbon resin is particularly used among the above petroleum resins.
  • the alicyclic saturated hydrocarbon resin is typically a hydrogenated petroleum resin obtained by hydrogenating an aromatic petroleum resin. Addition of the alicyclic saturated hydrocarbon resin suppresses haze of the protective film obtained, and when used in a liquid crystal display device, a decrease in front contrast is effectively suppressed.
  • the alicyclic saturated hydrocarbon resin is colorless and transparent, and has advantageous characteristics as a protective film material that is excellent in weather resistance.
  • the alicyclic saturated hydrocarbon resin used in the present invention preferably has a softening point in the range of 110 ° C. or higher and 145 ° C. or lower.
  • a more preferable softening point is 115 ° C. or higher and 135 ° C. or lower.
  • the softening point is lower than 110 ° C., the heat resistance of the obtained protective film tends to be lowered, and when the softening point exceeds 145 ° C., the flexibility of the obtained protective film tends to be lowered.
  • a commercially available product can also be used as the alicyclic saturated hydrocarbon resin.
  • Examples of such commercially available products include “Arcon” series manufactured by Arakawa Chemical Industries, Ltd.
  • the “Arcon” series is a hydrogenated petroleum resin obtained by hydrogenating an aromatic petroleum resin.
  • the protective film can be composed of a polypropylene resin composition containing an alicyclic saturated hydrocarbon resin in the range of 0.1 to 30% by weight, but has the effect of blending the alicyclic saturated hydrocarbon resin.
  • the blending amount is preferably in the range of 3 to 20% by weight.
  • the unstretched film to be a protective film is formed from the above-described polypropylene resin alone, or mainly composed of a polypropylene resin, and an alicyclic saturated hydrocarbon resin. Can be obtained by a method of forming a film of a resin composition containing.
  • the thickness of the protective film is preferably about 5 to 200 ⁇ m. More preferably, it is 10 micrometers or more, More preferably, it is 150 micrometers or less.
  • the preparation method of the resin composition is at least an alicyclic group in the obtained resin composition. Any method may be used as long as the saturated hydrocarbon resin is uniformly dispersed.
  • the method of adding an alicyclic saturated hydrocarbon resin to the polymerization reaction mixture during the polymerization reaction in the polymerization process for preparing the polypropylene resin or immediately after the polymerization reaction can be mentioned.
  • the alicyclic saturated hydrocarbon resin may be added as a solution dissolved in a solvent, or may be pulverized into a powder form so that it can be easily dispersed, added as a powder, or heated and melted. May be added.
  • the above resin composition can be obtained by a method of adding an alicyclic saturated hydrocarbon resin while melt-kneading a polypropylene resin and further melt-kneading.
  • melt-kneading can be performed using kneading machines, such as a ribbon blender, a mixing roll, a Banbury mixer, a roll, various kneaders, a single screw extruder, a twin screw extruder, for example.
  • the resin composition thus obtained may be subjected to molding into a film in the molten state without being cooled after melt-kneading, or after cooling to form a molded article such as a pellet, You may heat and use for the shaping
  • a polypropylene resin constituting a protective film, or a resin composition mainly composed of a polypropylene resin and blended with other resins (hereinafter, including the form in which other resins are blended in this manner,
  • a resin mainly composed of a resin is a known additive within a range that does not impair the effects of the present invention. You may contain.
  • the additive include an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a nucleating agent, an antifogging agent, and an antiblocking agent. These additives can be used alone or in combination of two or more.
  • Antioxidants include, for example, phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, hindered amine light stabilizers, and the like, and for example, a phenolic antioxidant mechanism in one molecule.
  • a composite antioxidant having a unit having a phosphorus-based antioxidant mechanism can also be used.
  • the ultraviolet absorber include a 2-hydroxybenzophenone ultraviolet absorber, a hydroxyphenylbenzotriazole ultraviolet absorber, and a benzoate ultraviolet absorber.
  • the antistatic agent may be polymer type, oligomer type or monomer type.
  • the lubricant include higher fatty acid amides such as erucic acid amide and oleic acid amide, higher fatty acids such as stearic acid, and salts thereof.
  • fine particles having a spherical shape or a shape close thereto can be used regardless of inorganic type or organic type.
  • the nucleating agent may be either an inorganic nucleating agent or an organic nucleating agent.
  • the inorganic nucleating agent include talc, clay, calcium carbonate and the like.
  • the organic nucleating agent include metal salts such as aromatic carboxylic acid metal salts and aromatic phosphoric acid metal salts, high-density polyethylene, poly-3-methylbutene-1, polycyclopentene, and polyvinylcyclohexane. It is done. Among these, organic nucleating agents are preferable, and the above metal salts and high density polyethylene are more preferable.
  • the addition amount of the nucleating agent is 0.01 to 3% by weight relative to 100% by weight of the polypropylene resin constituting the protective film (in the case where other resins are blended, the polypropylene resin itself). It is preferably within the range, and more preferably within the range of 0.05 to 1.5% by weight.
  • a film can be formed by forming a resin mainly composed of polypropylene resin by an arbitrary method.
  • This film is transparent and substantially free of in-plane retardation.
  • film forming methods include 1) a method of extrusion molding from a molten state, 2) a solvent casting method in which a resin solution dissolved in an organic solvent is cast on a flat plate, and the solvent is removed to form a film. 3) Examples thereof include a method of press molding a resin plate-shaped molded body. By these methods, a resin film having substantially no in-plane retardation can be obtained.
  • a film forming method by extrusion As an example of a preferable method for producing an unstretched film to be a protective film, a film forming method by extrusion will be described in detail.
  • a polypropylene resin is melt-kneaded by rotation of a screw in an extruder and extruded from a T die into a sheet.
  • the temperature of the extruded molten sheet is about 180 to 300 ° C. If the temperature of the molten sheet at this time is lower than 180 ° C., the spreadability is not sufficient, the thickness of the obtained film becomes non-uniform, and there is a possibility that the film has a phase difference unevenness. Further, when the temperature exceeds 300 ° C., the polypropylene resin or the resin composition is liable to be deteriorated or decomposed, and bubbles may be generated or carbides may be contained in the sheet.
  • the extruder may be a single screw extruder or a twin screw extruder.
  • L / D which is the ratio of the screw length L to the diameter D
  • the compression ratio which is the ratio (V 1 / V 2 ) to the space volume V 2
  • a screw such as a full flight type, a barrier type, and a type having a Maddock type kneading part is used.
  • a barrier type having an L / D of 28 to 36 and a compression ratio V 1 / V 2 of 2.5 to 3.5 It is preferable to use a screw.
  • the inside of the extruder is preferably a nitrogen atmosphere or a vacuum.
  • an orifice of about 1 mm ⁇ to 5 mm ⁇ at the tip of the extruder to increase the resin pressure at the tip of the extruder.
  • Increasing the resin pressure at the leading end of the extruder by installing an orifice means increasing the back pressure at the leading end, thereby improving the stability of extrusion.
  • the diameter of the orifice to be used is more preferably 2 mm ⁇ or more and 4 mm ⁇ or less.
  • the T-die used for extrusion preferably has no fine steps or scratches on the resin flow path surface, and the lip portion is plated or coated with a material having a low coefficient of friction with the molten polypropylene resin. Further, a sharp edge shape with a lip tip polished to 0.3 mm ⁇ or less is preferable. Examples of the material having a small friction coefficient include tungsten carbide type and fluorine type special plating.
  • the manifold has a coat hanger shape and preferably satisfies the following condition (A) or (B), and more preferably satisfies the condition (C) or (D).
  • the flow of the molten polypropylene resin inside the T die can be adjusted, and the lip portion can be extruded while suppressing thickness unevenness, so that the thickness is increased.
  • a resin film having excellent accuracy and a more uniform retardation can be obtained.
  • a gear pump via an adapter between the extruder and the T die from the viewpoint of suppressing resin extrusion fluctuation.
  • a leaf disk filter to remove foreign substances in the resin.
  • the desired resin film can be obtained by cooling and solidifying the molten resin sheet extruded from the T-die with a metal cooling roll (also referred to as a chill roll or a casting roll). At this time, cooling of the melt can be promoted by improving the adhesion between the melt extruded from the T-die and the casting roll.
  • a film-like melt is adhered to a casting roll with air using an air chamber or the like, a wire-like, needle-like or band-like metal electrode is used to electrostatically fix the film-like melt.
  • the surface temperature of the casting roll when producing the raw film is preferably 0 to 30 ° C.
  • the touch roll may be one in which an elastic body such as rubber is directly on the surface, or may be one in which the surface of the elastic body roll is covered with an outer cylinder made of a metal sleeve.
  • the molten resin sheet is usually sandwiched between the metal cooling roll and the touch roll for cooling.
  • a biaxially stretched film of another thermoplastic resin may be interposed between the molten resin sheet and the touch roll for sandwiching.
  • the surface temperature of both rolls is preferably adjusted to a range of 0 ° C. or higher and 30 ° C. or lower. When these surface temperatures exceed 30 ° C., it takes time to cool and solidify the molten sheet, so that the crystal component in the molten resin sheet grows and the transparency of the resulting film may be lowered.
  • the surface temperature of both rolls is more preferably less than 30 ° C, and even more preferably 25 ° C or less.
  • condensation occurs on the surface of the metallic cooling roll, and water droplets adhere to the roll, which tends to deteriorate the appearance of the film.
  • the surface state of the metal cooling roll to be used is transferred to the surface of the film, if the surface has irregularities, there is a possibility that the thickness accuracy of the resulting film is lowered. Therefore, it is preferable that the surface of the metal cooling roll be in a mirror surface state as much as possible.
  • the roughness of the surface of the metal cooling roll is preferably 0.4 S or less, more preferably 0.1 S to 0.2 S, expressed as a standard sequence of the maximum height. .
  • the metal cooling roll and the touch roll that forms the nip part have a surface hardness of 65 to 80 as a value measured by a spring-type hardness test (A type) specified in JIS K 6301. Preferably, it is more preferably 70-80.
  • a type spring-type hardness test
  • the pressure (linear pressure) when sandwiching the molten sheet is determined by the pressure for pressing the touch roll against the metal cooling roll.
  • the linear pressure is preferably 50 N / cm or more and 300 N / cm or less, and more preferably 100 N / cm or more and 250 N / cm or less.
  • the thermoplastic resin constituting the biaxially stretched film is a melt mainly composed of a polypropylene resin.
  • Any resin that does not strongly heat-bond to the sheet-like sheet may be used, and specifically, polyester, polyamide, polyvinyl chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacrylonitrile, or the like can be used. Among these, polyesters that have little dimensional change due to humidity, heat, and the like are most preferable.
  • the thickness of the biaxially stretched film is usually about 5 to 50 ⁇ m, preferably 10 to 30 ⁇ m.
  • the distance (air gap) from the lip of the T die to the pressure between the metal cooling roll and the touch roll is preferably 200 mm or less, and more preferably 160 mm or less.
  • the molten sheet extruded from the T die is stretched between the lip and the roll, and orientation is likely to occur.
  • the lower limit value of the air gap is determined by the diameter of the metal cooling roll to be used, the diameter of the touch roll, and the tip shape of the lip to be used, and is usually 50 mm or more.
  • the processing speed when producing a film by this method is determined by the time required for cooling and solidifying the molten sheet.
  • the processing speed is about 5 to 20 m / min at the maximum.
  • the molten resin sheet sandwiched between the metal cooling roll and the touch roll is cooled and solidified by contact with the roll. And after slitting an edge part as needed, it is wound up by a winder. Under the present circumstances, in order to protect the surface until using the obtained film, you may wind up in the state which bonded the surface protection film which consists of another thermoplastic resin to the single side
  • the biaxially stretched film can be used as one surface protective film.
  • an unstretched film made of a resin mainly composed of a polypropylene resin can be produced.
  • the endless belt is preferably held by a plurality of arranged rolls. More preferably, the endless belt having a thickness in the range of 100 to 500 ⁇ m is held by two rolls having a diameter of 100 to 300 mm.
  • the protective film used in the present invention has a haze value of 1% or less.
  • a method for suppressing the haze value at the stage of an unstretched film (E) a method for producing a polypropylene resin obtained by random copolymerization of propylene and an unsaturated hydrocarbon other than propylene, (F) a polypropylene resin And (G) a method of forming a film by increasing the cooling efficiency of the casting roll during extrusion molding. These methods are appropriately combined so that the haze value of the film is lowered.
  • (E) Method by Random Copolymerization there is a method of producing a random copolymer mainly composed of propylene and with any unsaturated hydrocarbon.
  • a method by the above random copolymerization there is a method of producing a random copolymer mainly composed of propylene and with any unsaturated hydrocarbon.
  • Specific examples thereof include propylene / ethylene random copolymer, propylene / 1-butene random copolymer, propylene / 1-hexene random copolymer, propylene / ethylene / 1-octene random copolymer, propylene / ethylene /
  • Examples thereof include 1-butene random copolymers, and among them, a copolymer with ethylene is particularly preferable.
  • the unsaturated hydrocarbon other than propylene is preferably in the range of about 1 to 20% by weight, and more preferably in the range of 1 to 10% by weight. More preferably, it is more preferably in the range of 2 to 8% by weight.
  • the unit of unsaturated hydrocarbons other than propylene 1% by weight or more, processability and transparency tend to be improved. However, if the ratio is too large, the melting point of the resin is lowered and the heat resistance tends to deteriorate.
  • the total content of the unit derived from all the comonomers contained in the copolymer is the said range.
  • the nucleating agent used for that purpose is an inorganic nucleating agent or an organic nucleating agent. Any of nucleating agents may be used. Examples of the inorganic nucleating agent include talc, clay, calcium carbonate and the like. Examples of the organic nucleating agent include metal salts such as aromatic carboxylic acid metal salts and aromatic phosphoric acid metal salts, high-density polyethylene, poly-3-methylbutene-1, polycyclopentene, and polyvinylcyclohexane. It is done.
  • organic nucleating agents are preferable, and the above metal salts and high density polyethylene are more preferable.
  • the addition amount of the nucleating agent with respect to the propylene polymer is preferably 0.01 to 3% by weight, and more preferably 0.05 to 1.5% by weight. A plurality of these nucleating agents may be used in combination.
  • the addition method of the nucleating agent is not particularly limited as long as it can be uniformly dispersed, and can be added by a usual method.
  • a nucleating agent may be added to the polymerization reaction mixture during the polymerization reaction or immediately after the completion of the polymerization reaction.
  • the nucleating agent may be added in the form of a solution dissolved in a solvent, may be added in a state of being pulverized into a powder form so that it can be easily dispersed, or heated and added in a molten state. Also good.
  • the protective film used in the present invention presses the molten sheet extruded from the T die in the circumferential direction of the metal cooling roll and the metal cooling roll. Then, it can be obtained by being pinched with a touch roll including an elastic body that rotates and then cooled and solidified. At this time, from the viewpoint of suppressing the haze value, it is preferable that the surface temperature of the touch roll is kept low to quench the molten sheet.
  • the surface temperature of both rolls is preferably adjusted to a range of 0 ° C. or higher and 30 ° C. or lower.
  • the film thickness of the molten sheet is also effective to reduce the film thickness of the molten sheet. This is because by controlling the film thickness to be thin, the haze value can be reduced, and at the same time, the cooling efficiency by the metal cooling roll can be increased. In that case, the extrusion amount of the molten resin sheet can be arbitrarily selected.
  • the unstretched film mainly composed of the polypropylene-based resin obtained as described above can be used as a protective film as it is, You can also First, the form which uses an unstretched film as a protective film as it is is demonstrated.
  • the haze value is preferably smaller, for example, it is preferably 0.5% or less.
  • the in-plane retardation at a wavelength of 590 nm is preferably less than 20 nm, more preferably 15 nm or less.
  • the in-plane retardation of the unstretched film is 20 nm or more, light leakage during black display increases, and the contrast ratio may be significantly reduced.
  • this measurement wavelength of 590 nm may be omitted.
  • the in-plane retardation R 0 is the refractive index in the in-plane slow axis direction (the direction in which the refractive index is maximum in the plane) of the film, n x , and the in-plane fast axis direction (the slow axis and the in-plane direction).
  • n y is the refractive index
  • the angle between the protective film MD (machine direction, the longitudinal direction of the film obtained in a long shape) and the optical axis (slow axis) is ⁇ 15 ° or less, further ⁇ 10 ° or less, especially It is preferably ⁇ 5 ° or less, and more preferably ⁇ 3 ° or less.
  • this angle exceeds ⁇ 15 °, light leakage at the time of black display becomes large, and the reduction of the contrast ratio becomes remarkable.
  • the in-plane retardation at a wavelength of 590 nm is 400 nm or less. More preferably, it is 150 nm or less, more preferably 100 nm or less. If complete biaxial stretching, that is, biaxial stretching is performed so that the stretching ratios in two directions orthogonal to each other in the plane are substantially equal, the in-plane retardation of the obtained stretched film can be made substantially zero.
  • the in-plane retardation at the same wavelength of the obtained stretched film is preferably 40 nm or more. From this range, the phase difference value may be appropriately selected according to the characteristics required for the applied liquid crystal display device.
  • the in-plane retardation is more preferably 40 nm to 150 nm, and still more preferably 40 nm to 100 nm.
  • n in the formula R 0 (n x -n y ) ⁇ d indicated above the difference between the x and n y tends to be large. Therefore, a film obtained by stretching such a polypropylene resin film can exhibit a desired retardation value by appropriate stretching even if the thickness d is reduced. Therefore, a stretched film (retardation film) made of a polypropylene resin as defined in the present invention or made of a resin composition mainly composed of an alicyclic saturated hydrocarbon resin has a thickness of 60 ⁇ m or less. Good. However, if it is too thin, the handleability may be lowered, and therefore it is preferably 5 ⁇ m or more. The thickness of this stretched film is more preferably 10 ⁇ m or more and 40 ⁇ m or less.
  • the haze value can be significantly reduced by stretching as compared with an unstretched film that is a raw fabric. For example, even if the haze value of an unstretched film that is a raw fabric is around 10%, the haze value of the resulting film may be 1% or less by stretching.
  • the stretched film can be produced by subjecting the unstretched film described above to a known stretching process such as uniaxial stretching or biaxial stretching.
  • the biaxial stretching may be simultaneous biaxial stretching in which stretching is performed simultaneously in two stretching directions (generally orthogonal directions in the plane), or the other direction (generally the first stretching is performed after stretching in a predetermined direction).
  • Sequential biaxial stretching that extends in a direction orthogonal to the direction in the plane may be used.
  • the stretching direction can be, for example, a machine flow direction (MD) of the unstretched film, a direction perpendicular to the machine flow direction (TD), or a direction oblique to the machine flow direction (MD).
  • [5-1] Fixed-end stretching A stretched film is obtained by directly performing fixed-end stretching on the unstretched film described above, or by subjecting the unstretched film to other stretching treatments and fixed-end stretching. Thus, it can be manufactured.
  • the fixed end stretching is a method of stretching the film in the widened direction by fixing both ends in the width direction of the film to be stretched and applying heat to the film while widening the distance between the fixed ends. It is.
  • the fixed end stretching is preferably performed by fixed end transverse stretching.
  • a tenter method is mentioned as a typical method of fixed-end lateral stretching.
  • the tenter method is a method in which both ends in the film width direction are fixed with a chuck and stretched in an oven while widening the chuck interval.
  • the fixed end transverse stretching has the following steps: (I) a preheating step of preheating the film at a temperature near the melting point of the film mainly composed of polypropylene resin; (Ii) a stretching step for stretching the preheated film in the transverse direction (film width direction); and (iii) a heat setting step for heat-setting the film stretched in the transverse direction.
  • the stretching machine (tenter stretching machine) used for the tenter method preferably includes a mechanism capable of independently adjusting the temperatures in the zone for performing the preheating step, the zone for performing the stretching step, and the zone for performing the heat setting step.
  • the stretching ratio in the fixed end lateral uniaxial stretching is preferably 1.1 to 10 times.
  • a stretched film can be produced by performing other stretching processes such as free end stretching.
  • free end stretching free end uniaxial stretching is preferably used, and more preferably free end longitudinal uniaxial stretching is used.
  • Free-end longitudinal uniaxial stretching refers to a method of supporting a film to be stretched between a pair of stretching rollers, such as a transport roller, a supporting flat plate, or a supporting belt that contacts the stretching film and suppresses movement in the width direction. In this method, the film is stretched in the longitudinal direction in a state where there is no such member and the film can be freely contracted and expanded in the width direction.
  • Free end longitudinal uniaxial stretching includes a method of stretching a film by a difference in rotational speed between two or more rolls and a long span stretching method.
  • the long span stretching method uses a longitudinal stretching machine having two pairs of nip rolls and an oven disposed between the two nip rolls, and the film is stretched by the difference in rotational speed between the two pairs of nip rolls while heating the film in the oven. is there.
  • the long span longitudinal stretching method is preferable because a film having high optical uniformity can be easily obtained, and the long span longitudinal stretching method using an air floating oven is more preferable.
  • An air floating type oven is an oven having a structure in which hot air can be blown from the upper nozzle and the lower nozzle on both surfaces of a film introduced into the oven. In an air floating oven, a plurality of upper nozzles and lower nozzles are usually installed alternately in the film flow direction, and the film passes through the oven without contacting either the upper nozzle or the lower nozzle. Is stretched.
  • the stretching ratio in the free end longitudinal uniaxial stretching is preferably 1.1 to 2 times.
  • a stretched film can also be produced by a method of obliquely stretching an unstretched film in a direction oblique to the machine flow direction (MD). Also in this oblique stretching, the tenter stretching machine described for the above fixed end lateral stretching can be used.
  • a film in which both ends in the film width direction are fixed by a chuck is stretched in a direction oblique to the MD by providing a difference in moving speed and moving distance between the both ends.
  • the unstretched film is stretched in a direction oblique to MD in the stretching step in the tenter method.
  • the stretching step in the oblique stretching is performed by a tenter stretching machine for oblique stretching.
  • the film traveling direction in the stretching process is inclined by a predetermined angle from the traveling direction of the film sent from the preheating process.
  • the feeding speed of the obliquely stretched film fed through the stretching process is set higher than the feeding speed of the unstretched film fed into the oblique stretching apparatus.
  • the moving speed of one end in the direction (width direction) orthogonal to the feed direction of an unstretched film is made larger than the moving speed of the other end.
  • stretched film used in the present invention may be prepared by appropriately selecting the stretching method described above according to the required retardation value. Of course, these can be combined as appropriate. For example, as described above, a method of sequentially biaxially stretching by combining free end longitudinal uniaxial stretching and fixed end transverse uniaxial stretching is one of the preferred ones.
  • an optical axis (slow axis) may be developed in the transverse direction of the film, or an optical axis (slow axis) may be developed in the longitudinal direction.
  • the protective film mainly composed of the polypropylene-based resin described above may be laminated on both surfaces of the polarizing film or on one surface of the polarizing film. It may be laminated. In the latter case, a resin film other than a polypropylene resin may be laminated on the other surface as a protective film.
  • resin films other than polypropylene resins include films made of cellulose acetate resins such as triacetyl cellulose and diacetyl cellulose, polyester resin films, (meth) acrylic resin films, polycarbonate resin films, and the like.
  • a cellulose acetate resin film particularly a triacetyl cellulose film is preferably used.
  • the thickness of the protective film made of a resin other than polypropylene resin is usually about 10 to 200 ⁇ m, preferably 10 to 120 ⁇ m, and more preferably 10 to 85 ⁇ m.
  • An adhesive is preferably used for bonding the polarizing film and the protective film.
  • an adhesive having an epoxy resin, urethane resin, cyanoacrylate resin, acrylamide resin, or the like as an adhesive component can be used.
  • One of the adhesives preferably used in the present invention is a solventless adhesive.
  • Solventless adhesives do not contain a significant amount of solvent, and are curable compounds (monomers or oligomers) that are reactively cured by heating or irradiation with active energy rays (for example, ultraviolet rays, visible light, electron beams, X-rays, etc.) ), And an adhesive layer is formed by curing of the curable compound, and typically includes a curable compound that is reactively cured by heating or irradiation of active energy rays, and a polymerization initiator.
  • active energy rays for example, ultraviolet rays, visible light, electron beams, X-rays, etc.
  • the solventless epoxy adhesive that uses an epoxy compound as a curable compound includes a polarizing film and a polypropylene-based adhesive. Since it is excellent in the adhesiveness with the protective film which has resin as a main body, and the adhesiveness with a protective film consisting of resin other than a polarizing film and polypropylene resin, it is more preferable.
  • the epoxy compound, which is a curable compound contained in the solventless epoxy adhesive is not particularly limited, but is preferably one that is cured by cationic polymerization, and particularly from the viewpoint of weather resistance, refractive index, and the like. It is more preferable to use an epoxy compound that does not contain an aromatic ring. Examples of such epoxy compounds that do not contain an aromatic ring in the molecule include hydrides of aromatic epoxy compounds, alicyclic epoxy compounds, and aliphatic epoxy compounds. In addition, the epoxy compound that is a curable compound usually has two or more epoxy groups in the molecule.
  • the hydride of an aromatic epoxy compound is a nuclear water obtained by selectively subjecting an aromatic polyhydroxy compound, which is a raw material of an aromatic epoxy compound, to a hydrogen ring under pressure in the presence of a catalyst.
  • the additive polyhydroxy compound can be obtained by glycidyl etherification.
  • aromatic epoxy compounds include bisphenol-type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and diglycidyl ether of bisphenol S; phenol novolac epoxy resins, cresol novolac epoxy resins, hydroxybenzaldehyde Examples include novolak-type epoxy resins such as phenol novolac epoxy resins; glycidyl ethers of tetrahydroxyphenylmethane, glycidyl ethers of tetrahydroxybenzophenone, and polyfunctional epoxy resins such as epoxidized polyvinylphenol.
  • Aromatic polyhydroxy compounds typified by these raw materials, bisphenols, are hydrogenated as described above, and epichlorohydrin is reacted with the hydroxyl groups to obtain hydrides of aromatic epoxy compounds. .
  • An alicyclic epoxy compound means an epoxy compound having one or more epoxy groups bonded to an alicyclic ring, and “having one or more epoxy groups bonded to an alicyclic ring” means the following formula: Means having the structure shown. In the formula, m is an integer of 2 to 5.
  • the alicyclic epoxy compound is a compound having at least one structure represented by the above formula in the molecule and usually having at least two epoxy groups in the molecule. More specifically, a compound in which a group in a form in which one or more hydrogen atoms in (CH 2 ) m in the above formula are removed is bonded to another chemical structure can be an alicyclic epoxy compound. One or more hydrogen atoms in (CH 2 ) m may be appropriately substituted with a linear alkyl group such as a methyl group or an ethyl group.
  • the structure of the alicyclic epoxy compound preferably used in the present invention is specifically illustrated below, it is not limited to these compounds.
  • examples of the aliphatic epoxy compound include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. More specifically, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, propylene Polyethers of polyether polyols obtained by adding one or more alkylene oxides (ethylene oxide or propylene oxide) to aliphatic polyhydric alcohols such as glycol diglycidyl ether, ethylene glycol, propylene glycol and glycerin Examples thereof include glycidyl ether.
  • the epoxy compound may be used alone or in combination of two or more.
  • the epoxy equivalent of the epoxy compound contained in the solventless epoxy adhesive is usually in the range of 30 to 3,000 g / equivalent, preferably 50 to 1,500 g / equivalent.
  • the epoxy equivalent is less than 30 g / equivalent, the flexibility of the protective film after curing may be lowered, or the adhesive strength may be reduced.
  • the epoxy equivalent exceeds 3,000 g / equivalent, the compatibility with other components contained in the epoxy adhesive may be lowered.
  • the solventless epoxy adhesive preferably contains a cationic polymerization initiator in order to cause cationic polymerization of the epoxy compound.
  • the cationic polymerization initiator generates a cationic species or a Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, electron beams, or heating, and initiates an epoxy group polymerization reaction.
  • active energy rays such as visible light, ultraviolet rays, X-rays, electron beams, or heating
  • any type of cationic polymerization initiator may be used. However, it is preferable from the viewpoint of workability that the potential is imparted.
  • a cationic polymerization initiator that generates a cationic species or a Lewis acid upon irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams and initiates a polymerization reaction of an epoxy group is a photocationic polymerization initiator. Also called.
  • a cationic photopolymerization initiator allows the adhesive component to be cured at room temperature, reducing the need to take into account the heat resistance of the polarizing film or distortion due to expansion. Can be formed.
  • a cationic photopolymerization initiator acts catalytically by light, so that it is excellent in storage stability and workability even when mixed with an epoxy adhesive.
  • the photocationic polymerization initiator is not particularly limited, and examples thereof include aromatic diazonium salts; onium salts such as aromatic iodonium salts and aromatic sulfonium salts; iron-allene complexes. These cationic photopolymerization initiators may be used alone or in combination of two or more. Among these, aromatic sulfonium salts are particularly preferably used because they have ultraviolet absorption characteristics even in a wavelength region of 300 nm or more, and can provide a cured product having excellent curability and good mechanical strength and adhesive strength. It is done.
  • photocationic polymerization initiators can be easily obtained as commercial products, for example, “Kayarad (registered trademark) PCI-220” and “Kayarad (registered trademark) PCI-620” under the trade names, respectively.
  • “Kayarad (registered trademark) PCI-220” and “Kayarad (registered trademark) PCI-620” under the trade names, respectively.
  • UVI-6990 Union Carbide
  • Adeka (registered trademark) Optmer SP-150 “Adeka (registered trademark) Optomer SP-170” (above, (Made by ADEKA Corporation), “CI-5102”, “CIT-1370”, “CIT-1682”, “CIP-1866S”, “CIP-2048S”, “CIP-2064S” (above, Nippon Soda Co., Ltd.)
  • the amount of the cationic photopolymerization initiator is usually 0.5 to 20 parts by weight, preferably 1 part by weight or more, and preferably 15 parts by weight or less with respect to 100 parts by weight of the epoxy compound.
  • the solventless epoxy adhesive can further contain a photosensitizer as necessary together with the photocationic polymerization initiator.
  • a photosensitizer By using a photosensitizer, the reactivity is improved, and the mechanical strength and adhesive strength of the cured product can be improved.
  • the photosensitizer include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreductive dyes.
  • the amount is about 0.1 to 20 parts by weight with respect to 100 parts by weight of the epoxy compound.
  • thermal cationic polymerization initiator that generates a cationic species or a Lewis acid by heating and initiates a polymerization reaction of an epoxy group
  • a thermal cationic polymerization initiator that generates a cationic species or a Lewis acid by heating and initiates a polymerization reaction of an epoxy group
  • thermal cationic polymerization initiators can also be easily obtained as commercial products.
  • thermal cationic polymerization initiators may be used alone or in admixture of two or more. It is also preferable to use a photocationic polymerization initiator and a thermal cationic polymerization initiator in combination.
  • the solventless epoxy adhesive may further contain a compound that promotes cationic polymerization, such as oxetanes and polyols.
  • the polarizing film and the protective film can be bonded by applying the adhesive to the adhesive surface of the protective film and / or the polarizing film and bonding them together. it can.
  • the method of applying the solvent-free epoxy adhesive to the polarizing film and / or protective film For example, various coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater. A scheme is available.
  • each coating method has an optimum viscosity range, the viscosity may be adjusted using a small amount of solvent.
  • the solvent used for this is not particularly limited as long as it can dissolve the epoxy adhesive well without deteriorating the optical performance of the polarizing film.
  • hydrocarbons typified by toluene, typified by ethyl acetate, and the like.
  • Organic solvents such as esters can be used.
  • the adhesive layer After bonding a protective film to the polarizing film through an adhesive layer made of an uncured epoxy adhesive, the adhesive layer is cured and protected by irradiating active energy rays or heating.
  • the film is fixed on the polarizing film.
  • ultraviolet rays are preferably used.
  • Specific examples of the ultraviolet light source include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a black light lamp, and a metal halide lamp.
  • the irradiation intensity and irradiation amount of active energy rays are appropriately selected so as to sufficiently activate the cationic polymerization initiator and not adversely affect the cured adhesive layer, polarizing film, and protective film.
  • active energy rays such as ultraviolet rays
  • it can be heated by a generally known method, and the temperature and time at that time can sufficiently activate the cationic polymerization initiator, and the cured adhesive layer or It is appropriately selected so as not to adversely affect the polarizing film and the protective film.
  • the thickness of the adhesive layer made of the epoxy adhesive after curing obtained as described above is usually 0.1 to 50 ⁇ m, preferably 1 ⁇ m or more. More preferably, it is in the range of 1 to 20 ⁇ m, more preferably 2 to 10 ⁇ m.
  • the solventless epoxy adhesive is a laminate of a protective film mainly composed of a polypropylene resin and a polarizing film, or a laminate of a protective film made of a resin other than a polypropylene resin and a polarizing film, or these It can use preferably for both bonding.
  • a water-based adhesive that is, an adhesive component dissolved in water or a dispersion thereof in water.
  • a water-based adhesive an adhesive component dissolved in water or a dispersion thereof in water.
  • the thickness of the adhesive layer can be further reduced.
  • the water-based adhesive include those containing a water-soluble crosslinkable epoxy resin or a hydrophilic urethane-based resin as an adhesive component.
  • a water-soluble crosslinkable epoxy resin for example, a polyalkylene polyamine such as diethylenetriamine or triethylenetetramine and a polyamide polyamine obtained by a reaction of a dicarboxylic acid such as adipic acid are reacted with epichlorohydrin. Mention may be made of the polyamide epoxy resin obtained. Examples of such commercially available polyamide epoxy resins include “Smiles (registered trademark) Resin 650” and “Smiles (registered trademark) Resin 675” (both are trade names) sold by Sumika Chemtex Co., Ltd. is there.
  • a water-soluble crosslinkable epoxy resin is used as the adhesive component
  • it is preferable to mix other water-soluble resins such as a polyvinyl alcohol resin in order to further improve the coatability and adhesiveness.
  • Polyvinyl alcohol resins are modified such as partially saponified polyvinyl alcohol and fully saponified polyvinyl alcohol, as well as carboxyl group-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, methylol group-modified polyvinyl alcohol, and amino group-modified polyvinyl alcohol.
  • Polyvinyl alcohol resin may be used.
  • a saponified product of a copolymer of vinyl acetate and an unsaturated carboxylic acid or a salt thereof, that is, carboxyl group-modified polyvinyl alcohol is preferably used.
  • carboxyl group-modified polyvinyl alcohol is preferably used.
  • the “carboxyl group” is a concept including —COOH and a salt thereof.
  • suitable commercially available carboxyl group-modified polyvinyl alcohol examples include “Kuraray Poval KL-506”, “Kuraray Poval KL-318”, and “Kuraray Poval KL-118” sold by Kuraray Co., Ltd. “GOHSENAL (registered trademark) T-330” and “GOHSENAL (registered trademark) T-350” sold by Nippon Synthetic Chemical Industry Co., Ltd., and “DR-0415” sold by Electrochemical Industry Co., Ltd. ”,“ AF-17 ”,“ AT-17 ”,“ AP-17 ”and the like sold by Nippon Vinegar Poval Co., Ltd., respectively.
  • An adhesive containing a water-soluble crosslinkable epoxy resin can be prepared as an adhesive solution by dissolving the above epoxy resin and other water-soluble resin such as a polyvinyl alcohol resin added as necessary in water.
  • the water-soluble crosslinkable epoxy resin has a concentration in the range of about 0.2 to 2 parts by weight with respect to 100 parts by weight of water.
  • the amount thereof is preferably about 1 to 10 parts by weight, more preferably about 1 to 5 parts by weight with respect to 100 parts by weight of water.
  • suitable urethane resins include ionomer type urethane resins, especially polyester type ionomer type urethane resins.
  • the ionomer type is obtained by introducing a small amount of an ionic component (hydrophilic component) into the urethane resin constituting the skeleton.
  • the polyester ionomer type urethane resin is a urethane resin having a polyester skeleton, into which a small amount of an ionic component (hydrophilic component) is introduced.
  • Such an ionomer-type urethane resin is suitable as a water-based adhesive because it is emulsified directly in water without using an emulsifier to form an emulsion.
  • polyester ionomer type urethane resins include “Hydran (registered trademark) AP-20” and “Hydran (registered trademark) APX-101H” sold by Dainippon Ink and Chemicals, Inc. Both are available in the form of emulsions.
  • the isocyanate-based crosslinking agent is a compound having at least two isocyanato groups (—NCO) in the molecule.
  • Examples thereof include 2,4-tolylene diisocyanate, phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,
  • polyisocyanate monomers such as 6-hexamethylene diisocyanate and isophorone diisocyanate
  • isocyanurate forms in which isocyanurate rings are formed at the part, and polyisocyanate modified forms such as burettes formed by hydration and decarboxylation of the three diisocyanate molecules at the respective one-end isocyanato groups.
  • polyisocyanate modified forms such as burettes formed by hydration and decarboxylation of the three diisocyanate molecules at the respective one-end isocyanato groups.
  • isocyanate-based crosslinking agents examples include “Hydran (registered trademark) Assistor C-1” sold by Dainippon Ink and Chemicals, Inc.
  • the concentration of the urethane resin is about 10 to 70% by weight, further 20% by weight or more, and 50% by weight or less from the viewpoint of viscosity and adhesiveness. Thus, those dissolved or dispersed in water are preferred.
  • the isocyanate crosslinking agent is blended, the blending amount is appropriately selected so that the isocyanate crosslinking agent is about 5 to 100 parts by weight with respect to 100 parts by weight of the urethane resin.
  • the polarizing film and the protective film can be adhered by applying the adhesive to the adhesive surface of the protective film and / or the polarizing film and bonding them together.
  • a water-based adhesive is uniformly applied to the polarizing film and / or protective film by, for example, a coating method such as a doctor blade, a wire bar, a die coater, a comma coater, or a gravure coater.
  • the other film is stacked and bonded with a roll or the like and dried. Drying can be performed at a temperature of about 60 to 100 ° C., for example.
  • the water-based adhesive like the solvent-free epoxy adhesive, is bonded to a protective film mainly composed of a polypropylene resin and a polarizing film, or a protective film made of a resin other than a polypropylene resin and a polarizing film. It can be preferably used for pasting with a film or for pasting both of them.
  • a protective film mainly composed of a polypropylene resin is laminated on both surfaces of the polarizing film
  • a protective film mainly composed of a polypropylene resin is laminated on one surface of the polarizing film, and other than the polypropylene resin on the other surface
  • a protective film made of a resin including a retardation film such as a wave plate or a viewing angle compensation film, the same applies hereinafter
  • An adhesive may be used, or a different adhesive may be used, but it is preferable to use the same adhesive in order to simplify the manufacturing process and reduce the number of components of the polarizing plate.
  • a protective film mainly composed of a polypropylene resin and a protective film made of a resin other than a polypropylene resin are subjected to corona discharge treatment on the surface to be bonded to the polarizing film. It is preferable to keep it.
  • the corona discharge treatment is a treatment for activating the resin film disposed between the electrodes by discharging by applying a high voltage between the electrodes.
  • corona discharge treatment varies depending on the type of electrode, electrode interval, voltage, humidity, type of resin film used, etc., but for example, the electrode interval is set to 1 to 5 mm and the moving speed is set to about 3 to 20 m / min. It is preferable to do this.
  • a polarizing film is bonded to the treated surface via the adhesive as described above.
  • a protective film mainly composed of a polypropylene resin is laminated on one side of a polarizing film made of a polyvinyl alcohol resin on which dichroic dyes are adsorbed and oriented, and the other side is made of the same or different resin.
  • a polarizing plate on which the protective film is laminated or the protective film is not laminated is obtained.
  • the polarizing plate thus obtained can be formed as a polarizing plate with an adhesive layer by forming an adhesive layer on one protective film.
  • Such an adhesive layer can be suitably used, for example, for bonding with a liquid crystal cell when the polarizing plate is applied to a liquid crystal display device.
  • a protective film mainly composed of a polypropylene resin is laminated on one surface of a polarizing film and a protective film made of a resin other than a polypropylene resin is laminated on the other surface, an adhesive layer for bonding to a liquid crystal cell Is formed on a protective film mainly composed of polypropylene resin.
  • the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer those using a base polymer such as an acrylic ester, methacrylic ester, butyl rubber, or silicone can be used.
  • a base polymer such as an acrylic ester, methacrylic ester, butyl rubber, or silicone
  • (meth) acrylate esters such as butyl (meth) acrylate, ethyl (meth) acrylate, isooctyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate
  • polymers based on copolymers using two or more of these (meth) acrylic esters are preferably used.
  • a polar monomer is usually copolymerized in these base polymers.
  • Examples of the polar monomer include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid 2
  • Examples thereof include monomers having a carboxyl group, a hydroxyl group, an amino group, an epoxy group, and the like, such as -hydroxypropyl, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, and glycidyl (meth) acrylate.
  • the pressure-sensitive adhesive usually contains one or more crosslinking agents in addition to the base polymer.
  • Examples of the crosslinking agent include divalent or polyvalent metal salts that form a carboxylic acid metal salt with a carboxyl group, and polyisocyanate compounds that form an amide bond with a carboxyl group.
  • the thickness of the pressure-sensitive adhesive layer can be about 3 to 50 ⁇ m.
  • a surface treatment such as corona treatment may be applied to the surface of the protective film of the polarizing plate.
  • it is normal to cover the surface of an adhesive layer with a peeling film.
  • the polarizing plate of the present invention is used as a component of a liquid crystal display device.
  • the polarizing plate of the present invention can be used as a viewing side polarizing plate by being arranged on the viewing side from the liquid crystal cell of the liquid crystal display device, or can be used as a backlight side polarizing plate by being arranged on the backlight side from the liquid crystal cell. it can.
  • the liquid crystal display device usually has a configuration in which a viewing side polarizing plate, a liquid crystal cell, a backlight side polarizing plate, and a backlight are arranged in this order.
  • the polarizing plate of the present invention is disposed so that a protective film mainly composed of polypropylene resin and having a haze value of 1% or less, and a polarizing film are positioned in this order from the side closer to the liquid crystal cell. .
  • a configuration in which a polarizing plate having a protective film or a retardation film made of a resin different from the protective film is also effective. In the latter case, whichever is on the viewer side.
  • ⁇ Measurement of film thickness> The thickness of the film was measured using a digital micrometer MH-15M (manufactured by Nikon Corporation).
  • In-plane angular tolerance was measured at a measurement wavelength of 590 nm using a phase difference measuring apparatus Axoscan (registered trademark, manufactured by Axometrics, USA).
  • ⁇ Measurement of haze value of film> The haze value of the film was measured using a direct reading haze computer HGM-2DP (manufactured by Suga Test Instruments Co., Ltd.).
  • the extruded molten polypropylene resin was cooled by a casting roll (air gap was 90 mm) adjusted to 20 ° C. and an air chamber to prepare a protective film made of polypropylene resin having a thickness of 40 ⁇ m.
  • the obtained film had an in-plane retardation of 11.9 nm and a haze value of 0.3%, and had excellent transparency.
  • a protective film made of triacetyl cellulose was bonded to one side of a polarizing film obtained by adsorbing and orienting iodine to a polyvinyl alcohol resin film via the ultraviolet curable adhesive.
  • one side of the protective film made of the polypropylene resin was subjected to a corona discharge treatment under the condition of an integrated irradiation amount of 1,680 J / m 2 , and within 30 seconds after the corona discharge treatment, the corona treatment surface was applied to the polarizing film. It was bonded to the surface opposite to the side on which the triacetylcellulose film was bonded via the ultraviolet curable adhesive.
  • the protective film side made of polypropylene resin was irradiated with ultraviolet rays under the conditions of an output of 1,000 mW / cm 2 and an irradiation amount of 500 mJ / cm 2 , Was cured.
  • a polarizing plate was obtained in which a protective film made of triacetylcellulose was laminated on one side of the polarizing film, and a protective film made of polypropylene resin was laminated on the other side of the polarizing film via the ultraviolet curable adhesive.
  • Example 2 The thickness was adjusted to 110 ⁇ m, and a protective film was prepared in the same manner as in Example 1 (a). The obtained film had an in-plane retardation of 6.6 nm and a haze value of 1.0%.
  • a polarizing plate with a protective film was produced in the same manner as in (c) of Example 1 except that the 110 ⁇ m-thick film thus obtained was used as a protective film made of a polypropylene resin.
  • a polarizing plate with a protective film was produced in the same manner as in (c) of Example 1 except that the film having a thickness of 50 ⁇ m thus obtained was used as a protective film made of a polypropylene resin.
  • Example 1 The thickness was adjusted to 100 ⁇ m, the temperature of the casting roll was adjusted to 23 ° C., and the others were produced in the same manner as in Example 1 (a).
  • the obtained film had an in-plane retardation of 10.1 nm and a haze value of 3.8%.
  • a polarizing plate with a protective film was produced in the same manner as in (c) of Example 1 except that the thus obtained film having a thickness of 100 ⁇ m was used as a protective film made of a polypropylene resin.
  • Example 2 The thickness was adjusted to 100 ⁇ m, the temperature of the casting roll was adjusted to 28 ° C., and the others were produced in the same manner as in Example 1 (a).
  • the obtained film had an in-plane retardation of 13.1 nm and a haze value of 7.6%.
  • a polarizing plate with a protective film was produced in the same manner as in (c) of Example 1 except that the thus obtained film having a thickness of 100 ⁇ m was used as a protective film made of a polypropylene resin.
  • the viewing-side polarizing plate was peeled off from the liquid crystal display device “BRAVIA (registered trademark) KDL-40F1” (diagonal dimension: 40 inches) manufactured by Sony Corporation. Instead, Examples 1 to 3, Comparative Example 1 and Comparative Example were used. Each polarizing plate of 2 was affixed in the same axial direction as the original polarizing plate so that a protective film made of polypropylene resin, a polarizing film, and a triacetyl cellulose protective film were arranged in order from the side close to the liquid crystal cell. .
  • the polarizing plates produced in Examples 1 to 3 showed a high contrast ratio of 1000 or more when applied to a liquid crystal display device. That is, since the polarizing plates of Examples 1 to 3 have little light scattering during black display when applied to a liquid crystal display device and low black luminance, a reduction in front contrast can be suppressed.
  • the polarizing plate of Example 1 using a polypropylene resin film having a haze value of 0.5% or less as a protective film had a sufficiently high front contrast ratio of 3721.
  • a high contrast ratio was not obtained from the polarizing plates produced in Comparative Example 1 and Comparative Example 2.
  • a polarizing plate with a protective film was produced in the same manner as in (c) of Example 1 except that the film having a thickness of 50 ⁇ m thus obtained was used as a protective film made of a polypropylene resin.
  • Example 5 90 parts of the propylene homopolymer used in Example 4 and 10 parts of an alicyclic saturated hydrocarbon resin (“Arcon P-125” manufactured by Arakawa Chemical Industries, Ltd., softening point 125 ° C.) It was put into a 50 mm ⁇ extruder set at 250 ° C., melted and kneaded, and extruded from a 600 mm wide T-die attached to the extruder at an extrusion speed of 11.9 m / min. The extruded molten resin is cooled by a casting roll (air gap is 100 mm) adjusted to 20 ° C.
  • Air gap is 100 mm
  • Example 1 A polarizing plate with a protective film was produced in the same manner as that except that the thus obtained film having a thickness of 50 ⁇ m was used instead of the protective film made of the polypropylene resin in Example 1 (c).
  • Example 6 Extrusion speed was adjusted to 7.7 m / min. Other than that, a 50 ⁇ m-thick film in which 10% of alicyclic saturated hydrocarbon resin was blended with polypropylene was prepared according to Example 5. The obtained film had an in-plane retardation of 9.8 nm, an angle between the MD and the optical axis of 2.7 °, and a haze value of 0%. A polarizing plate with a protective film was produced in the same manner as that except that the thus obtained film having a thickness of 50 ⁇ m was used instead of the protective film made of the polypropylene resin in Example 1 (c).
  • the polarizing plate of Example 4 using a protective film having a haze value suppressed to 0.1% is applied to a liquid crystal display device even if it is a resin film made of a homopolymer of propylene.
  • the contrast ratio of the front surface was a sufficiently high value of 3000.
  • blended the alicyclic saturated hydrocarbon resin with the polypropylene has further improved the contrast ratio of the front when applied to a liquid crystal display device. It was.
  • Example 7 The thickness was adjusted to 100 ⁇ m, the temperature of the casting roll was adjusted to 10 ° C., and the others were prepared according to Example 1 (a).
  • the obtained film had an in-plane retardation of 0.7 nm and a haze value of 1.1%.
  • the film having a thickness of 100 ⁇ m thus obtained was successively biaxially stretched to prepare a biaxial retardation film having a thickness of 14 ⁇ m. This retardation film had an in-plane retardation of 60.1 nm and a haze value of 0.7%.
  • a polarizing plate with a protective film was produced in the same manner as in (c) of Example 1 except that the biaxially stretched film thus obtained was used as a protective film made of a polypropylene resin.
  • Example 8> The film produced in Comparative Example 1 was sequentially biaxially stretched to produce a biaxial retardation film having a thickness of 14 ⁇ m. This retardation film had an in-plane retardation of 58.4 nm and a haze value of 0.7%.
  • a polarizing plate with a protective film was produced in the same manner as in (c) of Example 1 except that the biaxially stretched film thus obtained was used as a protective film made of a polypropylene resin.
  • Example 9 The film produced in Comparative Example 2 was successively biaxially stretched to produce a biaxial retardation film having a thickness of 14 ⁇ m. This retardation film had an in-plane retardation of 60.5 nm and a haze value of 0.8%.
  • a polarizing plate with a protective film was produced in the same manner as in (c) of Example 1 except that the biaxially stretched film thus obtained was used as a protective film made of a polypropylene resin.
  • the polarizing plates of Examples 7 to 9 had a sufficiently high front contrast ratio of 3600 or more when applied to a liquid crystal display device.
  • the polarizing plate of Example 7 which used the biaxially stretched film produced from the raw film with a low haze as the protective film showed a very high front contrast ratio.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)

Abstract

La présente invention se rapporte à une plaque de polarisation qui est pourvue d'un film de polarisation et d'un film de protection disposé sur une surface du film de polarisation. Le film de protection comprend une résine de polypropylène comme composant principal et la valeur de Hayes est égale ou inférieure à 1 %. La plaque de polarisation est utilisée dans le dispositif d'affichage à cristaux liquides et est disposée de telle sorte que l'ordre soit le film de protection, ensuite le film de polarisation depuis le côté qui se trouve le plus près des cellules à cristaux liquides. En plus de pouvoir être formé à partir de la résine de polypropylène elle-même, ce film de protection, pour lequel la résine de polypropylène constitue le composant principal, peut être formé à partir d'une composition de résine dans laquelle une quantité comprise entre 0,1 et 30 % en poids d'une résine hydrocarbonée saturée alicyclique est mélangée dans la résine de polypropylène. La présente invention se rapporte à une plaque de polarisation qui comprend un film de protection stratifié sur un film de polarisation et qui peut obtenir une meilleure résistance à la chaleur et à l'humidité, des réductions de coût et la suppression des réductions de contraste.
PCT/JP2011/064489 2011-06-17 2011-06-17 Plaque de polarisation et dispositif d'affichage à cristaux liquides WO2012172696A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009114303A (ja) * 2007-11-06 2009-05-28 Fujifilm Corp 環状オレフィンフィルム
JP2010102310A (ja) * 2008-09-29 2010-05-06 Sumitomo Chemical Co Ltd 複合偏光板およびこれを用いた液晶表示装置
JP2010277063A (ja) * 2009-04-27 2010-12-09 Sumitomo Chemical Co Ltd 液晶表示装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009114303A (ja) * 2007-11-06 2009-05-28 Fujifilm Corp 環状オレフィンフィルム
JP2010102310A (ja) * 2008-09-29 2010-05-06 Sumitomo Chemical Co Ltd 複合偏光板およびこれを用いた液晶表示装置
JP2010277063A (ja) * 2009-04-27 2010-12-09 Sumitomo Chemical Co Ltd 液晶表示装置

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