WO2013051553A1 - 偏光板の製造方法 - Google Patents
偏光板の製造方法 Download PDFInfo
- Publication number
- WO2013051553A1 WO2013051553A1 PCT/JP2012/075502 JP2012075502W WO2013051553A1 WO 2013051553 A1 WO2013051553 A1 WO 2013051553A1 JP 2012075502 W JP2012075502 W JP 2012075502W WO 2013051553 A1 WO2013051553 A1 WO 2013051553A1
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- WIPO (PCT)
- Prior art keywords
- film
- roll
- adhesive
- active energy
- polarizing
- Prior art date
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00634—Production of filters
- B29D11/00644—Production of filters polarizing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
- B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
- B29C65/1429—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface
- B29C65/1435—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface at least passing through one of the parts to be joined, i.e. transmission welding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
- B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
- B29C65/1429—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface
- B29C65/1464—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface making use of several radiators
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
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- B29C65/1483—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation making use of an absorber or impact modifier coated on the article
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
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- B29C65/4845—Radiation curing adhesives, e.g. UV light curing adhesives
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- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
- B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
- B32B37/20—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of continuous webs only
- B32B37/203—One or more of the layers being plastic
- B32B37/206—Laminating a continuous layer between two continuous plastic layers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- 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 method for producing a polarizing plate useful as one of optical components constituting a liquid crystal display device or the like.
- Polarizing films are widely used as dichroic dyes adsorbed and oriented on polyvinyl alcohol resin films. Iodine polarizing films using iodine as a dichroic dye and dichroic direct dyes as dichroic Dye-type polarizing films used as pigments are known. These polarizing films are usually used as polarizing plates by laminating a transparent film such as a triacetyl cellulose film on one side or both sides via an adhesive.
- Patent Document 1 Japanese Patent Laid-Open No. 2004-245925
- Patent Document 2 Japanese Patent Laid-Open No. 2009-134190
- Patent Document 3 Special No. 2011-95560
- Patent Document 3 when the active energy ray-curable resin is cured by irradiating active energy rays, it is possible to suppress the occurrence of wave curl or the like by curing the laminate while adhering it to the outer peripheral surface of the roll.
- the appearance defect such as a wavy plate formed on the produced polarizing plate (below) This state is referred to as “corrugated undulation”).
- JP 2004-245925 A JP 2009-134190 A JP 2011-95560 A
- An object of the present invention is to suppress the occurrence of corrugated sheet swell in a method comprising a step of curing an active energy ray-curable resin while bringing the laminate as described above into close contact with the outer peripheral surface of a roll.
- the present invention is a method for producing a polarizing plate in which a transparent film is bonded to one side or both sides of a polarizing film, and the active energy ray-curable adhesive is attached to one side or both sides of the transparent film. And sandwiching a laminate in which the transparent film is laminated on one or both sides of the polarizing film via the adhesive between a pair of bonding rolls rotating in the conveying direction. While the laminate is transported in a state where the laminate is adhered to a rotating roll that rotates in the transport direction, the laminate is bonded to the laminate by laminating the transparent film and the polarizing film by applying pressure to the laminate.
- a first active energy ray irradiation step of irradiating active energy rays to cure the adhesive in this order, and at least one of the pair of bonding rolls is made of rubber. That a rubber roll which is rotationally driven has a surface, the rotational speed of the rotating rolls is faster than the rotational speed of the rubber roll.
- the rotating roll is preferably a cooling roll.
- the rotational speed of the rotating roll is preferably 100.1 or more and 102.0 or less, assuming that the rotational speed of the rubber roll is 100.
- the present invention it is possible to produce a polarizing plate with a good appearance in which the occurrence of corrugated sheet undulation is suppressed. Therefore, when the polarizing plate obtained by the manufacturing method of the present invention is used, a high-quality liquid crystal display device can be provided.
- the present invention is a method for producing a polarizing plate in which a transparent film is bonded to one side or both sides of a polarizing film, and an active energy ray-curable adhesive is applied to one side or both sides of a transparent film or a polarizing film.
- Adhesive application step to be applied, and a laminate formed by laminating a transparent film on one or both sides of the polarizing film via the adhesive is sandwiched between a pair of bonding rolls rotating in the conveying direction, and pressure is applied to the laminate
- the laminate is irradiated with active energy rays while the laminate is transported in a state of being adhered to a rotating roll that rotates in the transport direction, and a laminating step for pasting the transparent film and the polarizing film.
- At least one of the pair of bonding rolls is a rubber roll having a surface made of rubber and driven to rotate, and the rotation speed of the rotation roll is faster than the rotation speed of the rubber roll.
- the polarizing film used in the method for producing a polarizing plate of the present invention is obtained by adsorbing and orienting a dichroic dye on a uniaxially stretched polyvinyl alcohol-based resin film.
- the polyvinyl alcohol-based resin can be obtained by saponifying a polyvinyl acetate-based resin.
- Polyvinyl acetate resins include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith (for example, ethylene-vinyl acetate copolymer). Polymer).
- polyvinyl alcohol resins may be modified. For example, polyvinyl formal modified with aldehydes, polyvinyl acetal, polyvinyl butyral, and the like may be used.
- a film obtained by forming such a polyvinyl alcohol resin is used as an original film of a polarizing film.
- the method for forming the polyvinyl alcohol-based resin is not particularly limited, and can be formed by a conventionally known appropriate method.
- the film thickness of the raw film made of polyvinyl alcohol resin is not particularly limited, but is, for example, about 10 to 150 ⁇ m. Usually, it is supplied in the form of a roll, the thickness is in the range of 20 to 100 ⁇ m, preferably in the range of 30 to 80 ⁇ m, and the industrially practical width is in the range of 1500 to 6000 mm.
- the commercially available polyvinyl alcohol film (Vinylon VF-PS # 7500, Kuraray / OPL film M-7500, Nihon Gosei) has a thickness of 75 ⁇ m.
- the original fabric thickness of 6000 (manufactured by Kuraray) is 60 ⁇ m.
- the polarizing film is usually a process of dyeing a polyvinyl alcohol resin film with a dichroic dye to adsorb the dichroic dye (dyeing process), and a polyvinyl alcohol resin film adsorbed with the dichroic dye is boric acid. It is manufactured through a step of treating with an aqueous solution (boric acid treatment step) and a step of washing with water after the treatment with the boric acid aqueous solution (water washing treatment step).
- the polyvinyl alcohol-based resin film is usually uniaxially stretched, but this uniaxial stretching may be performed before the dyeing treatment step or during the dyeing treatment step, It may be performed after the dyeing process.
- the uniaxial stretching may be performed before the boric acid treatment step or during the boric acid treatment step.
- uniaxial stretching can be performed in these plural stages.
- the uniaxial stretching may be performed uniaxially between rolls having different peripheral speeds, or may be performed uniaxially using a hot roll. Moreover, the dry-type extending
- the draw ratio is usually about 3 to 8 times.
- the dyeing of the polyvinyl alcohol-based resin film with the dichroic dye in the dyeing process is performed, for example, by immersing the polyvinyl alcohol-based resin film in an aqueous solution containing the dichroic dye.
- the dichroic dye for example, iodine, a dichroic dye or the like is used.
- dichroic dyes include C.I. I. Dichroic direct dyes composed of disazo compounds such as DIRECT RED 39, and dichroic direct dyes composed of compounds such as trisazo and tetrakisazo are included.
- the polyvinyl alcohol-type resin film performs the immersion process to water before a dyeing process.
- iodine When iodine is used as the dichroic dye, a method of dyeing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide is usually employed.
- the content of iodine in this aqueous solution is usually 0.01 to 1 part by weight per 100 parts by weight of water, and the content of potassium iodide is usually 0.5 to 20 parts by weight per 100 parts by weight of water.
- the temperature of the aqueous solution used for dyeing is usually 20 to 40 ° C.
- the immersion time (dyeing time) in this aqueous solution is usually 20 to 1800 seconds.
- a method of immersing and dyeing a polyvinyl alcohol-based resin film in an aqueous solution containing the dichroic dye is usually employed.
- the content of the dichroic dye in this aqueous solution usually, 1 ⁇ 10 -4 ⁇ 10 parts by weight per 100 parts by weight of water, preferably 1 ⁇ 10 -3 ⁇ 1 parts by weight, particularly preferably 1 ⁇ 10 - 3 to 1 ⁇ 10 ⁇ 2 parts by weight.
- This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing assistant.
- the temperature of the dye aqueous solution used for dyeing is usually 20 to 80 ° C.
- the immersion time (dyeing time) in this aqueous solution is usually 10 to 1800 seconds. is there.
- the boric acid treatment step is performed by immersing a polyvinyl alcohol resin film dyed with a dichroic dye in a boric acid-containing aqueous solution.
- the amount of boric acid in the boric acid-containing aqueous solution is usually 2 to 15 parts by weight, preferably 5 to 12 parts by weight per 100 parts by weight of water.
- the boric acid-containing aqueous solution used in this boric acid treatment process preferably contains potassium iodide.
- the amount of potassium iodide in the boric acid-containing aqueous solution is usually 0.1 to 15 parts by weight, preferably 5 to 12 parts by weight, per 100 parts by weight of water.
- the immersion time in the boric acid-containing aqueous solution is usually 60 to 1200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds.
- the temperature of the boric acid-containing aqueous solution is usually 40 ° C. or higher, preferably 50 to 85 ° C., more preferably 55 to 75 ° C.
- the polyvinyl alcohol-based resin film after the boric acid treatment described above is washed with water, for example, by immersing it in water.
- the temperature of water in the water washing treatment is usually 4 to 40 ° C., and the immersion time is usually 1 to 120 seconds.
- a drying treatment is usually performed to obtain a polarizing film.
- the drying process is preferably performed using, for example, a hot air dryer or a far infrared heater.
- the temperature for the drying treatment is usually 30 to 100 ° C., preferably 50 to 80 ° C.
- the drying treatment time is usually 60 to 600 seconds, preferably 120 to 600 seconds.
- the polyvinyl alcohol resin film is subjected to uniaxial stretching, dyeing with a dichroic dye, boric acid treatment and water washing treatment to obtain a polarizing film.
- the thickness of this polarizing film is usually in the range of 5 to 50 ⁇ m.
- a transparent film is bonded to one side or both sides of the polarizing film described above.
- the material constituting the transparent film include cycloolefin resins, cellulose acetate resins, polyethylene terephthalate, polyethylene naphthalate, polyester resins such as polybutylene terephthalate, polycarbonate resins, acrylic resins, and polypropylene. Examples thereof include film materials that have been widely used in the field.
- each transparent film may be the same or a different type of film.
- the cycloolefin resin is a thermoplastic resin (also referred to as a thermoplastic cycloolefin resin) having a monomer unit made of a cyclic olefin (cycloolefin), such as norbornene or a polycyclic norbornene monomer.
- the cycloolefin-based resin may be a hydrogenated product of the above-mentioned cycloolefin ring-opening polymer or a ring-opening copolymer using two or more cycloolefins, and has a cycloolefin, a chain olefin, and a vinyl group.
- An addition polymer with an aromatic compound or the like may be used. Those having a polar group introduced are also effective.
- examples of the chain olefin include ethylene and propylene
- examples of the aromatic compound having a vinyl group include Examples include styrene, ⁇ -methylstyrene, and nuclear alkyl-substituted styrene.
- the monomer unit composed of cycloolefin may be 50 mol% or less (preferably 15 to 50 mol%).
- the amount of the monomer unit composed of cycloolefin can be made relatively small as described above.
- the unit of monomer composed of a chain olefin is usually 5 to 80 mol%
- the unit of monomer composed of an aromatic compound having a vinyl group is usually 5 to 80 mol%.
- Cycloolefin-based resins may be commercially available products such as Topas (manufactured by Ticona), Arton (manufactured by JSR), ZEONOR (manufactured by Nippon Zeon), ZEONEX (manufactured by Nippon Zeon ( Co., Ltd.), Apel (manufactured by Mitsui Chemicals, Inc.), Oxis (OXIS) (manufactured by Okura Kogyo Co., Ltd.) and the like can be suitably used.
- a known method such as a solvent casting method or a melt extrusion method is appropriately used.
- cycloolefin resin films such as Essina (manufactured by Sekisui Chemical Co., Ltd.), SCA40 (manufactured by Sekisui Chemical Co., Ltd.), Zeonoa Film (manufactured by Optes Co., Ltd.), etc. You may use goods.
- the cycloolefin resin film may be uniaxially stretched or biaxially stretched.
- Stretching is usually performed continuously while unwinding a film roll, and in a heating furnace, the roll traveling direction (film longitudinal direction), the direction perpendicular to the traveling direction (film width direction), or both Stretched.
- the temperature of the heating furnace a range from the vicinity of the glass transition temperature of the cycloolefin resin to the glass transition temperature + 100 ° C. is usually employed.
- the stretching ratio is usually 1.1 to 6 times, preferably 1.1 to 3.5 times.
- the cycloolefin-based resin film When the cycloolefin-based resin film is in a roll-wound state, the films tend to adhere to each other and easily cause blocking. Therefore, the cycloolefin-based resin film is usually rolled after the protective film is bonded.
- the surface to be bonded to the polarizing film is subjected to surface treatment such as plasma treatment, corona treatment, ultraviolet irradiation treatment, flame (flame) treatment, and saponification treatment. Is preferred.
- plasma treatment that can be carried out relatively easily, particularly atmospheric pressure plasma treatment, and corona treatment are preferable.
- the cellulose acetate-based resin is a cellulose part or a completely esterified product, and examples thereof include a film made of cellulose acetate ester, propionate ester, butyrate ester, and mixed ester thereof. More specifically, a triacetyl cellulose film, a diacetyl cellulose film, a cellulose acetate propionate film, a cellulose acetate butyrate film, and the like can be given.
- a cellulose ester resin film As such a cellulose ester resin film, an appropriate commercially available product, for example, Fujitac TD80 (manufactured by Fuji Film Co., Ltd.), Fujitac TD80UF (manufactured by Fuji Film Co., Ltd.), Fujitac TD80UZ (manufactured by Fuji Film Co., Ltd.) KC8UX2M (manufactured by Konica Minolta Opto), KC8UY (manufactured by Konica Minolta Opto), Fujitac TD60UL (manufactured by Fuji Film), KC2UAW (manufactured by Konica Minolta Opto), KC4UYW (Konica Minolta Opto) KC6UAW (manufactured by Konica Minolta Opto Co., Ltd.) and the like can be suitably used.
- Fujitac TD80 manufactured by Fuji Film Co., Ltd
- a cellulose acetate-based resin film imparted with retardation characteristics is also preferably used.
- Commercially available cellulose acetate resin films with such retardation characteristics include WV BZ 438 (Fuji Film Co., Ltd.), KC4FR-1 (Konica Minolta Opto Co., Ltd.), and KC4CR-1 (Konica Minolta). Opt Co., Ltd.), KC4AR-1 (Konica Minolta Opto Co., Ltd.) and the like.
- Cellulose acetate is also called acetyl cellulose or cellulose acetate.
- the moisture content during the production of the polarizing plate is preferably closer to the equilibrium moisture content in the storage environment of the polarizing plate, for example, a clean room production line or a roll storage warehouse, and depends on the configuration of the laminated film. About 5%, more preferably 2.5% to 3.0%.
- the numerical value of the moisture content of this polarizing plate was measured by the dry weight method and is a change in weight after 105 ° C./120 minutes.
- the thickness of the transparent film used in the method for producing a polarizing plate of the present invention is preferably thin, but if it is too thin, the strength is lowered and the processability is poor. On the other hand, when it is too thick, problems such as a decrease in transparency and a longer curing time after lamination occur. Therefore, a suitable thickness of the transparent film is, for example, 5 to 200 ⁇ m, preferably 10 to 150 ⁇ m, more preferably 10 to 100 ⁇ m.
- the polarizing film and / or the transparent film may be subjected to corona treatment, flame treatment, plasma treatment, ultraviolet treatment, primer coating treatment, saponification treatment, etc.
- a surface treatment may be applied.
- the transparent film may be subjected to surface treatments such as anti-glare treatment, anti-reflection treatment, hard coat treatment, antistatic treatment, and antifouling treatment individually or in combination of two or more.
- the transparent film and / or the transparent film surface protective layer may contain a UV absorber such as a benzophenone compound or a benzotriazole compound, or a plasticizer such as a phenyl phosphate compound or a phthalate compound.
- optical functions such as functions as a retardation film, function as a brightness enhancement film, function as a reflection film, function as a transflective film, function as a diffusion film, function as an optical compensation film, etc.
- a function for example, by laminating an optical functional film such as a retardation film, a brightness enhancement film, a reflection film, a transflective film, a diffusion film, and an optical compensation film on the surface of the transparent film, such a function is achieved.
- the transparent film itself can be given such a function.
- the transparent film may have a plurality of functions such as a diffusion film having the function of a brightness enhancement film.
- the above-mentioned transparent film is subjected to a stretching process described in Japanese Patent No. 2841377, Japanese Patent No. 3094113, or the like, or a process described in Japanese Patent No. 3168850 can be used as a retardation film.
- the function of can be provided.
- the retardation characteristics of the retardation film can be appropriately selected, for example, such that the front retardation value is in the range of 5 to 100 nm and the thickness direction retardation value is in the range of 40 to 300 nm.
- two or more layers having different central wavelengths of selective reflection are formed in the transparent film by forming micropores by a method as described in Japanese Patent Application Laid-Open Nos. 2002-169025 and 2003-29030. By superimposing these cholesteric liquid crystal layers, a function as a brightness enhancement film can be imparted.
- a function as a reflective film or a transflective film can be imparted.
- a function as a diffusion film can be imparted.
- the function as an optical compensation film can be provided by coating and aligning liquid crystalline compounds, such as a discotic liquid crystalline compound, on said transparent film.
- you may make the transparent film contain the compound which expresses retardation.
- various optical functional films may be directly bonded to the polarizing film using an appropriate adhesive.
- optical functional films examples include brightness enhancement films such as DBEF (manufactured by 3M, available from Sumitomo 3M Co., Ltd. in Japan), and viewing angle improvements such as WV film (manufactured by Fuji Film Co., Ltd.).
- Film, Arton Film (manufactured by JSR Corporation), Zeonoor Film (manufactured by Optes Corporation), Essina (manufactured by Sekisui Chemical Co., Ltd.), VA-TAC (manufactured by Comic Minolta Opto Corporation), Sumikalite (Sumitomo) (Chemical Co., Ltd.) etc. can be mentioned.
- the polarizing film and the transparent film are bonded via an active energy ray curable adhesive.
- the active energy ray-curable adhesive include an adhesive made of an epoxy resin composition containing an epoxy resin that is cured by irradiation with active energy rays from the viewpoint of weather resistance, refractive index, cationic polymerization, and the like.
- the present invention is not limited to this, and various active energy ray-curable adhesives (organic solvent adhesives, hot melt adhesives, solventless adhesives) that have been used in the manufacture of polarizing plates.
- an adhesive made of an acrylic resin composition such as acrylamide, acrylate, urethane acrylate, or epoxy acrylate can be used.
- An epoxy resin means a compound having two or more epoxy groups in a molecule.
- the epoxy resin contained in the curable epoxy resin composition that is an adhesive is an epoxy resin that does not contain an aromatic ring in the molecule (see, for example, Patent Document 1). It is preferable that Examples of such epoxy resins include hydrogenated epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, and the like.
- the hydrogenated epoxy resin is obtained by a method of glycidyl etherifying a nuclear hydrogenated polyhydroxy compound obtained by selectively subjecting a polyhydroxy compound, which is a raw material of an aromatic epoxy resin, to a nuclear hydrogenation reaction under pressure in the presence of a catalyst. Obtainable.
- aromatic epoxy resins include bisphenol-type epoxy resins such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and bisphenol S diglycidyl ether; phenol novolac epoxy resins, cresol novolac epoxy resins, and hydroxy Examples include novolak-type epoxy resins such as benzaldehyde phenol novolac epoxy resins; glycidyl ethers of tetrahydroxyphenylmethane, glycidyl ethers of tetrahydroxybenzophenone, and polyfunctional epoxy resins such as epoxidized polyvinylphenol.
- hydrogenated epoxy resins hydrogenated bisphenol A glycidyl ether is preferred.
- the alicyclic epoxy resin means an epoxy resin having at least one epoxy group bonded to the alicyclic ring in the molecule.
- the “epoxy group bonded to an alicyclic ring” means a bridged oxygen atom —O— in the structure represented by the following formula. In the following formula, m is an integer of 2 to 5.
- a compound in which a group 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 resin.
- 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 alicyclic epoxy resin used preferably below is specifically illustrated, it is not limited to these compounds.
- R 1 and R 2 each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).
- R 3 and R 4 each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms, and n represents an integer of 2 to 20).
- R 5 and R 6 independently of each other represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms, and p represents an integer of 2 to 20).
- R 7 and R 8 independently of each other represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms, and q represents an integer of 2 to 10).
- R 9 and R 10 independently of each other represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms, and r represents an integer of 2 to 20).
- R 11 and R 12 each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).
- R 13 and R 14 each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).
- R 16 and R 17 each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).
- R 18 represents a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms.
- the following alicyclic epoxy resins are commercially available or their analogs, and are more preferably used because they are relatively easy to obtain.
- examples of the aliphatic epoxy resin 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 Diglycidyl ether of glycol; Polyether of polyether polyol obtained by adding one or more alkylene oxides (ethylene oxide or propylene oxide) to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin A glycidyl ether etc. are mentioned.
- the epoxy resin which comprises the adhesive agent which consists of an epoxy-type resin composition may be used individually by 1 type, and may use 2 or more types together.
- the epoxy equivalent of the epoxy resin used in this composition 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 composite polarizing plate after curing may be reduced, or the adhesive strength may be reduced.
- it exceeds 3,000 g / equivalent the compatibility with other components contained in the adhesive may be lowered.
- cationic polymerization is preferably used as a curing reaction of the epoxy resin from the viewpoint of reactivity. Therefore, it is preferable to mix
- 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, and electron beams, and initiates an epoxy group polymerization reaction.
- a cationic polymerization initiator that generates a cationic species or a Lewis acid by irradiation of active energy rays and initiates a polymerization reaction of an epoxy group is referred to as a “photo cationic polymerization initiator”.
- the method of curing the adhesive by irradiating with active energy rays using a cationic photopolymerization initiator enables curing at room temperature, reducing the need to consider the distortion due to heat resistance or expansion of the polarizing film, and between the films Is advantageous in that it can be bonded well.
- the photocationic polymerization initiator acts catalytically by light, it is excellent in storage stability and workability even when mixed with an epoxy resin.
- photocationic polymerization initiator examples include aromatic diazonium salts; onium salts such as aromatic iodonium salts and aromatic sulfonium salts; iron-allene complexes and the like.
- aromatic diazonium salt examples include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, benzenediazonium hexafluoroborate, and the like.
- aromatic iodonium salt examples include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and the like.
- aromatic sulfonium salt examples include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4′-bis (diphenylsulfonio) diphenyl sulfide bis ( Hexafluorophosphate), 4,4′-bis [di ( ⁇ -hydroxyethoxy) phenylsulfonio] diphenyl sulfide, bis (hexafluoroantimonate), 4,4′-bis [di ( ⁇ -hydroxyethoxy) phenylsulfonio ] Diphenyl sulfide bis (hexafluorophosphate), 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluor
- iron-allene complex examples include xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, xylene-cyclopentadienyl iron (II). -Tris (trifluoromethylsulfonyl) methanide and the like.
- photocationic polymerization initiators can be easily obtained.
- “Kayarad PCI-220” and “Kayarad PCI-620” Nippon Kayaku Co., Ltd. )
- “UVI-6990” manufactured by Union Carbide
- “Adekaoptomer SP-150” and “Adekaoptomer SP-170” manufactured by ADEKA Corporation
- “CI-5102”, “ “CIT-1370”, “CIT-1682”, “CIP-1866S”, “CIP-2048S” and “CIP-2064S” aboveve, Nippon Soda Co., Ltd.
- the photocationic polymerization initiator may be used alone or in combination of two or more.
- aromatic sulfonium salts are preferably used because they have ultraviolet absorption characteristics even in a wavelength region of 300 nm or more, and thus can provide a cured product having excellent curability and good mechanical strength and adhesive strength.
- 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 based on 100 parts by weight of the epoxy resin.
- the blending amount of the cationic photopolymerization initiator is less than 0.5 parts by weight with respect to 100 parts by weight of the epoxy resin, curing becomes insufficient, and mechanical strength and adhesive strength tend to decrease.
- the compounding quantity of a photocationic polymerization initiator exceeds 20 weight part with respect to 100 weight part of epoxy resins, the hygroscopic property of hardened
- the curable epoxy resin composition may further contain a photosensitizer as necessary.
- a photosensitizer By using a photosensitizer, the reactivity of cationic polymerization 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.
- photosensitizers include, for example, benzoin derivatives such as benzoin methyl ether, benzoin isopropyl ether, and ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, o Benzophenone derivatives such as methyl benzoylbenzoate, 4,4′-bis (dimethylamino) benzophenone, and 4,4′-bis (diethylamino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-isopropylthioxanthone; 2 Anthraquinone derivatives such as chloroanthraquinone and 2-methylanthraquinone; acridone derivatives such as N-methylacridone and N-butylacridone; other ⁇ , ⁇ -diethoxyacetophenone, ben Examples include zil, fluorenone
- the epoxy resin contained in the adhesive is cured by photocationic polymerization, but may be cured by both photocationic polymerization and thermal cationic polymerization. In the latter case, it is preferable to use a photocationic polymerization initiator and a thermal cationic polymerization initiator in combination.
- thermal cationic polymerization initiator examples include benzylsulfonium salt, thiophenium salt, thiolanium salt, benzylammonium, pyridinium salt, hydrazinium salt, carboxylic acid ester, sulfonic acid ester, and amine imide.
- thermal cationic polymerization initiators can be easily obtained as commercial products. For example, “Adeka Opton CP77” and “Adeka Opton CP66” (manufactured by ADEKA Corporation), “CI” are available under the trade names.
- the active energy ray-curable adhesive may further contain a compound that promotes cationic polymerization, such as oxetanes and polyols.
- Oxetanes are compounds having a 4-membered ring ether in the molecule, such as 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3 -Ethyl-3- (phenoxymethyl) oxetane, di [(3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, phenol novolac oxetane and the like. These oxetanes can be easily obtained as commercial products.
- polyols those having no acidic groups other than phenolic hydroxyl groups are preferable.
- polyol compounds having no functional groups other than hydroxyl groups polyester polyol compounds, polycaprolactone polyol compounds, polyol compounds having phenolic hydroxyl groups, polycarbonates A polyol etc. can be mentioned.
- the molecular weight of these polyols is usually 48 or more, preferably 62 or more, more preferably 100 or more, and preferably 1,000 or less.
- These polyols are usually contained in the curable epoxy resin composition in a proportion of 50% by weight or less, preferably 30% by weight or less.
- Active energy ray-curable adhesives include ion trapping agents, antioxidants, chain transfer agents, tackifiers, thermoplastic resins, fillers, flow regulators, leveling agents, plasticizers, antifoaming agents, etc. Additives can be blended.
- the ion trapping agent include powdered bismuth-based, antimony-based, magnesium-based, aluminum-based, calcium-based, titanium-based, and mixed inorganic compounds.
- the antioxidant is a hindered phenol-based antioxidant. Etc.
- Active energy ray-curable adhesives can be used as solventless adhesives that are substantially free of solvent components, but each coating method has an optimum viscosity range, A solvent may be included. It is preferable to use a solvent that dissolves the epoxy resin composition and the like well without degrading the optical performance of the polarizing film.
- a solvent that dissolves the epoxy resin composition and the like well without degrading the optical performance of the polarizing film.
- organic solvents such as The viscosity of the active energy ray-curable adhesive used in the present invention is, for example, in the range of about 5 to 1000 mPa ⁇ s, preferably 10 to 200 mPa ⁇ s, and more preferably 20 to 100 mPa ⁇ s.
- FIG. 1 is a schematic view showing an embodiment of a production apparatus used in the method for producing a polarizing plate of the present invention.
- the polarizing plate manufacturing apparatus shown in FIG. 1 bonds adhesive coating apparatuses 11 and 12 for applying an adhesive to one side of transparent films 2 and 3, transparent films 2 and 3, and polarizing film 1. Bonding rolls (nip rolls) 51 and 52 for obtaining the laminated body 4, the rotating roll 13 in close contact with the laminated body 4, and the first activity installed at a position facing the outer peripheral surface of the rotating roll 13. Energy beam irradiation devices 31, 32, second active energy beam irradiation devices 16 to 18 installed on the downstream side in the transport direction, and a transport nip roll 19 are sequentially provided along the transport direction.
- an active energy ray-curable adhesive is applied to one side of the transparent films 2 and 3 that are continuously drawn out from a rolled state (adhesive application). Process).
- coated on both surfaces of the polarizing film 1 continuously drawn out from the state wound by roll shape via an adhesive agent is conveyed.
- Transparent film 1 by pressing at least one bonding roll in the direction of the other bonding roll and applying pressure to the laminate while sandwiched between a pair of bonding rolls 51 and 52 rotating in the direction.
- polarizing films 2 and 3 are bonded together to form a laminate 4 (bonding step).
- the active energy rays are irradiated from the first active energy ray irradiation devices 31, 32 toward the outer peripheral surface of the rotating roll 13. Then, the adhesive is polymerized and cured (first active energy ray irradiation step).
- the second active energy ray irradiating devices 16 to 18 arranged on the downstream side in the transport direction are devices for completely polymerizing and curing the adhesive (second active energy ray irradiating step). Can be added or omitted.
- the laminate 4 passes through the conveyance nip roll 19 and is wound around the winding roll 20 as a polarizing plate.
- the method for applying the adhesive to the transparent films 2 and 3 is not particularly limited, and various coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used. Of these, taking into consideration the thin film coating, the degree of freedom of the pass line, the wideness, etc., gravure rolls are preferable as the adhesive coating apparatuses 11 and 12.
- the thickness of the applied adhesive is preferably about 0.1 to 10 ⁇ m, more preferably 0.2 ⁇ m to 4 ⁇ m.
- the coating thickness of the adhesive is adjusted by the draw ratio, which is the speed ratio of the gravure roll to the line speed of the transparent film. Generally, by adjusting the draw ratio (gravure roll speed / line speed) to 0.5 to 10, the coating thickness of the adhesive can be adjusted to about 0.1 to 10 ⁇ m.
- the line speed of the transparent films 2 and 3 is set to 10 to 100 m / min
- the gravure roll is rotated in the direction opposite to the conveying direction of the transparent films 2 and 3
- the speed of the gravure roll is set to 5 to 1000 m / min.
- the adhesive is usually at a predetermined temperature ⁇ 5 ° C. within the range of 15 to 40 ° C. (for example, 30 ° C. ⁇ 5 ° C. when the predetermined temperature is 30 ° C.), preferably ⁇ 3 ° C., more preferably It is applied in an environment adjusted to ⁇ 1 ° C.
- the transparent films 2 and 3 to which the adhesive is applied by the above-described steps are laminated on both surfaces of the polarizing film 1 that is continuously drawn out from the state wound in a roll shape.
- the bonding roll 51 is pressed in the direction of the bonding roll 52 so that the polarizing film 1 and the transparent film are pressed. 2 and 3 are bonded together to form a laminate 4.
- the adhesive is uniformly applied to one side of the transparent films 2, 3, and the polarizing film 1 is overlapped on the surface of the transparent films 2, 3 applied with the bonding rolls 51, 52.
- the adhesive agent is apply
- the material of the bonding rolls 51 and 52 includes a metal roll and a rubber roll whose surface is made of rubber. At least one of the pair of bonding rolls 51 and 52 is a rubber roll that has a surface made of rubber and is rotationally driven. In the manufacturing apparatus shown in FIG. 1, for example, the lower roll 52 can be a rubber roll. Usually, the rotational speed of the rubber roll that is rotationally driven matches the line speed of the laminate that passes between the pair of bonding rolls. As the other laminating roll, a metal roll is preferably used, which may follow the movement of the line of the laminate or be rotationally driven. The rotation speed of the rubber roll is, for example, 10 to 50 m / min.
- the material of the rubber roll is not particularly limited, and examples thereof include EPDM, NBR, urethane, titan, and silicon.
- the hardness of the rubber roll is not particularly limited, but is usually 60 to 100 °, preferably 85 to 95 °.
- the hardness of a rubber roll can be measured with the hardness meter based on JISK6253.
- a rubber hardness meter “Type-A” manufactured by Asuka Corporation is used. Specifically, the resistance of the surface of the rubber roll when the surface is pressed with a stick or the like is measured with a hardness meter.
- the instantaneous pressure in a two-sheet type press case (for ultra-low pressure) made of Fuji Film is preferably 0.5 to 3.0 MPa, more preferably 0.7 ⁇ 2.3 MPa.
- the diameter of the bonding rolls 51 and 52 is not particularly limited, but is usually 50 to 400 mm. Moreover, the diameter of the two (pair) bonding rolls 51 and 52 may be the same, and may differ.
- the rotating roll 13 forms a convex curved surface having a mirror-finished outer peripheral surface, and the laminate 4 is conveyed while closely contacting the surface.
- the adhesive is polymerized and cured by the active energy ray irradiation devices 31 and 32.
- the diameter of the rotating roll 13 is not particularly limited when the adhesive is polymerized and cured and the laminate 4 is sufficiently adhered.
- the rotating roll 13 shall be driven at a rotational speed faster than the rotational speed of the rubber roll that is rotationally driven among the pair of bonding rolls 51 and 52.
- the rotational speed of the rotary roll 13 is preferably 100.1 or more and 102.0 or less, more preferably 100. 1 to 101.5. If it is less than 100.1, wave curling is likely to occur in the laminate. On the other hand, if it exceeds 102.0, there is a possibility that the film and the roll slip to cause scratches.
- the rotation speed of the rotary roll 13 is, for example, 10 to 50 m / min.
- the rotational speed of the rotary roll 13 does not need to be controlled at a constant level.
- the rotational speed of the rotary roll 13 may be appropriately controlled while confirming the state of occurrence of corrugated swell according to the type of film and the slipperiness of the roll surface. .
- the rotating roll 13 may act as a cooling roll for radiating heat generated in the laminated body 4 at the time of polymerization and curing by irradiation with active energy rays.
- the surface temperature of the cooling roll is preferably set to 4 to 30 ° C.
- the light source used for polymerizing and curing the adhesive by irradiation with active energy rays is not particularly limited, but is preferably a light source having an emission distribution at a wavelength of 400 nm or less.
- Examples of such a light source include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, and a metal halide lamp.
- the active energy ray irradiation in the first active energy ray irradiating step is preferably performed in a plurality of times.
- FIG. 1 shows a case where irradiation of active energy rays is performed twice, that is, two light sources (active energy ray irradiation devices 31 and 32) are arranged along the transport direction of the laminate. .
- the intensity of light irradiation to the active energy ray-curable adhesive each time is determined for each composition of the adhesive and is not particularly limited, but is preferably 10 to 5000 mW / cm 2 .
- the reaction time becomes too long, and when it exceeds 5000 mW / cm 2 , adhesion occurs due to heat radiated from the light source and heat generated during polymerization of the composition.
- yellowing of the epoxy resin composition as a constituent material of the agent or deterioration of the polarizing film may occur.
- the irradiation intensity is preferably an intensity in a wavelength region effective for activation of the photocationic polymerization initiator, more preferably an intensity in a wavelength region of a wavelength of 400 nm or less, and further preferably a wavelength region of a wavelength of 280 to 320 nm. It is the intensity in (UVB).
- the irradiation time is 0.1 while applying a tension of 100 to 800 N / m in the longitudinal direction (transport direction) to the laminate 4. It is preferable that the laminate 4 is conveyed at a line speed that is at least 2 seconds.
- Integrated light intensity in the entire process, in conjunction with the first active energy ray irradiation process is 10 mJ / cm 2 or more is preferably set particularly so that 10 ⁇ 5,000mJ / cm 2.
- active species derived from the initiator are not sufficiently generated, and the adhesive is not sufficiently cured.
- the integrated light quantity exceeds 5,000 mJ / cm 2 , the irradiation time becomes very long, which is disadvantageous for improving productivity.
- the integrated light amount in which wavelength region (UVA (320 to 390 nm), UVB (280 to 320 nm), etc.) is required differs depending on the combination of the film to be used and the type of adhesive.
- the ratio at which the active energy ray-curable resin is cured, that is, the reaction rate is preferably 90% or more, more preferably 95% or more.
- it is 30 N / cm 2 to 120 N / cm 2 . If it is less than 30 N / cm 2, it is not preferable because winding deviation occurs when a long roll is transferred. When it is larger than 150 N / cm 2 , the tightness of the winding is strong and the tarmi is likely to occur.
- the length of the polarizing plate wound around the core is not particularly limited, but is preferably 100 m or more and 4000 m or less.
- the diameter of the cylindrical core is preferably 6 inches to 12 inches.
- the core diameter is preferably as large as possible, and more preferably 11 inches or 12 inches, but if it is too large, it becomes difficult to transport and store.
- the material of the cylindrical core is not particularly limited as long as it can be used in a clean room and does not easily generate dust, and can secure an appropriate strength so that a wide-width polarizing plate can be wound.
- FRP glass fiber reinforced plastic
- Etc. can be selected.
- Example 1 Preparation of polarizing film
- a long polyvinyl alcohol film “OPL film M-7500 manufactured by Nippon Gosei Co., Ltd.” having a polymerization degree of 2400, a saponification degree of 99.9 mol%, a thickness of 75 ⁇ m, and a width of 3000 mm was used. Stretching was performed with a difference in peripheral speed between the driving nip rolls before and after the treatment tank.
- the film was sufficiently swollen by immersing it in a swelling tank containing pure water at 30 ° C. for 80 seconds while keeping the tension state of the film so that the raw film did not loosen.
- the inlet / outlet roll speed ratio accompanying the swelling in the swelling tank was 1.2.
- After draining with a nip roll it was immersed in a water immersion tank containing 30 ° C. pure water for 160 seconds.
- the draw ratio in the machine direction in this tank was 1.09 times.
- uniaxial stretching was performed at a draw ratio of about 1.5 times while being immersed in a dyeing tank containing an aqueous solution of 0.02 / 2.0 / 100 in weight ratio of iodine / potassium iodide / water. Then, while being immersed in a boric acid bath containing an aqueous solution of potassium iodide / boric acid / water at a weight ratio of 12 / 3.7 / 100 at 55.5 ° C. for 130 seconds, the cumulative draw ratio from the original fabric is 5 Uniaxial stretching was performed until it became 7 times. Then, it was immersed at 40 ° C. for 60 seconds in a boric acid bath containing an aqueous solution of potassium iodide / boric acid / water at a weight ratio of 9 / 2.4 / 100.
- acetic acid cellulose resin film “KC4CR-1 (manufactured by Konica Minolta Opto Co., Ltd.)” having a retardation characteristic of 40 ⁇ m in thickness and a triacetyl cellulose film “KC8UX2MW” (Konica Minolta, Inc.) having a thickness of 80 ⁇ m are used. Prepared).
- a polarizing plate was produced by the apparatus shown in FIG. 1 using the polarizing film and the transparent film prepared as described above.
- an epoxy resin composition “KR series” (manufactured by ADEKA), which is an ultraviolet curable adhesive, is applied to one side of an acetic acid cellulose resin film “KC4CR-1” to which the above retardation characteristics are imparted. Coating was performed using an apparatus (microchamber doctor: manufactured by Fuji Machine Co., Ltd.).
- an epoxy resin composition “KR series” manufactured by ADEKA
- ADEKA an ultraviolet curable adhesive
- the line speed of the polarizing film laminate in the adhesive coating apparatus is set to 25 m / min
- the thickness of the adhesive layer on the cellulose acetate-based resin film “KC4CR-1” is set to about 4.0 ⁇ m
- triacetyl cellulose is used.
- the thickness of the adhesive layer on the film “KC8UX2MW” was set to about 3.3 ⁇ m (total of about 7.3 ⁇ m).
- the polarizing film on which the above two types of transparent films are bonded is transferred at a line speed of 25 m / min while applying a tension of 600 N / m in the longitudinal direction and in close contact with the cooling roll.
- Two metal halide lamps manufactured by GS-YUSAS
- the first active energy ray irradiation process is performed by passing through the ultraviolet rays irradiated from one lamp with a power of 130 W / cm, and then three electrodeless D bulb lamps ("Light Hammer” manufactured by Fusion) 10 ", the amount of electric power of one lamp (216 mW / cm) was passed through the ultraviolet rays irradiated to perform the second active energy ray irradiation step, and a polarizing plate was produced.
- the above three electrodeless D bulb lamps were composed of 6 units of electrodeless D bulb lamps arranged in the width direction of the film and arranged in three rows in the longitudinal direction of the film.
- the triacetyl cellulose film “KC8UX2MW” bonded to the polarizing film is brought into contact with the outer peripheral surface of the cooling roll set at 23 ° C., and the cellulose acetate resin film “KC4CR-1” side is contacted. Irradiated with ultraviolet rays.
- the rotation speed of the rubber roll driven and rotated in the bonding step was 25.00 m / min, and the rotation speed of the cooling roll was 25.23 m / min. That is, assuming that the rotation speed of the rubber roll is 100, the rotation speed of the cooling roll was 100.9.
- the integrated light amount of the first active energy ray irradiation step and the second active energy ray irradiation step was 468 mJ / cm 2 .
- the integrated light amount here is based on a value measured by a light irradiation intensity measuring device (UV Power Pack II manufactured by FusionUV) in a wavelength region (UVB) of wavelengths 280 to 320 nm.
- Example 2 Example 1 except that a 60 ⁇ m-thick cycloolefin resin film “ZEONOR” (manufactured by Nippon Zeon Co., Ltd.) was used instead of the cellulose acetate resin film “KC4CR-1” as the transparent film.
- a polarizing plate of Example 2 was produced in the same manner as described above.
- Example 3 As a transparent film, instead of the cellulose acetate-based resin film “KC4CR-1”, a cycloolefin-based resin film “ZEONOR” (manufactured by Nippon Zeon Co., Ltd.) having a thickness of 25 ⁇ m is applied to the triacetyl cellulose film “KC8UX2MW”. Instead, a triacetyl cellulose film “K2UAW” (manufactured by Konica Minolta Co., Ltd.) having a thickness of 25 ⁇ m is used, the rotational speed of the rubber roll driven and rotated in the bonding step is 25.00 m / min, and the rotational speed of the cooling roll is 25.08 m. / Min. That is, assuming that the rotation speed of the rubber roll is 100, the rotation speed of the cooling roll was 100.3. Except for these points, the polarizing plate of Example 3 was produced in the same manner as Example 1.
- Example 4 As a transparent film, instead of the cellulose acetate-based resin film “KC4CR-1”, a cycloolefin-based resin film “ZEONOR” (manufactured by ZEON Corporation) having a thickness of 50 ⁇ m is applied to the triacetyl cellulose film “KC8UX2MW”. Instead, a triacetyl cellulose film “TD60UL” (manufactured by Fuji Film Co., Ltd.) having a thickness of 60 ⁇ m is used, the rotational speed of the rubber roll driven and rotated in the bonding step is 25.00 m / min, and the rotational speed of the cooling roll is 25. .28 m / min. That is, assuming that the rotation speed of the rubber roll is 100, the rotation speed of the cooling roll was 101.1. Except for these points, the polarizing plate of Example 4 was produced in the same manner as Example 1.
- Example 5 A polarizing plate was produced in the same manner as in Example 1 except that the rotation speed of the cooling roll was set to 102.2 with respect to the rotation speed 100 of the rubber roll driven and rotated in the bonding step.
- the polarizing plate of the present invention can be effectively applied to various display devices including liquid crystal display devices.
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Abstract
Description
(偏光フィルム)
本発明の偏光板の製造方法に用いられる偏光フィルムは、具体的には、一軸延伸したポリビニルアルコール系樹脂フィルムに二色性色素を吸着配向させたものである。ポリビニルアルコール系樹脂は、ポリビニル酢酸系樹脂をケン化することにより得られる。ポリ酢酸ビニル系樹脂としては、酢酸ビニルの単独重合体であるポリ酢酸ビニルの他に、酢酸ビニルとこれに共重合可能な他の単量体との共重合体(例えば、エチレン-酢酸ビニル共重合体)などが挙げられる。酢酸ビニルと共重合可能な他の単量体としては、他に、不飽和カルボン酸類、オレフィン類、ビニルエーテル類、不飽和スルホン酸類、アンモニウム基を有するアクリルアミド類などが挙げられる。ポリビニルアルコール系樹脂のケン化度は、85モル%以上、好ましくは90モル%以上、より好ましくは98~100モル%である。ポリビニルアルコール系樹脂の平均重合度は、通常1000~10000、好ましくは1500~5000である。これらのポリビニルアルコール系樹脂は、変性されていてもよく、たとえばアルデヒド類で変性されたポリビニルホルマール、ポリビニルアセタール、ポリビニルブチラールなども使用し得る。
本発明において、上述した偏光フィルムの片面または両面には透明フィルムが貼合される。透明フィルムを構成する材料としては、たとえば、シクロオレフィン系樹脂、酢酸セルロース系樹脂、ポリエチレンテレフタレートやポリエチレンナフタレート、ポリブチレンテレフタレートのようなポリエステル系樹脂、ポリカーボネート系樹脂、アクリル系樹脂、ポリプロピレンなど、当分野において従来より広く用いられてきているフィルム材料を挙げることができる。偏光フィルムの両面に透明フィルムが貼合される場合、各々の透明フィルムは同じものであってもよく、異なる種類のフィルムであってもよい。
偏光フィルムと透明フィルムとは、活性エネルギー線硬化型の接着剤を介して貼合される。活性エネルギー線硬化型の接着剤としては、耐候性や屈折率、カチオン重合性などの観点から、活性エネルギー線の照射により硬化するエポキシ樹脂を含有するエポキシ系樹脂組成物からなる接着剤が挙げられる。ただし、これに限定されるものではなく、従来から偏光板の製造に使用されている各種の活性エネルギー線硬化型の接着剤(有機溶剤系接着剤、ホットメルト系接着剤、無溶剤型接着剤など)、たとえばアクリルアミド、アクリレート、ウレタンアクリレート、エポキシアクリレートなどのアクリル系樹脂組成物からなる接着剤などが採用可能である。
(i)次式(IX)で示されるエポキシシクロペンチルエーテル類:
上記例示した脂環式エポキシ樹脂の中でも、次の脂環式エポキシ樹脂は、市販されているか、またはその類似物であって、入手が比較的容易である等の理由からより好ましく用いられる。
(B)4-メチル-7-オキサビシクロ[4.1.0]ヘプタン-3-カルボン酸と(4-メチル-7-オキサ-ビシクロ[4.1.0]ヘプト-3-イル)メタノールとのエステル化物[式(I)において、R1=4-CH3、R2=4-CH3の化合物]、
(C)7-オキサビシクロ[4.1.0]ヘプタン-3-カルボン酸と1,2-エタンジオールとのエステル化物[式(II)において、R3=R4=H、n=2の化合物]、
(D)(7-オキサビシクロ[4.1.0]ヘプト-3-イル)メタノールとアジピン酸とのエステル化物[式(III)において、R5=R6=H、p=4の化合物]、
(E)(4-メチル-7-オキサビシクロ[4.1.0]ヘプト-3-イル)メタノールとアジピン酸とのエステル化物[式(III)において、R5=4-CH3、R6=4-CH3、p=4の化合物]、
(F)(7-オキサビシクロ[4.1.0]ヘプト-3-イル)メタノールと1,2-エタンジオールとのエーテル化物[式(V)において、R9=R10=H、r=2の化合物]。
次に図面を参照しながら本発明の偏光板の製造装置および製造方法を説明する。図1は本発明の偏光板の製造方法に用いられる製造装置の一実施形態を示す概略図である。
透明フィルム2,3への接着剤の塗工方法は特に限定されないが、例えば、ドクターブレード、ワイヤーバー、ダイコーター、カンマコーター、グラビアコーターなど、種々の塗工方式が利用できる。このうち、薄膜塗工、パスラインの自由度、幅広への対応などを考慮すると、接着剤塗工装置11,12としてはグラビアロールが好ましい。
本工程では、ロール状に巻回された状態から連続的に繰り出された偏光フィルム1の両面に、上記工程により接着剤が塗布された透明フィルム2,3が接着剤を介して積層される。この積層体を、搬送方向に回転する一対の貼合ロール51,52の間に挟んだ状態で、例えば貼合ロール51を貼合ロール52の方向に押圧することで、偏光フィルム1と透明フィルム2,3とが貼合され、積層体4が形成される。この際、貼合ロールの押圧方向に垂直な面に対して±3°の範囲内の角度をなすように、好ましくは±1°の範囲内の角度をなすように、特に好ましくは押圧方向に垂直な面と重なるようにして偏光フィルムを貼合ロール間に搬送することが好ましい。このようにすることで、偏光フィルムと透明フィルムが貼合ロールの手前で接触して気泡が発生してしまうことがない。
回転ロール13は、外周面が鏡面仕上げされた凸曲面を構成しており、その表面に積層体4を密着させながら搬送し、その過程で活性エネルギー線照射装置31,32により接着剤を重合硬化させる。接着剤を重合硬化させ、積層体4を充分に密着させる上で、回転ロール13の直径は特に限定されない。回転ロール13は、一対の貼合ロール51,52の内、回転駆動されるゴムロールの回転速度より速い回転速度で駆動されるものとする。一対の貼合ロール51,52の内、回転駆動されるゴムロールの回転速度を100とすると、回転ロール13の回転速度は100.1以上かつ102.0以下であることが好ましく、より好ましくは100.1~101.5である。100.1未満であると、積層体にウェーブカールが発生しやすくなる。一方、102.0を超えると、フィルムとロールの間が滑ってすりキズなどが入る可能性がある。
活性エネルギー線照射装置31,32による活性エネルギー線の積算光量が不十分な場合は、さらに第2以降の活性エネルギー線照射装置16~18を設け、活性エネルギー線を追加照射させ、積層体4の接着剤の硬化を促進することが好ましい。第1の活性エネルギー線照射工程とあわせた全工程における積算光量が10mJ/cm2以上、特に10~5,000mJ/cm2となるように設定されることが好ましい。上記接着剤への積算光量が10mJ/cm2未満であると、開始剤由来の活性種の発生が十分でなく、接着剤の硬化が不十分となる。一方でその積算光量が5,000mJ/cm2を超えると、照射時間が非常に長くなり、生産性向上には不利なものとなる。この際、使用するフィルムや接着剤種の組み合わせなどによって、どの波長領域(UVA(320~390nm)やUVB(280~320nm)など)での積算光量が必要かは異なる。
積層体(偏光板)4を巻き取る張力を30N/cm2~150N/cm2とする。好ましくは、30N/cm2~120N/cm2である。30N/cm2未満では長尺のロール巻きを移送する際、巻きズレが起きるため好ましくない。150N/cm2より大きい場合は、巻き締まりが強く、タルミが発生し易い。
(偏光フィルムの作製)
ポリビニルアルコールの原反フィルムとしては、重合度2400、ケン化度99.9モル%、厚み75μm、幅3000mmの長尺のポリビニルアルコールフィルム「OPLフィルム M-7500(日本合成製)」を用いた。延伸は、処理槽前後の駆動ニップロールに周速差をつけて行った。
透明フィルムとして、厚さ40μmの位相差特性が付与された酢酸セルロール系樹脂フィルム「KC4CR-1(コニカミノルタオプト(株)製)」と、厚さ80μmのトリアセチルセルロースフィルム「KC8UX2MW」(コニカミノルタ社製)とを準備した。
上記のように作製された実施例1の偏光板について、蛍光灯を当てた反射検査にて外観を観察したところ、波板状うねりの発生は確認されなかった。
透明フィルムとして、酢酸セルロール系樹脂フィルム「KC4CR-1」に代えて厚さ60μmのシクロオレフィン系樹脂フィルム「ゼオノア(ZEONOR)」(日本ゼオン(株)製)を用いた点以外は、実施例1と同様に実施例2の偏光板を作製した。
上記のように作製された実施例2の偏光板について、実施例1と同様に外観を観察したところ、波板状うねりの発生は確認されなかった。
透明フィルムとして、酢酸セルロール系樹脂フィルム「KC4CR-1」に代えて厚さ25μmのシクロオレフィン系樹脂フィルム「ゼオノア(ZEONOR)」(日本ゼオン(株)製)を、トリアセチルセルロースフィルム「KC8UX2MW」に代えて厚さ25μmのトリアセチルセルロースフィルム「K2UAW」(コニカミノルタ社製)を用い、貼合工程において駆動回転されるゴムロールの回転速度を25.00m/分、冷却ロールの回転速度を25.08m/分とした。すなわち、ゴムロールの回転速度を100とすると、冷却ロールの回転速度は100.3であった。これらの点以外は、実施例1と同様に実施例3の偏光板を作製した。
上記のように作製された実施例3の偏光板について、実施例1と同様に外観を観察したところ、波板状うねりの発生は確認されなかった。
透明フィルムとして、酢酸セルロール系樹脂フィルム「KC4CR-1」に代えて厚さ50μmのシクロオレフィン系樹脂フィルム「ゼオノア(ZEONOR)」(日本ゼオン(株)製)を、トリアセチルセルロースフィルム「KC8UX2MW」に代えて厚さ60μmのトリアセチルセルロースフィルム「TD60UL」(富士フィルム(株)製)を用い、貼合工程において駆動回転されるゴムロールの回転速度を25.00m/分、冷却ロールの回転速度を25.28m/分とした。すなわち、ゴムロールの回転速度を100とすると、冷却ロールの回転速度は101.1であった。これらの点以外は、実施例1と同様に実施例4の偏光板を作製した。
上記のように作製された実施例4の偏光板について、実施例1と同様に外観を観察したところ、波板状うねりの発生は確認されなかった。
冷却ロールの回転速度を、貼合工程において駆動回転されるゴムロールの回転速度100に対して102.2としたこと以外は、実施例1と同様に偏光板を作製した。
上記のように作製された比較例2の偏光板について、外観を観察したところ、波板状うねりの発生は確認されなかったものの、擦り傷の発生が確認された。
冷却ロールの回転速度は、貼合工程において駆動回転されるゴムロールの回転速度100に対して100、すなわち同じ回転速度とした点以外は、実施例1と同様に比較例1の偏光板を作製した。
上記のように作製された比較例1の偏光板について、外観を観察したところ、波板状うねりの発生が確認された。
Claims (3)
- 偏光フィルムの片面または両面に透明フィルムが貼合されてなる偏光板の製造方法であって、
前記透明フィルムの片面または前記偏光フィルムの片面もしくは両面に、活性エネルギー線硬化型の接着剤を塗布する接着剤塗布工程と、
前記透明フィルムが前記偏光フィルムの片面または両面に前記接着剤を介して積層されてなる積層体を、搬送方向に回転する一対の貼合ロールの間に挟み前記積層体に圧力を加えることで前記透明フィルムと前記偏光フィルムとを貼合する貼合工程と、
前記積層体を搬送方向に回転する回転ロールに密着させた状態で搬送する間に、前記積層体に活性エネルギー線を照射して前記接着剤を硬化させる第1の活性エネルギー線照射工程とをこの順で備え、
前記一対の貼合ロールの少なくとも一方は、ゴムからなる表面を有し回転駆動されるゴムロールであり、
前記回転ロールの回転速度は、前記ゴムロールの回転速度より速い、偏光板の製造方法。 - 前記回転ロールは冷却ロールである、請求項1に記載の偏光板の製造方法。
- 前記回転ロールの回転速度は、前記ゴムロールの回転速度を100とすると100.1以上かつ102.0以下である、請求項1または2に記載の偏光板の製造方法。
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