WO2013061953A9 - Method for manufacturing polarizing plate, and apparatus for manufacturing polarizing plate - Google Patents
Method for manufacturing polarizing plate, and apparatus for manufacturing polarizing plate Download PDFInfo
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- WO2013061953A9 WO2013061953A9 PCT/JP2012/077332 JP2012077332W WO2013061953A9 WO 2013061953 A9 WO2013061953 A9 WO 2013061953A9 JP 2012077332 W JP2012077332 W JP 2012077332W WO 2013061953 A9 WO2013061953 A9 WO 2013061953A9
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- roll
- film
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- transparent film
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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
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
- JP 2004-245925 A JP 2009-134190 A JP 2011-95560 A
- the present invention has been made to solve the above-described problems, and is a method for producing a polarizing plate that can prevent dents and bubbles from occurring in a laminate (polarizing film and transparent film) constituting the polarizing plate. It is an object to provide a method and an apparatus for manufacturing a polarizing plate.
- 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, An adhesive coating step of applying an active energy ray-curable adhesive to one side or both sides of the transparent film or the polarizing film; At least one laminating roll in a state where the transparent film is sandwiched between a pair of laminating rolls rotating in the conveying direction, with a laminate in which the transparent film is laminated on one or both sides of the polarizing film via the adhesive.
- a bonding step of bonding the transparent film and the polarizing film By pressing in the direction of the other bonding roll, a bonding step of bonding the transparent film and the polarizing film; An active energy ray irradiation step of irradiating the laminate with an active energy ray to cure the adhesive; and It is a manufacturing method of a polarizing plate, wherein a dust removal roll for removing dust adhering to the surface of the bonding roll is provided so as to contact at least one of the pair of bonding rolls.
- a transfer adhesive roll for removing dust adhering to the surface of the dust removing roll is provided so as to be in contact with the dust removing roll.
- the present invention is a polarizing plate manufacturing apparatus in which a transparent film is bonded to one side or both sides of a polarizing film, An adhesive coating device for applying an active energy ray-curable adhesive on one side or both sides of the transparent film or the polarizing film; A pair of the transparent film and the polarizing film are bonded together by sandwiching the transparent film while transporting a laminate in which the transparent film is laminated on one or both sides of the polarizing film via the adhesive.
- the present invention also relates to a polarizing plate manufacturing apparatus, wherein at least one dust removing roll is provided so as to be in contact with at least one of the pair of bonding rolls.
- the manufacturing method of a polarizing plate and the manufacturing apparatus of a polarizing plate which can prevent that a dent and a bubble arise in the laminated body (polarizing film and transparent film) which comprise a polarizing plate are provided. it can.
- the polarizing film used in the polarizing plate of the present invention is obtained by adsorbing and orienting a dichroic dye on a uniaxially stretched polyvinyl alcohol 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 (vinylon VF-PS # 6000, made by Kuraray, vinylon VF-PE #).
- 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 an aqueous 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 80 ° 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.
- Transparent film In the present invention, a transparent film is bonded to one side or both sides of the polarizing film described above. When a transparent film is bonded on both surfaces of a polarizing film, each transparent film may be the same or a different type of film.
- Examples of the material constituting the transparent film include cycloolefin resins, cellulose acetate resins, polyethylene terephthalate, polyethylene naphthalate, polyester resins such as polybutylene terephthalate, polycarbonate resins, and polymethyl methacrylate (PMMA).
- Examples thereof include film materials that have been widely used in the art, such as acrylic resins and olefin resins such as polypropylene.
- 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.
- 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.
- surface modification treatment such as plasma treatment, corona treatment, ultraviolet irradiation treatment, flame (flame) treatment, and saponification treatment is applied to the surface to be bonded to the polarizing film. Is preferably performed.
- 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), KC4UYW (manufactured by Konica Minolta Opto), KC6UAW (Konica Minolta Opto) Etc.) can be used preferably.
- Fujitac TD80 manufactured by Fuji Film Co., Ltd.
- Fujitac TD80UF 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 polarizing plate of the present invention is preferably thin, but if it is too thin, the strength is lowered and the workability 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 modification treatment may be performed.
- 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 the form of removing one or more hydrogen atoms in (CH 2 ) m in the above formula 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 each independently 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-arene 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-arene 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 polarizing plate production apparatus of the present invention.
- the adhesive coating apparatuses 11 and 12 for applying an adhesive to one side of the transparent films 2 and 3, and the transparent films 2 and 3 and the polarizing film 1 are bonded.
- the roll 13 for bringing the transparent films 2 and 3 and the polarizing film 1 into close contact with each other in the laminate 4 and the outer peripheral surface of the roll 13
- First active energy beam irradiating devices 14 and 15 installed at opposite positions, second and subsequent active energy beam irradiating devices 16 to 18 installed further downstream in the transport direction, and a transport nip roll 19 Are provided in order 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 by an adhesive application device 11 or 12 (adhesive coating). Construction 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.
- the polarizing film 1 and the transparent films 2 and 3 are pressed by pressing at least one bonding roll in the direction of the other bonding roll while being sandwiched between a pair of bonding rolls 51 and 52 rotating in the direction. Are pasted together to form the laminate 4 (a pasting step).
- the active energy rays are irradiated from the first active energy ray irradiating devices 14, 15 toward the outer peripheral surface of the roll 13, and bonded.
- the agent is polymerized and cured (active energy ray irradiation step).
- the second and subsequent active energy ray irradiation devices 16 to 18 arranged on the downstream side in the transport direction are devices for completely polymerizing and curing the adhesive, and can be added or omitted as necessary.
- 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 present invention is characterized in that a dust removing roll for removing dust adhering to the surface of the bonding roll is provided so as to be in contact with at least one of the pair of bonding rolls 51 and 52.
- the dust removal roll is a roll having a mechanism for removing foreign matters such as dust adhering to the surface of the bonding roll.
- an adsorption layer made of a material capable of adsorbing foreign matters such as dust is provided on the surface of the dust removal roll.
- the material constituting the adsorption layer is preferably a material that can remove foreign matters such as dust attached to the surface of the bonding roll and does not adhere to the surface of the bonding roll.
- Non-adhesive polymer rubber may be mentioned. Examples of non-adhesive polymer rubber include silicon. Silicon-based polymer rubber can provide a proper adhesive strength.
- various commercially available products can be used.
- examples of such commercially available products include a polymer rubber dust removal roll (RUS series, HSS series, LPS series, SRR series, etc.) manufactured by YanGo, and a dust removal roller manufactured by TEKNEK.
- two or more dust removal rolls may be provided so that each of the bonding rolls 51 and 52 may contact, and a dust removal roll may be provided so that only one of the bonding rolls 51 and 52 may be contacted.
- FIG. 2 shows a schematic side view of a bonding roll and a dust removal roll in one embodiment of the present invention.
- a dust removing roll 51 a for removing dust attached to the surface of the bonding roll 51 is provided so as to be in contact with the bonding roll 51, and bonding is performed so as to be in contact with the bonding roll 52.
- a dust removal roll 52 a for removing dust attached to the surface of the roll 52 is provided. Thereby, the dust adhering to the surface of the bonding rolls 51 and 52 is removed, and a dent and a bubble may arise in the laminated body 4 (polarizing film 1 and transparent films 2 and 3) which comprise a polarizing plate. Is prevented.
- FIG. 3 shows a schematic side view of a bonding roll, a dust removal roll and a transfer adhesive roll according to another embodiment of the present invention.
- dust removal rolls 51 a and 52 a are provided in the same manner as in FIG. 2, and a transfer adhesive roll 51 b for removing dust adhering to the surface of the dust removal roll 51 a so as to be in contact with the dust removal roll 51 a.
- a transfer adhesive roll 52b for removing dust adhering to the surface of the dust removing roll 52a is provided so as to be in contact with the dust removing roll 52a.
- the transfer pressure-sensitive adhesive roll includes a pressure-sensitive adhesive layer for adsorbing foreign matters such as dust on the surface thereof.
- a plurality of the pressure-sensitive adhesive layers are laminated on the surface of the transfer pressure-sensitive adhesive roll, and a new pressure-sensitive adhesive layer can be easily exposed on the outermost surface by peeling off the used adhesive layer on the outermost surface.
- the adsorption force of the transfer pressure-sensitive adhesive roll is maintained even during use. Therefore, it is possible to prevent dust from accumulating on the surface of the dust removal roll and reducing the adsorption force of the dust removal roll. Thereby, the dust adhering to the surface of the bonding rolls 51 and 52 can be more reliably removed stably for a long time.
- the material of the transfer adhesive roll is not particularly limited, but at least the outermost surface of the outer periphery is made of an adhesive material that can adsorb foreign substances such as dust.
- adhesive materials include acrylic and urethane adhesives.
- transfer pressure-sensitive adhesive roll As described above.
- Examples of such commercially available products include, for example, a dust transfer adhesive tape roll manufactured by YanGo, “Gapress TM ULT” (trade name), “Gapress TM SRR” (trade name), and “AMS adhesive sheet roll (trade name) manufactured by YanGo.
- the adhesive force of the material constituting the surface of the dust removal roll to the transfer adhesive roll is preferably 0.20 to 2.00 kgf. More preferably, it is 0.30 to 1.00 kgf. If it is less than 0.20 kgf, it is inconvenient in that the dust removal capability is insufficient, and if it exceeds 2.00 kgf, it is inconvenient in that the rotation of the roll becomes unstable.
- the adhesive force of the material that makes up the surface of the dust removal roll uses a digital push-pull gauge, attaches a piece of adhesive roll for transfer to the measurement terminal, contacts the material on the surface of the dust removal roll, and then pulls the gauge to release it. It corresponds to the load when
- the diameter of the bonding roll is not particularly limited, but is preferably 50 to 400 mm. In addition, the diameter of each of a pair of bonding roll may be the same, and may differ.
- the width of the bonding roll is preferably 300 to 3000 mm.
- the diameters of the dust removal roll and the transfer pressure-sensitive adhesive roll are not particularly limited, but are preferably smaller than the diameter of the bonding roll in contact with the dust removal roll, and more preferably 50 to 150 mm.
- the diameters of the dust removal roll and the transfer pressure-sensitive adhesive roll may be the same or different.
- the width of the dust removal roll and the transfer adhesive roll is preferably 300 to 3000 mm, and more preferably the same as or slightly longer than the width of the bonding roll in contact with the dust removal roll.
- the material of the bonding roll includes metal and rubber. It is preferable that one of the pair of bonding rolls is a metal roll and the other is a rubber roll. When a pair of bonding rolls are both made of metal, it is difficult to use them continuously because they are easily damaged between the rolls.
- the upper bonding roll to be pressed is usually made of rubber, and the lower bonding roll is made of metal.
- the lower laminating roll is made of metal, and the lower laminating roll is not deformed when pressed because the lower laminating roll is made of metal because the drive motor is attached to the lower laminating roll. It is because it is easy to maintain the peripheral speed of a bonding roll constant.
- the pressed (upper) bonding roll is made of metal, and at least the outer peripheral surface of the other (lower) bonding roll Is preferably made of rubber.
- the base material of the metal roll various known materials can be used, preferably stainless steel, and more preferably SUS304 (stainless steel containing 18% Cr and 8% Ni).
- the surface of the metal roll is preferably subjected to chrome plating.
- the material of the rubber constituting at least the outer peripheral surface of the rubber roll is not particularly limited, and examples thereof include NBR (nitrile rubber), titan, urethane, silicon, EPDM (ethylene-propylene-diene rubber), and preferably NBR, Titan, urethane.
- 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 pressure applied to a laminated body by a bonding roll is not specifically limited, When using a metal roll and a rubber roll as a pair of bonding roll, in Fujifilm two sheet type press case (for ultra-low pressure)
- the instantaneous pressure is preferably 0.5 to 3.0 MPa, more preferably 0.7 to 2.3 MPa.
- the pressure applied to the bonding roll of the dust removing roll is preferably 0.01 to 0.10 MPa, and is appropriately adjusted depending on the mounting angle of the dust removing roll.
- the pressure for pressing the transfer adhesive roll to the dust removing roll is preferably 0.01 to 0.10 MPa. It is adjusted appropriately depending on the angle.
- the peripheral speed of the bonding roll (1st bonding roll) installed in the surface side bonded to the liquid crystal panel of the laminated body 4 is the peripheral speed of the opposite bonding roll (2nd bonding roll). Is faster. Thereby, it is possible to give the obtained polarizing plate a curl (positive curl) in which the surface bonded to the liquid crystal panel becomes convex and the opposite surface becomes concave.
- the obtained polarizing plate is curled (reverse curl) so that the surface to be bonded to the liquid crystal panel is concave and the opposite surface is convex, the polarizing plate is bonded to the liquid crystal cell.
- the ratio of the peripheral speeds of the first laminating roll is more preferably 1.0050 to 1.0200.
- the peripheral speed of the first laminating roll is faster than this range, the curl amount of the positive curl becomes too large, causing problems such as entrapment of bubbles at the end when laminating the polarizing plate to the liquid crystal cell. This is because, when placed in a harsh environment, the positive curl is further promoted and the end of the polarizing plate may be peeled off from the liquid crystal cell.
- the roll 13 constitutes a convex curved surface whose outer peripheral surface is mirror-finished, and the laminate 4 is conveyed while closely contacting the surface, and the adhesive is polymerized and cured by the active energy ray irradiation devices 14 and 15 in the process. .
- the diameter of the roll 13 is not particularly limited when the adhesive is polymerized and cured and the laminate 4 is sufficiently adhered.
- the laminated body 4 in which the adhesive is in an uncured state is preferably irradiated with active energy rays so that the cumulative amount of light while passing through the roll 13 is 10 mJ / cm 2 or more.
- the roll 13 may be driven or rotated according to the movement of the line of the laminate 4 or may be fixed so that the laminate 4 slides on the surface.
- the roll 13 may act as a cooling roll for dissipating heat generated in the laminate 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 light irradiation intensity to the active energy ray-curable adhesive 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 lamp 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. Strength.
- the irradiation time of the active energy ray to the active energy ray-curable adhesive is controlled for each composition to be cured, and is not particularly limited, but the integrated light amount expressed as the product of the irradiation intensity and the irradiation time is 10 mJ / cm 2 or more, preferably is preferably set to be 10 ⁇ 5,000mJ / cm 2.
- the integrated light amount to the adhesive is less than 10 mJ / cm 2 , the generation of active species derived from the initiator is not sufficient, 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 laminate is irradiated with active energy rays to polymerize and cure the adhesive, but polymerization curing by heating may be used in combination.
- 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. Moreover, it is preferable that the irradiation intensity
- Integrated light intensity in these whole process is 10 mJ / cm 2 or more, preferably is preferably set to be 10 ⁇ 5,000mJ / cm 2.
- the irradiation of the active energy ray is preferably performed in a plurality of times.
- 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 polyvinyl alcohol raw film a long polyvinyl alcohol film “Vinylon VF-PS # 7500 (manufactured by Kuraray)” 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).
- an epoxy resin composition “KR series” (manufactured by ADEKA Co., Ltd.), which is an ultraviolet curable adhesive, is applied to one side of the cellulose acetate resin film “KC4CR-1” to which the retardation property of 40 ⁇ m thickness is given. , Including a cationic polymerization initiator) was applied using an adhesive coating apparatus (Microchamber Doctor: manufactured by Fuji Machine Co., Ltd.). Also, an epoxy resin composition “KR series” (made by ADEKA, including a cationic polymerization initiator) which is an ultraviolet curable adhesive is applied to the same adhesive on one side of the 80 ⁇ m thick triacetyl cellulose film “KC8UX2MW”. Coating was performed using a coating apparatus.
- the line speed of the polarizing film laminate in the adhesive coating apparatus was set to 25 m / min, the gravure roll was rotated in the direction opposite to the conveying direction of the laminated material, and the cellulose acetate roll provided with a retardation property of 40 ⁇ m in thickness.
- the thickness of the adhesive layer on the resin film “KC4CR-1” was about 3.5 ⁇ m, and the thickness of the adhesive layer on the 80 ⁇ m thick triacetyl cellulose film “KC8UX2MW” was about 3.5 ⁇ m.
- the cellulose acetate resin film “KC4CR-1” and the 80 ⁇ m-thick triacetyl cellulose film “KC8UX2MW” to which the retardation property of 40 ⁇ m thickness is imparted on both surfaces of the polarizing film are combined with the epoxy resin. It bonded together by a pair of bonding roll through the composition (ultraviolet curable adhesive).
- the silicon-based dust removal roll “HSS series (manufactured by YanGo)” is used as the bonding roll
- the adhesive force with respect to the adhesive roll for transfer of the material which comprises the surface of a dust removal roll was 0.74 kgf.
- 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 closely contacting the cooling roll, and 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 W / cm) was passed through the ultraviolet rays irradiated to irradiate the second active energy ray, and a polarizing plate was produced.
- the one electrodeless D bulb lamp is a unit in which six units of electrodeless D bulb lamps are arranged in the width direction of the film and arranged in one row in the longitudinal direction of the film.
- the 80 ⁇ m thick triacetylcellulose 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 retardation characteristic of 40 ⁇ m thickness is obtained.
- Ultraviolet rays were irradiated from the side of the applied cellulose acetate resin film “KC4CR-1”.
- Example 1 Evaluation of defect rate
- the number of occurrences of defects due to the foreign matter adhering to the bonding roll was investigated with respect to the length (m) of the produced polarizing plate, and was 4 times / 1,000,000 m. The results are shown in Table 1.
- Example 2 A silicon-based dust removal roll “LPS series (YanGo)” and a transfer adhesive roll (YanGo) in contact with this dust removal roll are provided on the bonding roll, and the transfer adhesive for the material constituting the surface of the dust removal roll A polarizing plate was produced in the same manner as in Example 1 except that the adhesive strength to the roll was 0.52 kgf.
- Example 2 Evaluation of defect rate
- the number of occurrences of defects due to foreign matters adhering to the bonding roll was investigated with respect to the length (m) of the produced polarizing plate, and was 4 times / 1,000,000 m. The results are shown in Table 1.
- Example 3 A silicon-based dust removal roll “RUS series (YanGo)” and a transfer adhesive roll (YanGo) in contact with this dust removal roll are provided on the bonding roll, and transfer adhesive for the material constituting the surface of the dust removal roll.
- a polarizing plate was produced in the same manner as in Example 1 except that the adhesive strength to the roll was 0.38 kgf.
- Example 3 Evaluation of defect rate
- the number of occurrences of defects due to the foreign matter adhering to the laminating roll was investigated with respect to the length (m) of the produced polarizing plate, and was 6 times / 1,000,000 m. The results are shown in Table 1.
- Example 4 A polarizing plate was produced in the same manner as in Example 1, except that the transfer roll was not provided on the bonding roll.
- Example 4 Evaluation of occurrence rate of defects due to foreign matter adhered to the bonding roll
- Example 4 when the occurrence rate of the defect caused by the foreign matter adhering to the bonding roll was investigated with respect to the produced quantity, it was 4 times / 300,000 m.
- the results are shown in Table 1.
- Example 1 A polarizing plate was produced in the same manner as in Example 1 except that the dust removal roll and the transfer adhesive roll were not provided on the bonding roll.
- 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
The present invention is a method for manufacturing a polarizing plate by bonding a transparent film on one surface or both surfaces of a polarizing film, said method being characterized by comprising an adhesive application step in which active-energy-ray-curable adhesive is applied to one surface of the transparent film or to one surface or both surfaces of the polarizing film, a bonding step in which at least one bonding roller in a pair of bonding rollers that rotate in the conveyance direction is pressed towards the other bonding roller while a laminate formed by laminating the transparent film on one surface or both surfaces of the polarizing film with the adhesive therebetween is held between the bonding rollers in order to bond the transparent film and the polarizing film, and an active-energy-ray irradiation step in which the adhesive is cured by irradiating the laminate body with active energy rays, and being characterized in that a dust removal roller for removing dust adhered to the surfaces of the bonding rollers is provided adjacent to at least one bonding roller of the pair of bonding rollers.
Description
本発明は、液晶表示装置等を構成する光学部品の一つとして有用な偏光板の製造方法に関する。
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.
偏光フィルムは、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として広く用いられており、ヨウ素を二色性色素とするヨウ素系偏光フィルムや、二色性直接染料を二色性色素とする染料系偏光フィルムなどが知られている。これらの偏光フィルムは、通常、その片面または両面に接着剤を介してトリアセチルセルロースフィルムなどの透明フィルムを貼合して、偏光板とされる。
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.
偏光フィルムの片面または両面に透明フィルムを積層する方法として、予め透明フィルムの表面に活性エネルギー線硬化型樹脂を塗布した後、偏光フィルムと透明フィルムとを一対のニップロール(貼合ロール)で挟圧することにより貼合し、次いで活性エネルギー線を照射して接着硬化させる方法がある(特許文献1:特開2004-245925号公報、特許文献2:特開2009-134190号公報、特許文献3:特開2011-95560号公報)。
As a method of laminating a transparent film on one or both sides of a polarizing film, after applying an active energy ray-curable resin to the surface of the transparent film in advance, the polarizing film and the transparent film are sandwiched between a pair of nip rolls (bonding rolls). There are methods of bonding and curing by irradiation with active energy rays (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).
しかし、貼合ロールの表面に製造工程で生じる塵等の異物が付着した場合、貼合ロールと透明フィルムとの間に異物が挟み込まれた状態で押圧が行われるため、得られる積層体に打痕(へこみ)や気泡が生じてしまうという問題があった。かかる問題は、活性エネルギー線硬化型樹脂を接着剤として用いる場合に特に生じやすい。活性エネルギー線硬化型樹脂は、他のポリビニルアルコール系樹脂等を接着剤として用いる場合に比べて粘度が高いため、積層体に比較的高い圧力を加える必要があるからである。
However, when foreign matter such as dust generated in the manufacturing process adheres to the surface of the bonding roll, pressing is performed in a state where the foreign matter is sandwiched between the bonding roll and the transparent film. There was a problem that dents and bubbles were generated. Such a problem is particularly likely to occur when an active energy ray-curable resin is used as an adhesive. This is because the active energy ray-curable resin has a higher viscosity than the case where other polyvinyl alcohol resins or the like are used as an adhesive, and therefore it is necessary to apply a relatively high pressure to the laminate.
本発明は、上記課題を解決するためになされたものであって、偏光板を構成する積層体(偏光フィルムおよび透明フィルム)に打痕(へこみ)や気泡が生じることを防止できる偏光板の製造方法および偏光板の製造装置を提供することを目的とする。
The present invention has been made to solve the above-described problems, and is a method for producing a polarizing plate that can prevent dents and bubbles from occurring in a laminate (polarizing film and transparent film) constituting the polarizing plate. It is an object to provide a method and an apparatus for manufacturing a polarizing plate.
本発明は、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工工程と、
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んだ状態で、少なくとも一方の貼合ロールを他方の貼合ロールの方向に押圧することで、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活性エネルギー線照射工程とを備え、
前記一対の貼合ロールの少なくとも一方に接するように、前記貼合ロールの表面に付着した塵を除去するための除塵ロールが設けられていることを特徴とする、偏光板の製造方法である。 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,
An adhesive coating step of applying an active energy ray-curable adhesive to one side or both sides of the transparent film or the polarizing film;
At least one laminating roll in a state where the transparent film is sandwiched between a pair of laminating rolls rotating in the conveying direction, with a laminate in which the transparent film is laminated on one or both sides of the polarizing film via the adhesive. By pressing in the direction of the other bonding roll, a bonding step of bonding the transparent film and the polarizing film;
An active energy ray irradiation step of irradiating the laminate with an active energy ray to cure the adhesive; and
It is a manufacturing method of a polarizing plate, wherein a dust removal roll for removing dust adhering to the surface of the bonding roll is provided so as to contact at least one of the pair of bonding rolls.
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工工程と、
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んだ状態で、少なくとも一方の貼合ロールを他方の貼合ロールの方向に押圧することで、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活性エネルギー線照射工程とを備え、
前記一対の貼合ロールの少なくとも一方に接するように、前記貼合ロールの表面に付着した塵を除去するための除塵ロールが設けられていることを特徴とする、偏光板の製造方法である。 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,
An adhesive coating step of applying an active energy ray-curable adhesive to one side or both sides of the transparent film or the polarizing film;
At least one laminating roll in a state where the transparent film is sandwiched between a pair of laminating rolls rotating in the conveying direction, with a laminate in which the transparent film is laminated on one or both sides of the polarizing film via the adhesive. By pressing in the direction of the other bonding roll, a bonding step of bonding the transparent film and the polarizing film;
An active energy ray irradiation step of irradiating the laminate with an active energy ray to cure the adhesive; and
It is a manufacturing method of a polarizing plate, wherein a dust removal roll for removing dust adhering to the surface of the bonding roll is provided so as to contact at least one of the pair of bonding rolls.
さらに、前記除塵ロールに接するように、前記除塵ロールの表面に付着した塵を除去するための転写用粘着ロールが設けられることが好ましい。
Furthermore, it is preferable that a transfer adhesive roll for removing dust adhering to the surface of the dust removing roll is provided so as to be in contact with the dust removing roll.
また、本発明は、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装置であって、
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ための接着剤塗工装置と、
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、搬送しながら挟圧することにより、前記透明フィルムと前記偏光フィルムとを貼合するための一対の貼合ロールと、
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ための活性エネルギー線照射装置とを備え、
前記一対の貼合ロールの少なくとも一方に接するように、少なくとも1つの除塵ロールが設けられていることを特徴とする、偏光板の製造装置にも関する。 In addition, the present invention is a polarizing plate manufacturing apparatus in which a transparent film is bonded to one side or both sides of a polarizing film,
An adhesive coating device for applying an active energy ray-curable adhesive on one side or both sides of the transparent film or the polarizing film;
A pair of the transparent film and the polarizing film are bonded together by sandwiching the transparent film while transporting a laminate in which the transparent film is laminated on one or both sides of the polarizing film via the adhesive. A bonding roll;
An active energy ray irradiating device for irradiating the laminate with an active energy ray to cure the adhesive;
The present invention also relates to a polarizing plate manufacturing apparatus, wherein at least one dust removing roll is provided so as to be in contact with at least one of the pair of bonding rolls.
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ための接着剤塗工装置と、
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、搬送しながら挟圧することにより、前記透明フィルムと前記偏光フィルムとを貼合するための一対の貼合ロールと、
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ための活性エネルギー線照射装置とを備え、
前記一対の貼合ロールの少なくとも一方に接するように、少なくとも1つの除塵ロールが設けられていることを特徴とする、偏光板の製造装置にも関する。 In addition, the present invention is a polarizing plate manufacturing apparatus in which a transparent film is bonded to one side or both sides of a polarizing film,
An adhesive coating device for applying an active energy ray-curable adhesive on one side or both sides of the transparent film or the polarizing film;
A pair of the transparent film and the polarizing film are bonded together by sandwiching the transparent film while transporting a laminate in which the transparent film is laminated on one or both sides of the polarizing film via the adhesive. A bonding roll;
An active energy ray irradiating device for irradiating the laminate with an active energy ray to cure the adhesive;
The present invention also relates to a polarizing plate manufacturing apparatus, wherein at least one dust removing roll is provided so as to be in contact with at least one of the pair of bonding rolls.
本発明によれば、偏光板を構成する積層体(偏光フィルムおよび透明フィルム)に打痕(へこみ)や気泡が生じることを防止できる偏光板の製造方法および偏光板の製造装置を提供することができる。
ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a polarizing plate and the manufacturing apparatus of a polarizing plate which can prevent that a dent and a bubble arise in the laminated body (polarizing film and transparent film) which comprise a polarizing plate are provided. it can.
(偏光フィルム)
本発明の偏光板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。 (Polarizing film)
Specifically, the polarizing film used in the polarizing plate of the present invention is obtained by adsorbing and orienting a dichroic dye on a uniaxially stretched polyvinyl alcohol 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). Other monomers that can be copolymerized with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, acrylamides having an ammonium group, and the like. The degree of saponification of the polyvinyl alcohol resin is 85 mol% or more, preferably 90 mol% or more, more preferably 98 to 100 mol%. The average degree of polymerization of the polyvinyl alcohol-based resin is usually 1000 to 10000, preferably 1500 to 5000. These polyvinyl alcohol resins may be modified. For example, polyvinyl formal modified with aldehydes, polyvinyl acetal, polyvinyl butyral, and the like may be used.
本発明の偏光板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。 (Polarizing film)
Specifically, the polarizing film used in the polarizing plate of the present invention is obtained by adsorbing and orienting a dichroic dye on a uniaxially stretched polyvinyl alcohol 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). Other monomers that can be copolymerized with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, acrylamides having an ammonium group, and the like. The degree of saponification of the polyvinyl alcohol resin is 85 mol% or more, preferably 90 mol% or more, more preferably 98 to 100 mol%. The average degree of polymerization of the polyvinyl alcohol-based resin is usually 1000 to 10000, preferably 1500 to 5000. These polyvinyl alcohol resins may be modified. For example, polyvinyl formal modified with aldehydes, polyvinyl acetal, polyvinyl butyral, and the like may be used.
かかるポリビニルアルコール系樹脂を製膜したものが、偏光フィルムの原反フィルムとして用いられる。ポリビニルアルコール系樹脂を製膜する方法は、特に限定されるものではなく、従来公知の適宜の方法で製膜することができる。ポリビニルアルコール系樹脂からなる原反フィルムの膜厚は特に限定されるものではないが、たとえば10~150μm程度である。通常、ロール状で供給され、厚みが20~100μmの範囲内、好ましくは30~80μmの範囲内であり、また、工業的に実用的な幅が1500~6000mmの範囲内である。
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 μm. Usually, it is supplied in the form of a roll, the thickness is in the range of 20 to 100 μm, preferably in the range of 30 to 80 μm, and the industrially practical width is in the range of 1500 to 6000 mm.
市販のポリビニルアルコール系フィルム(ビニロンVF-PS#7500、クラレ製/OPLフィルム M-7500、日本合成製)の原反厚みは75μm、(ビニロンVF-PS#6000、クラレ製、ビニロンVF-PE#6000、クラレ製)の原反厚みは60μmなどがある。
The commercially available polyvinyl alcohol film (vinylon VF-PS # 7500, Kuraray / OPL film M-7500, Nihon Gosei) has a thickness of 75 μm (vinylon VF-PS # 6000, made by Kuraray, vinylon VF-PE #). The original fabric thickness of 6000 (manufactured by Kuraray) is 60 μm.
偏光フィルムは、通常、ポリビニルアルコール系樹脂フィルムを二色性色素で染色して二色性色素を吸着させる工程(染色処理工程)、二色性色素が吸着されたポリビニルアルコール系樹脂フィルムをホウ酸水溶液で処理する工程(ホウ酸処理工程)、ならびに、このホウ酸水溶液による処理後に水洗する工程(水洗処理工程)を経て、製造される。
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).
また、偏光フィルムの製造に際し、通常、ポリビニルアルコール系樹脂フィルムは一軸延伸されるが、この一軸延伸は、染色処理工程の前に行ってもよいし、染色処理工程中に行ってもよいし、染色処理工程の後に行ってもよい。一軸延伸を染色処理工程の後に行う場合には、この一軸延伸は、ホウ酸処理工程の前に行ってもよいし、ホウ酸処理工程中に行ってもよい。勿論、これらの複数の段階で一軸延伸を行うことも可能である。
In the production of the polarizing film, 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. When uniaxial stretching is performed after the dyeing treatment step, the uniaxial stretching may be performed before the boric acid treatment step or during the boric acid treatment step. Of course, uniaxial stretching can be performed in these plural stages.
一軸延伸は、周速の異なるロール間で一軸に延伸するようにしてもよいし、熱ロールを用いて一軸に延伸するようにしてもよい。また、大気中で延伸を行う乾式延伸であってもよいし、溶剤にて膨潤させた状態で延伸を行う湿式延伸であってもよい。延伸倍率は、通常3~8倍程度である。
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 | stretching which extends | stretches in air | atmosphere may be sufficient, and the wet extending | stretching which extends | stretches in the state swollen with the solvent may be sufficient. The draw ratio is usually about 3 to 8 times.
染色処理工程におけるポリビニルアルコール系樹脂フィルムの二色性色素による染色は、たとえば、ポリビニルアルコール系樹脂フィルムを、二色性色素を含有する水溶液に浸漬することによって行われる。二色性色素としては、たとえばヨウ素、二色性染料などが用いられる。二色性染料には、たとえば、C.I.DIRECT RED 39などのジスアゾ化合物からなる二色性直接染料、トリスアゾ、テトラキスアゾなどの化合物からなる二色性直接染料が包含される。なお、ポリビニルアルコール系樹脂フィルムは、染色処理の前に水への浸漬処理を施しておくことが好ましい。
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. As the dichroic dye, for example, iodine, a dichroic dye or the like is used. Examples of 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. In addition, it is preferable that the polyvinyl alcohol-type resin film performs the immersion process to water before a dyeing process.
二色性色素としてヨウ素を用いる場合は、通常ヨウ素およびヨウ化カリウムを含有する水溶液に、ポリビニルアルコール系樹脂フィルムを浸漬して染色する方法が採用される。この水溶液におけるヨウ素の含有量は通常、水100重量部あたり0.01~1重量部であり、ヨウ化カリウムの含有量は通常、水100重量部あたり0.5~20重量部である。二色性色素としてヨウ素を用いる場合、染色に用いる水溶液の温度は、通常20~40℃であり、この水溶液への浸漬時間(染色時間)は、通常20~1800秒である。
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. When iodine is used as the dichroic dye, the temperature of the aqueous solution used for dyeing is usually 20 to 40 ° C., and the immersion time (dyeing time) in this aqueous solution is usually 20 to 1800 seconds.
一方、二色性色素として二色性染料を用いる場合は、通常、水溶液二色性染料を含む水溶液に、ポリビニルアルコール系樹脂フィルムを浸漬して染色する方法が採用される。この水溶液における二色性染料の含有量は、通常、水100重量部あたり1×10-4~10重量部、好ましくは1×10-3~1重量部であり、特に好ましくは1×10-3~1×10-2重量部である。この水溶液は、硫酸ナトリウムなどの無機塩を染色助剤として含有していてもよい。二色性色素として二色性染料を用いる場合、染色に用いる染料水溶液の温度は、通常20~80℃であり、また、この水溶液への浸漬時間(染色時間)は、通常10~1800秒である。
On the other hand, when a dichroic dye is used as the dichroic dye, a method of immersing and dyeing a polyvinyl alcohol-based resin film in an aqueous solution containing an aqueous 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. When a dichroic dye is used as the dichroic dye, the temperature of the dye aqueous solution used for dyeing is usually 20 to 80 ° C., and the immersion time (dyeing time) in this aqueous solution is usually 10 to 1800 seconds. is there.
ホウ酸処理工程は、二色性色素により染色されたポリビニルアルコール系樹脂フィルムをホウ酸含有水溶液に浸漬することにより行われる。ホウ酸含有水溶液におけるホウ酸の量は、水100重量部あたり、通常2~15重量部、好ましくは5~12重量部である。上述した染色処理工程における二色性色素としてヨウ素を用いた場合には、このホウ酸処理工程に用いるホウ酸含有水溶液はヨウ化カリウムを含有することが好ましい。この場合、ホウ酸含有水溶液におけるヨウ化カリウムの量は、水100重量部あたり、通常0.1~15重量部、好ましくは5~12重量部である。ホウ酸含有水溶液への浸漬時間は、通常、60~1200秒、好ましくは150~600秒、さらに好ましくは200~400秒である。ホウ酸含有水溶液の温度は、通常40℃以上であり、好ましくは50~85℃、より好ましくは55~80℃である。
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. When iodine is used as the dichroic dye in the dyeing process described above, the boric acid-containing aqueous solution used in this boric acid treatment process preferably contains potassium iodide. In this case, 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 80 ° C.
続く水洗処理工程では、上述したホウ酸処理後のポリビニルアルコール系樹脂フィルムを、たとえば水に浸漬することによって水洗処理する。水洗処理における水の温度は、通常4~40℃であり、浸漬時間は、通常1~120秒である。水洗処理後は、通常乾燥処理が施されて、偏光フィルムが得られる。乾燥処理は、たとえば熱風乾燥機、遠赤外線ヒータなどを好適に用いて行われる。乾燥処理の温度は通常30~100℃、好ましくは50~80℃である。乾燥処理の時間は、通常60~600秒、好ましくは120~600秒である。
In the subsequent washing process, 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. After the water washing treatment, 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.
こうしてポリビニルアルコール系樹脂フィルムに、一軸延伸、二色性色素による染色、ホウ酸処理および水洗処理を施して、偏光フィルムが得られる。この偏光フィルムの厚みは、通常、5~50μmの範囲内である。
Thus, 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 μm.
(透明フィルム)
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。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。 (Transparent film)
In the present invention, a transparent film is bonded to one side or both sides of the polarizing film described above. When a transparent film is bonded on both surfaces of a polarizing film, each transparent film may be the same or a different type of film.
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。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。 (Transparent film)
In the present invention, a transparent film is bonded to one side or both sides of the polarizing film described above. When a transparent film is bonded on both surfaces of a polarizing film, each transparent film may be the same or a different type of film.
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、ポリメチルメタクリレート(PMMA)などのようなアクリル系樹脂、ポリプロピレンなどのようなオレフィン系樹脂など、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。
Examples of the material constituting the transparent film include cycloolefin resins, cellulose acetate resins, polyethylene terephthalate, polyethylene naphthalate, polyester resins such as polybutylene terephthalate, polycarbonate resins, and polymethyl methacrylate (PMMA). Examples thereof include film materials that have been widely used in the art, such as acrylic resins and olefin resins such as polypropylene.
シクロオレフィン系樹脂とは、たとえば、ノルボルネン、多環ノルボルネン系モノマーのような、環状オレフィン(シクロオレフィン)からなるモノマーのユニットを有する熱可塑性の樹脂(熱可塑性シクロオレフィン系樹脂とも呼ばれる)である。シクロオレフィン系樹脂は、上記シクロオレフィンの開環重合体または2種以上のシクロオレフィンを用いた開環共重合体の水素添加物であってもよく、シクロオレフィンと鎖状オレフィン、ビニル基を有する芳香族化合物などとの付加重合体であってもよい。また、極性基が導入されているものも有効である。
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.
シクロオレフィンと鎖状オレフィンまたは/およびビニル基を有する芳香族化合物との共重合体を用いる場合、鎖状オレフィンとしては、エチレン、プロピレンなどが挙げられ、またビニル基を有する芳香族化合物としては、スチレン、α-メチルスチレン、核アルキル置換スチレンなどが挙げられる。このような共重合体において、シクロオレフィンからなるモノマーのユニットが50モル%以下(好ましくは15~50モル%)であってもよい。特に、シクロオレフィンと鎖状オレフィンとビニル基を有する芳香族化合物との三元共重合体を用いる場合、シクロオレフィンからなるモノマーのユニットは、上述したように比較的少ない量とすることができる。かかる三元共重合体において、鎖状オレフィンからなるモノマーのユニットは、通常5~80モル%、ビニル基を有する芳香族化合物からなるモノマーのユニットは、通常5~80モル%である。
When using a copolymer of a cycloolefin and a chain olefin or / and an aromatic compound having a vinyl group, examples of the chain olefin include ethylene and propylene, and examples of the aromatic compound having a vinyl group include Examples include styrene, α-methylstyrene, and nuclear alkyl-substituted styrene. In such a copolymer, the monomer unit composed of cycloolefin may be 50 mol% or less (preferably 15 to 50 mol%). In particular, when a terpolymer of a cycloolefin, a chain olefin, and an aromatic compound having a vinyl group is used, the amount of the monomer unit composed of cycloolefin can be made relatively small as described above. In such a terpolymer, the unit of monomer composed of a chain olefin is usually 5 to 80 mol%, and the unit of monomer composed of an aromatic compound having a vinyl group is usually 5 to 80 mol%.
シクロオレフィン系樹脂は、適宜の市販品、たとえば、Topas(Ticona社製)、アートン(JSR(株)製)、ゼオノア(ZEONOR)(日本ゼオン(株)製)、ゼオネックス(ZEONEX)(日本ゼオン(株)製)、アペル(三井化学(株)製)、オキシス(OXIS)(大倉工業社製)などを好適に用いることができる。このようなシクロオレフィン系樹脂を製膜してフィルムとする際には、溶剤キャスト法、溶融押出法などの公知の方法が適宜用いられる。また、たとえばエスシーナ(積水化学工業(株)製)、SCA40(積水化学工業(株)製)、ゼオノアフィルム((株)オプテス製)などの予め製膜されたシクロオレフィン系樹脂製のフィルムの市販品を用いてもよい。
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. When such a cycloolefin-based resin is formed into a film, a known method such as a solvent casting method or a melt extrusion method is appropriately used. In addition, for example, commercially available 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.
シクロオレフィン系樹脂フィルムは、一軸延伸または二軸延伸されたものであってもよい。延伸することで、シクロオレフィン系樹脂フィルムに任意の位相差値を付与することができる。延伸は、通常、フィルムロールを巻き出しながら連続的に行われ、加熱炉にて、ロールの進行方向(フィルムの長手方向)、その進行方向と垂直の方向(フィルムの幅方向)、あるいはその両方へ延伸される。加熱炉の温度は、通常、シクロオレフィン系樹脂のガラス転移温度近傍からガラス転移温度+100℃の範囲が、採用される。延伸の倍率は、通常1.1~6倍であり、好ましくは1.1~3.5倍である。
The cycloolefin resin film may be uniaxially stretched or biaxially stretched. By stretching, an arbitrary retardation value can be given to the cycloolefin-based resin film. 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. As 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.
シクロオレフィン系樹脂フィルムは、ロール巻き状態にあると、フィルム同士が接着してブロッキングを生じ易い傾向にあるため、通常は、プロテクトフィルムを貼合した後にロール巻きとされる。また、シクロオレフィン系樹脂フィルムは、一般に表面活性が劣るため、偏光フィルムと接着させる表面には、プラズマ処理、コロナ処理、紫外線照射処理、フレーム(火炎)処理、ケン化処理などの表面改質処理を行うのが好ましい。中でも、比較的容易に実施可能なプラズマ処理、特に大気圧プラズマ処理、コロナ処理が好適である。
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. In addition, since cycloolefin resin films generally have poor surface activity, surface modification treatment such as plasma treatment, corona treatment, ultraviolet irradiation treatment, flame (flame) treatment, and saponification treatment is applied to the surface to be bonded to the polarizing film. Is preferably performed. Among these, plasma treatment that can be carried out relatively easily, particularly atmospheric pressure plasma treatment, and corona treatment are preferable.
酢酸セルロース系樹脂とは、セルロースの部分または完全エステル化物であって、たとえば、セルロースの酢酸エステル、プロピオン酸エステル、酪酸エステル、それらの混合エステルなどからなるフィルムを挙げることができる。より具体的には、トリアセチルセルロースフィルム、ジアセチルセルロースフィルム、セルロースアセテートプロピオネートフィルム、セルロースアセテートブチレートフィルムなどが挙げられる。このようなセルロースエステル系樹脂フィルムとしては、適宜の市販品、たとえば、フジタックTD80(富士フィルム(株)製)、フジタックTD80UF(富士フィルム(株)製)、フジタックTD80UZ(富士フィルム(株)製)、KC8UX2M(コニカミノルタオプト(株)製)、KC8UY(コニカミノルタオプト(株)製)フジタックTD60UL(富士フィルム(株)製)、KC4UYW(コニカミノルタオプト(株)製)、KC6UAW(コニカミノルタオプト(株)製)などを好適に用いることができる。
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. 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), KC4UYW (manufactured by Konica Minolta Opto), KC6UAW (Konica Minolta Opto) Etc.) can be used preferably.
また、透明フィルムとして、位相差特性を付与した酢酸セルロース系樹脂フィルムも好適に用いられる。かかる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の市販品としては、WV BZ 438(富士フィルム(株)製)、KC4FR-1(コニカミノルタオプト(株)製)、KC4CR-1(コニカミノルタオプト(株)製)、KC4AR-1(コニカミノルタオプト(株)製)などが挙げられる。酢酸セルロースは、アセチルセルロースとも、セルロースアセテートとも呼ばれる。
Further, as the transparent film, 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.
これらの酢酸セルロース系樹脂フィルムは吸水し易く、偏光板の水分率が偏光板の端部タルミに影響する場合がある。偏光板製造時の水分率は、偏光板の保管環境、たとえばクリーンルームの製造ラインやロール巻き保管倉庫における平衡水分率に近いほど好ましく、積層フィルムの構成にもよるが、たとえば、2.0~3.5%程度であり、さらに好ましくは2.5%~3.0%である。この偏光板の水分率の数値は乾燥重量法で測定されたもので、105℃/120分後の重量変化である。
These cellulose acetate-based resin films are easy to absorb water, and the moisture content of the polarizing plate may affect the end talmi of the polarizing plate. 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.
本発明の偏光板に用いられる透明フィルムの厚みは、薄い方が好ましいが、余り薄すぎると強度が低下し、加工性に劣るものとなる。一方で厚すぎると透明性が低下したり、積層後に必要な養生時間が長くなったりするなどの問題が生じる。そこで、透明フィルムの適当な厚みは、たとえば5~200μmであり、好ましくは10~150μm、より好ましくは10~100μmである。
The thickness of the transparent film used in the polarizing plate of the present invention is preferably thin, but if it is too thin, the strength is lowered and the workability 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 μm, preferably 10 to 150 μm, more preferably 10 to 100 μm.
接着剤と偏光フィルムおよび/または透明フィルムとの接着性を向上させるために、偏光フィルムおよび/または透明フィルムに、コロナ処理、火炎処理、プラズマ処理、紫外線処理、プライマー塗布処理、ケン化処理などの表面改質処理を施してもよい。
In order to improve the adhesion between the adhesive and the polarizing film and / or the transparent film, 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 modification treatment may be performed.
また、透明フィルムには、アンチグレア処理、アンチリフレクション処理、ハードコート処理、帯電防止処理、防汚処理などの表面処理が、それぞれ単独で、または2種以上組み合わせて施されてもよい。また、透明フィルムおよび/または透明フィルム表面保護層は、ベンゾフェノン系化合物、ベンゾトリアゾール系化合物などの紫外線吸収剤や、フェニルホスフェート系化合物、フタル酸エステル化合物などの可塑剤を含有していてもよい。
Further, 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.
さらに、透明フィルムに、位相差フィルムとしての機能、輝度向上フィルムとしての機能、反射フィルムとしての機能、半透過反射フィルムとしての機能、拡散フィルムとしての機能、光学補償フィルムとしての機能など、光学的機能を持たせることができる。この場合、例えば、透明フィルムの表面に、位相差フィルム、輝度向上フィルム、反射フィルム、半透過反射フィルム、拡散フィルム、光学補償フィルムなどの光学機能性フィルムを積層することにより、このような機能を持たせることができるほか、透明フィルム自体にこのような機能を付与することもできる。また、輝度向上フィルムの機能を持った拡散フィルムなどのように、複数の機能を透明フィルムに持たせてもよい。
Furthermore, 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. Can have a function. In this case, 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. In addition, the transparent film itself can be given such a function. Further, the transparent film may have a plurality of functions such as a diffusion film having the function of a brightness enhancement film.
例えば、上述した透明フィルムに、特許第2841377号公報、特許第3094113号公報などに記載の延伸処理を施したり、特許第3168850号公報に記載された処理を施したりすることにより、位相差フィルムとしての機能を付与することができる。位相差フィルムにおける位相差特性は、例えば、正面位相差値が5~100nm、厚み方向位相差値が40~300nmの範囲など、適宜選択できる。また、上記の透明フィルムに、特開2002-169025号公報や特開2003-29030号公報に記載されるような方法で微細孔を形成することにより、あるいは選択反射の中心波長が異なる2層以上のコレステリック液晶層を重畳することにより、輝度向上フィルムとしての機能を付与することができる。
For example, 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. Further, 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.
上記の透明フィルムに蒸着やスパッタリングなどで金属薄膜を形成すれば、反射フィルムまたは半透過反射フィルムとしての機能を付与することができる。上述した透明フィルムに微粒子を含む樹脂溶液をコーティングすることにより、拡散フィルムとしての機能を付与することができる。また、上記の透明フィルムにディスコティック液晶性化合物などの液晶性化合物をコーティングして配向させることにより、光学補償フィルムとしての機能を付与することができる。また、透明フィルムに位相差を発現する化合物を含有させてもよい。さらに、適当な接着剤を用いて、各種の光学機能性フィルムを偏光フィルムに直接貼合してもよい。光学機能性フィルムの市販品としては、例えば、DBEF(3M社製、日本では住友スリーエム(株)から入手できる)などの輝度向上フィルム、WVフィルム(富士フィルム(株)製)などの視野角改良フィルム、アートンフィルム(JSR(株)製)、ゼオノアフィルム((株)オプテス製)、エスシーナ(積水化学工業(株)製)、VA-TAC(コミカミノルタオプト(株)製)、スミカライト(住友化学(株)製)などの位相差フィルムなどを挙げることができる。
If a metal thin film is formed on the transparent film by vapor deposition or sputtering, a function as a reflective film or a transflective film can be imparted. By coating the transparent film described above with a resin solution containing fine particles, a function as a diffusion film can be imparted. Moreover, 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. Moreover, you may make the transparent film contain the compound which expresses retardation. Further, various optical functional films may be directly bonded to the polarizing film using an appropriate adhesive. Examples of commercially available optical functional films 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.
(活性エネルギー線硬化型接着剤)
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。 (Active energy ray-curable adhesive)
The polarizing film and the transparent film are bonded via an active energy ray curable adhesive. Examples of 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. . However, 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. For example, an adhesive made of an acrylic resin composition such as acrylamide, acrylate, urethane acrylate, or epoxy acrylate can be used.
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。 (Active energy ray-curable adhesive)
The polarizing film and the transparent film are bonded via an active energy ray curable adhesive. Examples of 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. . However, 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. For example, an adhesive made of an acrylic resin composition such as acrylamide, acrylate, urethane acrylate, or epoxy acrylate can be used.
エポキシ樹脂とは、分子内に2個以上のエポキシ基を有する化合物を意味する。耐候性、屈折率、カチオン重合性等の観点から、接着剤である硬化性エポキシ樹脂組成物に含有されるエポキシ樹脂は、分子内に芳香環を含まないエポキシ樹脂(例えば、特許文献1参照)であることが好ましい。このようなエポキシ樹脂として、水素化エポキシ樹脂、脂環式エポキシ樹脂、脂肪族エポキシ樹脂等が例示できる。
An epoxy resin means a compound having two or more epoxy groups in a molecule. From the viewpoint of weather resistance, refractive index, cationic polymerizability, and the like, 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.
水素化エポキシ樹脂は、芳香族エポキシ樹脂の原料であるポリヒドロキシ化合物を触媒の存在下、加圧下で選択的に核水素化反応して得られる核水添ポリヒドロキシ化合物をグリシジルエーテル化する方法により得ることができる。芳香族エポキシ樹脂としては、たとえば、ビスフェノールAのジグリシジルエーテル、ビスフェールFのジグリシジルエーテル、およびビスフェノールSのジグリシジルエーテル等のビスフェノール型エポキシ樹脂;フェノールノボラックエポキシ樹脂、クレゾールノボラックエポキシ樹脂、およびヒドロキシベンズアルデヒドフェノールノボラックエポキシ樹脂等のノボラック型のエポキシ樹脂;テトラヒドロキシフェニルメタンのグリシジルエーテル、テトラヒドロキシベンゾフェノンのグリシジルエーテル、およびエポキシ化ポリビニルフェノール等の多官能型のエポキシ樹脂等が挙げられる。水素化エポキシ樹脂中でも、水素化したビスフェノールAのグリシジルエーテルが好ましい。
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. Examples of 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. Of the hydrogenated epoxy resins, hydrogenated bisphenol A glycidyl ether is preferred.
脂環式エポキシ樹脂とは、脂環式環に結合したエポキシ基を分子内に1個以上有するエポキシ樹脂を意味する。「脂環式環に結合したエポキシ基」とは、次式に示される構造における橋かけの酸素原子-O-を意味する。次式中、mは2~5の整数である。
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.
上記式における(CH2)m中の1個または複数個の水素原子を取り除いた形の基が他の化学構造に結合している化合物が、脂環式エポキシ樹脂となり得る。(CH2)m中の1個または複数個の水素原子は、メチル基やエチル基等の直鎖状アルキル基で適宜置換されていてもよい。脂環式エポキシ樹脂の中でも、オキサビシクロヘキサン環(上記式においてm=3のもの)や、オキサビシクロヘプタン環(上記式においてm=4のもの)を有するエポキシ樹脂は、優れた接着性を示すことから好ましく用いられる。以下に、好ましく用いられる脂環式エポキシ樹脂を具体的に例示するが、これらの化合物に限定されるものではない。
A compound in which a group in the form of removing one or more hydrogen atoms in (CH 2 ) m in the above formula 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. Among alicyclic epoxy resins, an epoxy resin having an oxabicyclohexane ring (m = 3 in the above formula) or an oxabicycloheptane ring (m = 4 in the above formula) exhibits excellent adhesion. Therefore, it is preferably used. Although the alicyclic epoxy resin used preferably below is specifically illustrated, it is not limited to these compounds.
(a)次式(I)で示されるエポキシシクロヘキシルメチル エポキシシクロヘキサンカルボキシレート類:
(A) Epoxycyclohexylmethyl epoxycyclohexanecarboxylates represented by the following formula (I):
(式中、R1およびR2は、互いに独立して、水素原子または炭素数1~5の直鎖状アルキル基を表す)。
(Wherein R 1 and R 2 each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).
(b)次式(II)で示されるアルカンジオールのエポキシシクロヘキサンカルボキシレート類:
(B) Epoxycyclohexanecarboxylates of alkanediol represented by the following formula (II):
(式中、R3およびR4は、互いに独立して、水素原子または炭素数1~5の直鎖状アルキル基を表し、nは2~20の整数を表す)。
(Wherein 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).
(c)次式(III)で示されるジカルボン酸のエポキシシクロヘキシルメチルエステル類:
(C) Epoxycyclohexyl methyl esters of dicarboxylic acid represented by the following formula (III):
(式中、R5およびR6は、互いに独立して、水素原子または炭素数1~5の直鎖状アルキル基を表し、pは2~20の整数を表す)。
(Wherein, R 5 and R 6 each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms, and p represents an integer of 2 to 20).
(d)次式(IV)で示されるポリエチレングリコールのエポキシシクロヘキシルメチルエーテル類:
(D) Epoxycyclohexyl methyl ethers of polyethylene glycol represented by the following formula (IV):
(式中、R7およびR8は、互いに独立して、水素原子または炭素数1~5の直鎖状アルキル基を表し、qは2~10の整数を表す)。
(Wherein 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).
(e)次式(V)で示されるアルカンジオールのエポキシシクロヘキシルメチルエーテル類:
(E) Epoxycyclohexyl methyl ethers of alkanediols represented by the following formula (V):
(式中、R9およびR10は、互いに独立して、水素原子または炭素数1~5の直鎖状アルキル基を表し、rは2~20の整数を表す)。
(Wherein 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).
(f)次式(VI)で示されるジエポキシトリスピロ化合物:
(F) Diepoxy trispiro compound represented by the following formula (VI):
(式中、R11およびR12は、互いに独立して、水素原子または炭素数1~5の直鎖状アルキル基を表す)。
(Wherein R 11 and R 12 each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).
(g)次式(VII)で示されるジエポキシモノスピロ化合物:
(G) Diepoxy monospiro compound represented by the following formula (VII):
(式中、R13およびR14は、互いに独立して、水素原子または炭素数1~5の直鎖状アルキル基を表す)。
(Wherein R 13 and R 14 each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).
(h)次式(VIII)で示されるビニルシクロヘキセンジエポキシド類:
(H) Vinylcyclohexene diepoxides represented by the following formula (VIII):
(式中、R15は、水素原子または炭素数1~5の直鎖状アルキル基を表す)。
(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: (Wherein R 15 represents a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).
(I) Epoxycyclopentyl ethers represented by the following formula (IX):
(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: (Wherein R 15 represents a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).
(I) Epoxycyclopentyl ethers represented by the following formula (IX):
(式中、R16およびR17は、互いに独立して、水素原子または炭素数1~5の直鎖状アルキル基を表す)。
(Wherein R 16 and R 17 each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).
(j)次式(X)で示されるジエポキシトリシクロデカン類:
(J) Diepoxytricyclodecanes represented by the following formula (X):
(式中、R18は、水素原子または炭素数1~5の直鎖状アルキル基を表す)。
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。 (Wherein R 18 represents a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).
Among the alicyclic epoxy resins exemplified above, the following alicyclic epoxy resins are commercially available or their analogs, and are more preferably used because they are relatively easy to obtain.
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。 (Wherein R 18 represents a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).
Among the alicyclic epoxy resins exemplified above, the following alicyclic epoxy resins are commercially available or their analogs, and are more preferably used because they are relatively easy to obtain.
(A)7-オキサビシクロ[4.1.0]ヘプタン-3-カルボン酸と(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=R2=Hの化合物]、
(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]。 (A) Esterified product of 7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and (7-oxa-bicyclo [4.1.0] hept-3-yl) methanol [formula (I) In which R 1 = R 2 = H]
(B) 4-methyl-7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and (4-methyl-7-oxa-bicyclo [4.1.0] hept-3-yl) methanol Ester compound of [In the formula (I), R 1 = 4-CH 3 , R 2 = 4-CH 3 compound],
(C) Esterified product of 7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and 1,2-ethanediol [in the formula (II), R 3 = R 4 = H, n = 2 Compound],
(D) (7-oxabicyclo [4.1.0] hept-3-yl) methanol and adipic acid ester compound [in the formula (III), R 5 = R 6 = H, p = 4 compound] ,
(E) (4-Methyl-7-oxabicyclo [4.1.0] hept-3-yl) esterified product of methanol and adipic acid [in formula (III), R 5 = 4-CH 3 , R 6 = 4-CH 3 , p = 4 compound]
(F) Etherified product of (7-oxabicyclo [4.1.0] hept-3-yl) methanol and 1,2-ethanediol [in the formula (V), R 9 = R 10 = H, r = Compound of 2].
(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]。 (A) Esterified product of 7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and (7-oxa-bicyclo [4.1.0] hept-3-yl) methanol [formula (I) In which R 1 = R 2 = H]
(B) 4-methyl-7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and (4-methyl-7-oxa-bicyclo [4.1.0] hept-3-yl) methanol Ester compound of [In the formula (I), R 1 = 4-CH 3 , R 2 = 4-CH 3 compound],
(C) Esterified product of 7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and 1,2-ethanediol [in the formula (II), R 3 = R 4 = H, n = 2 Compound],
(D) (7-oxabicyclo [4.1.0] hept-3-yl) methanol and adipic acid ester compound [in the formula (III), R 5 = R 6 = H, p = 4 compound] ,
(E) (4-Methyl-7-oxabicyclo [4.1.0] hept-3-yl) esterified product of methanol and adipic acid [in formula (III), R 5 = 4-CH 3 , R 6 = 4-CH 3 , p = 4 compound]
(F) Etherified product of (7-oxabicyclo [4.1.0] hept-3-yl) methanol and 1,2-ethanediol [in the formula (V), R 9 = R 10 = H, r = Compound of 2].
また、脂肪族エポキシ樹脂としては、脂肪族多価アルコールまたはそのアルキレンオキサイド付加物のポリグリシジルエーテルを挙げることができる。より具体的には、1,4-ブタンジオールのジグリシジルエーテル;1,6-ヘキサンジオールのジグリシジルエーテル;グリセリンのトリグリシジルエーテル;トリメチロールプロパンのトリグリシジルエーテル;ポリエチレングリコールのジグリシジルエーテル;プロピレングリコールのジグリシジルエーテル;エチレングリコール、プロピレングリコール、およびグリセリン等の脂肪族多価アルコールに1種または2種以上のアルキレンオキサイド(エチレンオキサイドやプロピレンオキサイド)を付加することにより得られるポリエーテルポリオールのポリグリシジルエーテル等が挙げられる。
In addition, 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.
エポキシ系樹脂組成物からなる接着剤を構成するエポキシ樹脂は、1種のみを単独で使用してもよいし2種以上を併用してもよい。この組成物に用いられるエポキシ樹脂のエポキシ当量は通常、30~3,000g/当量、好ましくは50~1,500g/当量の範囲内である。エポキシ当量が30g/当量を下回ると、硬化後の複合偏光板の可撓性が低下したり、接着強度が低下したりする可能性がある。一方、3,000g/当量を超えると、接着剤に含有される他の成分との相溶性が低下する可能性がある。
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. When 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. On the other hand, if it exceeds 3,000 g / equivalent, the compatibility with other components contained in the adhesive may be lowered.
この接着剤においては、反応性の観点から、エポキシ樹脂の硬化反応としてカチオン重合が好ましく用いられる。そのために、活性エネルギー線硬化型の接着剤である硬化性エポキシ樹脂組成物には、カチオン重合開始剤を配合することが好ましい。カチオン重合開始剤は、可視光線、紫外線、X線、電子線等の活性エネルギー線の照射によってカチオン種またはルイス酸を発生し、エポキシ基の重合反応を開始させる。以下、活性エネルギー線の照射によりカチオン種またはルイス酸を発生し、エポキシ基の重合反応を開始させるカチオン重合開始剤を「光カチオン重合開始剤」という。
In this adhesive, cationic polymerization is preferably used as a curing reaction of the epoxy resin from the viewpoint of reactivity. Therefore, it is preferable to mix | blend a cationic polymerization initiator with the curable epoxy resin composition which is an active energy ray hardening-type adhesive agent. 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. Hereinafter, 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”.
光カチオン重合開始剤を用い、活性エネルギー線の照射により接着剤の硬化を行なう方法は、常温での硬化が可能となり、偏光フィルムの耐熱性または膨張による歪を考慮する必要が減少し、フィルム間を良好に接着できる点において有利である。また、光カチオン重合開始剤は光で触媒的に作用するため、エポキシ樹脂に混合しても保存安定性や作業性に優れる。
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. In addition, since the photocationic polymerization initiator acts catalytically by light, it is excellent in storage stability and workability even when mixed with an epoxy resin.
[規則91に基づく訂正 21.03.2013]
光カチオン重合開始剤としては、たとえば、芳香族ジアゾニウム塩;芳香族ヨードニウム塩や芳香族スルホニウム塩等のオニウム塩;鉄-アレ-ン錯体等を挙げることができる。[Correction 21.03.2013 based on Rule 91]
Examples of the photocationic polymerization initiator include aromatic diazonium salts; onium salts such as aromatic iodonium salts and aromatic sulfonium salts; iron-arene complexes and the like.
光カチオン重合開始剤としては、たとえば、芳香族ジアゾニウム塩;芳香族ヨードニウム塩や芳香族スルホニウム塩等のオニウム塩;鉄-アレ-ン錯体等を挙げることができる。[Correction 21.03.2013 based on Rule 91]
Examples of the photocationic polymerization initiator include aromatic diazonium salts; onium salts such as aromatic iodonium salts and aromatic sulfonium salts; iron-arene complexes and the like.
芳香族ジアゾニウム塩としては、たとえば、ベンゼンジアゾニウム ヘキサフルオロアンチモネート、ベンゼンジアゾニウム ヘキサフルオロホスフェート、ベンゼンジアゾニウム ヘキサフルオロボレート等が挙げられる。また、芳香族ヨードニウム塩としては、たとえば、ジフェニルヨードニウム テトラキス(ペンタフルオロフェニル)ボレート、ジフェニルヨードニウム ヘキサフルオロホスフェート、ジフェニルヨードニウム ヘキサフルオロアンチモネート、ジ(4-ノニルフェニル)ヨードニウム ヘキサフルオロホスフェート等が挙げられる。
Examples of the aromatic diazonium salt include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, benzenediazonium hexafluoroborate, and the like. Examples of the aromatic iodonium salt include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and the like.
芳香族スルホニウム塩としては、たとえば、トリフェニルスルホニウム ヘキサフルオロホスフェート、トリフェニルスルホニウム ヘキサフルオロアンチモネート、トリフェニルスルホニウム テトラキス(ペンタフルオロフェニル)ボレート、4,4’-ビス(ジフェニルスルホニオ)ジフェニルスルフィド ビス(ヘキサフルオロホスフェート)、4,4’-ビス[ジ(β-ヒドロキシエトキシ)フェニルスルホニオ]ジフェニルスルフィド ビス(ヘキサフルオロアンチモネート)、4,4’-ビス[ジ(β-ヒドロキシエトキシ)フェニルスルホニオ]ジフェニルスルフィド ビス(ヘキサフルオロホスフェート)、7-[ジ(p-トルイル)スルホニオ]-2-イソプロピルチオキサントン ヘキサフルオロアンチモネート、7-[ジ(p-トルイル)スルホニオ]-2-イソプロピルチオキサントン テトラキス(ペンタフルオロフェニル)ボレート、4-フェニルカルボニル-4’-ジフェニルスルホニオ-ジフェニルスルフィド ヘキサフルオロホスフェート、4-(p-tert-ブチルフェニルカルボニル)-4’-ジフェニルスルホニオ-ジフェニルスルフィド ヘキサフルオロアンチモネート、4-(p-tert-ブチルフェニルカルボニル)-4’-ジ(p-トルイル)スルホニオ-ジフェニルスルフィド テトラキス(ペンタフルオロフェニル)ボレート等が挙げられる。
Examples of the aromatic sulfonium salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4′-bis (diphenylsulfonio) diphenyl sulfide bis ( Hexafluorophosphate), 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide, bis (hexafluoroantimonate), 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio ] Diphenyl sulfide bis (hexafluorophosphate), 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate, 7 -[Di (p-toluyl) sulfonio] -2-isopropylthioxanthone tetrakis (pentafluorophenyl) borate, 4-phenylcarbonyl-4'-diphenylsulfonio-diphenyl sulfide hexafluorophosphate, 4- (p-tert-butylphenyl) Carbonyl) -4'-diphenylsulfonio-diphenyl sulfide, hexafluoroantimonate, 4- (p-tert-butylphenylcarbonyl) -4'-di (p-toluyl) sulfonio-diphenyl sulfide, tetrakis (pentafluorophenyl) borate, etc. Is mentioned.
[規則91に基づく訂正 21.03.2013]
また、鉄-アレ-ン錯体としては、たとえば、キシレン-シクロペンタジエニル鉄(II)ヘキサフルオロアンチモネート、クメン-シクロペンタジエニル鉄(II)ヘキサフルオロホスフェート、キシレン-シクロペンタジエニル鉄(II)-トリス(トリフルオロメチルスルホニル)メタナイド等が挙げられる。[Correction 21.03.2013 based on Rule 91]
Examples of the iron-arene complex include xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, xylene-cyclopentadienyl iron ( II) -tris (trifluoromethylsulfonyl) methanide and the like.
また、鉄-アレ-ン錯体としては、たとえば、キシレン-シクロペンタジエニル鉄(II)ヘキサフルオロアンチモネート、クメン-シクロペンタジエニル鉄(II)ヘキサフルオロホスフェート、キシレン-シクロペンタジエニル鉄(II)-トリス(トリフルオロメチルスルホニル)メタナイド等が挙げられる。[Correction 21.03.2013 based on Rule 91]
Examples of the iron-arene complex include xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, xylene-cyclopentadienyl iron ( II) -tris (trifluoromethylsulfonyl) methanide and the like.
これらの光カチオン重合開始剤の市販品は、容易に入手することが可能であり、たとえば、それぞれ商品名で、「カヤラッド PCI-220」および「カヤラッド PCI-620」(以上、日本化薬(株)製)、「UVI-6990」(ユニオンカーバイド社製)、「アデカオプトマー SP-150」および「アデカオプトマー SP-170」(以上、(株)ADEKA製)、「CI-5102」、「CIT-1370」、「CIT-1682」、「CIP-1866S」、「CIP-2048S」および「CIP-2064S」(以上、日本曹達(株)製)、「DPI-101」、「DPI-102」、「DPI-103」、「DPI-105」、「MPI-103」、「MPI-105」、「BBI-101」、「BBI-102」、「BBI-103」、「BBI-105」、「TPS-101」、「TPS-102」、「TPS-103」、「TPS-105」、「MDS-103」、「MDS-105」、「DTS-102」および「DTS-103」(以上、みどり化学(株)製)、「PI-2074」(ローディア社製)等を挙げることができる。
Commercial products of these photocationic polymerization initiators can be easily obtained. For example, “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" (above, Nippon Soda Co., Ltd.), "DPI-101", "DPI-102" , “DPI-103”, “DPI-105”, “MPI-103”, “MPI-105”, “BBI-101”, “BBI-1” 2 ”,“ BBI-103 ”,“ BBI-105 ”,“ TPS-101 ”,“ TPS-102 ”,“ TPS-103 ”,“ TPS-105 ”,“ MDS-103 ”,“ MDS-105 ” “DTS-102” and “DTS-103” (manufactured by Midori Chemical Co., Ltd.), “PI-2074” (manufactured by Rhodia), and the like.
光カチオン重合開始剤は、1種のみを単独で使用してもよいし2種以上を混合して使用してもよい。中でも、芳香族スルホニウム塩は、300nm以上の波長領域でも紫外線吸収特性を有することから、硬化性に優れ、良好な機械的強度や接着強度を有する硬化物を与えることができるため好ましく用いられる。
The photocationic polymerization initiator may be used alone or in combination of two or more. Among these, 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.
光カチオン重合開始剤の配合量は、エポキシ樹脂100重量部に対して通常、0.5~20重量部であり、好ましくは1重量部以上、また好ましくは15重量部以下である。光カチオン重合開始剤の配合量が、エポキシ樹脂100重量部に対して0.5重量部を下回ると、硬化が不十分になり、機械的強度や接着強度が低下する傾向にある。また、光カチオン重合開始剤の配合量が、エポキシ樹脂100重量部に対して20重量部を超えると、硬化物中のイオン性物質が増加することで硬化物の吸湿性が高くなり、耐久性能が低下する可能性がある。
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. When 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. Moreover, when 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 | cured material will become high because the ionic substance in hardened | cured material will increase, and durability performance. May be reduced.
光カチオン重合開始剤を用いる場合、硬化性エポキシ樹脂組成物は、必要に応じて、さらに光増感剤を含有することができる。光増感剤を用いることで、カチオン重合の反応性が向上し、硬化物の機械的強度や接着強度を向上させることができる。光増感剤としては、たとえば、カルボニル化合物、有機硫黄化合物、過硫化物、レドックス系化合物、アゾおよびジアゾ化合物、ハロゲン化合物、光還元性色素等が挙げられる。
When using a photocationic polymerization initiator, the curable epoxy resin composition may further contain a photosensitizer as necessary. 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. Examples of the photosensitizer include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreductive dyes.
光増感剤のより具体的な例を挙げれば、たとえば、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル、およびα,α-ジメトキシ-α-フェニルアセトフェノン等のベンゾイン誘導体;ベンゾフェノン、2,4-ジクロロベンゾフェノン、o-ベンゾイル安息香酸メチル、4,4’-ビス(ジメチルアミノ)ベンゾフェノン、および4,4’-ビス(ジエチルアミノ)ベンゾフェノン等のベンゾフェノン誘導体;2-クロロチオキサントン、および2-イソプロピルチオキサントン等のチオキサントン誘導体;2-クロロアントラキノン、および2-メチルアントラキノン等のアントラキノン誘導体;N-メチルアクリドン、およびN-ブチルアクリドン等のアクリドン誘導体;その他、α,α-ジエトキシアセトフェノン、ベンジル、フルオレノン、キサントン、ウラニル化合物、ハロゲン化合物等がある。光増感剤は、1種のみを単独で使用してもよいし、2種以上を併用してもよい。光増感剤は、硬化性エポキシ樹脂組成物100重量部中、0.1~20重量部の範囲内で含有されることが好ましい。
More specific examples of photosensitizers include, for example, benzoin derivatives such as benzoin methyl ether, benzoin isopropyl ether, and α, α-dimethoxy-α-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 α, α-diethoxyacetophenone, ben Examples include zil, fluorenone, xanthone, uranyl compound, and halogen compound. A photosensitizer may be used individually by 1 type and may use 2 or more types together. The photosensitizer is preferably contained within a range of 0.1 to 20 parts by weight in 100 parts by weight of the curable epoxy resin composition.
接着剤に含有されるエポキシ樹脂は、光カチオン重合より硬化されるが、光カチオン重合および熱カチオン重合の双方により硬化してもよい。後者の場合、光カチオン重合開始剤と熱カチオン重合開始剤とを併用することが好ましい。
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.
熱カチオン重合開始剤としては、ベンジルスルホニウム塩、チオフェニウム塩、チオラニウム塩、ベンジルアンモニウム、ピリジニウム塩、ヒドラジニウム塩、カルボン酸エステル、スルホン酸エステル、アミンイミド等を挙げることができる。これらの熱カチオン重合開始剤は、市販品として容易に入手することが可能であり、たとえば、いずれも商品名で、「アデカオプトンCP77」および「アデカオプトンCP66」(以上、株式会社ADEKA製)、「CI-2639」および「CI-2624」(以上、日本曹達株式会社製)、「サンエイドSI-60L」、「サンエイドSI-80L」および「サンエイドSI-100L」(以上、三新化学工業株式会社製)等が挙げられる。
Examples of the thermal cationic polymerization initiator include benzylsulfonium salt, thiophenium salt, thiolanium salt, benzylammonium, pyridinium salt, hydrazinium salt, carboxylic acid ester, sulfonic acid ester, and amine imide. These 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. -2639 "and" CI-2624 "(Nippon Soda Co., Ltd.)," Sun-Aid SI-60L "," Sun-Aid SI-80L "and" Sun-Aid SI-100L "(Made by Sanshin Chemical Industry Co., Ltd.) Etc.
活性エネルギー線硬化型の接着剤は、オキセタン類やポリオール類等、カチオン重合を促進する化合物をさらに含有してもよい。
The active energy ray-curable adhesive may further contain a compound that promotes cationic polymerization, such as oxetanes and polyols.
オキセタン類は、分子内に4員環エーテルを有する化合物であり、たとえば、3-エチル-3-ヒドロキシメチルオキセタン、1,4-ビス[(3-エチル-3-オキセタニル)メトキシメチル]ベンゼン、3-エチル-3-(フェノキシメチル)オキセタン、ジ[(3-エチル-3-オキセタニル)メチル]エーテル、3-エチル-3-(2-エチルヘキシロキシメチル)オキセタン、フェノールノボラックオキセタン等が挙げられる。これらのオキセタン類は、市販品として容易に入手することが可能であり、たとえば、いずれも商品名で、「アロンオキセタン OXT-101」、「アロンオキセタン OXT-121」、「アロンオキセタン OXT-211」、「アロンオキセタン OXT-221」および「アロンオキセタン OXT-212」(以上、東亞合成(株)製)等を挙げることができる。これらのオキセタン類は、硬化性エポキシ樹脂組成物中、通常、5~95重量%、好ましくは30~70重量%の割合で含有される。
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. For example, all of them are trade names such as “Aron Oxetane OXT-101”, “Aron Oxetane OXT-121”, “Aron Oxetane OXT-211”. "Aron Oxetane OXT-221" and "Aron Oxetane OXT-212" (manufactured by Toagosei Co., Ltd.). These oxetanes are usually contained in the curable epoxy resin composition in a proportion of 5 to 95% by weight, preferably 30 to 70% by weight.
ポリオール類としては、フェノール性水酸基以外の酸性基が存在しないものが好ましく、たとえば、水酸基以外の官能基を有しないポリオール化合物、ポリエステルポリオール化合物、ポリカプロラクトンポリオール化合物、フェノール性水酸基を有するポリオール化合物、ポリカーボネートポリオール等を挙げることができる。これらのポリオール類の分子量は通常、48以上、好ましくは62以上、さらに好ましくは100以上、また好ましくは1,000以下である。これらポリオール類は、硬化性エポキシ樹脂組成物中、通常、50重量%以下、好ましくは30重量%以下の割合で含有される。
As the polyols, those having no acidic groups other than phenolic hydroxyl groups are preferable. For example, 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.
活性エネルギー線硬化型の接着剤には、さらに、イオントラップ剤、酸化防止剤、連鎖移動剤、粘着付与剤、熱可塑性樹脂、充填剤、流動調整剤、レベリング剤、可塑剤、消泡剤等の添加剤を配合することができる。イオントラップ剤としては粉末状のビスマス系、アンチモン系、マグネシウム系、アルミニウム系、カルシウム系、チタン系およびこれらの混合系等の無機化合物が挙げられ、酸化防止剤としてはヒンダードフェノール系酸化防止剤等が挙げられる。
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. Examples of 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.
活性エネルギー線硬化型の接着剤は、溶剤成分を実質的に含まない無溶剤型接着剤として用いることができるが、各塗工方式には各々最適な粘度範囲があるため、粘度調整のために溶剤を含有させてもよい。溶剤としては、偏光フィルムの光学性能を低下させることなく、エポキシ樹脂組成物等を良好に溶解するものを用いることが好ましく、たとえば、トルエンに代表される炭化水素類、酢酸エチルに代表されるエステル類等の有機溶剤を挙げることができる。本発明で用いられる活性エネルギー線硬化型の接着剤の粘度は、例えば5~1000mPa・s程度の範囲であり、好ましくは10~200mPa・sであり、より好ましくは20~100mPa・sである。
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. For example, hydrocarbons represented by toluene, esters represented by ethyl acetate, and the like. And 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.
<偏光板の製造方法>
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装置の一実施形態を示す概略図である。 <Production method of polarizing plate>
Next, the manufacturing apparatus and manufacturing method of the polarizing plate of this invention are demonstrated, referring drawings. FIG. 1 is a schematic view showing an embodiment of a polarizing plate production apparatus of the present invention.
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装置の一実施形態を示す概略図である。 <Production method of polarizing plate>
Next, the manufacturing apparatus and manufacturing method of the polarizing plate of this invention are demonstrated, referring drawings. FIG. 1 is a schematic view showing an embodiment of a polarizing plate production apparatus of the present invention.
図1に示す偏光板の製造装置30では、透明フィルム2,3の片面に接着剤を塗布するための接着剤塗工装置11,12と、透明フィルム2,3と偏光フィルム1とを貼合して積層体4を得るための貼合ロール(ニップロール)51,52と、積層体4において透明フィルム2、3と偏光フィルム1とを密着させるためのロール13と、該ロール13の外周面と相対する位置に設置された第1の活性エネルギー線照射装置14,15と、さらにこれより搬送方向下流側に設置された第2以降の活性エネルギー線照射装置16~18と、搬送用ニップロール19とが、搬送方向に沿って順に設けられている。
In the polarizing plate manufacturing apparatus 30 shown in FIG. 1, the adhesive coating apparatuses 11 and 12 for applying an adhesive to one side of the transparent films 2 and 3, and the transparent films 2 and 3 and the polarizing film 1 are bonded. Bonding rolls (nip rolls) 51 and 52 for obtaining the laminate 4, the roll 13 for bringing the transparent films 2 and 3 and the polarizing film 1 into close contact with each other in the laminate 4, and the outer peripheral surface of the roll 13 First active energy beam irradiating devices 14 and 15 installed at opposite positions, second and subsequent active energy beam irradiating devices 16 to 18 installed further downstream in the transport direction, and a transport nip roll 19 Are provided in order along the transport direction.
まず、ロール状に巻回された状態から連続的に繰り出される透明フィルム2,3の片面に、接着剤塗工装置11、12によって活性エネルギー線硬化型の接着剤が塗布される(接着剤塗工工程)。
First, 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 by an adhesive application device 11 or 12 (adhesive coating). Construction process).
そして、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、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てなる積層体を、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、少なくとも一方の貼合ロールを他方の貼合ロール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(貼合工程)。
And the laminated body formed by laminating | stacking the transparent films 2 and 3 with which the adhesive agent was apply | 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. The polarizing film 1 and the transparent films 2 and 3 are pressed by pressing at least one bonding roll in the direction of the other bonding roll while being sandwiched between a pair of bonding rolls 51 and 52 rotating in the direction. Are pasted together to form the laminate 4 (a pasting step).
次に、この積層体4をロール13の外周面に密着させながら搬送する過程で、第1の活性エネルギー線照射装置14,15からロール13の外周面に向かって活性エネルギー線を照射し、接着剤を重合硬化させる(活性エネルギー線照射工程)。
Next, in the process of transporting the laminate 4 in close contact with the outer peripheral surface of the roll 13, the active energy rays are irradiated from the first active energy ray irradiating devices 14, 15 toward the outer peripheral surface of the roll 13, and bonded. The agent is polymerized and cured (active energy ray irradiation step).
なお、搬送方向下流側に配置される第2以降の活性エネルギー線照射装置16~18は、接着剤を完全に重合硬化させるための装置であり、必要に応じて追加・省略することができる。最終的に、積層体4は搬送用ニップロール19を通過して、偏光板として巻取ロール20に巻き取られる。以下、各工程について詳細に説明する。
Note that the second and subsequent active energy ray irradiation devices 16 to 18 arranged on the downstream side in the transport direction are devices for completely polymerizing and curing the adhesive, and can be added or omitted as necessary. Finally, the laminate 4 passes through the conveyance nip roll 19 and is wound around the winding roll 20 as a polarizing plate. Hereinafter, each step will be described in detail.
(接着剤塗工工程)
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。 (Adhesive coating process)
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.
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。 (Adhesive coating process)
The method for applying the adhesive to the
接着剤塗工装置11,12としてグラビアロールを用いて接着剤の塗布を行う場合、塗布された接着剤の厚さ(塗布厚)は、好ましくは約0.1~10μmであり、より好ましくは0.2μm~4μmである。接着剤の塗布厚は、透明フィルムのライン速度に対するグラビアロールの速度比であるドロー比によって調整する。一般的には、ドロー比(グラビアロールの速度/ライン速度)を0.5~10に調整することで、接着剤の塗布厚を約0.1~10μmに調整することができる。より具体的には、透明フィルム2,3のライン速度を10~100m/分とし、グラビアロールを透明フィルム2、3の搬送方向と逆方向に回転させ、グラビアロールの速度を5~1000m/分とすることで、接着剤の塗布厚を約0.1~10μmに調整することができる。
When applying the adhesive using a gravure roll as the adhesive application device 11 or 12, the thickness of the applied adhesive (application thickness) is preferably about 0.1 to 10 μm, more preferably 0.2 μm to 4 μm. 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 μm. More specifically, 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, and the speed of the gravure roll is set to 5 to 1000 m / min. By doing so, the coating thickness of the adhesive can be adjusted to about 0.1 to 10 μm.
接着剤は、調製後、通常は15~40℃の範囲内の所定温度±5℃(例えば、所定温度が30℃である場合、30℃±5℃)、好ましくは±3℃、より好ましくは±1℃に調整された環境下で塗布される。
After preparation, 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.
(貼合工程)
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。なお、貼合ロール52を貼合ロール51の方向に押圧してもよく、貼合ロール51および貼合ロール52の両方を互いに近接する方向に押圧してもよい。 (Bonding process)
In this step, 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. In a state where the laminate is sandwiched between a pair of bonding rolls 51 and 52 rotating in the transport direction, for example, 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. At this time, an angle within a range of ± 3 °, preferably an angle within a range of ± 1 °, particularly preferably in the pressing direction, with respect to a plane perpendicular to the pressing direction of the bonding roll. It is preferable to transport the polarizing film between the bonding rolls so as to overlap the vertical surface. By doing in this way, a polarizing film and a transparent film will contact before the bonding roll, and a bubble will not generate | occur | produce. In addition, you may press the bonding roll 52 in the direction of the bonding roll 51, and you may press both the bonding roll 51 and the bonding roll 52 in the direction which mutually adjoins.
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。なお、貼合ロール52を貼合ロール51の方向に押圧してもよく、貼合ロール51および貼合ロール52の両方を互いに近接する方向に押圧してもよい。 (Bonding process)
In this step, the
また、図1では、透明フィルム2,3の片面に接着剤を均一に塗布し、透明フィルム2,3の接着剤が塗布された面に偏光フィルム1を重ねて貼合ロール51,52により貼合する方法を示しているが、偏光フィルム1の両面に接着剤を均一に塗布し、偏光フィルム1の接着剤が塗布された面に透明フィルム2,3を重ねて貼合ロール51,52により貼合してもよい。
In FIG. 1, 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. Although the method to combine is shown, the adhesive agent is apply | coated uniformly on both surfaces of the polarizing film 1, and the transparent films 2 and 3 are piled up on the surface by which the adhesive agent of the polarizing film 1 was apply | coated, and the bonding rolls 51 and 52 You may paste.
本発明は、一対の貼合ロール51,52の少なくとも一方に接するように、貼合ロールの表面に付着した塵を除去するための除塵ロールが設けられていることを特徴とする。除塵ロールとは、貼合ロールの表面に付着した塵等の異物を除去するための機構を有するロールである。例えば、除塵ロールの表面に塵等の異物を吸着することのできる材料からなる吸着層を備えている。かかる吸着層を構成する材料は、貼合ロールの表面に付着した塵等の異物を除去することができ、かつ、貼合ロールの表面に付着することのない材料であることが好ましく、例えば、非粘着性の高分子ゴムが挙げられる。非粘着性の高分子ゴムとしては、例えばシリコンなどが挙げられる。シリコン系の高分子ゴムの方が適度な粘着力が得られる。
The present invention is characterized in that a dust removing roll for removing dust adhering to the surface of the bonding roll is provided so as to be in contact with at least one of the pair of bonding rolls 51 and 52. The dust removal roll is a roll having a mechanism for removing foreign matters such as dust adhering to the surface of the bonding roll. For example, an adsorption layer made of a material capable of adsorbing foreign matters such as dust is provided on the surface of the dust removal roll. The material constituting the adsorption layer is preferably a material that can remove foreign matters such as dust attached to the surface of the bonding roll and does not adhere to the surface of the bonding roll. Non-adhesive polymer rubber may be mentioned. Examples of non-adhesive polymer rubber include silicon. Silicon-based polymer rubber can provide a proper adhesive strength.
上述のような除塵ロールとしては、各種の市販品を使用することができる。かかる市販品としては、例えば、YanGo社製の高分子ゴム除塵ロール(RUSシリーズ、HSSシリーズ、LPSシリーズ、SRRシリーズなど)、TEKNEK社製の除塵ローラーが挙げられる。
As the dust removal roll as described above, various commercially available products can be used. Examples of such commercially available products include a polymer rubber dust removal roll (RUS series, HSS series, LPS series, SRR series, etc.) manufactured by YanGo, and a dust removal roller manufactured by TEKNEK.
なお、貼合ロール51,52の各々に接するように、2つ以上の除塵ロールが設けられてもよく、貼合ロール51,52の一方のみに接するように、除塵ロールが設けられてもよい。
In addition, two or more dust removal rolls may be provided so that each of the bonding rolls 51 and 52 may contact, and a dust removal roll may be provided so that only one of the bonding rolls 51 and 52 may be contacted. .
図2に、本発明の一実施形態における貼合ロールおよび除塵ロールの概略側面図を示す。図2において、貼合ロール51に接するように、貼合ロール51の表面に付着した塵を除去するための除塵ロール51aが設けられており、また、貼合ロール52に接するように、貼合ロール52の表面に付着した塵を除去するための除塵ロール52aが設けられている。これにより、貼合ロール51,52の表面に付着した塵が除去され、偏光板を構成する積層体4(偏光フィルム1および透明フィルム2,3)に打痕(へこみ)や気泡が生じることが防止される。
FIG. 2 shows a schematic side view of a bonding roll and a dust removal roll in one embodiment of the present invention. In FIG. 2, a dust removing roll 51 a for removing dust attached to the surface of the bonding roll 51 is provided so as to be in contact with the bonding roll 51, and bonding is performed so as to be in contact with the bonding roll 52. A dust removal roll 52 a for removing dust attached to the surface of the roll 52 is provided. Thereby, the dust adhering to the surface of the bonding rolls 51 and 52 is removed, and a dent and a bubble may arise in the laminated body 4 (polarizing film 1 and transparent films 2 and 3) which comprise a polarizing plate. Is prevented.
図3に、本発明の別の実施形態における貼合ロール、除塵ロールおよび転写用粘着ロールの概略側面図を示す。図3においては、図2と同様に除塵ロール51a,52aが設けられており、さらに、除塵ロール51aに接するように、除塵ロール51aの表面に付着した塵を除去するための転写用粘着ロール51bが設けられ、また、除塵ロール52aに接するように、除塵ロール52aの表面に付着した塵を除去するための転写用粘着ロール52bが設けられている。転写用粘着ロールは、その表面に塵等の異物を吸着させるための粘着層を備えている。例えば、この粘着層は、転写用粘着ロールの表面に複数枚積層されており、最表面の使用済み粘着層を剥がすことで、容易に新しい粘着層を最表面に露出させることができる。このような操作により、使用中も転写用粘着ロールの吸着力が維持されるため、除塵ロールの表面に塵が堆積して除塵ロールの吸着力が下がることを防止することができる。これにより、貼合ロール51,52の表面に付着した塵をより確実に長時間安定して除去することができる。
FIG. 3 shows a schematic side view of a bonding roll, a dust removal roll and a transfer adhesive roll according to another embodiment of the present invention. In FIG. 3, dust removal rolls 51 a and 52 a are provided in the same manner as in FIG. 2, and a transfer adhesive roll 51 b for removing dust adhering to the surface of the dust removal roll 51 a so as to be in contact with the dust removal roll 51 a. Further, a transfer adhesive roll 52b for removing dust adhering to the surface of the dust removing roll 52a is provided so as to be in contact with the dust removing roll 52a. The transfer pressure-sensitive adhesive roll includes a pressure-sensitive adhesive layer for adsorbing foreign matters such as dust on the surface thereof. For example, a plurality of the pressure-sensitive adhesive layers are laminated on the surface of the transfer pressure-sensitive adhesive roll, and a new pressure-sensitive adhesive layer can be easily exposed on the outermost surface by peeling off the used adhesive layer on the outermost surface. By such an operation, the adsorption force of the transfer pressure-sensitive adhesive roll is maintained even during use. Therefore, it is possible to prevent dust from accumulating on the surface of the dust removal roll and reducing the adsorption force of the dust removal roll. Thereby, the dust adhering to the surface of the bonding rolls 51 and 52 can be more reliably removed stably for a long time.
転写用粘着ロールの材質は特に限定されないが、少なくとも外周の最表面は、塵等の異物を吸着できる粘着性材料から構成される。このような粘着性材料としては、例えば、アクリル系、ウレタン系粘着剤などが挙げられる。
The material of the transfer adhesive roll is not particularly limited, but at least the outermost surface of the outer periphery is made of an adhesive material that can adsorb foreign substances such as dust. Examples of such adhesive materials include acrylic and urethane adhesives.
上述のような転写用粘着ロールとしては、各種の市販品を使用することができる。かかる市販品としては、例えば、YanGo社製の塵埃転写用粘着テープロールや「Gapless TM ULT」(商品名)、「Gapless TM SRR」(商品名)、またYanGo社製の「AMS粘着シートロール(製品名)/ARSPプリカット粘着シートロール(商品名)」、TEKNEK社製の粘着ロールが挙げられる。
Various commercial products can be used as the transfer pressure-sensitive adhesive roll as described above. Examples of such commercially available products include, for example, a dust transfer adhesive tape roll manufactured by YanGo, “Gapress ™ ULT” (trade name), “Gapress ™ SRR” (trade name), and “AMS adhesive sheet roll (trade name) manufactured by YanGo. Product name) / ARSP pre-cut adhesive sheet roll (trade name) ”, TEKNEK's adhesive roll.
除塵ロールの表面を構成する材料の転写用粘着ロールに対する粘着力は、好ましくは0.20~2.00kgfである。より好ましくは、0.30~1.00kgfである。0.20kgf未満では、除塵能力が不足する点で不都合であり、2.00kgfを超えると、ロールの回転が不安定になる点で不都合である。なお、除塵ロール表面を構成する材料の粘着力は、デジタルプッシュプルゲージを使用し、測定端子に転写用粘着ロールの紙片を取り付け、除塵ロール表面の材料に接触させた後、ゲージを引っ張り、剥離する際の荷重に相当する。
The adhesive force of the material constituting the surface of the dust removal roll to the transfer adhesive roll is preferably 0.20 to 2.00 kgf. More preferably, it is 0.30 to 1.00 kgf. If it is less than 0.20 kgf, it is inconvenient in that the dust removal capability is insufficient, and if it exceeds 2.00 kgf, it is inconvenient in that the rotation of the roll becomes unstable. The adhesive force of the material that makes up the surface of the dust removal roll uses a digital push-pull gauge, attaches a piece of adhesive roll for transfer to the measurement terminal, contacts the material on the surface of the dust removal roll, and then pulls the gauge to release it. It corresponds to the load when
貼合ロールの直径は特に限定されないが、好ましくは50~400mmである。なお、一対の貼合ロールの各々の直径は、同じでも良く、異なっていても良い。貼合ロールの幅は、好ましくは300~3000mmである。
The diameter of the bonding roll is not particularly limited, but is preferably 50 to 400 mm. In addition, the diameter of each of a pair of bonding roll may be the same, and may differ. The width of the bonding roll is preferably 300 to 3000 mm.
除塵ロールおよび転写用粘着ロールの直径は特に限定されないが、除塵ロールに接する貼合ロールの直径より小さいことが好ましく、より好ましくは50~150mmである。なお、除塵ロールおよび転写用粘着ロールの各々の直径は、同じでも良く、異なっていても良い。除塵ロールおよび転写用粘着ロールの幅は、好ましくは300~3000mmであり、除塵ロールに接する貼合ロールの幅と同じか、やや長いことがより好ましい。
The diameters of the dust removal roll and the transfer pressure-sensitive adhesive roll are not particularly limited, but are preferably smaller than the diameter of the bonding roll in contact with the dust removal roll, and more preferably 50 to 150 mm. The diameters of the dust removal roll and the transfer pressure-sensitive adhesive roll may be the same or different. The width of the dust removal roll and the transfer adhesive roll is preferably 300 to 3000 mm, and more preferably the same as or slightly longer than the width of the bonding roll in contact with the dust removal roll.
貼合ロールの材質としては、金属やゴムが挙げられる。一対の貼合ロールの一方が金属製ロールであり、他方がゴム製ロールであることが好ましい。一対の貼合ロールが共に金属製である場合、使用によりロール間に傷が付きやすいため、連続して使用することが難しい。
The material of the bonding roll includes metal and rubber. It is preferable that one of the pair of bonding rolls is a metal roll and the other is a rubber roll. When a pair of bonding rolls are both made of metal, it is difficult to use them continuously because they are easily damaged between the rolls.
従来の貼合ロールは、通常、押圧される上側の貼合ロールがゴム製であり、下側の貼合ロールが金属製であった。これは、下側の貼合ロールに駆動モーターをつけて回転速度を制御するため、下側の貼合ロールが金属製であった方が、押圧時に下側の貼合ロールが変形せず、貼合ロールの周速度を一定に維持しやすいためである。しかし、後述する正カールのカール調整をしやすくするため、本発明においては、押圧される(上側の)貼合ロールが金属製であり、他方の(下側の)貼合ロールの少なくとも外周表面がゴム製であることが好ましい。
In the conventional bonding roll, the upper bonding roll to be pressed is usually made of rubber, and the lower bonding roll is made of metal. This is because the lower laminating roll is made of metal, and the lower laminating roll is not deformed when pressed because the lower laminating roll is made of metal because the drive motor is attached to the lower laminating roll. It is because it is easy to maintain the peripheral speed of a bonding roll constant. However, in order to facilitate the curl adjustment of the positive curl described later, in the present invention, the pressed (upper) bonding roll is made of metal, and at least the outer peripheral surface of the other (lower) bonding roll Is preferably made of rubber.
金属製ロールの母材としては、種々公知の材質を用いることができるが、好ましくはステンレスであり、より好ましくはSUS304(18%のCrと8%のNiを含むステンレス鋼)である。金属製ロールの表面には、クロムめっき処理が施されていることが好ましい。
As the base material of the metal roll, various known materials can be used, preferably stainless steel, and more preferably SUS304 (stainless steel containing 18% Cr and 8% Ni). The surface of the metal roll is preferably subjected to chrome plating.
ゴム製ロールの少なくとも外周表面を構成するゴムの材質は、特に限定されないが、NBR(ニトリルゴム)、タイタン、ウレタン、シリコン、EPDM(エチレン-プロピレン-ジエンゴム)などが挙げられ、好ましくは、NBR、タイタン、ウレタンである。ゴムロールの硬度は、特に限定されないが、通常60~100°であり、好ましくは85~95°である。なお、ゴムロールの硬度は、JISK6253に準拠した硬度計で測定することができる。市販の硬度計としては、例えばアスカ社製のゴム硬度計「Type-A」などが用いられる。具体的には、表面を棒のようなもので押しつけた時の、ゴムロールの表面の抵抗を硬度計で測定する。
The material of the rubber constituting at least the outer peripheral surface of the rubber roll is not particularly limited, and examples thereof include NBR (nitrile rubber), titan, urethane, silicon, EPDM (ethylene-propylene-diene rubber), and preferably NBR, Titan, urethane. The hardness of the rubber roll is not particularly limited, but is usually 60 to 100 °, preferably 85 to 95 °. In addition, the hardness of a rubber roll can be measured with the hardness meter based on JISK6253. As a commercially available hardness meter, for example, 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.
貼合ロールによって積層体に加えられる圧力は、特に限定されないが、一対の貼合ロールとして金属製ロールとゴム製ロールとを用いる場合は、富士フィルム製ツーシートタイププレスケース(超低圧用)における瞬間圧が0.5~3.0MPaであることが好ましく、より好ましくは0.7~2.3MPaである。
Although the pressure applied to a laminated body by a bonding roll is not specifically limited, When using a metal roll and a rubber roll as a pair of bonding roll, in Fujifilm two sheet type press case (for ultra-low pressure) The instantaneous pressure is preferably 0.5 to 3.0 MPa, more preferably 0.7 to 2.3 MPa.
除塵ロールの貼合ロールへの押圧の圧力(除塵ロールと貼合ロールの接触面にかかる圧力)は、0.01~0.10MPaであることが好ましく、除塵ロールの取り付け角度によって適宜調整される。また、転写用粘着ロールの除塵ロールへの押圧の圧力(転写用粘着ロールと除塵ロールの接触面にかかる圧力)は、0.01~0.10MPaであることが好ましく、転写用粘着ロールの取り付け角度によって適宜調整される。
The pressure applied to the bonding roll of the dust removing roll (pressure applied to the contact surface between the dust removing roll and the bonding roll) is preferably 0.01 to 0.10 MPa, and is appropriately adjusted depending on the mounting angle of the dust removing roll. . In addition, the pressure for pressing the transfer adhesive roll to the dust removing roll (pressure applied to the contact surface between the transfer adhesive roll and the dust removing roll) is preferably 0.01 to 0.10 MPa. It is adjusted appropriately depending on the angle.
積層体4の液晶パネルに貼合される面側に設置された貼合ロール(第1の貼合ロール)の周速度は、反対側の貼合ロール(第2の貼合ロール)の周速度よりも速いことが好ましい。これにより、得られる偏光板に、液晶パネルに貼合される面が凸になり、その反対側の面が凹になるようなカール(正カール)を与えることができる。得られる偏光板に、液晶パネルに貼合される面が凹になり、その反対側の面が凸になるようなカール(逆カール)が付与された場合は、偏光板を液晶セルに貼合するときに、中央部に気泡を噛み込むなどの不具合が生じやすくなってしまう。なお、この場合、第1の貼合ロールとして金属製ロールを使用し、第2の貼合ロールとして少なくとも外周表面がゴム製のロールを使用することが好ましい。
The peripheral speed of the bonding roll (1st bonding roll) installed in the surface side bonded to the liquid crystal panel of the laminated body 4 is the peripheral speed of the opposite bonding roll (2nd bonding roll). Is faster. Thereby, it is possible to give the obtained polarizing plate a curl (positive curl) in which the surface bonded to the liquid crystal panel becomes convex and the opposite surface becomes concave. When the obtained polarizing plate is curled (reverse curl) so that the surface to be bonded to the liquid crystal panel is concave and the opposite surface is convex, the polarizing plate is bonded to the liquid crystal cell. When it does, it will become easy to produce malfunctions, such as a bubble biting in a center part. In this case, it is preferable to use a metal roll as the first laminating roll and to use a roll whose outer peripheral surface is made of rubber as the second laminating roll.
さらに、第2の貼合ロールの周速度を1としたとき、第1の貼合ロールの周速度の比が1.0050~1.0200であることがより好ましい。この範囲より第1の貼合ロールの周速度が速い場合は、正カールのカール量が大きくなりすぎ、偏光板を液晶セルに貼合するときに端部に気泡を噛み込むなどの不具合が生じやすく、さらには過酷な環境下に置かれた場合に正カールがさらに助長されて偏光板の端部が液晶セルから剥れる恐れがあるからである。
Furthermore, when the peripheral speed of the second laminating roll is 1, the ratio of the peripheral speeds of the first laminating roll is more preferably 1.0050 to 1.0200. When the peripheral speed of the first laminating roll is faster than this range, the curl amount of the positive curl becomes too large, causing problems such as entrapment of bubbles at the end when laminating the polarizing plate to the liquid crystal cell. This is because, when placed in a harsh environment, the positive curl is further promoted and the end of the polarizing plate may be peeled off from the liquid crystal cell.
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14,15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、ロール13の直径は特に限定されない。接着剤が未硬化状態の積層体4には、ロール13を通過する間の積算光量が10mJ/cm2以上となるように活性エネルギー線が照射されることが好ましい。ロール13は、積層体4のラインの動きに従動または回転駆動させてもよく、あるいは固定させて表面を積層体4が滑るようにしてもよい。また、ロール13は、活性エネルギー線の照射による重合硬化時に、積層体4に生じる熱を放熱させるための冷却ロールとして作用させてもよい。その場合、冷却ロールの表面温度は、4~30℃に設定されることが好ましい。
The roll 13 constitutes a convex curved surface whose outer peripheral surface is mirror-finished, and the laminate 4 is conveyed while closely contacting the surface, and the adhesive is polymerized and cured by the active energy ray irradiation devices 14 and 15 in the process. . The diameter of the roll 13 is not particularly limited when the adhesive is polymerized and cured and the laminate 4 is sufficiently adhered. The laminated body 4 in which the adhesive is in an uncured state is preferably irradiated with active energy rays so that the cumulative amount of light while passing through the roll 13 is 10 mJ / cm 2 or more. The roll 13 may be driven or rotated according to the movement of the line of the laminate 4 or may be fixed so that the laminate 4 slides on the surface. Further, the roll 13 may act as a cooling roll for dissipating heat generated in the laminate 4 at the time of polymerization and curing by irradiation with active energy rays. In that case, the surface temperature of the cooling roll is preferably set to 4 to 30 ° C.
(活性エネルギー線照射工程)
活性エネルギー線の照射により接着剤の重合硬化を行うために用いる光源は、特に限定されないが、波長400nm以下に発光分布を有する光源であることが好ましい。このような光源としては、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、ブラックライトランプ、マイクロウェーブ励起水銀灯、メタルハライドランプが挙げられる。 (Active energy ray irradiation process)
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.
活性エネルギー線の照射により接着剤の重合硬化を行うために用いる光源は、特に限定されないが、波長400nm以下に発光分布を有する光源であることが好ましい。このような光源としては、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、ブラックライトランプ、マイクロウェーブ励起水銀灯、メタルハライドランプが挙げられる。 (Active energy ray irradiation process)
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.
活性エネルギー線硬化型接着剤への光照射強度は、接着剤の組成ごとに決定されるものであって特に限定されないが、10~5000mW/cm2であることが好ましい。樹脂組成物への光照射強度が10mW/cm2未満であると、反応時間が長くなりすぎ、5000mW/cm2を超えると、ランプから輻射される熱および組成物の重合時の発熱により、接着剤の構成材料であるエポキシ樹脂組成物などの黄変や偏光フィルムの劣化を生じる可能性がある。なお、照射強度は、好ましくは光カチオン重合開始剤の活性化に有効な波長領域における強度であり、より好ましくは波長400nm以下の波長領域における強度であり、さらに好ましくは波長280~320nmの波長領域における強度である。
The light irradiation intensity to the active energy ray-curable adhesive is determined for each composition of the adhesive and is not particularly limited, but is preferably 10 to 5000 mW / cm 2 . When the light irradiation intensity to the resin composition is less than 10 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 lamp and heat generated during polymerization of the composition. There is a possibility that 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. Strength.
活性エネルギー線硬化型接着剤への活性エネルギー線の照射時間は、硬化する組成物毎に制御されるものであって、特に限定されないが、照射強度と照射時間の積として表される積算光量が10mJ/cm2以上、好ましくは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。
The irradiation time of the active energy ray to the active energy ray-curable adhesive is controlled for each composition to be cured, and is not particularly limited, but the integrated light amount expressed as the product of the irradiation intensity and the irradiation time is 10 mJ / cm 2 or more, preferably is preferably set to be 10 ~ 5,000mJ / cm 2. When the integrated light amount to the adhesive is less than 10 mJ / cm 2 , the generation of active species derived from the initiator is not sufficient, and the adhesive is not sufficiently cured. On the other hand, when the integrated light quantity exceeds 5,000 mJ / cm 2 , the irradiation time becomes very long, which is disadvantageous for improving productivity. At this time, 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.
本発明においては、積層体に活性エネルギー線を照射して接着剤を重合硬化させるが、加熱による重合硬化を併用してもよい。
In the present invention, the laminate is irradiated with active energy rays to polymerize and cure the adhesive, but polymerization curing by heating may be used in combination.
活性エネルギー線が紫外線である場合、積層体4に活性エネルギー線を照射する工程では、積層体4に長手方向(搬送方向)に100~800N/mの張力をかけながら、照射時間が0.1秒以上となるようなライン速度で積層体4が搬送されることが好ましい。また、紫外線の照射強度は10mW/cm2以上とすることが好ましい。
When the active energy rays are ultraviolet rays, in the step of irradiating the laminate 4 with the active energy rays, 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. Moreover, it is preferable that the irradiation intensity | strength of an ultraviolet-ray shall be 10 mW / cm < 2 > or more.
また、活性エネルギー線照射装置14,15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。これらの全工程における積算光量が10mJ/cm2以上、好ましくは10~5,000mJ/cm2となるように設定されることが好ましい。このように、活性エネルギー線を照射する工程においては、活性エネルギー線の照射は複数回に分けて行われることが好ましい。
When the accumulated amount of active energy rays by the active energy ray irradiating devices 14 and 15 is insufficient, second and subsequent active energy ray irradiating devices 16 to 18 are further provided to additionally irradiate active energy rays, and the laminated body It is preferable to accelerate the curing of the adhesive No. 4. Integrated light intensity in these whole process is 10 mJ / cm 2 or more, preferably is preferably set to be 10 ~ 5,000mJ / cm 2. As described above, in the step of irradiating the active energy ray, the irradiation of the active energy ray is preferably performed in a plurality of times.
偏光板(積層体)端部の接着剤の硬化を確実に行うためには、例えば、無電極DバルブランプであるFUSION製「Light Hammer 10」をフィルム走行に対して横断するように並べる方法などが挙げられる。
In order to surely cure the adhesive at the end of the polarizing plate (laminate), for example, a method of arranging “Light Hammer 10” made by FUSION, which is an electrodeless D bulb lamp, so as to cross the film running. Is mentioned.
活性エネルギー線硬化型樹脂が硬化した割合、即ち反応率は、好ましくは90%以上、より好ましくは95%以上である。
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.
(偏光板巻取り工程)
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。 (Polarizing plate winding process)
The tension for winding the laminate (polarizing plate) 4 to 30N / cm 2 ~ 150N / cm 2. Preferably, 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.
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。 (Polarizing plate winding process)
The tension for winding the laminate (polarizing plate) 4 to 30N / cm 2 ~ 150N / cm 2. Preferably, 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.
なお、巻き長さが長くなるほど、同一張力では巻き締まり(繰り出した際に平坦な状態に戻り難くなる現象)が起き易くなるため、偏光板をコアに巻きながら張力を連続的または段階的に低下させてもよい。このような所謂テーパーをかけて張力を下げる方法においても、その際の張力は150N/cm2以下とする。
Note that the longer the winding length, the more likely it is that tight tightening (a phenomenon that makes it difficult to return to a flat state when unwinding) occurs at the same tension, so the tension decreases continuously or stepwise while winding the polarizing plate around the core. You may let them. Even in such a method of reducing the tension by applying a so-called taper, the tension at that time is 150 N / cm 2 or less.
コアに巻き取られる偏光板の長さは、特に限定されないが、好ましくは100m以上4000m以下である。
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.
円筒状のコアの直径は、6インチ~12インチが好ましい。コアの直径は大きいほど好ましく、11インチ、12インチなどより好ましいが、さらに大きすぎると移送や保管が難しくなる。
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.
円筒状コアの材質は、クリーンルームで使用するため、それ自身が発塵し難く、広い幅の偏光板を巻き取れるように適切な強度が確保できれば特に限定はないが、FRP(ガラス繊維強化プラスチック)などを選択できる。
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.
以下に実施例を挙げて、本発明をさらに詳しく説明するが、本発明はこれら実施例に限定されるものではない。
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
[実施例1]
(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「ビニロンVF-PS#7500(クラレ製)」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。 [Example 1]
(Preparation of polarizing film)
As a polyvinyl alcohol raw film, a long polyvinyl alcohol film “Vinylon VF-PS # 7500 (manufactured by Kuraray)” having a polymerization degree of 2400, a saponification degree of 99.9 mol%, a thickness of 75 μm, 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.
(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「ビニロンVF-PS#7500(クラレ製)」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。 [Example 1]
(Preparation of polarizing film)
As a polyvinyl alcohol raw film, a long polyvinyl alcohol film “Vinylon VF-PS # 7500 (manufactured by Kuraray)” having a polymerization degree of 2400, a saponification degree of 99.9 mol%, a thickness of 75 μm, 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.
まず、原反フィルムが弛まないように、フィルムの緊張状態を保ったまま、30℃の純水が入った膨潤槽に80秒間浸漬し、フィルムを十分に膨潤させた。膨潤槽での膨潤に伴う入口と出口のロール速度比は1.2であった。ニップロールでの水切りを行った後、30℃の純水が入った水浸漬槽に160秒間浸漬した。この槽中での機械方向の延伸倍率は1.09倍とした。
First, 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.
次に、ヨウ素/ヨウ化カリウム/水が重量比で0.02/2.0/100の水溶液が入った染色槽に浸漬しつつ、延伸倍率約1.5倍で一軸延伸を行った。その後、ヨウ化カリウム/ホウ酸/水が重量比で12/3.7/100の水溶液が入ったホウ酸槽に55.5℃で130秒間浸漬しつつ、原反からの積算延伸倍率が5.7倍になるまで一軸延伸を行った。その後、ヨウ化カリウム/ホウ酸/水が重量比で9/2.4/100の水溶液が入ったホウ酸槽に40℃で60秒間浸漬した。
Next, 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.
さらに、水洗槽にて8℃の純水で約16秒間洗浄し、その後、約60℃の乾燥炉、次に約85℃の乾燥炉を順次通過させ、それら乾燥炉での滞留時間を合計160秒間として乾燥を行った。こうして、ヨウ素が吸着配向された厚み28μmの偏光フィルムを得た。
Further, it is washed with pure water at 8 ° C. for about 16 seconds in a water washing tank, and then sequentially passed through a drying furnace at about 60 ° C. and then a drying furnace at about 85 ° C., and the residence time in these drying furnaces is 160 in total. Drying was performed for a second. Thus, a polarizing film having a thickness of 28 μm on which iodine was adsorbed and oriented was obtained.
(偏光板の作製)
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。 (Preparation of polarizing plate)
As a transparent film, an acetic acid cellulose resin film “KC4CR-1 (manufactured by Konica Minolta Opto Co., Ltd.)” having a retardation characteristic of 40 μm in thickness and a triacetyl cellulose film “KC8UX2MW” (Konica Minolta, Inc.) having a thickness of 80 μm are used. Prepared).
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。 (Preparation of polarizing plate)
As a transparent film, an acetic acid cellulose resin film “KC4CR-1 (manufactured by Konica Minolta Opto Co., Ltd.)” having a retardation characteristic of 40 μm in thickness and a triacetyl cellulose film “KC8UX2MW” (Konica Minolta, Inc.) having a thickness of 80 μm are used. Prepared).
次に、上記の厚さ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」の片面に、紫外線硬化型の接着剤であるエポキシ樹脂組成物「KRシリーズ」(ADEKA社製、カチオン重合開始剤含)を接着剤塗工装置(マイクロチャンバードクター:富士機械社製)を用いて塗工した。また、上記の厚さ80μmのトリアセチルセルロースフィルム「KC8UX2MW」の片面に、紫外線硬化型の接着剤であるエポキシ樹脂組成物「KRシリーズ」(ADEKA社製、カチオン重合開始剤含)を同じ接着剤塗工装置を用いて塗工した。この際、接着剤塗工装置における偏光フィルム積層体のライン速度を25m/分とし、グラビアロールを積層材の搬送方向と逆方向に回転させ、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」上の接着剤層の厚さを約3.5μmとし、厚さ80μmのトリアセチルセルロースフィルム「KC8UX2MW」上の接着剤層の厚さを約3.5μmとした。
Next, an epoxy resin composition “KR series” (manufactured by ADEKA Co., Ltd.), which is an ultraviolet curable adhesive, is applied to one side of the cellulose acetate resin film “KC4CR-1” to which the retardation property of 40 μm thickness is given. , Including a cationic polymerization initiator) was applied using an adhesive coating apparatus (Microchamber Doctor: manufactured by Fuji Machine Co., Ltd.). Also, an epoxy resin composition “KR series” (made by ADEKA, including a cationic polymerization initiator) which is an ultraviolet curable adhesive is applied to the same adhesive on one side of the 80 μm thick triacetyl cellulose film “KC8UX2MW”. Coating was performed using a coating apparatus. At this time, the line speed of the polarizing film laminate in the adhesive coating apparatus was set to 25 m / min, the gravure roll was rotated in the direction opposite to the conveying direction of the laminated material, and the cellulose acetate roll provided with a retardation property of 40 μm in thickness. The thickness of the adhesive layer on the resin film “KC4CR-1” was about 3.5 μm, and the thickness of the adhesive layer on the 80 μm thick triacetyl cellulose film “KC8UX2MW” was about 3.5 μm.
次に、上記偏光フィルムの両面に、上記の厚さ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」と厚さ80μmのトリアセチルセルロースフィルム「KC8UX2MW」を、上記エポキシ樹脂組成物(紫外線硬化型接着剤)を介して、一対の貼合ロールによって貼り合わせた。この際、貼合ロールにシリコン系除塵ロール「HSSシリーズ(YanGo社製)」と、この除塵ロールに接するように転写用粘着ロール「AMS粘着シートロール(製品名)/ARSPプリカット粘着シートロール(商品名)(YanGo社製)」を設けた。また、除塵ロールの表面を構成する材料の転写用粘着ロールに対する粘着力は0.74kgfであった。
Next, the cellulose acetate resin film “KC4CR-1” and the 80 μm-thick triacetyl cellulose film “KC8UX2MW” to which the retardation property of 40 μm thickness is imparted on both surfaces of the polarizing film are combined with the epoxy resin. It bonded together by a pair of bonding roll through the composition (ultraviolet curable adhesive). At this time, the silicon-based dust removal roll “HSS series (manufactured by YanGo)” is used as the bonding roll, and the transfer adhesive roll “AMS pressure-sensitive adhesive sheet roll (product name) / ARSP pre-cut pressure-sensitive adhesive sheet roll (product) Name) (manufactured by YanGo) ". Moreover, the adhesive force with respect to the adhesive roll for transfer of the material which comprises the surface of a dust removal roll was 0.74 kgf.
上記2種の透明フィルムが貼合された偏光フィルムを、長手方向に600N/mの張力を掛け冷却ロールに密着させながらライン速度25m/分で移送し、メタルハライドランプ2灯(GS-YUASA社製、1灯の電力量130W/cm)から照射される紫外線中を通過させて第1の活性エネルギー線照射工程を行ない、その後に設けられた無電極Dバルブランプ3灯(Fusion社製「Light Hammer 10」、1灯の電力量216W/cm)から照射される紫外線中を通過させて第2の活性エネルギー線照射を行ない、偏光板を作製した。
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 closely contacting the cooling roll, and 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 W / cm) was passed through the ultraviolet rays irradiated to irradiate the second active energy ray, and a polarizing plate was produced.
上記無電極Dバルブランプ1灯は、フィルムの幅方向に無電極Dバルブランプを6台並べてなるユニットを、フィルムの長手方向に1列配置させたものであった。
The one electrodeless D bulb lamp is a unit in which six units of electrodeless D bulb lamps are arranged in the width direction of the film and arranged in one row in the longitudinal direction of the film.
メタルハライドランプ通過時は、上記偏光フィルムに貼合された厚さ80μmのトリアセチルセルロースフィルム「KC8UX2MW」を、23℃に設定された冷却ロールの外周面に接触させ、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」側から紫外線を照射した。
When passing through the metal halide lamp, the 80 μm thick triacetylcellulose 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 retardation characteristic of 40 μm thickness is obtained. Ultraviolet rays were irradiated from the side of the applied cellulose acetate resin film “KC4CR-1”.
(欠陥発生率の評価)
実施例1において、生産した偏光板の長さ(m)に対し、貼合ロールに付着した異物起因の欠陥の発生回数を調査したところ、4回/100万mであった。結果を表1に示す。 (Evaluation of defect rate)
In Example 1, the number of occurrences of defects due to the foreign matter adhering to the bonding roll was investigated with respect to the length (m) of the produced polarizing plate, and was 4 times / 1,000,000 m. The results are shown in Table 1.
実施例1において、生産した偏光板の長さ(m)に対し、貼合ロールに付着した異物起因の欠陥の発生回数を調査したところ、4回/100万mであった。結果を表1に示す。 (Evaluation of defect rate)
In Example 1, the number of occurrences of defects due to the foreign matter adhering to the bonding roll was investigated with respect to the length (m) of the produced polarizing plate, and was 4 times / 1,000,000 m. The results are shown in Table 1.
[実施例2]
貼合ロールにシリコン系除塵ロール「LPSシリーズ(YanGo社製)」と、この除塵ロールに接するように転写用粘着ロール(YanGo社製)を設け、除塵ロールの表面を構成する材料の転写用粘着ロールに対する粘着力が0.52kgfであったこと以外は、実施例1と同様にして偏光板を作製した。 [Example 2]
A silicon-based dust removal roll “LPS series (YanGo)” and a transfer adhesive roll (YanGo) in contact with this dust removal roll are provided on the bonding roll, and the transfer adhesive for the material constituting the surface of the dust removal roll A polarizing plate was produced in the same manner as in Example 1 except that the adhesive strength to the roll was 0.52 kgf.
貼合ロールにシリコン系除塵ロール「LPSシリーズ(YanGo社製)」と、この除塵ロールに接するように転写用粘着ロール(YanGo社製)を設け、除塵ロールの表面を構成する材料の転写用粘着ロールに対する粘着力が0.52kgfであったこと以外は、実施例1と同様にして偏光板を作製した。 [Example 2]
A silicon-based dust removal roll “LPS series (YanGo)” and a transfer adhesive roll (YanGo) in contact with this dust removal roll are provided on the bonding roll, and the transfer adhesive for the material constituting the surface of the dust removal roll A polarizing plate was produced in the same manner as in Example 1 except that the adhesive strength to the roll was 0.52 kgf.
(欠陥発生率の評価)
実施例2において、生産した偏光板の長さ(m)に対し、貼合ロールに付着した異物起因の欠陥の発生回数を調査したところ、4回/100万mであった。結果を表1に示す。 (Evaluation of defect rate)
In Example 2, the number of occurrences of defects due to foreign matters adhering to the bonding roll was investigated with respect to the length (m) of the produced polarizing plate, and was 4 times / 1,000,000 m. The results are shown in Table 1.
実施例2において、生産した偏光板の長さ(m)に対し、貼合ロールに付着した異物起因の欠陥の発生回数を調査したところ、4回/100万mであった。結果を表1に示す。 (Evaluation of defect rate)
In Example 2, the number of occurrences of defects due to foreign matters adhering to the bonding roll was investigated with respect to the length (m) of the produced polarizing plate, and was 4 times / 1,000,000 m. The results are shown in Table 1.
[実施例3]
貼合ロールにシリコン系除塵ロール「RUSシリーズ(YanGo社製)」と、この除塵ロールに接するように転写用粘着ロール(YanGo社製)を設け、除塵ロールの表面を構成する材料の転写用粘着ロールに対する粘着力が0.38kgfであったこと以外は、実施例1と同様にして偏光板を作製した。 [Example 3]
A silicon-based dust removal roll “RUS series (YanGo)” and a transfer adhesive roll (YanGo) in contact with this dust removal roll are provided on the bonding roll, and transfer adhesive for the material constituting the surface of the dust removal roll. A polarizing plate was produced in the same manner as in Example 1 except that the adhesive strength to the roll was 0.38 kgf.
貼合ロールにシリコン系除塵ロール「RUSシリーズ(YanGo社製)」と、この除塵ロールに接するように転写用粘着ロール(YanGo社製)を設け、除塵ロールの表面を構成する材料の転写用粘着ロールに対する粘着力が0.38kgfであったこと以外は、実施例1と同様にして偏光板を作製した。 [Example 3]
A silicon-based dust removal roll “RUS series (YanGo)” and a transfer adhesive roll (YanGo) in contact with this dust removal roll are provided on the bonding roll, and transfer adhesive for the material constituting the surface of the dust removal roll. A polarizing plate was produced in the same manner as in Example 1 except that the adhesive strength to the roll was 0.38 kgf.
(欠陥発生率の評価)
実施例3において、生産した偏光板の長さ(m)に対し、貼合ロールに付着した異物起因の欠陥の発生回数を調査したところ、6回/100万mであった。結果を表1に示す。 (Evaluation of defect rate)
In Example 3, the number of occurrences of defects due to the foreign matter adhering to the laminating roll was investigated with respect to the length (m) of the produced polarizing plate, and was 6 times / 1,000,000 m. The results are shown in Table 1.
実施例3において、生産した偏光板の長さ(m)に対し、貼合ロールに付着した異物起因の欠陥の発生回数を調査したところ、6回/100万mであった。結果を表1に示す。 (Evaluation of defect rate)
In Example 3, the number of occurrences of defects due to the foreign matter adhering to the laminating roll was investigated with respect to the length (m) of the produced polarizing plate, and was 6 times / 1,000,000 m. The results are shown in Table 1.
[実施例4]
貼合ロールに転写用粘着ロールを設けなかったこと以外は、実施例1と同様にして偏光板を作製した。 [Example 4]
A polarizing plate was produced in the same manner as in Example 1, except that the transfer roll was not provided on the bonding roll.
貼合ロールに転写用粘着ロールを設けなかったこと以外は、実施例1と同様にして偏光板を作製した。 [Example 4]
A polarizing plate was produced in the same manner as in Example 1, except that the transfer roll was not provided on the bonding roll.
(貼合ロール付着異物起因欠陥の発生率の評価)
実施例4において、生産した数量に対し、貼合ロールに付着した異物起因の欠陥の発生率を調査したところ、4回/30万mであった。結果を表1に示す。 (Evaluation of occurrence rate of defects due to foreign matter adhered to the bonding roll)
In Example 4, when the occurrence rate of the defect caused by the foreign matter adhering to the bonding roll was investigated with respect to the produced quantity, it was 4 times / 300,000 m. The results are shown in Table 1.
実施例4において、生産した数量に対し、貼合ロールに付着した異物起因の欠陥の発生率を調査したところ、4回/30万mであった。結果を表1に示す。 (Evaluation of occurrence rate of defects due to foreign matter adhered to the bonding roll)
In Example 4, when the occurrence rate of the defect caused by the foreign matter adhering to the bonding roll was investigated with respect to the produced quantity, it was 4 times / 300,000 m. The results are shown in Table 1.
[比較例1]
貼合ロールに除塵ロールおよび転写用粘着ロールを設けなかったこと以外は、実施例1と同様にして偏光板を作製した。 [Comparative Example 1]
A polarizing plate was produced in the same manner as in Example 1 except that the dust removal roll and the transfer adhesive roll were not provided on the bonding roll.
貼合ロールに除塵ロールおよび転写用粘着ロールを設けなかったこと以外は、実施例1と同様にして偏光板を作製した。 [Comparative Example 1]
A polarizing plate was produced in the same manner as in Example 1 except that the dust removal roll and the transfer adhesive roll were not provided on the bonding roll.
(貼合ロール付着異物起因欠陥の発生率の評価)
比較例1において、生産した数量に対し、貼合ロールに付着した異物起因の欠陥の発生率を調査したところ、4回以上/10万mであった。結果を表1に示す。 (Evaluation of occurrence rate of defects due to foreign matter adhered to the bonding roll)
In the comparative example 1, when the incidence rate of the defect by the foreign material adhering to the bonding roll was investigated with respect to the produced quantity, it was 4 times / 100,000 m or more. The results are shown in Table 1.
比較例1において、生産した数量に対し、貼合ロールに付着した異物起因の欠陥の発生率を調査したところ、4回以上/10万mであった。結果を表1に示す。 (Evaluation of occurrence rate of defects due to foreign matter adhered to the bonding roll)
In the comparative example 1, when the incidence rate of the defect by the foreign material adhering to the bonding roll was investigated with respect to the produced quantity, it was 4 times / 100,000 m or more. The results are shown in Table 1.
本発明の偏光板は、液晶表示装置をはじめとする各種表示装置に有効に適用することができる。
The polarizing plate of the present invention can be effectively applied to various display devices including liquid crystal display devices.
1 偏光フィルム、2,3 透明フィルム、4 積層体(偏光板)、11,12 接着剤塗工装置、13 ロール(冷却ロール)、14,15,16,17,18 活性エネルギー線照射装置、19 搬送用ニップロール、20 巻取ロール、51,52 貼合ロール、51a,52a 除塵ロール、51b,52b 転写用粘着ロール。
1 polarizing film, 2, 3 transparent film, 4 laminate (polarizing plate), 11, 12 adhesive coating device, 13 roll (cooling roll), 14, 15, 16, 17, 18 active energy ray irradiation device, 19 Transport nip roll, 20 take-up roll, 51, 52 bonding roll, 51a, 52a dust removal roll, 51b, 52b transfer adhesive roll.
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工工程と、
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んだ状態で、少なくとも一方の貼合ロールを他方の貼合ロールの方向に押圧することで、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活性エネルギー線照射工程とを備え、
前記一対の貼合ロールの少なくとも一方に接するように、前記貼合ロールの表面に付着した塵を除去するための除塵ロールが設けられていることを特徴とする、偏光板の製造方法。 A method for producing a polarizing plate in which a transparent film is bonded to one side or both sides of a polarizing film,
An adhesive coating step of applying an active energy ray-curable adhesive to one side or both sides of the transparent film or the polarizing film;
At least one laminating roll in a state where the transparent film is sandwiched between a pair of laminating rolls rotating in the conveying direction, with a laminate in which the transparent film is laminated on one or both sides of the polarizing film via the adhesive. By pressing in the direction of the other bonding roll, a bonding step of bonding the transparent film and the polarizing film;
An active energy ray irradiation step of irradiating the laminate with an active energy ray to cure the adhesive; and
A method for producing a polarizing plate, wherein a dust removing roll for removing dust attached to the surface of the bonding roll is provided so as to be in contact with at least one of the pair of bonding rolls. - さらに、前記除塵ロールに接するように、前記除塵ロールの表面に付着した塵を除去するための転写用粘着ロールが設けられた、請求項1に記載の偏光板の製造方法。 Furthermore, the manufacturing method of the polarizing plate of Claim 1 with which the adhesion roll for transcription | transfer for removing the dust adhering to the surface of the said dust removal roll was provided so that the said dust removal roll might be contacted.
- 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装置であって、
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ための接着剤塗工装置と、
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、搬送しながら挟圧することにより、前記透明フィルムと前記偏光フィルムとを貼合するための一対の貼合ロールと、
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ための活性エネルギー線照射装置とを備え、
前記一対の貼合ロールの少なくとも一方に接するように、少なくとも1つの除塵ロールが設けられていることを特徴とする、偏光板の製造装置。 A polarizing plate manufacturing apparatus in which a transparent film is bonded to one side or both sides of a polarizing film,
An adhesive coating device for applying an active energy ray-curable adhesive on one side or both sides of the transparent film or the polarizing film;
A pair of the transparent film and the polarizing film are bonded together by sandwiching the transparent film while transporting a laminate in which the transparent film is laminated on one or both sides of the polarizing film via the adhesive. A bonding roll;
An active energy ray irradiating device for irradiating the laminate with an active energy ray to cure the adhesive;
An apparatus for producing a polarizing plate, wherein at least one dust removing roll is provided so as to be in contact with at least one of the pair of bonding rolls.
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-
2012
- 2012-10-23 KR KR1020147013843A patent/KR101815347B1/en active IP Right Grant
- 2012-10-23 CN CN201280052820.4A patent/CN103907036B/en active Active
- 2012-10-23 WO PCT/JP2012/077332 patent/WO2013061953A1/en active Application Filing
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CN103907036A (en) | 2014-07-02 |
KR101815347B1 (en) | 2018-01-04 |
WO2013061953A1 (en) | 2013-05-02 |
TW201331642A (en) | 2013-08-01 |
JP2013109335A (en) | 2013-06-06 |
JP6071413B2 (en) | 2017-02-01 |
TWI553353B (en) | 2016-10-11 |
KR20140094569A (en) | 2014-07-30 |
CN103907036B (en) | 2016-06-08 |
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