WO2012091145A1 - 光学フィルムの製造方法、偏光板および画像表示装置 - Google Patents

光学フィルムの製造方法、偏光板および画像表示装置 Download PDF

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Publication number
WO2012091145A1
WO2012091145A1 PCT/JP2011/080553 JP2011080553W WO2012091145A1 WO 2012091145 A1 WO2012091145 A1 WO 2012091145A1 JP 2011080553 W JP2011080553 W JP 2011080553W WO 2012091145 A1 WO2012091145 A1 WO 2012091145A1
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active energy
coating layer
film
region
meth
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PCT/JP2011/080553
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English (en)
French (fr)
Japanese (ja)
Inventor
昌 神崎
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住友化学株式会社
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Priority to KR1020137016778A priority Critical patent/KR101875244B1/ko
Priority to CN201180062702.7A priority patent/CN103269839B/zh
Publication of WO2012091145A1 publication Critical patent/WO2012091145A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/0266—Local curing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/10—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation for articles of indefinite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/14—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of indefinite length
    • B29C39/18—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of indefinite length incorporating preformed parts or layers, e.g. casting around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/04—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts
    • B29C59/046—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts for layered or coated substantially flat surfaces
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0034—Polarising

Definitions

  • the present invention relates to a method for producing an optical film in which a coating liquid containing an active energy ray-curable resin is applied on a base film and cured.
  • the present invention also relates to a polarizing plate and an image display device using the optical film.
  • An optical film formed by coating a resin layer having a predetermined optical function on a base film is used in various image display devices such as a liquid crystal display device as an antiglare film, a light diffusion film, a hard coat film, etc. ing.
  • the resin layer provided in the optical film is formed by applying a coating liquid containing an active energy ray-curable resin onto a substrate film, and irradiating the obtained coating layer with an active energy ray to be cured. It is formed by.
  • a mold having a predetermined surface shape may be pressed against the coating layer surface and cured in this state.
  • an ultraviolet curable resin is applied to a base film, and an ultraviolet ray is applied in a state where the resin-coated surface is in close contact with an uneven roller (embossing roll) that rotates in synchronization with the base film.
  • an uneven roller embssing roll
  • Resin residue is a continuous defect in the optical film obtained in the continuous production of an optical film in which a resin layer is continuously formed on a long base film (resin adhesion to the optical film surface or the surface of the optical film). Such as defects in shape or optical properties). Also, removing and cleaning the resin residue every time it occurs will greatly reduce the production efficiency.
  • the present invention has been made in view of the above, and provides a method capable of preventing the occurrence of resin residue and continuously and efficiently producing an optical film without causing defects such as defects. is there.
  • the resin layer peeling causing the resin residue when the optical film is peeled from the mold is a region where the coating layer thickness increases rapidly, that is, the film in the coating layer. It has been found that it is concentrated in the leading region (front end region of the coating layer) and the trailing region (rear end region of the coating layer) in the transport direction. Furthermore, as a means for preventing the resin residue, it is extremely effective to harden a region where the resin layer is easily peeled in advance before the step of curing the coating layer while pressing the mold. I found. In particular, precuring the leading region of the coating layer is extremely advantageous in preventing continuous defects when an optical film is produced by continuously forming a resin layer on a long base film. is there. On the other hand, precuring the tail region of the coating layer in advance is extremely advantageous in preventing continuous defects in the production of the optical film of the next lot (using the next base film).
  • the present invention includes the following.
  • a coating process for forming a coating layer by coating a coating film containing an active energy ray-curable resin on a substrate film that is continuously conveyed, and a leading region of the coating layer In the first curing step of irradiating active energy rays from the coating layer side and the surface of the mold pressed against the surface of the coating layer, the active energy rays are irradiated from the substrate film side to the coating layer And a second curing step.
  • [3] is an active energy ray is ultraviolet
  • the irradiation amount of the active energy ray to the top region in the first curing step an accumulated amount of light at UVA ultraviolet is 70 mJ / cm 2 or more 400 mJ / cm 2 or less [ [1] or [2].
  • the active energy ray is changed to the tail adjacent region prior to the irradiation of the active energy ray to the tail region, and the accumulated light amount gradually increases from 0 at the start point of the tail adjacent region.
  • [7] is an active energy ray is ultraviolet ray irradiation amount of the active energy ray to the tail region, in at 400 mJ / cm 2 or less 70 mJ / cm 2 or more in accumulated light amount of UVA ultraviolet [5] or [6] The method described.
  • a polarizing plate provided.
  • An image display device comprising the polarizing plate according to [9] and an image display element, wherein the polarizing plate is disposed on the image display element such that the polarizing film is on the image display element side.
  • the method of the present invention it is possible to effectively prevent the occurrence of resin residue when the optical film is peeled from the mold.
  • This causes continuous defects (resin adhesion to the surface, defects in surface shape or optical characteristics, etc.) in the continuous production of optical films in which a resin layer is continuously formed on a long base film.
  • the optical film can be produced continuously and efficiently without any trouble. Moreover, since it is not necessary to remove and clean the resin residue, the production efficiency can be greatly improved.
  • the optical film obtained by the present invention can be suitably applied to image display devices such as polarizing plates and liquid crystal display devices.
  • the method for producing an optical film of the present invention includes the following steps: [1] A coating process in which a coating liquid containing an active energy ray-curable resin is coated on a continuously transported base film to form a coating layer; [2] A first curing step of irradiating active energy rays from the coating layer side to the head region of the coating layer, [3] A second curing step of irradiating the coating layer with active energy rays from the base film side to cure the coating layer in a state where the surface of the mold is pressed against the surface of the coating layer. including.
  • FIG. 1 is a diagram schematically showing a preferred example of the method for producing an optical film of the present invention and a production apparatus used therefor.
  • FIG. 2 is a cross-sectional view schematically showing the first curing step. The arrows in the figure indicate the film transport direction or roll rotation direction.
  • Coating step In this step, a coating layer containing an active energy ray-curable resin is coated on a continuously transported substrate film to form a coating layer.
  • the coating process continuously unwinds the base film 11 from an original fabric (a long base film wound product) attached to the film unwinding device 31, It can be performed by applying a coating solution onto the substrate film 11 using the coating device 32.
  • Application of the coating liquid onto the base film 11 can be performed, for example, by a gravure coating method, a micro gravure coating method, a rod coating method, a knife coating method, an air knife coating method, a kiss coating method, a die coating method, or the like. .
  • the base film 11 only needs to be translucent, and for example, glass or plastic film can be used.
  • the plastic film only needs to have appropriate transparency and mechanical strength. Specific examples include cellulose acetate resins such as TAC (triacetylcellulose), acrylic resins, polycarbonate resins, polyester resins such as polyethylene terephthalate, and polyolefin resins such as polyethylene and polypropylene.
  • the thickness of the base film 11 is, for example, 10 to 500 ⁇ m, and is preferably 10 to 300 ⁇ m, more preferably 20 to 300 ⁇ m from the viewpoint of thinning the optical film.
  • Various surface treatments may be performed on the surface of the base film 11 (surface on the coating layer side) for the purpose of improving the coating property of the coating liquid or improving the adhesion with the coating layer.
  • the surface treatment include corona discharge treatment, glow discharge treatment, acid surface treatment, alkali surface treatment, and ultraviolet irradiation treatment.
  • other layers such as a primer layer, may be formed on the base film 11, and a coating liquid may be applied on this other layer.
  • the surface of the base film (on the side opposite to the coating layer) is used in order to improve the adhesion between the base film and the polarizing film.
  • the surface is preferably hydrophilized by various surface treatments. You may perform this surface treatment after manufacture of an optical film.
  • the coating liquid contains an active energy ray-curable resin and usually further contains a photopolymerization initiator (radical polymerization initiator). If necessary, other components such as translucent fine particles, solvents such as organic solvents, leveling agents, dispersants, antistatic agents, antifouling agents, and surfactants may be contained.
  • the active energy ray-curable resin can be an ultraviolet curable resin, an electron beam curable resin, or the like, and for example, one containing a polyfunctional (meth) acrylate compound is preferably used. be able to.
  • the polyfunctional (meth) acrylate compound is a compound having at least two (meth) acryloyloxy groups in the molecule.
  • Specific examples of the polyfunctional (meth) acrylate compound include, for example, ester compounds of polyhydric alcohol and (meth) acrylic acid, urethane (meth) acrylate compounds, polyester (meth) acrylate compounds, epoxy (meth) acrylate compounds, and the like. And a polyfunctional polymerizable compound containing two or more (meth) acryloyl groups.
  • polyhydric alcohol examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, propanediol, butanediol, and pentanediol.
  • Hexanediol Hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, 2,2'-thiodiethanol, divalent alcohols such as 1,4-cyclohexanedimethanol; trimethylolpropane, glycerol, pentaerythritol , Trihydric or higher alcohols such as diglycerol, dipentaerythritol and ditrimethylolpropane.
  • esterified products of polyhydric alcohol and (meth) acrylic acid include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and neopentyl glycol.
  • Examples of the urethane (meth) acrylate compound include urethanization reaction products of an isocyanate having a plurality of isocyanate groups in one molecule and a (meth) acrylic acid derivative having a hydroxyl group.
  • Examples of organic isocyanates having a plurality of isocyanate groups in one molecule include two isocyanates in one molecule such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, and dicyclohexylmethane diisocyanate.
  • Organic isocyanate having a group organic isocyanate having three isocyanate groups in one molecule obtained by subjecting these organic isocyanates to isocyanurate modification, adduct modification, biuret modification, and the like.
  • the (meth) acrylic acid derivative having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- Examples thereof include hydroxy-3-phenoxypropyl (meth) acrylate and pentaerythritol triacrylate.
  • the polyester (meth) acrylate compound is a polyester (meth) acrylate obtained by reacting a hydroxyl group-containing polyester with (meth) acrylic acid.
  • the hydroxyl group-containing polyester preferably used is a hydroxyl group-containing polyester obtained by an esterification reaction of a polyhydric alcohol, a carboxylic acid, a compound having a plurality of carboxyl groups, and / or an anhydride thereof.
  • the polyhydric alcohol include the same compounds as those described above.
  • bisphenol A etc. are mentioned as phenols other than a polyhydric alcohol.
  • the carboxylic acid include formic acid, acetic acid, butyl carboxylic acid, benzoic acid and the like.
  • the compounds having a plurality of carboxyl groups and / or their anhydrides include maleic acid, phthalic acid, fumaric acid, itaconic acid, adipic acid, terephthalic acid, maleic anhydride, phthalic anhydride, trimellitic acid, cyclohexanedicarboxylic anhydride Thing etc. are mentioned.
  • Ester compounds such as acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate; hexamethylene diisocyanate and 2-hydroxyethyl ( Addition product of (meth) acrylate; addition product of isophorone diisocyanate and 2-hydroxyethyl (meth) acrylate; attachment of tolylene diisocyanate and 2-hydroxyethyl (meth) acrylate Body; adduct adduct modified isophorone diisocyanate with 2-hydroxyethyl (meth) acrylate; and adducts of biuret of isophorone diisocyanate and 2-hydroxyethyl (meth) acrylate. Furthermore, each of these polyfunctional (meth) acrylate compounds can be used alone or in combination with one
  • the active energy ray curable resin may contain a monofunctional (meth) acrylate compound in addition to the polyfunctional (meth) acrylate compound.
  • the monofunctional (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and 2-hydroxyethyl (meth) ) Acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycidyl (meth) acrylate, acryloylmorpholine N-vinylpyrrolidone, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, 2-eth
  • the active energy ray curable resin may contain a polymerizable oligomer.
  • the polymerizable oligomer is, for example, the polyfunctional (meth) acrylate compound, that is, an ester compound of a polyhydric alcohol and (meth) acrylic acid, a urethane (meth) acrylate compound, a polyester (meth) acrylate compound, or an epoxy (meth). It can be an oligomer such as a dimer, trimer or the like such as an acrylate.
  • polymerizable oligomers include urethane (meth) acrylate oligomers obtained by reacting polyisocyanates having at least two isocyanate groups in the molecule with polyhydric alcohols having at least one (meth) acryloyloxy group.
  • polyisocyanate examples include hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, a polymer of xylylene diisocyanate, and the like.
  • Hydroxyl group-containing (meth) acrylic acid ester obtained by esterification reaction of alcohol and (meth) acrylic acid and as polyhydric alcohol, for example, 1,3-butanediol, 1,4-butanediol, 1,6 -Hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, glycerin, pentaerythritol What is dipentaerythritol and the like.
  • 1,3-butanediol, 1,4-butanediol, 1,6 -Hexanediol diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, glycerin, pentaerythritol What is dipentaerythritol and the like.
  • this polyhydric alcohol having at least one (meth) acryloyloxy group a part of the alcoholic hydroxyl group of the polyhydric alcohol is esterified with (meth) acrylic acid, and the alcoholic hydroxyl group is present in the molecule. It remains.
  • a polyhydric alcohol having at least one (meth) acryloyloxy group is an organic compound having at least one (meth) acryloyloxy group.
  • Acrylate oligomers examples of the compound having a plurality of carboxyl groups and / or anhydrides thereof are the same as those described for the polyester (meth) acrylate of the polyfunctional (meth) acrylate compound.
  • the polyhydric alcohol having at least one (meth) acryloyloxy group include those described for the urethane (meth) acrylate oligomer.
  • examples of urethane (meth) acrylate oligomers are obtained by reacting isocyanates with hydroxyl groups of a hydroxyl group-containing polyester, a hydroxyl group-containing polyether or a hydroxyl group-containing (meth) acrylic acid ester.
  • the hydroxyl group-containing polyester preferably used is a hydroxyl group-containing polyester obtained by an esterification reaction of a polyhydric alcohol, a carboxylic acid, a compound having a plurality of carboxyl groups, and / or an anhydride thereof.
  • polyhydric alcohol examples include the same as those described for the polyester (meth) acrylate compound of the polyfunctional (meth) acrylate compound.
  • the hydroxyl group-containing polyether preferably used is a hydroxyl group-containing polyether obtained by adding one or more alkylene oxides and / or ⁇ -caprolactone to a polyhydric alcohol.
  • the polyhydric alcohol may be the same as that which can be used for the hydroxyl group-containing polyester.
  • the hydroxyl group-containing (meth) acrylic acid ester examples include the same as those described for the polymerizable oligomeric urethane (meth) acrylate oligomer.
  • isocyanates compounds having one or more isocyanate groups in the molecule are preferable, and divalent isocyanate compounds such as tolylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate are particularly preferable.
  • Each of these polymerizable oligomer compounds can be used alone or in combination with one or more other compounds.
  • Photopolymerization initiator examples include acetophenone photopolymerization initiators, benzoin photopolymerization initiators, benzophenone photopolymerization initiators, thioxanthone photopolymerization initiators, and triazine photopolymerization initiators.
  • An oxadiazole-based photopolymerization initiator is used.
  • photopolymerization initiator examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 '-Biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound and the like can also be used.
  • the amount of the photopolymerization initiator used is usually 0.5 to 20 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the active energy ray-curable resin.
  • the translucent fine particles are not particularly limited.
  • inorganic fine particles made of calcium carbonate, silica, aluminum oxide, barium carbonate, barium sulfate, titanium oxide, glass, or the like can be used.
  • An organic polymer balloon or hollow beads can also be used.
  • These translucent fine particles may be used individually by 1 type, and 2 or more types may be mixed and used for them.
  • the shape of the translucent fine particles may be any of a spherical shape, a flat shape, a plate shape, a needle shape, an indefinite shape, and the like.
  • the particle diameter and refractive index of the light-transmitting fine particles are not particularly limited, but when the optical film is a light diffusion film or an antiglare film, the particle diameter is 0 from the viewpoint of effectively developing internal haze. It is preferably in the range of 5 ⁇ m to 20 ⁇ m. For the same reason, the difference between the refractive index of the cured active energy ray-curable resin and the refractive index of the translucent fine particles is preferably in the range of 0.04 to 0.15.
  • the content of the light-transmitting fine particles is usually 3 to 60 parts by weight, preferably 5 to 50 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin.
  • the content of the translucent fine particles is less than 3 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin, the light diffusibility or the antiglare property may not be sufficiently provided. On the other hand, if it exceeds 60 parts by weight, the transparency of the optical film may be impaired, and the antiglare property and the light diffusibility become too high and the contrast tends to be lowered.
  • distribution of the translucent fine particles in a coating liquid is isotropic dispersion
  • the coating liquid can contain a solvent such as an organic solvent.
  • organic solvents include aliphatic hydrocarbons such as hexane, cyclohexane, and octane; aromatic hydrocarbons such as toluene and xylene; alcohols such as ethanol, 1-propanol, isopropanol, 1-butanol, and cyclohexanol; methyl ethyl ketone and methyl isobutyl.
  • Ketones such as ketone and cyclohexanone; esters such as ethyl acetate, butyl acetate and isobutyl acetate; glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether Ethers; ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, etc.
  • Stealted glycol ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol; 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2- It can be selected from carbitols such as butoxyethoxy) ethanol in consideration of viscosity and the like.
  • These solvents may be used alone or as a mixture of several kinds as required. After coating, it is necessary to evaporate the organic solvent. Therefore, the boiling point is desirably in the range of 60 ° C to 160 ° C.
  • the saturated vapor pressure at 20 ° C. is preferably in the range of 0.1 kPa to 20 kPa.
  • the coating liquid contains a solvent
  • the drying temperature is appropriately selected depending on the solvent used and the type of substrate film. Generally, it is in the range of 20 ° C. to 120 ° C., but is not limited thereto. When there are a plurality of drying furnaces, the temperature may be changed for each drying furnace.
  • the head region (front end region) of the coating layer is irradiated with active energy rays from the coating layer side, and this head region is pressed against the mold surface.
  • This is a step of curing in advance prior to the second curing step of curing the coating layer.
  • the leading region of the coating layer is a portion where the thickness of the coating layer is remarkably increased, and is a portion where the resin peeling is concentrated.
  • the resin residue when an optical film is produced by continuously forming a resin layer on a long base film, if a resin residue occurs from the production start stage, the resin residue The entire optical film produced using the film is adversely affected.
  • the head region and the tail region described later can be identified by continuously measuring the film thickness.
  • a coating layer obtained by a general coating method unless the film thickness is intentionally changed, almost all of the region where the film thickness rapidly increases is from a part considerably smaller than 1 cm from the tip part, or from the rear end part. Since it is formed only in a portion considerably smaller than 1 cm, in practice, the above-described film thickness measurement or the like is not performed, and for example, 1 cm from the front end can be regarded as the head region and 1 cm from the rear end as the rear region.
  • the irradiation of the active energy ray to the coating layer head region is performed, for example, on the coating layer 12 that has passed through the coating device 32 (drying furnace 33 when drying). It can carry out by irradiating an active energy ray with respect to the base film 11 which has it using active energy ray irradiation apparatuses 10, such as an ultraviolet irradiation device installed in the coating layer 12 side. Specifically, the active energy ray irradiation device 10 is turned on (a state where the active energy rays are irradiated) before the head region A of the coating layer 12 passes immediately below the active energy ray irradiation device 10. After passing through the head region A, the active energy ray irradiating apparatus 10 is turned off (the active energy ray irradiation is stopped).
  • active energy ray irradiation apparatus 10 is turned on (a state where the active energy rays are irradiated) before the head region A of the coating layer 12 passes immediately below the active energy ray irradi
  • the active energy ray can be appropriately selected from ultraviolet rays, electron rays, near ultraviolet rays, visible light, near infrared rays, infrared rays, X-rays and the like according to the type of the active energy ray curable resin contained in the coating liquid.
  • ultraviolet rays and electron beams are preferred, and ultraviolet rays are particularly preferred because they are easy to handle and provide high energy.
  • a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
  • An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used.
  • an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a xenon arc, and a metal halide lamp are preferably used.
  • the electron beam 50 to 1000 keV emitted from various electron beam accelerators such as Cockloft Walton type, Bande graph type, resonance transformation type, insulation core transformation type, linear type, dynamitron type, and high frequency type, preferably 100
  • An electron beam having an energy of ⁇ 300 keV can be mentioned.
  • Irradiation amount to the head area in the first curing step when the active energy ray is ultraviolet, an accumulated amount of light at UVA ultraviolet, is preferably 70 mJ / cm 2 or more 400 mJ / cm 2 or less, more preferably 100mJ / Cm 2 or more and 250 mJ / cm 2 or less. If the integrated light quantity is less than 70 mJ / cm 2 , the degree of cure of the leading region A is too low, and there is a possibility that resin peeling (and hence resin residue) may occur.
  • the curing reaction proceeds excessively, and as a result, the resin peels off at the boundary between the cured portion (leading region A) and the uncured portion due to a difference in film thickness or distortion of internal stress. May occur.
  • the active energy ray After the irradiation of the active energy ray to the head region A in the first curing step, in the head adjacent region in contact with the head region, the active energy ray continues to the head adjacent region, and the integrated light amount is determined from the irradiation amount to the head region. It is preferable to irradiate so that it may decrease gradually along the conveyance direction of a film to 0 at the end point. Thereby, since the degree of curing in the leading region A gradually decreases to an uncured state along the film conveyance direction, the film at the boundary between the cured portion (leading region A) and the uncured portion of the coating layer Resin peeling that may occur due to thickness difference or distortion of internal stress can be prevented.
  • the head adjacent region refers to a region adjacent to the head region and until the irradiation dose becomes zero by irradiating the active energy ray while gradually decreasing the irradiation amount to the head region.
  • the irradiation amount may start to decrease immediately from the start point of the head adjacent region that is in contact with the head region, and the irradiation amount to the head region may continue from the start point to the head region, and then start to decrease.
  • the start point of the head adjacent region is also specified by looking.
  • the reduction rate of the integrated light amount per second in UVA of ultraviolet rays is preferably 1500 mJ / cm 2 ⁇ sec or less, and 1000 mJ / cm 2. -More preferably, it is less than a second. If the reduction rate of the integrated light amount is too high, even if the integrated light amount is gradually decreased, the effect cannot be sufficiently obtained, and at the boundary between the cured portion (leading region A) and the uncured portion, Resin peeling may occur due to a difference in film thickness or distortion of internal stress.
  • the width of the head adjacent area can be appropriately determined by adjusting the irradiation amount to the head area and the decreasing rate of the integrated light amount, but is usually about 0.3 to 500 cm.
  • the first curing step it is preferable to irradiate an active energy ray to the tail region in addition to the leading region A of the coating layer to cure it. This is because the film thickness of the coating layer is also remarkably thick in the tail region, and the resin peeling is concentrated.
  • the resin residue on the mold can be effectively prevented.
  • preventing the resin residue caused by the tail region of the coating layer is extremely advantageous in preventing continuous defects in manufacturing the optical film of the next lot (using the next base film). is there.
  • the irradiation of the active energy ray to the tail region of the coating layer is specifically performed with reference to FIG. 2 when the tail region B of the coating layer 12 approaches or directly below the active energy ray irradiation device 10.
  • the active energy beam irradiation device 10 is turned on (a state where the active energy beam has been irradiated) immediately before passing through, and this state is maintained until the tail region B has passed.
  • the irradiation amount to the tail region when the active energy ray is ultraviolet, an accumulated amount of light at UVA ultraviolet, preferably be 70 mJ / cm 2 or more 400 mJ / cm 2 or less , more preferably 100 mJ / cm 2 or more 250 mJ / cm 2 or less.
  • the active energy ray Prior to irradiation of the active energy ray to the coating layer tail region B, for the same reason as in the case of the head region A, the active energy ray is placed in the tail adjacent region, and the integrated light quantity is from 0 at the start point of the tail adjacent region.
  • the tail adjacent region refers to a region that is adjacent to the tail region and is irradiated with the active energy ray so as to gradually increase from the above-described irradiation amount of 0 to reach the irradiation amount in the trailing region.
  • the irradiation dose may be increased so as to reach the irradiation dose to the tail region at the end point of the tail adjacent region in contact with the tail region, and the irradiation amount to the tail region is reached at an appropriate point before the end point.
  • the irradiation amount to the tail area may be continued until the end point.
  • the end point of the tail adjacent area is also specified by looking.
  • the increase rate of the integrated light amount per second in UVA of ultraviolet rays is 1500 mJ / cm 2 for the same reason as in the head region A.
  • -It is preferable that it is 2 seconds or less, and it is more preferable that it is 1000 mJ / cm 2 ⁇ second or less.
  • the rear adjacent region width can be appropriately determined by adjusting the irradiation amount in the rear region and the increasing rate of the integrated light quantity, but is usually about 0.3 to 500 cm.
  • the method of gradually changing (decreasing or increasing) the integrated light quantity is not particularly limited, and for example, a method of gradually changing the voltage applied to the active energy ray irradiation device 10; A method of using a comb filter having a plurality of tapered comb teeth whose width gradually decreases in the shutter opening / closing direction as the shutter. (As a result, when the shutter is closed / opened, the integrated light amount gradually decreases / increases depending on the opening area between the comb teeth.) As the shutter, a neutral density filter having a different attenuation rate is gradually reduced.
  • a method using an arrangement in which the rate changes (for example, an arrangement in which the light attenuation rate gradually increases from the end of the shutter) If the shutter is used, when the shutter is closed / opened, the integrated light quantity gradually decreases / increases depending on the light attenuation rate of the filter.); Or a combination of any two or more of the above Can do.
  • Second curing step This step irradiates the coating layer with active energy rays from the substrate film side in a state where the surface of the mold having a predetermined surface shape is pressed against the surface of the coating layer. It is a step of forming a cured resin layer on the base film by curing the coating layer. Thereby, the coating layer is cured, and the surface shape of the mold is transferred to the coating layer surface.
  • this step uses a pressure bonding device such as a nip roll 13 on the surface of the coating layer 12 of the laminate of the base film 11 and the coating layer 12 that has undergone the first curing step.
  • the roll-shaped mold 14 is pressed, and in this state, the active energy ray irradiation device 15 is used to irradiate the coating layer 12 with the active energy ray from the base film 11 side to cure the coating layer 12.
  • the use of a nip roll is effective in preventing air bubbles from being mixed between the coating layer and the mold.
  • One or a plurality of active energy ray irradiation apparatuses can be used.
  • the laminate After irradiation with active energy rays, the laminate is peeled from the mold 14 with the nip roll 16 on the exit side as a fulcrum.
  • the obtained optical film consisting of the base film and the cured resin layer is usually wound up by a film winding device 34. At this time, for the purpose of protecting the resin layer, it may be wound up while a protective film made of polyethylene terephthalate, polyethylene or the like is attached to the surface of the resin layer through a pressure-sensitive adhesive layer having removability.
  • the shape of the mold used is not limited to a roll shape.
  • additional active energy ray irradiation may be performed.
  • the substrate film on which the uncured coating layer is formed may be peeled from the mold and then cured by irradiation with active energy rays.
  • the integrated amount of light at UVA ultraviolet is preferably at 40 mJ / cm 2 or more 2000 mJ / cm 2 or less, more preferably at 70 mJ / cm 2 or more 1800 mJ / cm 2 or less.
  • the integrated light quantity is less than 40 mJ / cm 2 , the coating layer is insufficiently cured, the resulting resin layer has low hardness, or uncured resin adheres to the guide roll, etc. There is a tendency to become.
  • the integrated light quantity exceeds 2000 mJ / cm 2 , the base film may shrink due to heat radiated from the ultraviolet irradiation device, which may cause wrinkles.
  • the mold used in this step is for imparting a desired shape to the surface of the resin layer formed on the base film, and has a surface shape composed of a transfer structure of the desired shape.
  • the surface shape of the mold can be transferred onto the surface of the resin layer by curing the coating layer while pressing the surface shape against the surface of the coating layer.
  • the mold include a mold having a mirror surface (for example, a mirror roll) and a mold having an uneven surface (for example, an emboss roll).
  • the uneven pattern may be a regular pattern, a random pattern, or a pseudo random pattern in which one or more random patterns of a specific size are spread. Although it is good, it is preferably a random pattern or a pseudo-random pattern from the viewpoint of preventing the reflected image from becoming iridescent due to interference of reflected light caused by the surface shape.
  • the outer shape of the mold is not particularly limited, and may be a flat plate shape or a cylindrical or cylindrical roll. From the viewpoint of continuous productivity, a mirror surface roll, an emboss roll, etc. A columnar or cylindrical mold is preferred. In this case, a predetermined surface shape is formed on the side surface of the columnar or cylindrical mold.
  • the material of the base material of the mold is not particularly limited, and can be appropriately selected from metal, glass, carbon, resin, or a composite thereof, but metal is preferable from the viewpoint of workability.
  • Suitable metal materials include aluminum, iron, or an alloy mainly composed of aluminum or iron from the viewpoint of cost.
  • a method for obtaining a mold for example, a method of polishing a substrate, sandblasting, and then applying electroless nickel plating (JP2006-53371-A); after applying copper plating or nickel plating to the substrate, Polishing, sand blasting, and chromium plating (JP2007-188952-A); copper plating or nickel plating, polishing, sand blasting, etching process or copper plating process And then applying chromium plating (JP 2007-237541-A); applying copper plating or nickel plating to the surface of the substrate, polishing, applying a photosensitive resin film on the polished surface, The pattern is exposed on the photosensitive resin film, then developed, and etched using the developed photosensitive resin film as a mask.
  • the surface irregularity shape of the template comprising a random pattern or a pseudo-random pattern is, for example, an FM screen method, a DLDS (Dynamic Low-Discretion Sequence) method, a method using a microphase separation pattern of a block copolymer, or a bandpass filter method.
  • the random pattern generated by the above can be formed by exposing and developing on the photosensitive resin film, and performing an etching process using the developed photosensitive resin film as a mask.
  • the optical film of the present invention obtained as described above is suitably applied to an image display device such as a liquid crystal display device.
  • the resin layer on the base film is damaged due to various external forces.
  • Hard coat film which may contain translucent fine particles
  • a light diffusion layer for improving the viewing angle by diffusing light emitted from the liquid crystal cell
  • Viewing-side light diffusing film that contains translucent fine particles as a light diffusing agent
  • Antiglare layer containing translucent fine particles
  • a light diffusing layer (translucent fine particles as a light diffusing agent) for diffusing light incident on the liquid crystal cell and preventing moire caused by the backlight unit.
  • the Back-side light-diffusing film is a) (can be diffusion plate) is like.
  • the hard coat film, the viewing-side light diffusion film and the antiglare film are usually used by being bonded to a polarizing film as a viewing-side protective film for the viewing-side polarizing plate (that is, disposed on the surface of the image display device).
  • the back side light diffusion film is usually bonded to the polarizing film as a backlight side protective film of the backlight side polarizing plate.
  • the optical film of the present invention may further include an antireflection layer laminated on the resin layer (surface opposite to the base film).
  • the antireflection layer is provided to reduce the reflectance as much as possible, and reflection on the display screen can be prevented by forming the antireflection layer.
  • As the antireflection layer a low refractive index layer composed of a material lower than the refractive index of the resin layer; a high refractive index layer composed of a material higher than the refractive index of the resin layer, and the refractive index of the high refractive index layer
  • a laminated structure with a low refractive index layer composed of a lower material can be exemplified.
  • the antireflection layer may be laminated directly on the resin layer, or separately prepared by previously laminating the antireflection layer on the base film, and using a pressure sensitive adhesive or the like. You may paste on the layer.
  • the polarizing plate of this invention is equipped with a polarizing film and the optical film obtained by the above-mentioned manufacturing method laminated
  • a polarizing film has a function which takes out linearly polarized light from incident light, The kind is not specifically limited.
  • a suitable polarizing film there can be mentioned a polarizing film in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol resin.
  • polyvinyl alcohol-based resin examples include polyvinyl alcohol, which is a saponified product of vinyl acetate, partially formalized polyvinyl alcohol, and a saponified product of an ethylene / vinyl acetate copolymer.
  • dichroic dye iodine or a dichroic organic dye is used.
  • a polyene-oriented film of a polyvinyl alcohol dehydrated product or a polyvinyl chloride dehydrochlorinated product can also be a polarizing film. The thickness of the polarizing film is usually about 5 to 80 ⁇ m.
  • the polarizing plate of the present invention may be one in which the optical film according to the present invention is laminated on one side or both sides (usually one side) of the polarizing film, and a transparent protective layer is provided on one side of the polarizing film.
  • the optical film according to the present invention may be laminated on the other surface.
  • the optical film also has a function as a transparent protective layer (protective film) of the polarizing film.
  • the transparent protective layer can be formed on the polarizing film by a method of laminating a transparent resin film using an adhesive or the like, a method of applying a transparent resin-containing coating solution, or the like.
  • the optical film according to the present invention can be bonded to a polarizing film using an adhesive or the like.
  • the transparent resin film serving as the transparent protective layer is preferably excellent in transparency, mechanical strength, thermal stability, moisture shielding properties, etc., and examples thereof include triacetyl cellulose, diacetyl cellulose, cellulose acetate propio Cellulose resins such as cellulose acetate such as nates; Polycarbonate resins; (Meth) acrylic resins such as polyacrylate and polymethyl methacrylate; Polyester resins such as polyethylene terephthalate and polyethylene naphthalate; Chains such as polyethylene and polypropylene Examples thereof include films made of polyolefin resin; cyclic polyolefin resin; styrene resin; polysulfone; polyether sulfone; polyvinyl chloride resin. These transparent resin films may be optically isotropic, or have optical anisotropy for the purpose of compensating the viewing angle when incorporated in an image display device. Also good.
  • the image display device of the present invention is a combination of the polarizing plate of the present invention and an image display element that displays various information on a screen.
  • the type of the image display device of the present invention is not particularly limited.
  • LCD liquid crystal display
  • CRT cathode ray tube
  • PDP plasma display
  • FED field emission display
  • SED conduction electron-emitting device display
  • OLED organic EL display
  • laser display and a projector television screen.
  • the polarizing plate when a liquid crystal panel is manufactured by arranging the polarizing plate of the present invention on a liquid crystal cell, the polarizing plate is placed on the liquid crystal cell so that the polarizing film is on the liquid crystal cell side (with the resin layer on the outside). Be placed.
  • the optical film may be disposed on the viewing side of the image display element, on the backlight side, or on both.
  • the optical film when the optical film is arranged on the viewing side, the optical film can function as a hard coat film, a light diffusion film, an antiglare film, an antireflection film, or the like.
  • the optical film when the optical film is disposed on the backlight side, the optical film can function as a light diffusion film (diffusion plate) that diffuses light incident on the liquid crystal cell and prevents moiré or the like.
  • UV curable resin 60 parts by weight of pentaerythritol triacrylate and 40 parts by weight of polyfunctional urethanized acrylate (reaction product of hexamethylene diisocyanate and pentaerythritol triacrylate)
  • Photopolymerization initiator “Lucillin TPO” (manufactured by BASF, chemical name: 2,4,6-trimethylbenzoyldiphenylphosphine oxide) 5 parts by weight
  • -Diluting solvent 100 parts by weight of ethyl acetate.
  • a coating layer is formed by applying the coating liquid on a triacetyl cellulose (TAC) film (base film) having a thickness of 80 ⁇ m with a gravure coater, and a laminate of the base film and the coating layer is formed. Obtained [Coating process]. After the obtained laminate is dried in a drying furnace, an accumulated light amount in UVA is a first predetermined amount using an ultraviolet irradiation device provided with a comb filter having a plurality of tapered comb teeth whose width gradually decreases in the opening and closing direction.
  • TAC triacetyl cellulose
  • the ultraviolet ray is irradiated from the coating layer side to the leading region of the coating layer so that the value (irradiation amount to the leading region) gradually decreases to 0, and the accumulated light amount in UVA is changed from 0 to a second predetermined value
  • the ultraviolet rays were irradiated from the coating layer side to the rear region of the coating layer so as to gradually increase the irradiation amount to the rear region) [first curing step].
  • the first and second predetermined values are set to 100 mJ / cm 2, and the decrease rate (irradiation to the head region) and increase rate (irradiation to the tail region) per second in UVA of ultraviolet rays. [In the following, the rate of decrease and the rate of increase are collectively referred to as the rate of change] were both 700 mJ / cm 2 ⁇ sec.
  • a chromium plating roll that had been polished so that the surface became a mirror surface was pressed and adhered to the coating layer surface of the laminate that had undergone the first curing step using a nip roll.
  • the coating layer was cured by irradiating with ultraviolet rays so that the maximum illuminance in UVA was 700 mW / cm 2 and the integrated light amount in UVA was 300 mJ / cm 2 from the substrate film side [second curing step]. .
  • cured material of an ultraviolet curable resin was 10 micrometers was obtained by peeling a laminated body from a chromium plating roll.
  • Example 2 to 5 An optical film was produced in the same manner as in Example 1, except that the first and second predetermined values and the rate of change of the integrated light quantity per second in UVA of ultraviolet rays were changed as shown in Table 1. In Example 4, no comb filter was used.
  • Example 3 The resin residue slightly generated in Example 3 and the resin residue in Comparative Example 1 were generated at the position 1) above. Further, the resin residue generated in Examples 4 and 5 was generated at the position 2).
  • the resin residue can be reduced by performing the first curing step in which the end region of the coating layer is cured in advance. Moreover, it turns out that the resin remainder can be prevented effectively by making the integrated light quantity and its change rate of the ultraviolet-ray in a 1st hardening process into the predetermined range.

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  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Laminated Bodies (AREA)
  • Liquid Crystal (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Toxicology (AREA)
  • Polarising Elements (AREA)
PCT/JP2011/080553 2010-12-27 2011-12-22 光学フィルムの製造方法、偏光板および画像表示装置 WO2012091145A1 (ja)

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