WO2017159454A1 - Method for producing one-side-protected polarizing film having transparent resin layer, method for producing polarizing film having adhesive layer, and method for producing optical laminate - Google Patents

Method for producing one-side-protected polarizing film having transparent resin layer, method for producing polarizing film having adhesive layer, and method for producing optical laminate Download PDF

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Publication number
WO2017159454A1
WO2017159454A1 PCT/JP2017/008984 JP2017008984W WO2017159454A1 WO 2017159454 A1 WO2017159454 A1 WO 2017159454A1 JP 2017008984 W JP2017008984 W JP 2017008984W WO 2017159454 A1 WO2017159454 A1 WO 2017159454A1
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Prior art keywords
transparent resin
resin layer
polarizing film
polarizer
film
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PCT/JP2017/008984
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French (fr)
Japanese (ja)
Inventor
友徳 上野
聡司 三田
健太郎 池嶋
岸　敦史
佑輔 茂手木
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日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN201780016889.4A priority Critical patent/CN108780179B/en
Priority to KR1020187024097A priority patent/KR102166983B1/en
Publication of WO2017159454A1 publication Critical patent/WO2017159454A1/en

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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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details

Definitions

  • This invention relates to the manufacturing method of the piece protection polarizing film with a transparent resin layer.
  • the present invention also provides a method for producing a polarizing film with a pressure-sensitive adhesive layer in which a pressure-sensitive adhesive layer is formed on the transparent resin layer of the piece-protecting polarizing film with a transparent resin layer, and an optical device using the polarizing film with a pressure-sensitive adhesive layer.
  • the present invention relates to a method for manufacturing a laminate.
  • the single protective polarizing film with a transparent resin layer and the polarizing film with a pressure-sensitive adhesive layer obtained by the production method of the present invention are used alone or as an optical laminated body obtained by laminating them, as a liquid crystal display (LCD), an organic EL display An image display device such as a device can be formed.
  • LCD liquid crystal display
  • organic EL display An image display device such as a device can be formed.
  • liquid crystal display devices In watches, mobile phones, PDAs, notebook computers, personal computer monitors, DVD players, TVs, etc., liquid crystal display devices are expanding rapidly.
  • the liquid crystal display device visualizes the polarization state by switching of the liquid crystal, and a polarizer is used from the display principle.
  • the polarizer since it has a high transmittance and a high degree of polarization, for example, an iodine-based polarizer having a stretched structure in which iodine is adsorbed on a polyvinyl alcohol film is most widely used.
  • a polarizer has a disadvantage that the mechanical strength is extremely weak, and the polarizing function is remarkably lowered due to contraction due to heat and moisture. Therefore, the obtained polarizer is immediately bonded to the protective film coated with the adhesive via the adhesive and used as a polarizing film.
  • thinning is also performed for the polarizer.
  • thickness reduction can be performed by providing a protective film only on one side of the polarizer and using a single protective polarizing film not provided with a protective film on the other side. Such a single-protective polarizing film can be thinned because there is less protective film than both protective polarizing films provided with protective films on both sides of the polarizer.
  • a resin layer is formed by providing an uncoated portion where a resin solution is not applied in each region of 0.5 cm or more from both ends in the width direction of the base film.
  • a method for producing a polarizing laminated film by cutting and removing the uncoated portion from the laminated film, and then performing a stretching treatment and a dyeing treatment (see, for example, Patent Document 3).
  • a protective layer (transparent resin layer) is formed on a single protective polarizing film.
  • a polarizing film often curls, and when the obtained polarizing film is conveyed, the polarizing layer is polarized.
  • the film ends may break, breakage may occur due to the breaks, and other members may have problems such as being pinched during lamination.
  • an object of the present invention is to provide a method for producing a piece protective polarizing film with a transparent resin layer that can suppress the occurrence of curling. Furthermore, an object of this invention is to provide the manufacturing method of the polarizing film with an adhesive layer, and the manufacturing method of an optical laminated body.
  • the present inventors have found that the above problem can be solved by the following method for producing a piece-protecting polarizing film with a transparent resin layer, and have reached the present invention.
  • the present invention is a piece with a transparent resin layer having a single protective polarizing film having a protective film only on one side of the polarizer and a transparent resin layer provided on the other side of the polarizer of the single protective polarizing film.
  • a method for producing a protective polarizing film includes a polyvinyl alcohol resin and has a thickness of 10 ⁇ m or less,
  • the transparent resin layer is formed by applying a coating liquid containing a curable component capable of constituting a resin component or a transparent resin layer to the polarizer, and a step of solidifying or curing the obtained coating film.
  • the coating liquid In the application step of the coating liquid, it has an uncoated part where the coating liquid is not applied in a region less than 20 mm inward from both ends in the width direction of the polarizer, or over the entire width direction of the polarizer. It is related with the manufacturing method of the piece protection polarizing film with a transparent resin layer characterized by apply
  • the coating liquid is applied by coating the coating liquid over the entire width direction of the polarizer.
  • the width of the polarizer is preferably 1100 to 2000 mm.
  • the transparent resin layer is preferably formed by solidifying the coating film, and the solidification is preferably performed by drying.
  • the drying temperature is preferably 120 ° C. or lower.
  • the drying time is preferably within 180 seconds.
  • the coating liquid is a coating liquid containing a resin component, and the resin component is a polyvinyl alcohol resin.
  • this invention includes the process of forming an adhesive layer on the transparent resin layer of the piece protection polarizing film with a transparent resin layer obtained by the said manufacturing method, The manufacture of the polarizing film with an adhesive layer characterized by the above-mentioned Regarding the method.
  • this invention includes the process of bonding to an optical member through the said adhesive layer, without winding up the polarizing film with an adhesive layer obtained by the said manufacturing method, The manufacture of the optical laminated body characterized by the above-mentioned. Regarding the method.
  • the method for producing a piece-protecting polarizing film with a transparent resin layer of the present invention comprises applying a coating solution containing a curable component capable of constituting a resin component or a transparent resin layer to the polarizer.
  • a coating solution containing a curable component capable of constituting a resin component or a transparent resin layer In order to apply the coating liquid over the entire width direction of the polarizer, it has an uncoated part where the coating liquid is not applied in each region of less than 20 mm inward from both ends in the width direction. Curling of the single-sided protective polarizing film with a layer can be suppressed. Moreover, curling generation is also suppressed in the polarizing film with the pressure-sensitive adhesive layer in which the pressure-sensitive adhesive layer is provided on the transparent resin layer of the piece protective polarizing film with the transparent resin layer.
  • the piece-protective polarizing film with a transparent resin layer and the polarizing film with a pressure-sensitive adhesive layer obtained by the production method of the present invention are laminated on an optical member used for an image display device or the like without being wound on a roll or the like after production. can do.
  • the polarizer includes a polyvinyl alcohol resin and has a thickness of 10 ⁇ m or less
  • the transparent resin layer is formed by applying a coating liquid containing a curable component capable of constituting a resin component or a transparent resin layer to the polarizer, and a step of solidifying or curing the obtained coating film.
  • the coating liquid In the application step of the coating liquid, it has an uncoated part where the coating liquid is not applied in a region less than 20 mm inward from both ends in the width direction of the polarizer, or over the entire width direction of the polarizer. It is characterized by applying a coating liquid.
  • the piece protective polarizing film 3 used in the present invention has the protective film 2 only on one side of the polarizer 1.
  • the polarizer 1 and the protective film 2 can be laminated via an intervening layer (not shown) such as an adhesive layer, an adhesive layer, and an undercoat layer (primer layer).
  • an intervening layer such as an adhesive layer, an adhesive layer, and an undercoat layer (primer layer).
  • a transparent resin layer 4 is formed on a surface (other surface) of the polarizer 1 of the piece protective polarizing film 3 that does not have the protective film 2, and the single protective polarization with a transparent resin layer is provided. This is a method for manufacturing the film 10.
  • the transparent resin layer 4 is formed by applying a coating liquid containing a curable component capable of constituting the resin component or the transparent resin layer 4 to the polarizer 1, and solidifying the obtained coating film or It is formed by a curing process.
  • the coating liquid application step as shown in FIG. 1, the coating liquid is not applied in a region less than 20 mm inward from both ends in the width direction (A direction in the figure) of the polarizer 1. It has the part 5 or, as shown in FIG. 2, it is characterized by apply
  • the width direction of the polarizer 1 means a direction orthogonal to the stretching direction (conveying direction) of the polarizer 1.
  • the uncoated portion when the uncoated portion is included, is an area of less than 20 mm inward from both ends in the width direction of the polarizer, and is preferably an area of 15 mm or less. The following region is more preferable. By making an uncoated part into the said range, it is preferable at the point which can suppress generation
  • the lower limit value of the area of the uncoated portion is not particularly limited, and is preferably as small as possible, and a method of applying the coating liquid over the entire width direction of the polarizer, that is, having no uncoated portion. Particularly preferred.
  • the uncoated portion when the uncoated portion is included, is preferably a region of 5% or less with respect to the width of the polarizer, respectively, from both ends in the width direction of the polarizer.
  • the region is preferably less than 3% with respect to the width of the polarizer, and more preferably 2% or less with respect to the width of the polarizer.
  • the lower limit of the area of the uncoated portion is not particularly limited, and is preferably as small as possible.
  • a method of applying the coating liquid over the entire width direction of the polarizer, that is, 0% with respect to the width of the polarizer. (Not having an uncoated portion) is particularly preferable.
  • the manufacturing method of this invention can comprise a resin component or a transparent resin layer in the surface (other surface) which does not have the protective film 2 of the polarizer 1 of the said piece protection polarizing film 3.
  • a polarizer having a thickness of 10 ⁇ m or less is used.
  • the thickness of the polarizer is preferably 8 ⁇ m or less, more preferably 7 ⁇ m or less, and even more preferably 6 ⁇ m or less.
  • the thickness of the polarizer is preferably 2 ⁇ m or more, and more preferably 3 ⁇ m or more.
  • Such a thin polarizer has less thickness unevenness, excellent visibility, and less dimensional change, and therefore excellent durability against thermal shock.
  • the polarizer 1 is made of a polyvinyl alcohol resin.
  • a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or an ethylene / vinyl acetate copolymer partially saponified film, and two colors of iodine and a dichroic dye are used.
  • polyene-based oriented films such as those obtained by adsorbing a volatile substance and uniaxially stretched, polyvinyl alcohol dehydrated products, polyvinyl chloride dehydrochlorinated products, and the like.
  • a polarizer composed of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable.
  • a polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. If necessary, it may contain boric acid, zinc sulfate, zinc chloride or the like, or may be immersed in an aqueous solution of potassium iodide or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing.
  • the polyvinyl alcohol film In addition to washing the polyvinyl alcohol film surface with stains and antiblocking agents by washing the polyvinyl alcohol film with water, the polyvinyl alcohol film is also swollen to prevent unevenness such as uneven coloring. is there. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched even in an aqueous solution of boric acid or potassium iodide or in a water bath.
  • the polarizer 1 preferably contains boric acid from the viewpoint of stretching stability and optical durability.
  • the boric acid content contained in the polarizer 1 is preferably 25% by weight or less, more preferably 20% by weight or less, based on the total amount of the polarizer, from the viewpoint of suppressing the occurrence of penetration cracks and nanoslits and suppressing expansion. It is more preferably 18% by weight or less, and particularly preferably 16% by weight or less.
  • the boric acid content with respect to the total amount of the polarizer is preferably 10% by weight or more, and more preferably 12% by weight or more.
  • the thin polarizer described in the publication 2014/077636 pamphlet etc. or the thin polarizer obtained from the manufacturing method as described in these can be mentioned.
  • the polarizer 1 has an optical characteristic expressed by a single transmittance T and a polarization degree P of the following formula: P> ⁇ (10 0.929T-42.4 ⁇ 1) ⁇ 100 (where T ⁇ 42.3). Or it is preferable to be configured to satisfy the condition of P ⁇ 99.9 (however, T ⁇ 42.3).
  • a polarizer configured so as to satisfy the above-described conditions uniquely has performance required as a display for a liquid crystal television using a large display element. Specifically, the contrast ratio is 1000: 1 or more and the maximum luminance is 500 cd / m 2 or more. As other uses, for example, it is bonded to the viewing side of the organic EL display device.
  • Patent No. 4751486, Patent in that it can be stretched at a high magnification and the polarization performance can be improved.
  • stretching in a boric-acid aqueous solution as described in the 4751481 specification and the patent 4815544 specification is preferable, and it describes especially in the patent 4751481 specification and the patent 4815544 specification.
  • stretching in the boric-acid aqueous solution which has this is preferable.
  • These thin polarizers can be obtained by a production method including a step of stretching a polyvinyl alcohol-based resin layer and a stretching resin substrate in the state of a laminate and a step of dyeing.
  • a production method including a step of stretching a polyvinyl alcohol-based resin layer and a stretching resin substrate in the state of a laminate and a step of dyeing.
  • the material constituting the protective film 2 is preferably a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like.
  • polyester polymers such as polyethylene terephthalate and polyethylene naphthalate
  • cellulose polymers such as diacetyl cellulose and triacetyl cellulose
  • acrylic polymers such as polymethyl methacrylate
  • styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin)
  • AS resin acrylonitrile / styrene copolymer
  • polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or the above Polymer blends and the like can also be cited as examples of polymers forming the protective film.
  • the protective film 2 may contain one or more arbitrary appropriate additives.
  • the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a mold release agent, a coloring inhibitor, a flame retardant, a nucleating agent, an antistatic agent, a pigment, and a coloring agent.
  • the content of the thermoplastic resin in the protective film is preferably 50 to 100% by mass, more preferably 50 to 99% by mass, further preferably 60 to 98% by mass, and particularly preferably 70 to 97% by mass. When content of the said thermoplastic resin in a protective film is less than 50 mass%, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.
  • a retardation film, a brightness enhancement film, a diffusion film, or the like can also be used.
  • the retardation film include those having a front retardation of 40 nm or more and / or a retardation having a thickness direction retardation of 80 nm or more.
  • the front phase difference is usually controlled in the range of 40 to 200 nm
  • the thickness direction phase difference is usually controlled in the range of 80 to 300 nm.
  • the retardation film functions also as a polarizer protective film, so that the thickness can be reduced.
  • the retardation film examples include a birefringent film obtained by uniaxially or biaxially stretching a thermoplastic resin film.
  • the stretching temperature, stretching ratio, and the like are appropriately set depending on the retardation value, film material, and thickness.
  • the thickness of the protective film 2 can be determined as appropriate, but generally it is preferably 3 to 200 ⁇ m, more preferably 3 to 100 ⁇ m, from the viewpoints of workability such as strength and handleability, and thin layer properties. Is preferred.
  • the thickness of the protective film (when a film is formed in advance) is preferably 10 to 60 ⁇ m, more preferably 10 to 50 ⁇ m from the viewpoint of transportability.
  • the thickness of the protective film (when formed by coating and curing) is preferably 3 to 25 ⁇ m, more preferably 3 to 20 ⁇ m from the viewpoint of transportability.
  • the protective film may be used in a plurality of layers or in a plurality of layers.
  • a functional layer such as a hard coat layer, an antireflection layer, an antisticking layer, a diffusion layer or an antiglare layer can be provided on the surface of the protective film 2 on which the polarizer 1 is not adhered.
  • the hard coat layer, the antireflection layer, the antisticking layer, the diffusion layer, the antiglare layer and other functional layers can be provided on the protective film 2 itself, and separately provided separately from the protective film. You can also.
  • the protective film 2 and the polarizer 1 can be laminated via an intervening layer such as an adhesive layer, a pressure-sensitive adhesive layer, or an undercoat layer (primer layer). At this time, it is desirable that the both are laminated without an air gap by an intervening layer.
  • an intervening layer of the polarizer 1 and the protective film 2 is not shown in the drawing.
  • the adhesive layer is formed by an adhesive.
  • the type of the adhesive is not particularly limited, and various types can be used.
  • the adhesive layer is not particularly limited as long as it is optically transparent. Examples of the adhesive include water-based, solvent-based, hot-melt-based, active energy ray-curable types, and the like. Or an active energy ray hardening-type adhesive agent is suitable.
  • water-based adhesives examples include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, vinyl-based latex systems, and water-based polyesters.
  • the water-based adhesive is usually used as an adhesive composed of an aqueous solution, and usually contains 0.5 to 60% by weight of solid content.
  • the active energy ray curable adhesive is an adhesive that cures by an active energy ray such as an electron beam and ultraviolet rays (radical curable type and cationic curable type). Can be used.
  • an active energy ray such as an electron beam and ultraviolet rays (radical curable type and cationic curable type).
  • a photo radical curable adhesive can be used.
  • the photo radical curable active energy ray curable adhesive is used as an ultraviolet curable adhesive, the adhesive contains a radical polymerizable compound and a photo polymerization initiator.
  • the adhesive coating method is appropriately selected depending on the viscosity of the adhesive and the target thickness.
  • coating methods include reverse coaters, gravure coaters (direct, reverse and offset), bar reverse coaters, roll coaters, die coaters, bar coaters, rod coaters and the like.
  • a method such as a dipping method can be appropriately used for coating.
  • the adhesive is preferably applied so that the finally formed adhesive layer has a thickness of 30 to 300 nm.
  • the thickness of the adhesive layer is more preferably 60 to 150 nm.
  • the thickness of the adhesive layer is preferably 0.2 to 20 ⁇ m.
  • an easily bonding layer can be provided between a protective film and an adhesive bond layer.
  • the easy adhesion layer can be formed of, for example, various resins having a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, a silicone-based, a polyamide skeleton, a polyimide skeleton, a polyvinyl alcohol skeleton, and the like. These polymer resins can be used alone or in combination of two or more. Moreover, you may add another additive for formation of an easily bonding layer. Specific examples include stabilizers such as tackifiers, ultraviolet absorbers, antioxidants and heat stabilizers.
  • the easy-adhesion layer is usually provided in advance on a protective film, and the easy-adhesion layer side of the protective film and the polarizer are laminated with an adhesive layer.
  • the easy-adhesion layer is formed by applying and drying a material for forming the easy-adhesion layer on a protective film by a known technique.
  • the material for forming the easy adhesion layer is usually adjusted as a solution diluted to an appropriate concentration in consideration of the thickness after drying, the smoothness of coating, and the like.
  • the thickness of the easy-adhesion layer after drying is preferably 0.01 to 5 ⁇ m, more preferably 0.02 to 2 ⁇ m, and still more preferably 0.05 to 1 ⁇ m. Note that a plurality of easy-adhesion layers can be provided, but also in this case, the total thickness of the easy-adhesion layers is preferably in the above range.
  • the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive.
  • Various pressure-sensitive adhesives can be used as the pressure-sensitive adhesive, such as rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, vinyl alkyl ether-based pressure-sensitive adhesives, polyvinylpyrrolidone-based pressure-sensitive adhesives, Examples include acrylamide-based adhesives and cellulose-based adhesives.
  • An adhesive base polymer is selected according to the type of the adhesive.
  • acrylic pressure-sensitive adhesives are preferably used because they are excellent in optical transparency, exhibit appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and are excellent in weather resistance, heat resistance, and the like. .
  • the undercoat layer (primer layer) is formed in order to improve the adhesion between the polarizer 1 and the protective film 2.
  • the material constituting the primer layer is not particularly limited as long as the material exhibits a certain degree of strong adhesion to both the polarizer 1 and the protective film 2.
  • a thermoplastic resin having excellent transparency, heat stability, stretchability, and the like are used.
  • the thermoplastic resin include an acrylic resin, a polyolefin resin, a polyester resin, a polyvinyl alcohol resin, or a mixture thereof.
  • Coating liquid A coating liquid contains the curable component which can comprise a resin component or a transparent resin layer.
  • the transparent resin layer 4 can be formed by applying the coating liquid to the polarizer 1 and solidifying or curing.
  • the form of the coating liquid (hereinafter sometimes referred to as a forming material) is not particularly limited as long as it shows a liquid state, and may be any of water-based, water-dispersed, solvent-based, and solvent-free.
  • the coating liquid has a lower viscosity because when the damaged portion is present on the surface of the polarizer 1, it easily penetrates into the damaged portion.
  • the viscosity measured at 25 ° C. is preferably 2000 mPa ⁇ s or less, more preferably 1000 mPa ⁇ s or less, further preferably 500 mPa ⁇ s or less, and particularly preferably 100 mPa ⁇ s or less.
  • the thickness of the transparent resin layer 4 is 0.2 ⁇ m or more.
  • the thickness of the transparent resin layer 4 is more preferably 0.5 ⁇ m or more, and further preferably 0.7 ⁇ m or more.
  • the thickness of the transparent resin layer 4 is preferably 3 ⁇ m or less, more preferably less than 3 ⁇ m, and preferably 2 ⁇ m or less. More preferably.
  • Various methods are used as the coating method of the coating liquid. Specifically, for example, by roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples thereof include an extrusion coating method.
  • Examples of the material for forming the transparent resin layer 4 include polyester resins, polyether resins, polycarbonate resins, polyurethane resins, silicone resins, polyamide resins, polyimide resins, polyvinyl alcohol (PVA) resins, An acrylic resin, an epoxy resin, etc. can be mentioned. These resin materials can be used singly or in combination of two or more, but among these, one kind selected from the group consisting of polyurethane resins, polyvinyl alcohol resins, acrylic resins, and epoxy resins The above is preferable, and a polyvinyl alcohol resin and an acrylic resin are more preferable.
  • the coating liquid is preferably a coating liquid containing a resin component dissolved or dispersed in water.
  • the resin component dissolved or dispersed in water means a resin dissolved in water at room temperature (25 ° C.) or a resin soluble in water dissolved in an aqueous solvent.
  • the coating liquid is an aqueous or water-dispersed system, when the damaged portion is present on the surface of the polarizer 1, the surface of the polarizer 1 is swollen so that the coating liquid is adapted to the damaged portion, which is advantageous. It is.
  • the coating liquid is an aqueous system or an aqueous dispersion system
  • the orientation of the polyvinyl alcohol molecules around the damaged part constituting the polarizer is partially relaxed and the boric acid content around the damaged part is reduced. Therefore, even if the thickness of the transparent resin layer 4 is small (for example, even if it is less than 3 ⁇ m, preferably 2 ⁇ m or less), the expansion of the damaged portion can be effectively suppressed.
  • the resin component that can be dissolved or dispersed in water include, for example, polyvinyl alcohol resin, poly (meth) acrylic acid, polyacrylamide, methylolated melamine resin, methylolated urea resin, resol type phenolic resin, poly Examples thereof include ethylene oxide and carboxymethyl cellulose. These may be used alone or in combination.
  • polyvinyl alcohol resin, poly (meth) acrylic acid, and methylolated melamine are preferably used.
  • a polyvinyl alcohol resin is suitable as the resin component from the viewpoint of adhesion to the polyvinyl alcohol resin constituting the polarizer. Below, the case where a polyvinyl alcohol-type resin is used is demonstrated.
  • the transparent resin layer 4 is preferably formed from a forming material (coating liquid) containing a polyvinyl alcohol resin.
  • the polyvinyl alcohol resin forming the transparent resin layer may be the same as or different from the polyvinyl alcohol resin contained in the polarizer as long as it is a “polyvinyl alcohol resin”.
  • polyvinyl alcohol resin examples include polyvinyl alcohol.
  • Polyvinyl alcohol is obtained by saponifying polyvinyl acetate.
  • polyvinyl alcohol-based resin examples include a saponified product of a copolymer of vinyl acetate and a monomer having copolymerizability.
  • the copolymerizable monomer is ethylene
  • an ethylene-vinyl alcohol copolymer is obtained.
  • the copolymerizable monomer include unsaturated carboxylic acids such as (anhydrous) maleic acid, fumaric acid, crotonic acid, itaconic acid, (meth) acrylic acid, and esters thereof; ethylene, propylene, etc.
  • ⁇ -olefin (meth) allylsulfonic acid (soda), sulfonic acid soda (monoalkylmalate), disulfonic acid soda alkylmalate, N-methylolacrylamide, acrylamide alkylsulfonic acid alkali salt, N-vinylpyrrolidone, N- Examples include vinyl pyrrolidone derivatives. These polyvinyl alcohol resins can be used alone or in combination of two or more.
  • the saponification degree of the polyvinyl alcohol-based resin can be, for example, 95 mol% or more, but from the viewpoint of satisfying moisture heat resistance and water resistance, the saponification degree is preferably 99 mol% or more, Is preferably 99.7 mol% or more.
  • the degree of saponification represents the proportion of units that are actually saponified to vinyl alcohol units among the units that can be converted to vinyl alcohol units by saponification, and the residue is a vinyl ester unit.
  • the degree of saponification can be determined according to JIS-K6726-1994.
  • the average degree of polymerization of the polyvinyl alcohol-based resin can be, for example, 500 or more, but from the viewpoint of satisfying moisture and heat resistance and water resistance, the average degree of polymerization is preferably 1000 or more, more preferably 1500 or more. Preferably, 2000 or more is more preferable.
  • the average degree of polymerization of the polyvinyl alcohol resin is measured according to JIS-K6726.
  • a modified polyvinyl alcohol resin having a hydrophilic functional group in the side chain of the polyvinyl alcohol or a copolymer thereof can be used.
  • the hydrophilic functional group include an acetoacetyl group and a carbonyl group.
  • modified polyvinyl alcohol obtained by acetalization, urethanization, etherification, grafting, phosphoric esterification or the like of a polyvinyl alcohol resin can be used.
  • the ratio of the polyvinyl alcohol resin in the transparent resin layer 4 or the coating liquid (solid content) is preferably 80% by weight or more, more preferably 90% by weight or more, and further preferably 95% by weight or more.
  • the coating liquid is prepared as a solution in which the polyvinyl alcohol resin is dissolved in a solvent.
  • the solvent include water, dimethyl sulfoxide, dimethylformamide, dimethylacetate, amide N-methylpyrrolidone, various glycols, polyhydric alcohols such as trimethylolpropane, and amines such as ethylenediamine and diethylenetriamine. These may be used alone or in combination of two or more. Among these, it is preferable to use it as an aqueous solution using water as a solvent.
  • the concentration of the polyvinyl alcohol-based resin in the forming material is not particularly limited, but is preferably 0.1 to 15% by weight in consideration of coating properties, storage stability, and the like. 5 to 10% by weight is more preferable.
  • an additive can be added to the coating liquid (for example, an aqueous solution).
  • the additive include a plasticizer and a surfactant.
  • the plasticizer include polyhydric alcohols such as ethylene glycol and glycerin.
  • the surfactant include nonionic surfactants.
  • a coupling agent such as a silane coupling agent and a titanium coupling agent, various tackifiers, an ultraviolet absorber, an antioxidant, a heat stabilizer, a hydrolysis stabilizer, and the like can also be blended.
  • the curable component can be roughly classified into an active energy ray curable type such as an electron beam curable type, an ultraviolet ray curable type, and a visible light curable type, and a thermosetting type. Furthermore, the ultraviolet curable type and the visible light curable type can be classified into a radical polymerization curable type and a cationic polymerization curable type. In the present invention, an active energy ray having a wavelength range of 10 nm to less than 380 nm is expressed as ultraviolet light, and an active energy ray having a wavelength range of 380 nm to 800 nm is expressed as visible light.
  • the radical polymerization curable component can be used as a thermosetting curable component.
  • the curable component examples include a radical polymerizable compound.
  • the radical polymerizable compound examples include compounds having a radical polymerizable functional group of a carbon-carbon double bond such as a (meth) acryloyl group and a vinyl group.
  • these curable components either a monofunctional radical polymerizable compound or a bifunctional or higher polyfunctional radical polymerizable compound can be used.
  • these radically polymerizable compounds can be used individually by 1 type or in combination of 2 or more types.
  • compounds having a (meth) acryloyl group are suitable.
  • (meth) acryloyl means an acryloyl group and / or methacryloyl group, and “(meth)” has the same meaning hereinafter.
  • Examples of the monofunctional radical polymerizable compound include (meth) acrylamide derivatives having a (meth) acrylamide group.
  • the (meth) acrylamide derivative is preferable in terms of ensuring adhesion with the polarizer and having a high polymerization rate and excellent productivity.
  • (meth) acrylamide derivatives include, for example, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N N-alkyl group-containing (meth) acrylamide derivatives such as butyl (meth) acrylamide and N-hexyl (meth) acrylamide; N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylol-N— N-hydroxyalkyl group-containing (meth) acrylamide derivatives such as propane (meth) acrylamide; N-aminoalkyl group-containing (meth) acrylamide derivatives such as aminomethyl (meth) acrylamide and aminoethyl (meth) acrylamide; N-methoxymethyl N-alkoxy group-containing (meth) acrylamide derivatives such as
  • heterocyclic-containing (meth) acrylamide derivative in which the nitrogen atom of the (meth) acrylamide group forms a heterocyclic ring examples include, for example, N-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine. Etc.
  • N-hydroxyalkyl group-containing (meth) acrylamide derivatives are preferable from the viewpoint of adhesion to a polarizer, and N-hydroxyethyl (meth) acrylamide is particularly preferable.
  • examples of the monofunctional radical polymerizable compound include various (meth) acrylic acid derivatives having a (meth) acryloyloxy group. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-methyl-2-nitropropyl (meth) acrylate, n-butyl ( (Meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, t-pentyl (meth) acrylate, 3-pentyl (meth) acrylate, 2,2-dimethylbutyl (meth) acrylate, n-hexyl (meth) acrylate, cetyl (meth) acrylate, n-
  • Examples of the (meth) acrylic acid derivative include cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and cyclopentyl (meth) acrylate; Aralkyl (meth) acrylates such as benzyl (meth) acrylate; 2-isobornyl (meth) acrylate, 2-norbornylmethyl (meth) acrylate, 5-norbornen-2-yl-methyl (meth) acrylate, 3-methyl-2-norbornylmethyl (meth) acrylate, dicyclo Polycyclic (meth) acrylates such as pentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxymethoxyethyl (
  • Examples of the (meth) acrylic acid derivative include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, etc.
  • hydroxyl groups such as [4- (hydroxymethyl) cyclohexyl] methyl acrylate, cyclohexanedimethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc.
  • Meth) acrylate Epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether; 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2-trifluoroethylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) ) Halogen-containing (meth) acrylates such as acrylate, heptadecafluorodecyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate; Alkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate; 3-oxetanylmethyl (meth) acrylate
  • examples of the monofunctional radically polymerizable compound include carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
  • carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
  • Examples of the monofunctional radical polymerizable compound include lactam vinyl monomers such as N-vinylpyrrolidone, N-vinyl- ⁇ -caprolactam, and methylvinylpyrrolidone; vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, Examples thereof include vinyl monomers having a nitrogen-containing heterocyclic ring such as vinyl pyrrole, vinyl imidazole, vinyl oxazole and vinyl morpholine.
  • lactam vinyl monomers such as N-vinylpyrrolidone, N-vinyl- ⁇ -caprolactam, and methylvinylpyrrolidone
  • vinylpyridine vinylpiperidone
  • vinylpyrimidine vinylpiperazine
  • vinylpyrazine examples thereof include vinyl monomers having a nitrogen-containing heterocyclic ring such as vinyl pyrrole, vinyl imidazole, vinyl oxazole and vinyl morpholine.
  • a radically polymerizable compound having an active methylene group can be used as the monofunctional radically polymerizable compound.
  • the radically polymerizable compound having an active methylene group is a compound having an active methylene group having an active double bond group such as a (meth) acryl group in the terminal or in the molecule.
  • the active methylene group include an acetoacetyl group, an alkoxymalonyl group, and a cyanoacetyl group.
  • the active methylene group is preferably an acetoacetyl group.
  • radical polymerizable compound having an active methylene group examples include, for example, 2-acetoacetoxyethyl (meth) acrylate, 2-acetoacetoxypropyl (meth) acrylate, 2-acetoacetoxy-1-methylethyl (meth) acrylate Acetoacetoxyalkyl (meth) acrylate such as 2-ethoxymalonyloxyethyl (meth) acrylate, 2-cyanoacetoxyethyl (meth) acrylate, N- (2-cyanoacetoxyethyl) acrylamide, N- (2-propionylacetoxybutyl) ) Acrylamide, N- (4-acetoacetoxymethylbenzyl) acrylamide, N- (2-acetoacetylaminoethyl) acrylamide and the like.
  • the radical polymerizable compound having an active methylene group is preferably acetoacetoxyalkyl (meth) acrylate.
  • polyfunctional radical polymerizable compound examples include tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 -Nonanediol di (meth) acrylate, 1,10-decanediol diacrylate, 2-ethyl-2-butylpropanediol di (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) ) Acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) Acryte, cyclic trimethylolprop
  • Aronix M-220 and M-306 manufactured by Toagosei Co., Ltd.
  • light acrylate 1,9ND-A manufactured by Kyoeisha Chemical Co., Ltd.
  • light acrylate DGE-4A manufactured by Kyoeisha Chemical Co., Ltd.
  • Light acrylate DCP-A manufactured by Kyoeisha Chemical Co., Ltd.
  • SR-531 manufactured by Sartomer
  • CD-536 manufactured by Sartomer
  • various epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, various (meth) acrylate monomers, and the like are included as necessary.
  • the radical polymerizable compound is preferably used in combination with a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound from the viewpoint of achieving both adhesion to the polarizer and optical durability.
  • the radical polymerization curable forming material can be used as an active energy ray curable forming material or a thermosetting forming material.
  • the active energy ray curable forming material does not need to contain a photopolymerization initiator, but when using an ultraviolet ray or visible light for the active energy ray, It preferably contains a photopolymerization initiator.
  • the curable component when used as a thermosetting component, the forming material preferably contains a thermal polymerization initiator.
  • the photopolymerization initiator in the case of using the radical polymerizable compound is appropriately selected depending on the active energy ray. In the case of curing with ultraviolet light or visible light, a photopolymerization initiator for ultraviolet light or visible light cleavage is used.
  • photopolymerization initiator examples include benzophenone compounds such as benzyl, benzophenone, benzoylbenzoic acid, and 3,3′-dimethyl-4-methoxybenzophenone; 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2 -Propyl) ketone, aromatic ketone compounds such as ⁇ -hydroxy- ⁇ , ⁇ ′-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, ⁇ -hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy- Acetophenone compounds such as 2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) -phenyl] -2-morpholinopropane-1; benzoin methyl ether; Benzoin ethyl ether, benzoin isop Benzoin ether compounds such as propyl ether, benzoin butyl ether
  • the blending amount of the photopolymerization initiator is 20 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component (radical polymerizable compound).
  • the blending amount of the photopolymerization initiator is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, and further preferably 0.1 to 5 parts by weight.
  • a photopolymerization initiator that is particularly sensitive to light of 380 nm or more.
  • a photopolymerization initiator that is highly sensitive to light of 380 nm or more will be described later.
  • the compound represented by following General formula (1) (Wherein R 1 and R 2 represent —H, —CH 2 CH 3 , —iPr or Cl, and R 1 and R 2 may be the same or different), respectively, or a general formula ( It is preferable to use together the compound represented by 1) and a photopolymerization initiator that is highly sensitive to light of 380 nm or more, which will be described later.
  • the adhesion is excellent as compared with the case where a photopolymerization initiator having high sensitivity to light of 380 nm or more is used alone.
  • diethylthioxanthone in which R 1 and R 2 are —CH 2 CH 3 is particularly preferable.
  • the composition ratio of the compound represented by the general formula (1) in the forming material (coating liquid) is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable component, The amount is more preferably 0.5 to 4 parts by weight, and further preferably 0.9 to 3 parts by weight.
  • polymerization initiators include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and the like. Among them, ethyl 4-dimethylaminobenzoate is particularly preferable.
  • a polymerization initiation assistant When a polymerization initiation assistant is used, its addition amount is usually 0 to 5 parts by weight, preferably 0 to 4 parts by weight, most preferably 0 to 3 parts by weight, based on 100 parts by weight of the total amount of the curable component. is there.
  • a known photopolymerization initiator can be used in combination as necessary. Since the protective film having UV absorbing ability does not transmit light of 380 nm or less, it is preferable to use a photopolymerization initiator that is highly sensitive to light of 380 nm or more as the photopolymerization initiator.
  • 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine Oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) 1-yl) -phenyl) titanium and the like.
  • a compound represented by the following general formula (2) in addition to the photopolymerization initiator of the general formula (1), a compound represented by the following general formula (2); (Wherein R 3 , R 4 and R 5 represent —H, —CH 3 , —CH 2 CH 3 , —iPr or Cl, and R 3 , R 4 and R 5 may be the same or different). It is preferable to use it.
  • the compound represented by the general formula (2) include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: IRGACURE907, manufactured by BASF) which is a commercially available product. It can be suitably used.
  • 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE369, manufactured by BASF)
  • 2- (dimethylamino) -2-[(4-methylphenyl ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE379, manufactured by BASF) is preferred because of its high sensitivity.
  • thermal polymerization initiator those in which polymerization does not start by thermal cleavage are preferable.
  • thermal polymerization initiator those having a 10-hour half-life temperature of 65 ° C. or higher, more preferably 75 to 90 ° C. are preferable.
  • the half-life is an index representing the decomposition rate of the polymerization initiator, and means the time until the remaining amount of the polymerization initiator is halved.
  • the decomposition temperature for obtaining a half-life at an arbitrary time and the half-life time at an arbitrary temperature are described in the manufacturer catalog, for example, “Organic Peroxide Catalog No. 9 of Nippon Oil & Fats Co., Ltd.” Edition (May 2003) ".
  • thermal polymerization initiator examples include lauroyl peroxide (10 hour half-life temperature: 64 ° C.), benzoyl peroxide (10 hour half-life temperature: 73 ° C.), 1,1-bis (t-butylperoxy) -3.
  • thermal polymerization initiator examples include 2,2′-azobisisobutyronitrile (10 hour half-life temperature: 67 ° C.), 2,2′-azobis (2-methylbutyronitrile) (10 hours). And azo compounds such as 1,1-azobis-cyclohexane-1-carbonitrile (10 hour half-life temperature: 87 ° C.).
  • the blending amount of the thermal polymerization initiator is 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of the curable component (radical polymerizable compound).
  • the blending amount of the thermal polymerization initiator is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 3 parts by weight.
  • the curable component of the cationic polymerization curable forming material examples include compounds having an epoxy group or an oxetanyl group.
  • the compound having an epoxy group is not particularly limited as long as it has at least two epoxy groups in the molecule, and various generally known curable epoxy compounds can be used.
  • a preferable epoxy compound a compound having at least two epoxy groups and at least one aromatic ring in the molecule (aromatic epoxy compound), or at least two epoxy groups in the molecule, at least one of them. Examples thereof include a compound (alicyclic epoxy compound) formed between two adjacent carbon atoms constituting an alicyclic ring.
  • the cationic polymerization curable forming material contains the epoxy compound and the oxetane compound described above as curable components, and these are cured by cationic polymerization, and therefore, a photocationic polymerization initiator is blended therein.
  • This cationic photopolymerization 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 starts a polymerization reaction of an epoxy group or an oxetanyl group.
  • the manufacturing method of this invention includes the process of solidifying or hardening the obtained coating film.
  • the transparent resin layer 4 can be formed by solidifying or curing the coating film.
  • the coating liquid is a coating liquid containing a resin component
  • the resin component is solidified according to the type.
  • the coating liquid containing the resin component is a solution obtained by dissolving or dispersing the resin component in a solvent, and is used as, for example, an aqueous solution, an aqueous dispersion, or a solvent solution.
  • the solidification means forming the transparent resin layer 4 by removing the solvent from the coating liquid.
  • the resin component is a polyvinyl alcohol-based resin
  • the coating liquid can be used as an aqueous solution and can be solidified by heating (drying) or the like.
  • the resin component is water-soluble acrylic, it can be solidified similarly.
  • the drying temperature is not particularly limited and is usually about 60 to 200 ° C., but in the present invention, it is preferably 120 ° C. or less and more preferably 100 ° C. or less from the viewpoint of curling suppression.
  • the drying time is preferably within 180 seconds, more preferably within 120 seconds, and even more preferably within 60 seconds.
  • the curable component is transparent according to the type of the curable component. Curing that can form a resin layer is performed.
  • the coating liquid containing a curable component that can constitute the resin can be used in a solventless system as long as the curable component exhibits a coating liquid. Moreover, the said coating liquid can use the solution which melt
  • the curable component can also be used as a solution when presenting a coating solution.
  • the solvent can be appropriately selected according to the curable component to be used.
  • the coating liquid containing the curable component is irradiated with active energy rays ( Curing by ultraviolet irradiation or the like can be performed.
  • the formation of the transparent resin layer 4 with the curable forming material (coating liquid) is performed by coating the curable forming material on the surface of the polarizer and then curing.
  • the polarizer 1 may be subjected to a surface modification treatment before coating the curable forming material.
  • Specific examples of the treatment include corona treatment, plasma treatment, and saponification treatment.
  • the curable forming material is used as an active energy ray curable forming material or a thermosetting forming material.
  • the active energy ray curable forming material can be used in an electron beam curable type, an ultraviolet curable type, or a visible light curable type.
  • the aspect of the curable forming material is preferably an active energy ray curable forming material rather than a thermosetting forming material from the viewpoint of productivity, and moreover, the active energy ray curable forming material is a visible light curable forming material. It is preferable from the viewpoint of productivity.
  • the active energy ray curable forming material In the active energy ray curable forming material, the active energy ray curable forming material is applied to the polarizer, and then the active energy ray (electron beam, ultraviolet ray, visible light, etc.) is applied to the active energy ray curable forming material.
  • the transparent resin layer 4 is formed by curing.
  • the irradiation direction of active energy rays can be irradiated from any appropriate direction. Preferably, it irradiates from the transparent resin layer 4 side.
  • the acceleration voltage is preferably 5 kV to 300 kV, more preferably 10 kV to 250 kV. If the acceleration voltage is less than 5 kV, the electron beam may not reach the deepest portion of the transparent resin layer 4 and may be insufficiently cured. If the acceleration voltage exceeds 300 kV, the penetration force through the sample is too strong, and the protective film 2 or There is a risk of damaging the polarizer 1.
  • the irradiation dose is 5 to 100 kGy, more preferably 10 to 75 kGy.
  • the transparent resin layer 4 becomes insufficiently cured, and when it exceeds 100 kGy, the protective film and the polarizer are damaged, resulting in a decrease in mechanical strength and yellowing, thereby obtaining predetermined optical characteristics. I can't.
  • the electron beam irradiation is usually performed in an inert gas, but if necessary, it may be performed in the atmosphere or under a condition where a little oxygen is introduced.
  • an active energy ray containing visible light having a wavelength range of 380 nm to 450 nm particularly an active energy ray having the largest irradiation amount of visible light having a wavelength range of 380 nm to 450 nm.
  • an active energy ray according to the present invention a gallium-encapsulated metal halide lamp and an LED light source that emits light in the wavelength range of 380 to 440 nm are preferable.
  • low-pressure mercury lamp medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, incandescent lamp, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, gallium lamp, excimer laser, or ultraviolet rays such as sunlight
  • a light source including visible light can be used, and ultraviolet light having a wavelength shorter than 380 nm can be blocked using a band pass filter.
  • thermosetting type On the other hand, in the thermosetting type forming material, by heating, polymerization is started by a thermal polymerization initiator to form a cured product layer.
  • the heating temperature is set according to the thermal polymerization initiator, but is about 60 to 200 ° C., preferably 80 to 150 ° C.
  • the manufacturing method of the polarizing film with an adhesive layer puts an adhesive layer on the transparent resin layer 4 of the piece protection polarizing film with a transparent resin layer obtained by the said manufacturing method.
  • Pressure-sensitive adhesive layer An appropriate pressure-sensitive adhesive can be used for forming the pressure-sensitive adhesive layer, and the type thereof is not particularly limited.
  • Adhesives include rubber adhesives, acrylic adhesives, silicone adhesives, urethane adhesives, vinyl alkyl ether adhesives, polyvinyl alcohol adhesives, polyvinyl pyrrolidone adhesives, polyacrylamide adhesives, Examples thereof include cellulose-based pressure-sensitive adhesives.
  • pressure-sensitive adhesives those having excellent optical transparency, suitable wettability, cohesiveness, and adhesive pressure characteristics, and excellent weather resistance, heat resistance and the like are preferably used.
  • An acrylic pressure-sensitive adhesive is preferably used as one exhibiting such characteristics.
  • the pressure-sensitive adhesive layer for example, a method of applying the pressure-sensitive adhesive to a separator or the like that has been subjected to a release treatment, drying and removing the polymerization solvent or the like to form a pressure-sensitive adhesive layer, and then transferring it onto the transparent resin layer 4
  • the pressure-sensitive adhesive is prepared by a method of applying the pressure-sensitive adhesive to the transparent resin layer 4 and drying and removing the polymerization solvent to form the pressure-sensitive adhesive layer on the transparent resin layer 4.
  • one or more solvents other than the polymerization solvent may be added as appropriate.
  • a silicone release liner is preferably used as the release-treated separator.
  • an appropriate method can be appropriately employed as a method for drying the pressure-sensitive adhesive according to the purpose.
  • a method of heating and drying the coating film is used.
  • the heating and drying temperature is preferably 40 ° C to 200 ° C, more preferably 50 ° C to 180 ° C, and further preferably 70 ° C to 170 ° C. By setting the heating temperature within the above range, an adhesive having excellent adhesive properties can be obtained.
  • the drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and even more preferably 10 seconds to 5 minutes.
  • Various methods are used as a method for forming the pressure-sensitive adhesive layer. Specifically, for example, by roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples thereof include an extrusion coating method.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited, and is, for example, about 1 to 100 ⁇ m, preferably 2 to 50 ⁇ m, more preferably 2 to 40 ⁇ m, and further preferably 5 to 35 ⁇ m.
  • the pressure-sensitive adhesive layer When the pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a peeled sheet (separator) until practical use.
  • constituent material of the separator examples include, for example, plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof.
  • plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films
  • porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof.
  • a plastic film is used suitably from the point which is excellent in surface smoothness.
  • the plastic film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer.
  • a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, and a vinyl chloride co-polymer are used.
  • examples thereof include a polymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
  • the thickness of the separator is usually about 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
  • silicone type, fluorine type, long chain alkyl type or fatty acid amide type release agent, release by a silica powder and antifouling treatment, coating type, kneading type, vapor deposition type, if necessary It is also possible to perform antistatic treatment such as.
  • the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, and fluorine treatment on the surface of the separator.
  • a surface protective film can be provided in the polarizing film of the present invention (including a piece protective polarizing film and a polarizing film with an adhesive layer).
  • the surface protective film usually has a base film and a pressure-sensitive adhesive layer, and protects the polarizing film via the pressure-sensitive adhesive layer.
  • a film material having isotropic property or close to isotropic property is selected from the viewpoints of inspection property and manageability.
  • film materials include polyester resins such as polyethylene terephthalate film, cellulose resins, acetate resins, polyether sulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, acrylic resins, and the like.
  • transparent polymers such as resins.
  • a polyester resin is preferable.
  • the base film can be used as a laminate of one kind or two or more kinds of film materials, and a stretched product of the film can also be used.
  • the thickness of the base film is generally 500 ⁇ m or less, preferably 10 to 200 ⁇ m.
  • a pressure-sensitive adhesive based on a (meth) acrylic polymer, silicone-based polymer, polyester, polyurethane, polyamide, polyether, fluorine-based or rubber-based polymer, etc. can be appropriately selected and used. From the viewpoints of transparency, weather resistance, heat resistance and the like, an acrylic pressure-sensitive adhesive having an acrylic polymer as a base polymer is preferable.
  • the thickness (dry film thickness) of the pressure-sensitive adhesive layer is determined according to the required adhesive force. Usually, it is about 1 to 100 ⁇ m, preferably 5 to 50 ⁇ m.
  • the surface protective film can be provided with a release treatment layer on the surface opposite to the surface on which the pressure-sensitive adhesive layer is provided on the base film, using a low adhesive material such as silicone treatment, long-chain alkyl treatment, or fluorine treatment. .
  • the method for producing an optical laminate of the present invention comprises the step of bonding to an optical member via the pressure-sensitive adhesive layer without winding up the polarizing film with the pressure-sensitive adhesive layer obtained by the production method. It is characterized by including.
  • the film can be used as it is in the next step without being wound on a roll or the like, that is, an optical laminate can be produced by being bonded to an optical member via an adhesive layer.
  • a piece-protecting polarizing film (with a transparent resin layer) is manufactured by a conventional manufacturing method, curling may occur at the end of the film. When curling occurs, it may be transferred to the film end during transport to the next process. Since the film breaks due to creases or wrinkles, it is difficult to use it in the next process as it is.
  • the optical member is not particularly limited.
  • a liquid crystal display such as a reflection plate, a semi-transmission plate, a retardation plate (including a wavelength plate such as 1/2 or 1/4), a viewing angle compensation film, and the like.
  • a retardation plate including a wavelength plate such as 1/2 or 1/4
  • a viewing angle compensation film and the like.
  • One layer or two or more layers that may be used for forming a device or the like can be used.
  • the optical laminate in which the optical member is laminated on the polarizing film with the pressure-sensitive adhesive layer of the present invention can be formed by a method of sequentially laminating separately in the manufacturing process of a liquid crystal display device or the like. What was made into the laminated body is excellent in the stability of quality, assembly work, etc., and has an advantage which can improve the manufacturing process of a liquid crystal display device etc.
  • an appropriate adhesive means such as a pressure-sensitive adhesive layer can be used.
  • the optical axes thereof can be set at an appropriate arrangement angle in accordance with the target retardation characteristics and the like.
  • the piece protective polarizing film with a transparent resin layer, the polarizing film with an adhesive layer, or the optical laminate obtained by the production method of the present invention can be preferably used for forming various devices such as a liquid crystal display device.
  • the liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device is generally formed by assembling components such as a liquid crystal cell, a single protective polarizing film or an optical film with a transparent resin layer, and an illumination system as necessary, and incorporating a drive circuit.
  • a piece protective polarizing film with a transparent resin layer obtained by the production method of the present invention, a polarizing film with an adhesive layer, or an optical laminate is used. It can conform to the conventional method.
  • As the liquid crystal cell for example, an arbitrary type such as an IPS type or a VA type can be used, but it is particularly suitable for the IPS type.
  • a liquid crystal display device or lighting system in which a single protective polarizing film with a transparent resin layer, a polarizing film with a pressure-sensitive adhesive layer, or an optical laminate obtained by the production method of the present invention is disposed on one or both sides of a liquid crystal cell.
  • An appropriate liquid crystal display device such as one using a light or a reflector can be formed.
  • the piece protective polarizing film with a transparent resin layer, the polarizing film with an adhesive layer, or the optical laminate obtained by the production method of the present invention can be installed on one side or both sides of the liquid crystal cell.
  • a transparent protective layer-provided piece protective polarizing film, a pressure-sensitive adhesive layer-attached polarizing film, or an optical laminate obtained by the production method of the present invention may be the same or different. There may be.
  • a single layer of appropriate parts such as a diffusion plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusion plate, and a backlight are provided at appropriate positions.
  • two or more layers can be arranged.
  • Production Example 1 (Production of Polarizer) One side of an amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA copolymerized PET) film (thickness: 100 ⁇ m) having a water absorption of 0.75% and a glass transition temperature (Tg) of 75 ° C. is subjected to corona treatment.
  • IPA copolymerized PET amorphous isophthalic acid copolymerized polyethylene terephthalate
  • Tg glass transition temperature
  • the laminate was immersed in an insolubilization bath (a boric acid aqueous solution obtained by blending 4 parts by weight of boric acid with respect to 100 parts by weight of water) for 30 seconds (insolubilization treatment). Subsequently, it was immersed in a dyeing bath having a liquid temperature of 30 ° C. while adjusting the iodine concentration and the immersion time so that the polarizing plate had a predetermined transmittance.
  • 0.2 parts by weight of iodine was blended with 100 parts by weight of water, and immersed in an aqueous iodine solution obtained by blending 1.0 part by weight of potassium iodide (dyeing treatment). .
  • a boric acid aqueous solution obtained by blending 3 parts by weight of potassium iodide and 3 parts by weight of boric acid with respect to 100 parts by weight of water was immersed for 30 seconds in a crosslinking bath having a liquid temperature of 30 ° C.
  • a boric acid aqueous solution obtained by blending 3 parts by weight of potassium iodide and 3 parts by weight of boric acid with respect to 100 parts by weight of water (Crosslinking treatment).
  • the laminate was immersed in a boric acid aqueous solution (an aqueous solution obtained by blending 4 parts by weight of boric acid and 5 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 70 ° C.
  • Production Example 2 (Production of a single protective polarizing film) A (meth) acrylic resin film having a lactone ring structure having a thickness of 40 ⁇ m and subjected to corona treatment on the easily adhesive-treated surface was used as a protective film.
  • An ultraviolet curable adhesive was prepared by mixing 40 parts by weight of N-hydroxyethylacrylamide (HEAA), 60 parts by weight of acryloylmorpholine (ACMO) and 3 parts by weight of a photoinitiator (trade name: IRGACURE 819, manufactured by BASF). . This was made into the adhesive for protective films.
  • HEAA N-hydroxyethylacrylamide
  • ACMO acryloylmorpholine
  • IRGACURE 819 3 parts by weight of a photoinitiator
  • the protective film was bonded to the surface of the polarizer of the optical film laminate obtained in Production Example 1 while applying the ultraviolet curable adhesive so that the thickness of the adhesive layer after curing was 1 ⁇ m. After that, ultraviolet rays were applied as active energy rays to cure the adhesive.
  • Ultraviolet irradiation is carried out using a gallium-filled metal halide lamp (irradiation device: Fusion UV Systems, Inc., Light HAMMER 10, Inc., bulb: V bulb, peak illuminance: 1600 mW / cm 2 , integrated irradiation amount: 1000 / mJ / cm 2 (wavelength 380 ⁇ 440 nm)), and the illuminance of ultraviolet rays was measured using a Sola-Check system manufactured by Solatell. Subsequently, the amorphous PET base material was peeled off, and a piece protective polarizing film (total thickness 46 ⁇ m) using a thin polarizer was produced. The optical properties of the obtained piece-protecting polarizing film were a single transmittance of 42.8% and a degree of polarization of 99.99%.
  • ⁇ Single transmittance T and degree of polarization P> The single transmittance T and polarization degree P of the obtained piece-protecting polarizing film were measured using a spectral transmittance measuring device with an integrating sphere (Dot-3c, Murakami Color Research Laboratory Co., Ltd.).
  • the degree of polarization P is the transmittance when two identical polarizing films are overlapped so that their transmission axes are parallel (parallel transmittance: Tp), and they are overlapped so that their transmission axes are orthogonal to each other. It is calculated
  • Polarization degree P (%) ⁇ (Tp ⁇ Tc) / (Tp + Tc) ⁇ 1/2 ⁇ 100
  • Each transmittance is represented by a Y value obtained by correcting visibility with a two-degree field of view (C light source) of JIS Z8701, with 100% of the completely polarized light obtained through the Granteller prism polarizer.
  • Production Example 3 Manufacture of a coating solution for forming a transparent resin layer
  • a polyvinyl alcohol resin having a polymerization degree of 2500 and a saponification degree of 99.7 mol% was dissolved in pure water to prepare an aqueous solution (coating liquid) having a solid content concentration of 4% by weight and a viscosity of 60 mPa ⁇ s (25 ° C.).
  • Viscosity measurement> The viscosity of the coating solution was measured under the following conditions using a VISCOMETER R85 viscometer RE85L (manufactured by Toki Sangyo Co., Ltd.). Measurement temperature: 25 ° C Rotation speed: 0.5-100rpm Cone rotor: 1 ° 34 ' ⁇ R24
  • Example 1 (Production of a piece protective polarizing film with a transparent resin layer)
  • the coating liquid obtained in Production Example 3 (the material for forming the transparent resin layer) It applied so that thickness might be set to 25 micrometers using a gravure roll.
  • the coating was performed on the entire surface in the width direction of the single protective polarizing film. After the application, it was dried with hot air at 95 ° C. for 30 seconds using a floating oven to form a transparent resin layer having a thickness of 1 ⁇ m, and a piece protective polarizing film with a transparent resin layer was produced.
  • Example 2 and Comparative Example 1 In Example 1, the piece protection with a transparent resin layer was carried out in the same manner as in Example 1 except that the uncoated portions listed in Table 1 were provided from both ends in the width direction of the piece protective polarizing film to the inside. A polarizing film was produced.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Electroluminescent Light Sources (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides a method for producing a one-side-protected polarized film having a transparent resin layer, the one-side-protected polarizing film having a one-side-protected polarizing film that has a protective film on only one surface of a polarizer, and a transparent resin layer provided on the other surface of the polarizer of the one-side-protected polarizing film, wherein the method is characterized in that: the polarizer includes a polyvinyl alcohol resin, and has a thickness of 10 μm or less; the transparent resin layer is formed through a step for applying, to the polarizer, a coating liquid that includes a resin component or a curable component that is capable of constituting a transparent resin layer, and a step for solidifying or curing the resulting coating film; and in the step for applying the coating liquid, there is an non-application portion in which the coating liquid is not applied in a region less than 20 mm inward from each of the two width-direction ends of the polarizer, or the coating liquid is applied across the entirety of the polarizer along the width direction. This production method makes it possible to suppress curling of the one-side-protected polarizing film having a transparent resin layer.

Description

透明樹脂層付の片保護偏光フィルムの製造方法、粘着剤層付偏光フィルムの製造方法、光学積層体の製造方法Method for producing piece protective polarizing film with transparent resin layer, method for producing polarizing film with pressure-sensitive adhesive layer, method for producing optical laminate
　本発明は、透明樹脂層付の片保護偏光フィルムの製造方法に関する。また、本発明は、前記透明樹脂層付の片保護偏光フィルムの透明樹脂層上に粘着剤層が形成された粘着剤層付偏光フィルムの製造方法、当該粘着剤層付偏光フィルムを用いた光学積層体の製造方法に関する。本発明の製造方法により得られた透明樹脂層付の片保護偏光フィルム、粘着剤層付偏光フィルムは、単独で、又はこれを積層した光学積層体として、液晶表示装置（ＬＣＤ）、有機ＥＬ表示装置等の画像表示装置を形成し得る。 This invention relates to the manufacturing method of the piece protection polarizing film with a transparent resin layer. The present invention also provides a method for producing a polarizing film with a pressure-sensitive adhesive layer in which a pressure-sensitive adhesive layer is formed on the transparent resin layer of the piece-protecting polarizing film with a transparent resin layer, and an optical device using the polarizing film with a pressure-sensitive adhesive layer. The present invention relates to a method for manufacturing a laminate. The single protective polarizing film with a transparent resin layer and the polarizing film with a pressure-sensitive adhesive layer obtained by the production method of the present invention are used alone or as an optical laminated body obtained by laminating them, as a liquid crystal display (LCD), an organic EL display An image display device such as a device can be formed.
　時計、携帯電話、ＰＤＡ、ノートパソコン、パソコン用モニタ、ＤＶＤプレーヤー、ＴＶ等では、液晶表示装置が急激に市場展開している。液晶表示装置は、液晶のスイッチングによる偏光状態を可視化させたものであり、その表示原理から、偏光子が用いられる。 In watches, mobile phones, PDAs, notebook computers, personal computer monitors, DVD players, TVs, etc., liquid crystal display devices are expanding rapidly. The liquid crystal display device visualizes the polarization state by switching of the liquid crystal, and a polarizer is used from the display principle.
　偏光子としては、高透過率、高偏光度を有することから、例えば、ポリビニルアルコールフィルムにヨウ素を吸着させ、延伸した構造のヨウ素系偏光子が最も一般的に広く使用されている。このような偏光子は、機械的強度が極端に弱く、熱や水分により収縮してしまい偏光機能が顕著に低下してしまう短所をもっている。従って、得られた偏光子は、直ちに、接着剤が塗工された保護フィルムと接着剤を介して貼り合わせられて、偏光フィルムとして用いられている。 As the polarizer, since it has a high transmittance and a high degree of polarization, for example, an iodine-based polarizer having a stretched structure in which iodine is adsorbed on a polyvinyl alcohol film is most widely used. Such a polarizer has a disadvantage that the mechanical strength is extremely weak, and the polarizing function is remarkably lowered due to contraction due to heat and moisture. Therefore, the obtained polarizer is immediately bonded to the protective film coated with the adhesive via the adhesive and used as a polarizing film.
　一方、液晶表示装置等の画像表示装置は、薄型化がすすんでおり、偏光フィルムについても薄型化が要求されている。そのため、薄型化は偏光子についても行われている。また、薄型化は、偏光子の片側にのみ保護フィルムを設け、他の片側には保護フィルムを設けていない片保護偏光フィルムを用いることにより行うことができる。このような片保護偏光フィルムは、偏光子の両面に保護フィルムを設けた両保護偏光フィルムに比べると、保護フィルムが一枚少ないため、薄化型を図ることができる。 On the other hand, image display devices such as liquid crystal display devices are becoming thinner, and the polarizing film is also required to be thinner. Therefore, thinning is also performed for the polarizer. Moreover, thickness reduction can be performed by providing a protective film only on one side of the polarizer and using a single protective polarizing film not provided with a protective film on the other side. Such a single-protective polarizing film can be thinned because there is less protective film than both protective polarizing films provided with protective films on both sides of the polarizer.
　一方、片保護偏光フィルムは、熱衝撃による耐久性が不十分なため、偏光子側に保護層
（透明樹脂層）を設けたものが提案されている（例えば、特許文献１、２参照）。 On the other hand, since the single-protective polarizing film has insufficient durability due to thermal shock, a film provided with a protective layer (transparent resin layer) on the polarizer side has been proposed (for example, see Patent Documents 1 and 2).
　また、偏光性積層フィルムを製造する方法として、基材フィルムの幅方向の両端から内側にそれぞれ０．５ｃｍ以上の領域において樹脂溶液を塗布しない未塗布部分を設けて樹脂層を形成し、得られた積層フィルムから前記未塗布部分を切断して除去し、その後、延伸処理、染色処理を施して、偏光性積層フィルムを製造する方法が提案されている（例えば、特許文献３参照）。 In addition, as a method for producing a polarizing laminated film, a resin layer is formed by providing an uncoated portion where a resin solution is not applied in each region of 0.5 cm or more from both ends in the width direction of the base film. There has been proposed a method for producing a polarizing laminated film by cutting and removing the uncoated portion from the laminated film, and then performing a stretching treatment and a dyeing treatment (see, for example, Patent Document 3).
特開２０１０－００９０２７号公報JP 2010-009027 A 特開２０１３－１６０７７５号公報JP 2013-160775 A 特開２０１１－２１２５５０号公報JP 2011-212550 A
　特許文献１、２において、片保護偏光フィルムに保護層（透明樹脂層）が形成されているが、このような偏光フィルムはカールすることが多く、得られた偏光フィルムを搬送した際に、偏光フィルム端部に折れが発生したり、当該折れに起因して破断が発生したり、また、他部材に積層時に揉まれ等の不具合が発生する場合があった。 In Patent Documents 1 and 2, a protective layer (transparent resin layer) is formed on a single protective polarizing film. However, such a polarizing film often curls, and when the obtained polarizing film is conveyed, the polarizing layer is polarized. In some cases, the film ends may break, breakage may occur due to the breaks, and other members may have problems such as being pinched during lamination.
　特許文献３の偏光性積層フィルムの製造方法では、未塗布部分を０．５ｃｍ以上設け、当該未塗布部分を削除することにより、得られたフィルムの反り返り現象を抑制するものである。特許文献３の方法では、未塗布部分を削除する工程が必要であり、製造工程が煩雑になるものであった。 In the method for producing a polarizing laminated film of Patent Document 3, an uncoated portion is provided by 0.5 cm or more, and the uncoated portion is deleted, thereby suppressing the warping phenomenon of the obtained film. In the method of Patent Document 3, a process of deleting an uncoated part is necessary, and the manufacturing process becomes complicated.
　従って、本発明においては、カール発生を抑制することができる透明樹脂層付の片保護偏光フィルムの製造方法を提供することを目的とする。さらに、本発明は、粘着剤層付偏光フィルムの製造方法、光学積層体の製造方法を提供することを目的とする。 Therefore, an object of the present invention is to provide a method for producing a piece protective polarizing film with a transparent resin layer that can suppress the occurrence of curling. Furthermore, an object of this invention is to provide the manufacturing method of the polarizing film with an adhesive layer, and the manufacturing method of an optical laminated body.
　本発明者らは、鋭意検討の結果、下記の透明樹脂層付の片保護偏光フィルムの製造方法により上記課題を解決し得ることを見出し、本発明に至った。 As a result of intensive studies, the present inventors have found that the above problem can be solved by the following method for producing a piece-protecting polarizing film with a transparent resin layer, and have reached the present invention.
　すなわち、本発明は、偏光子の片面にのみ保護フィルムを有する片保護偏光フィルム、及び、前記片保護偏光フィルムの偏光子の他の面に設けられた透明樹脂層を有する透明樹脂層付の片保護偏光フィルムの製造方法であって、
　前記偏光子は、ポリビニルアルコール系樹脂を含み、厚みが１０μｍ以下であり、
　前記透明樹脂層は、前記偏光子に、樹脂成分又は透明樹脂層を構成することができる硬化性成分を含む塗工液を塗布する工程、及び、得られた塗布膜を固化又は硬化する工程により形成され、
　前記塗工液の塗布工程において、前記偏光子の幅方向の両端から内側にそれぞれ２０ｍｍ未満の領域において前記塗工液を塗布しない未塗布部分を有するか、又は、前記偏光子の幅方向全体にわたって塗工液を塗布することを特徴とする透明樹脂層付の片保護偏光フィルムの製造方法に関する。 That is, the present invention is a piece with a transparent resin layer having a single protective polarizing film having a protective film only on one side of the polarizer and a transparent resin layer provided on the other side of the polarizer of the single protective polarizing film. A method for producing a protective polarizing film,
The polarizer includes a polyvinyl alcohol resin and has a thickness of 10 μm or less,
The transparent resin layer is formed by applying a coating liquid containing a curable component capable of constituting a resin component or a transparent resin layer to the polarizer, and a step of solidifying or curing the obtained coating film. Formed,
In the application step of the coating liquid, it has an uncoated part where the coating liquid is not applied in a region less than 20 mm inward from both ends in the width direction of the polarizer, or over the entire width direction of the polarizer. It is related with the manufacturing method of the piece protection polarizing film with a transparent resin layer characterized by apply | coating a coating liquid.
　前記塗工液の塗布が、前記偏光子の幅方向全体にわたって塗工液を塗布することにより行われることが好ましい。 It is preferable that the coating liquid is applied by coating the coating liquid over the entire width direction of the polarizer.
　前記偏光子の幅が、１１００～２０００ｍｍであることが好ましい。 The width of the polarizer is preferably 1100 to 2000 mm.
　前記透明樹脂層が、前記塗布膜を固化することにより形成されるものであって、当該固化が乾燥により行われることが好ましい。 The transparent resin layer is preferably formed by solidifying the coating film, and the solidification is preferably performed by drying.
　前記乾燥温度が、１２０℃以下であることが好ましい。 The drying temperature is preferably 120 ° C. or lower.
　前記乾燥時間が、１８０秒以内であることが好ましい。 The drying time is preferably within 180 seconds.
　前記塗工液が、樹脂成分を含む塗工液であって、前記樹脂成分が、ポリビニルアルコール系樹脂であることが好ましい。 It is preferable that the coating liquid is a coating liquid containing a resin component, and the resin component is a polyvinyl alcohol resin.
　また、本発明は、前記製造方法により得られた透明樹脂層付の片保護偏光フィルムの透明樹脂層上に粘着剤層を形成する工程を含むことを特徴とする粘着剤層付偏光フィルムの製造方法に関する。 Moreover, this invention includes the process of forming an adhesive layer on the transparent resin layer of the piece protection polarizing film with a transparent resin layer obtained by the said manufacturing method, The manufacture of the polarizing film with an adhesive layer characterized by the above-mentioned Regarding the method.
　さらに、本発明は、前記製造方法により得られた粘着剤層付偏光フィルムを巻き取ることなく、前記粘着剤層を介して光学部材に貼り合せる工程を含むことを特徴とする光学積層体の製造方法に関する。 Furthermore, this invention includes the process of bonding to an optical member through the said adhesive layer, without winding up the polarizing film with an adhesive layer obtained by the said manufacturing method, The manufacture of the optical laminated body characterized by the above-mentioned. Regarding the method.
　本発明の透明樹脂層付の片保護偏光フィルムの製造方法は、樹脂成分又は透明樹脂層を構成することができる硬化性成分を含む塗工液を偏光子に塗布する際に、前記偏光子の幅方向の両端から内側にそれぞれ２０ｍｍ未満の領域において前記塗工液を塗布しない未塗布部分を有するか、又は、前記偏光子の幅方向全体にわたって塗工液を塗布するため、得られた透明樹脂層付の片保護偏光フィルムのカール発生を抑制することができる。また、前記透明樹脂層付の片保護偏光フィルムの透明樹脂層に粘着剤層を設けた粘着剤層付偏光フィルムも、カール発生が抑制されているものである。従って、本発明の製造方法により得られた透明樹脂層付の片保護偏光フィルムや粘着剤層付偏光フィルムは、製造後、ロール等に巻き取ることなく、画像表示装置等に用いる光学部材に積層することができる。 The method for producing a piece-protecting polarizing film with a transparent resin layer of the present invention comprises applying a coating solution containing a curable component capable of constituting a resin component or a transparent resin layer to the polarizer. In order to apply the coating liquid over the entire width direction of the polarizer, it has an uncoated part where the coating liquid is not applied in each region of less than 20 mm inward from both ends in the width direction. Curling of the single-sided protective polarizing film with a layer can be suppressed. Moreover, curling generation is also suppressed in the polarizing film with the pressure-sensitive adhesive layer in which the pressure-sensitive adhesive layer is provided on the transparent resin layer of the piece protective polarizing film with the transparent resin layer. Accordingly, the piece-protective polarizing film with a transparent resin layer and the polarizing film with a pressure-sensitive adhesive layer obtained by the production method of the present invention are laminated on an optical member used for an image display device or the like without being wound on a roll or the like after production. can do.
本発明の製造方法により得られた透明樹脂層付の片保護偏光フィルムの概略断面図の一例である。It is an example of the schematic sectional drawing of the piece protection polarizing film with a transparent resin layer obtained by the manufacturing method of this invention. 本発明の製造方法により得られた透明樹脂層付の片保護偏光フィルムの概略断面図の一例である。It is an example of the schematic sectional drawing of the piece protection polarizing film with a transparent resin layer obtained by the manufacturing method of this invention.
　１．透明樹脂層付の片保護偏光フィルムの製造方法
　本発明の透明樹脂層付の片保護偏光フィルムの製造方法は、
　偏光子の片面にのみ保護フィルムを有する片保護偏光フィルム、及び、前記片保護偏光フィルムの偏光子の他の面に設けられた透明樹脂層を有する透明樹脂層付の片保護偏光フィルムを製造することができ、
　前記偏光子は、ポリビニルアルコール系樹脂を含み、厚みが１０μｍ以下であり、
　前記透明樹脂層は、前記偏光子に、樹脂成分又は透明樹脂層を構成することができる硬化性成分を含む塗工液を塗布する工程、及び、得られた塗布膜を固化又は硬化する工程により形成され、
　前記塗工液の塗布工程において、前記偏光子の幅方向の両端から内側にそれぞれ２０ｍｍ未満の領域において前記塗工液を塗布しない未塗布部分を有するか、又は、前記偏光子の幅方向全体にわたって塗工液を塗布することを特徴とする。 1. Manufacturing method of piece protection polarizing film with a transparent resin layer Manufacturing method of piece protection polarizing film with a transparent resin layer of the present invention,
A piece protective polarizing film having a protective film only on one side of the polarizer and a piece protective polarizing film with a transparent resin layer having a transparent resin layer provided on the other side of the polarizer of the piece protective polarizing film are produced. It is possible,
The polarizer includes a polyvinyl alcohol resin and has a thickness of 10 μm or less,
The transparent resin layer is formed by applying a coating liquid containing a curable component capable of constituting a resin component or a transparent resin layer to the polarizer, and a step of solidifying or curing the obtained coating film. Formed,
In the application step of the coating liquid, it has an uncoated part where the coating liquid is not applied in a region less than 20 mm inward from both ends in the width direction of the polarizer, or over the entire width direction of the polarizer. It is characterized by applying a coating liquid.
　本発明の製造方法により得られる透明樹脂層付の片保護偏光フィルムを、図１、２を参照しながら説明する。但し、本発明は、これらの図に限定されるものではない。 The piece protective polarizing film with a transparent resin layer obtained by the production method of the present invention will be described with reference to FIGS. However, the present invention is not limited to these drawings.
　本発明で用いる片保護偏光フィルム３は、偏光子１の片面にのみ保護フィルム２を有するものである。前記偏光子１と保護フィルム２とは、接着剤層、粘着剤層、下塗り層（プライマー層）等の介在層（不図示）を介して積層することができる。本発明の製造方法は、前記片保護偏光フィルム３の偏光子１の保護フィルム２を有さない面（他の面）に、透明樹脂層４を形成して、透明樹脂層付の片保護偏光フィルム１０を製造する方法である。 The piece protective polarizing film 3 used in the present invention has the protective film 2 only on one side of the polarizer 1. The polarizer 1 and the protective film 2 can be laminated via an intervening layer (not shown) such as an adhesive layer, an adhesive layer, and an undercoat layer (primer layer). In the production method of the present invention, a transparent resin layer 4 is formed on a surface (other surface) of the polarizer 1 of the piece protective polarizing film 3 that does not have the protective film 2, and the single protective polarization with a transparent resin layer is provided. This is a method for manufacturing the film 10.
　透明樹脂層４の形成は、前記偏光子１に、樹脂成分又は透明樹脂層４を構成することができる硬化性成分を含む塗工液を塗布する工程、及び、得られた塗布膜を固化又は硬化する工程により形成される。前記塗工液の塗布工程において、図１に示すように、前記偏光子１の幅方向（図中のＡ方向）の両端から内側にそれぞれ２０ｍｍ未満の領域において前記塗工液を塗布しない未塗布部分５を有するか、又は、図２に示すように、前記偏光子１の幅方向全体にわたって塗工液を塗布すること（未塗布部分を有さない）を特徴とする。このように塗布することで、得られた透明樹脂層付の片保護偏光フィルム１０のカール発生を抑制することができ、製造後、ロール等に巻き取ることなく、画像表示装置等に用いる光学部材に貼り合わせることができる。なお、ここで、偏光子１の幅方向とは、偏光子１の延伸方向（搬送方向）に直交する方向を意味する。 The transparent resin layer 4 is formed by applying a coating liquid containing a curable component capable of constituting the resin component or the transparent resin layer 4 to the polarizer 1, and solidifying the obtained coating film or It is formed by a curing process. In the coating liquid application step, as shown in FIG. 1, the coating liquid is not applied in a region less than 20 mm inward from both ends in the width direction (A direction in the figure) of the polarizer 1. It has the part 5 or, as shown in FIG. 2, it is characterized by apply | coating a coating liquid over the whole width direction of the said polarizer 1 (it does not have an uncoated part). By applying in this way, curling of the obtained piece-protecting polarizing film 10 with a transparent resin layer can be suppressed, and an optical member used for an image display device or the like without being wound on a roll or the like after manufacture. Can be pasted together. Here, the width direction of the polarizer 1 means a direction orthogonal to the stretching direction (conveying direction) of the polarizer 1.
　また、前記塗工において、前記未塗布部分を有する場合、未塗布部分は、偏光子の幅方向の両端から内側にそれぞれ２０ｍｍ未満の領域であって、１５ｍｍ以下の領域であることが好ましく、１０ｍｍ以下の領域であることがより好ましい。未塗布部分を前記範囲内にすることで、得られる透明樹脂層付の片保護偏光フィルムのカール発生を抑制することができる点で好ましい。未塗布部分の領域の下限値は特に限定されるものではなく、小さければ小さいほど好ましく、前記偏光子の幅方向全体にわたって塗工液を塗布する方法、すなわち、未塗布部分を有さないことが特に好ましい。 Further, in the coating, when the uncoated portion is included, the uncoated portion is an area of less than 20 mm inward from both ends in the width direction of the polarizer, and is preferably an area of 15 mm or less. The following region is more preferable. By making an uncoated part into the said range, it is preferable at the point which can suppress generation | occurrence | production of the curl of the piece protection polarizing film with a transparent resin layer obtained. The lower limit value of the area of the uncoated portion is not particularly limited, and is preferably as small as possible, and a method of applying the coating liquid over the entire width direction of the polarizer, that is, having no uncoated portion. Particularly preferred.
　また、前記塗工において、前記未塗布部分を有する場合、未塗布部分は、偏光子の幅方向の両端から内側にそれぞれ、偏光子の幅に対して５％以下の領域であることが好ましく、偏光子の幅に対して３％未満の領域であることがより好ましく、偏光子の幅に対して２％以下の領域であることがより好ましい。未塗布部分を前記範囲内にすることで、得られる透明樹脂層付の片保護偏光フィルムのカール発生を抑制することができる点で好ましい。未塗布部分の領域の下限値は特に限定されるものではなく、小さければ小さいほど好ましく、前記偏光子の幅方向全体にわたって塗工液を塗布する方法、すなわち、偏光子の幅に対して０％（未塗布部分を有さない）が特に好ましい。 Further, in the coating, when the uncoated portion is included, the uncoated portion is preferably a region of 5% or less with respect to the width of the polarizer, respectively, from both ends in the width direction of the polarizer. The region is preferably less than 3% with respect to the width of the polarizer, and more preferably 2% or less with respect to the width of the polarizer. By making an uncoated part into the said range, it is preferable at the point which can suppress generation | occurrence | production of the curl of the piece protection polarizing film with a transparent resin layer obtained. The lower limit of the area of the uncoated portion is not particularly limited, and is preferably as small as possible. A method of applying the coating liquid over the entire width direction of the polarizer, that is, 0% with respect to the width of the polarizer. (Not having an uncoated portion) is particularly preferable.
　以下本発明の製造方法の各工程について説明する。 Hereinafter, each step of the production method of the present invention will be described.
　１－１．塗工液塗布工程
　本発明の製造方法は、前記片保護偏光フィルム３の偏光子１の保護フィルム２を有さない面（他の面）に、樹脂成分又は透明樹脂層を構成することができる硬化性成分を含む塗工液を塗布する工程を含む。塗布方法は前述の通りである。 1-1. Coating liquid application process The manufacturing method of this invention can comprise a resin component or a transparent resin layer in the surface (other surface) which does not have the protective film 2 of the polarizer 1 of the said piece protection polarizing film 3. FIG. A step of applying a coating liquid containing a curable component; The application method is as described above.
　（１）片保護偏光フィルム
　（１－１）偏光子
　本発明では、厚み１０μｍ以下の偏光子を用いる。偏光子の厚みは、８μｍ以下であるのが好ましく、７μｍ以下がより好ましく、６μｍ以下がさらに好ましい。一方、偏光子の厚みは２μｍ以上が好ましく、３μｍ以上がより好ましい。このような薄型の偏光子は、厚みムラが少なく、視認性が優れており、また寸法変化が少ないため熱衝撃に対する耐久性に優れる。 (1) Single Protective Polarizing Film (1-1) Polarizer In the present invention, a polarizer having a thickness of 10 μm or less is used. The thickness of the polarizer is preferably 8 μm or less, more preferably 7 μm or less, and even more preferably 6 μm or less. On the other hand, the thickness of the polarizer is preferably 2 μm or more, and more preferably 3 μm or more. Such a thin polarizer has less thickness unevenness, excellent visibility, and less dimensional change, and therefore excellent durability against thermal shock.
　偏光子１は、ポリビニルアルコール系樹脂を用いたものが使用される。偏光子１としては、例えば、ポリビニルアルコール系フィルム、部分ホルマール化ポリビニルアルコール系フィルム、エチレン・酢酸ビニル共重合体系部分ケン化フィルム等の親水性高分子フィルムに、ヨウ素や二色性染料の二色性物質を吸着させて一軸延伸したもの、ポリビニルアルコールの脱水処理物やポリ塩化ビニルの脱塩酸処理物等のポリエン系配向フィルム等が挙げられる。これらの中でも、ポリビニルアルコール系フィルムとヨウ素等の二色性物質からなる偏光子が好適である。 The polarizer 1 is made of a polyvinyl alcohol resin. As the polarizer 1, for example, a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or an ethylene / vinyl acetate copolymer partially saponified film, and two colors of iodine and a dichroic dye are used. And polyene-based oriented films such as those obtained by adsorbing a volatile substance and uniaxially stretched, polyvinyl alcohol dehydrated products, polyvinyl chloride dehydrochlorinated products, and the like. Among these, a polarizer composed of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable.
　ポリビニルアルコール系フィルムをヨウ素で染色し一軸延伸した偏光子は、例えば、ポリビニルアルコールをヨウ素の水溶液に浸漬することによって染色し、元長の３～７倍に延伸することで作製することができる。必要に応じてホウ酸や硫酸亜鉛、塩化亜鉛等を含んでいても良いし、ヨウ化カリウム等の水溶液に浸漬することもできる。さらに必要に応じて染色前にポリビニルアルコール系フィルムを水に浸漬して水洗してもよい。ポリビニルアルコール系フィルムを水洗することでポリビニルアルコール系フィルム表面の汚れやブロッキング防止剤を洗浄することができるほかに、ポリビニルアルコール系フィルムを膨潤させることで染色のムラ等の不均一を防止する効果もある。延伸はヨウ素で染色した後に行っても良いし、染色しながら延伸しても良いし、また延伸してからヨウ素で染色しても良い。ホウ酸やヨウ化カリウム等の水溶液や水浴中でも延伸することができる。 A polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. If necessary, it may contain boric acid, zinc sulfate, zinc chloride or the like, or may be immersed in an aqueous solution of potassium iodide or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. In addition to washing the polyvinyl alcohol film surface with stains and antiblocking agents by washing the polyvinyl alcohol film with water, the polyvinyl alcohol film is also swollen to prevent unevenness such as uneven coloring. is there. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched even in an aqueous solution of boric acid or potassium iodide or in a water bath.
　偏光子１はホウ酸を含有していることが延伸安定性や光学耐久性の点から好ましい。また、偏光子１に含まれるホウ酸含有量は、貫通クラック及びナノスリットの発生抑制、拡張抑制の観点から、偏光子全量に対して２５重量％以下が好ましく、２０重量％以下がより好ましく、１８重量％以下がさらに好ましく、１６重量％以下が特に好ましい。偏光子１に含まれるホウ酸含有量が２０重量％を超える場合には、偏光子１の厚みを１０μｍ以下に制御した場合であっても偏光子１の収縮応力が高まり貫通クラックが発生しやすくなるため好ましくない。一方、偏光子１の延伸安定性や光学耐久性の観点から、偏光子全量に対するホウ酸含有量は１０重量％以上であることが好ましく、１２重量％以上であることがより好ましい。 The polarizer 1 preferably contains boric acid from the viewpoint of stretching stability and optical durability. In addition, the boric acid content contained in the polarizer 1 is preferably 25% by weight or less, more preferably 20% by weight or less, based on the total amount of the polarizer, from the viewpoint of suppressing the occurrence of penetration cracks and nanoslits and suppressing expansion. It is more preferably 18% by weight or less, and particularly preferably 16% by weight or less. When the content of boric acid contained in the polarizer 1 exceeds 20% by weight, even if the thickness of the polarizer 1 is controlled to 10 μm or less, the contraction stress of the polarizer 1 is increased and a through crack is easily generated. Therefore, it is not preferable. On the other hand, from the viewpoint of stretching stability and optical durability of the polarizer 1, the boric acid content with respect to the total amount of the polarizer is preferably 10% by weight or more, and more preferably 12% by weight or more.
　薄型の偏光子としては、代表的には、特許第４７５１４８６号明細書、特許第４７５１４８１号明細書、特許第４８１５５４４号明細書、特許第５０４８１２０号明細書、国際公開第２０１４／０７７５９９号パンフレット、国際公開第２０１４／０７７６３６号パンフレット、等に記載されている薄型偏光子又はこれらに記載の製造方法から得られる薄型偏光子を挙げることができる。 As a thin polarizer, typically, Japanese Patent No. 4751486, Japanese Patent No. 4751481, Japanese Patent No. 4815544, Japanese Patent No. 5048120, International Publication No. 2014/0777599, International Publication No. The thin polarizer described in the publication 2014/077636 pamphlet etc. or the thin polarizer obtained from the manufacturing method as described in these can be mentioned.
　前記偏光子１は、単体透過率Ｔ及び偏光度Ｐによって表される光学特性が、次式Ｐ＞－（１００．９２９Ｔ－４２．４－１）×１００（ただし、Ｔ＜４２．３）、又は、Ｐ≧９９．９（ただし、Ｔ≧４２．３）の条件を満足するように構成されたことが好ましい。前記条件を満足するように構成された偏光子は、一義的には、大型表示素子を用いた液晶テレビ用のディスプレイとして求められる性能を有する。具体的にはコントラスト比１０００：１以上かつ最大輝度５００ｃｄ／ｍ２以上である。他の用途としては、例えば、有機ＥＬ表示装置の視認側に貼り合される。 The polarizer 1 has an optical characteristic expressed by a single transmittance T and a polarization degree P of the following formula: P> − (10 0.929T-42.4 −1) × 100 (where T <42.3). Or it is preferable to be configured to satisfy the condition of P ≧ 99.9 (however, T ≧ 42.3). A polarizer configured so as to satisfy the above-described conditions uniquely has performance required as a display for a liquid crystal television using a large display element. Specifically, the contrast ratio is 1000: 1 or more and the maximum luminance is 500 cd / m 2 or more. As other uses, for example, it is bonded to the viewing side of the organic EL display device.
　前記薄型偏光子としては、積層体の状態で延伸する工程と染色する工程を含む製法の中でも、高倍率に延伸できて偏光性能を向上させることのできる点で、特許第４７５１４８６号明細書、特許第４７５１４８１号明細書、特許４８１５５４４号明細書に記載のあるようなホウ酸水溶液中で延伸する工程を含む製法で得られるものが好ましく、特に特許第４７５１４８１号明細書、特許４８１５５４４号明細書に記載のあるホウ酸水溶液中で延伸する前に補助的に空中延伸する工程を含む製法により得られるものが好ましい。これら薄型偏光子は、ポリビニルアルコール系樹脂層と延伸用樹脂基材を積層体の状態で延伸する工程と染色する工程を含む製法によって得ることができる。この製法であれば、ポリビニルアルコール系樹脂層が薄くても、延伸用樹脂基材に支持されていることにより延伸による破断等の不具合なく延伸することが可能となる。 As the thin polarizer, among the production methods including the step of stretching in the state of a laminate and the step of dyeing, Patent No. 4751486, Patent, in that it can be stretched at a high magnification and the polarization performance can be improved. What is obtained by the manufacturing method including the process of extending | stretching in a boric-acid aqueous solution as described in the 4751481 specification and the patent 4815544 specification is preferable, and it describes especially in the patent 4751481 specification and the patent 4815544 specification. What is obtained by the manufacturing method including the process of extending | stretching in the air auxiliary before extending | stretching in the boric-acid aqueous solution which has this is preferable. These thin polarizers can be obtained by a production method including a step of stretching a polyvinyl alcohol-based resin layer and a stretching resin substrate in the state of a laminate and a step of dyeing. With this production method, even if the polyvinyl alcohol-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.
　（１－２）保護フィルム
　前記保護フィルム２を構成する材料としては、透明性、機械的強度、熱安定性、水分遮断性、等方性等に優れるものが好ましい。例えば、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等のポリエステル系ポリマー、ジアセチルセルロースやトリアセチルセルロース等のセルロース系ポリマー、ポリメチルメタクリレート等のアクリル系ポリマー、ポリスチレンやアクリロニトリル・スチレン共重合体（ＡＳ樹脂）等のスチレン系ポリマー、ポリカーボネート系ポリマー等が挙げられる。また、ポリエチレン、ポリプロピレン、シクロ系ないしはノルボルネン構造を有するポリオレフィン、エチレン・プロピレン共重合体の如きポリオレフィン系ポリマー、塩化ビニル系ポリマー、ナイロンや芳香族ポリアミド等のアミド系ポリマー、イミド系ポリマー、スルホン系ポリマー、ポリエーテルスルホン系ポリマー、ポリエーテルエーテルケトン系ポリマー、ポリフェニレンスルフィド系ポリマー、ビニルアルコール系ポリマー、塩化ビニリデン系ポリマー、ビニルブチラール系ポリマー、アリレート系ポリマー、ポリオキシメチレン系ポリマー、エポキシ系ポリマー、又は上記ポリマーのブレンド物等も上記保護フィルムを形成するポリマーの例として挙げられる。 (1-2) Protective film The material constituting the protective film 2 is preferably a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like. For example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin) And polymers based on polycarbonate and polycarbonate. In addition, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or the above Polymer blends and the like can also be cited as examples of polymers forming the protective film.
　なお、保護フィルム２中には任意の適切な添加剤が１種類以上含まれていてもよい。添加剤としては、例えば、紫外線吸収剤、酸化防止剤、滑剤、可塑剤、離型剤、着色防止剤、難燃剤、核剤、帯電防止剤、顔料、着色剤等が挙げられる。保護フィルム中の上記熱可塑性樹脂の含有量は、５０～１００質量％が好ましく、５０～９９質量％がより好ましく、６０～９８質量％がさらに好ましく、７０～９７質量％が特に好ましい。保護フィルム中の上記熱可塑性樹脂の含有量が５０質量％未満の場合、熱可塑性樹脂が本来有する高透明性等が十分に発現できないおそれがある。 The protective film 2 may contain one or more arbitrary appropriate additives. Examples of the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a mold release agent, a coloring inhibitor, a flame retardant, a nucleating agent, an antistatic agent, a pigment, and a coloring agent. The content of the thermoplastic resin in the protective film is preferably 50 to 100% by mass, more preferably 50 to 99% by mass, further preferably 60 to 98% by mass, and particularly preferably 70 to 97% by mass. When content of the said thermoplastic resin in a protective film is less than 50 mass%, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.
　前記保護フィルム２としては、位相差フィルム、輝度向上フィルム、拡散フィルム等も用いることができる。位相差フィルムとしては、正面位相差が４０ｎｍ以上及び／又は、厚み方向位相差が８０ｎｍ以上の位相差を有するものが挙げられる。正面位相差は、通常、４０～２００ｎｍの範囲に、厚み方向位相差は、通常、８０～３００ｎｍの範囲に制御される。保護フィルムとして位相差フィルムを用いる場合には、当該位相差フィルムが偏光子保護フィルムとしても機能するため、薄型化を図ることができる。 As the protective film 2, a retardation film, a brightness enhancement film, a diffusion film, or the like can also be used. Examples of the retardation film include those having a front retardation of 40 nm or more and / or a retardation having a thickness direction retardation of 80 nm or more. The front phase difference is usually controlled in the range of 40 to 200 nm, and the thickness direction phase difference is usually controlled in the range of 80 to 300 nm. In the case where a retardation film is used as the protective film, the retardation film functions also as a polarizer protective film, so that the thickness can be reduced.
　位相差フィルムとしては、熱可塑性樹脂フィルムを一軸又は二軸延伸処理してなる複屈折性フィルムが挙げられる。上記延伸の温度、延伸倍率等は、位相差値、フィルムの材料、厚みにより適宜に設定される。 Examples of the retardation film include a birefringent film obtained by uniaxially or biaxially stretching a thermoplastic resin film. The stretching temperature, stretching ratio, and the like are appropriately set depending on the retardation value, film material, and thickness.
　前記保護フィルム２の厚さは、適宜に決定しうるが、一般には強度や取扱性等の作業性、薄層性等の点より３～２００μｍであるのが好ましく、さらには３～１００μｍであるのが好ましい。特に、前記保護フィルム（予めフィルムが形成されている場合）の厚みは、搬送性の点から１０～６０μｍが好ましく、さらには１０～５０μｍが好ましい。一方、前記保護フィルム（塗布、硬化により形成する場合）の厚みは搬送性の点から、３～２５μｍが好ましく、さらには３～２０μｍが好ましい。前記保護フィルムは、複数枚又は複数層で用いることもできる。 The thickness of the protective film 2 can be determined as appropriate, but generally it is preferably 3 to 200 μm, more preferably 3 to 100 μm, from the viewpoints of workability such as strength and handleability, and thin layer properties. Is preferred. In particular, the thickness of the protective film (when a film is formed in advance) is preferably 10 to 60 μm, more preferably 10 to 50 μm from the viewpoint of transportability. On the other hand, the thickness of the protective film (when formed by coating and curing) is preferably 3 to 25 μm, more preferably 3 to 20 μm from the viewpoint of transportability. The protective film may be used in a plurality of layers or in a plurality of layers.
　前記保護フィルム２の偏光子１を接着させない面には、ハードコート層、反射防止層、スティッキング防止層、拡散層ないしアンチグレア層等の機能層を設けることができる。なお、上記ハードコート層、反射防止層、スティッキング防止層、拡散層やアンチグレア層等の機能層は、保護フィルム２そのものに設けることができるほか、別途、保護フィルムとは別体のものとして設けることもできる。 A functional layer such as a hard coat layer, an antireflection layer, an antisticking layer, a diffusion layer or an antiglare layer can be provided on the surface of the protective film 2 on which the polarizer 1 is not adhered. In addition, the hard coat layer, the antireflection layer, the antisticking layer, the diffusion layer, the antiglare layer and other functional layers can be provided on the protective film 2 itself, and separately provided separately from the protective film. You can also.
　（１－３）介在層
　前記保護フィルム２と偏光子１は、接着剤層、粘着剤層、下塗り層（プライマー層）等の介在層を介して積層することができる。この際、介在層により両者を空気間隙なく積層することが望ましい。なお、偏光子１と保護フィルム２の介在層は図中では示していない。 (1-3) Intervening Layer The protective film 2 and the polarizer 1 can be laminated via an intervening layer such as an adhesive layer, a pressure-sensitive adhesive layer, or an undercoat layer (primer layer). At this time, it is desirable that the both are laminated without an air gap by an intervening layer. In addition, the intervening layer of the polarizer 1 and the protective film 2 is not shown in the drawing.
　接着剤層は、接着剤により形成される。接着剤の種類は特に制限されず、種々のものを用いることができる。前記接着剤層は光学的に透明であれば特に制限されず、接着剤としては、水系、溶剤系、ホットメルト系、活性エネルギー線硬化型等の各種形態のものが用いられるが、水系接着剤又は活性エネルギー線硬化型接着剤が好適である。 The adhesive layer is formed by an adhesive. The type of the adhesive is not particularly limited, and various types can be used. The adhesive layer is not particularly limited as long as it is optically transparent. Examples of the adhesive include water-based, solvent-based, hot-melt-based, active energy ray-curable types, and the like. Or an active energy ray hardening-type adhesive agent is suitable.
　水系接着剤としては、イソシアネート系接着剤、ポリビニルアルコール系接着剤、ゼラチン系接着剤、ビニル系ラテックス系、水系ポリエステル等を例示できる。水系接着剤は、通常、水溶液からなる接着剤として用いられ、通常、０．５～６０重量％の固形分を含有してなる。 Examples of water-based adhesives include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, vinyl-based latex systems, and water-based polyesters. The water-based adhesive is usually used as an adhesive composed of an aqueous solution, and usually contains 0.5 to 60% by weight of solid content.
　活性エネルギー線硬化型接着剤は、電子線、紫外線（ラジカル硬化型、カチオン硬化型）等の活性エネルギー線により硬化が進行する接着剤であり、例えば、電子線硬化型、紫外線硬化型の態様で用いることができる。活性エネルギー線硬化型接着剤は、例えば、光ラジカル硬化型接着剤を用いることができる。光ラジカル硬化型の活性エネルギー線硬化型接着剤を、紫外線硬化型として用いる場合には、当該接着剤は、ラジカル重合性化合物及び光重合開始剤を含有する。 The active energy ray curable adhesive is an adhesive that cures by an active energy ray such as an electron beam and ultraviolet rays (radical curable type and cationic curable type). Can be used. As the active energy ray curable adhesive, for example, a photo radical curable adhesive can be used. When the photo radical curable active energy ray curable adhesive is used as an ultraviolet curable adhesive, the adhesive contains a radical polymerizable compound and a photo polymerization initiator.
　接着剤の塗工方式は、接着剤の粘度や目的とする厚みによって適宜に選択される。塗工方式の例として、例えば、リバースコーター、グラビアコーター（ダイレクト，リバースやオフセット）、バーリバースコーター、ロールコーター、ダイコーター、バーコーター、ロッドコーター等が挙げられる。その他、塗工には、ディッピング方式等の方式を適宜に使用することができる。 The adhesive coating method is appropriately selected depending on the viscosity of the adhesive and the target thickness. Examples of coating methods include reverse coaters, gravure coaters (direct, reverse and offset), bar reverse coaters, roll coaters, die coaters, bar coaters, rod coaters and the like. In addition, a method such as a dipping method can be appropriately used for coating.
　また、前記接着剤の塗工は、水系接着剤等を用いる場合には、最終的に形成される接着剤層の厚みが３０～３００ｎｍになるように行うのが好ましい。前記接着剤層の厚さは、さらに好ましくは６０～１５０ｎｍである。一方、活性エネルギー線硬化型接着剤を用いる場合には、前記接着剤層の厚みは０．２～２０μｍになるよう行うのが好ましい。 In addition, when the water-based adhesive or the like is used, the adhesive is preferably applied so that the finally formed adhesive layer has a thickness of 30 to 300 nm. The thickness of the adhesive layer is more preferably 60 to 150 nm. On the other hand, when an active energy ray curable adhesive is used, the thickness of the adhesive layer is preferably 0.2 to 20 μm.
　なお、偏光子１と保護フィルム２の積層にあたって、保護フィルムと接着剤層の間には、易接着層を設けることができる。易接着層は、例えば、ポリエステル骨格、ポリエーテル骨格、ポリカーボネート骨格、ポリウレタン骨格、シリコーン系、ポリアミド骨格、ポリイミド骨格、ポリビニルアルコール骨格等を有する各種樹脂により形成することができる。これらポリマー樹脂は１種を単独で、又は２種以上を組み合わせて用いることができる。また易接着層の形成には他の添加剤を加えてもよい。具体的には、粘着付与剤、紫外線吸収剤、酸化防止剤、耐熱安定剤等の安定剤等を挙げることができる。 In addition, in laminating | stacking the polarizer 1 and the protective film 2, an easily bonding layer can be provided between a protective film and an adhesive bond layer. The easy adhesion layer can be formed of, for example, various resins having a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, a silicone-based, a polyamide skeleton, a polyimide skeleton, a polyvinyl alcohol skeleton, and the like. These polymer resins can be used alone or in combination of two or more. Moreover, you may add another additive for formation of an easily bonding layer. Specific examples include stabilizers such as tackifiers, ultraviolet absorbers, antioxidants and heat stabilizers.
　易接着層は、通常、保護フィルムに予め設けておき、当該保護フィルムの易接着層側と偏光子とを接着剤層により積層する。易接着層の形成は、易接着層の形成材を保護フィルム上に、公知の技術により塗工、乾燥することにより行われる。易接着層の形成材は、乾燥後の厚み、塗工の円滑性等を考慮して適当な濃度に希釈した溶液として、通常調整される。易接着層は乾燥後の厚みは、好ましくは０．０１～５μｍ、さらに好ましくは０．０２～２μｍ、さらに好ましくは０．０５～１μｍである。なお、易接着層は複数層設けることができるが、この場合にも、易接着層の総厚みは上記範囲になるようにするのが好ましい。 The easy-adhesion layer is usually provided in advance on a protective film, and the easy-adhesion layer side of the protective film and the polarizer are laminated with an adhesive layer. The easy-adhesion layer is formed by applying and drying a material for forming the easy-adhesion layer on a protective film by a known technique. The material for forming the easy adhesion layer is usually adjusted as a solution diluted to an appropriate concentration in consideration of the thickness after drying, the smoothness of coating, and the like. The thickness of the easy-adhesion layer after drying is preferably 0.01 to 5 μm, more preferably 0.02 to 2 μm, and still more preferably 0.05 to 1 μm. Note that a plurality of easy-adhesion layers can be provided, but also in this case, the total thickness of the easy-adhesion layers is preferably in the above range.
　粘着剤層は、粘着剤から形成される。粘着剤としては各種の粘着剤を用いることができ、例えば、ゴム系粘着剤、アクリル系粘着剤、シリコーン系粘着剤、ウレタン系粘着剤、ビニルアルキルエーテル系粘着剤、ポリビニルピロリドン系粘着剤、ポリアクリルアミド系粘着剤、セルロース系粘着剤等が挙げられる。前記粘着剤の種類に応じて粘着性のベースポリマーが選択される。前記粘着剤の中でも、光学的透明性に優れ、適宜な濡れ性と凝集性と接着性の粘着特性を示して、耐候性や耐熱性等に優れる点から、アクリル系粘着剤が好ましく使用される。 The pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive. Various pressure-sensitive adhesives can be used as the pressure-sensitive adhesive, such as rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, vinyl alkyl ether-based pressure-sensitive adhesives, polyvinylpyrrolidone-based pressure-sensitive adhesives, Examples include acrylamide-based adhesives and cellulose-based adhesives. An adhesive base polymer is selected according to the type of the adhesive. Among the pressure-sensitive adhesives, acrylic pressure-sensitive adhesives are preferably used because they are excellent in optical transparency, exhibit appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and are excellent in weather resistance, heat resistance, and the like. .
　下塗り層（プライマー層）は、偏光子１と保護フィルム２との密着性を向上させるために形成される。プライマー層を構成する材料としては、偏光子１と保護フィルム２との両方にある程度強い密着力を発揮する材料であれば特に限定されない。例えば、透明性、熱安定性、延伸性等に優れる熱可塑性樹脂等が用いられる。熱可塑性樹脂としては、例えば、アクリル系樹脂、ポリオレフィン系樹脂、ポリエステル系樹脂、ポリビニルアルコール系樹脂、又はそれらの混合物が挙げられる。 The undercoat layer (primer layer) is formed in order to improve the adhesion between the polarizer 1 and the protective film 2. The material constituting the primer layer is not particularly limited as long as the material exhibits a certain degree of strong adhesion to both the polarizer 1 and the protective film 2. For example, a thermoplastic resin having excellent transparency, heat stability, stretchability, and the like are used. Examples of the thermoplastic resin include an acrylic resin, a polyolefin resin, a polyester resin, a polyvinyl alcohol resin, or a mixture thereof.
　（２）塗工液
　塗工液は、樹脂成分又は透明樹脂層を構成することができる硬化性成分を含む。当該塗工液を偏光子１に塗布し、固化又は硬化することで透明樹脂層４を形成することができる。 (2) Coating liquid A coating liquid contains the curable component which can comprise a resin component or a transparent resin layer. The transparent resin layer 4 can be formed by applying the coating liquid to the polarizer 1 and solidifying or curing.
　また、前記塗工液（以下、形成材ということもある）の形態は、液状を示すものであれば特に制限はなく、水系、水分散系、溶剤系、無溶剤のいずれでもよい。 Further, the form of the coating liquid (hereinafter sometimes referred to as a forming material) is not particularly limited as long as it shows a liquid state, and may be any of water-based, water-dispersed, solvent-based, and solvent-free.
　前記塗工液は、粘度が低い方が、偏光子１の表面に損傷部が存在する場合に、当該損傷部に浸透しやすいため有利である。前記粘度は、２５℃で測定した値が、２０００ｍＰａ・ｓ以下であるのが好ましく、１０００ｍＰａ・ｓ以下がより好ましく、５００ｍＰａ・ｓ以下がさらに好ましく、１００ｍＰａ・ｓ以下が特に好ましい。 It is advantageous that the coating liquid has a lower viscosity because when the damaged portion is present on the surface of the polarizer 1, it easily penetrates into the damaged portion. The viscosity measured at 25 ° C. is preferably 2000 mPa · s or less, more preferably 1000 mPa · s or less, further preferably 500 mPa · s or less, and particularly preferably 100 mPa · s or less.
　前記塗工液の片保護偏光フィルム（偏光子側）への塗布は、乾燥後の塗布膜（透明樹脂層４）の厚みが０．２μｍ以上になるように行なうのが好ましい。前記透明樹脂層４の厚さは０．５μｍ以上であるのがより好ましく、０．７μｍ以上であるのがさらに好ましい。一方、透明樹脂層４が厚くなりすぎると光学信頼性と耐水性が低下するため、透明樹脂層４の厚さは３μｍ以下であるのが好ましく、３μｍ未満であるのがより好ましく、２μｍ以下であるのがさらに好ましい。 It is preferable to apply the coating liquid to the piece protective polarizing film (polarizer side) so that the thickness of the dried coating film (transparent resin layer 4) is 0.2 μm or more. The thickness of the transparent resin layer 4 is more preferably 0.5 μm or more, and further preferably 0.7 μm or more. On the other hand, if the transparent resin layer 4 becomes too thick, the optical reliability and water resistance deteriorate. Therefore, the thickness of the transparent resin layer 4 is preferably 3 μm or less, more preferably less than 3 μm, and preferably 2 μm or less. More preferably.
　前記塗工液の塗布方法としては、各種方法が用いられる。具体的には、例えば、ロールコート、キスロールコート、グラビアコート、リバースコート、ロールブラッシュ、スプレーコート、ディップロールコート、バーコート、ナイフコート、エアーナイフコート、カーテンコート、リップコート、ダイコーター等による押出しコート法等の方法が挙げられる。 Various methods are used as the coating method of the coating liquid. Specifically, for example, by roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples thereof include an extrusion coating method.
　前記透明樹脂層４の形成材料としては、例えば、ポリエステル系樹脂、ポリエーテル系樹脂、ポリカーボネート系樹脂、ポリウレタン系樹脂、シリコーン系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリビニルアルコール（ＰＶＡ）系樹脂、アクリル系樹脂、エポキシ系樹脂等を挙げることができる。これら樹脂材料は１種を単独で又は２種以上を組み合わせて用いることができるが、これらの中でもポリウレタン系樹脂、ポリビニルアルコール系樹脂、アクリル系樹脂、エポキシ系樹脂からなる群から選択される１種以上が好ましく、ポリビニルアルコール系樹脂、アクリル系樹脂がより好ましい。 Examples of the material for forming the transparent resin layer 4 include polyester resins, polyether resins, polycarbonate resins, polyurethane resins, silicone resins, polyamide resins, polyimide resins, polyvinyl alcohol (PVA) resins, An acrylic resin, an epoxy resin, etc. can be mentioned. These resin materials can be used singly or in combination of two or more, but among these, one kind selected from the group consisting of polyurethane resins, polyvinyl alcohol resins, acrylic resins, and epoxy resins The above is preferable, and a polyvinyl alcohol resin and an acrylic resin are more preferable.
　前記塗工液としては、水に溶解又は分散した樹脂成分を含む塗工液が好ましい。水に溶解又は分散した樹脂成分は、常温（２５℃）で、水に溶解した樹脂、水に可溶な樹脂を水系溶媒に溶解させたもののことをいう。塗工液が、水系又は水分散系であると、偏光子１の表面に損傷部が存在する場合に、偏光子１の表面が膨潤することで損傷部に、前記塗工液が馴染むため有利である。すなわち、塗工液が水系又は水分散系であると、偏光子を構成する当該損傷部周辺のポリビニルアルコール分子の配向性を一部緩和すると共に、当該損傷部周辺のホウ酸含有量を低減することができるため、透明樹脂層４の厚みが小さくても（例えば、３μｍ未満、好ましくは２μｍ以下であっても）、当該損傷部の拡大を効果的に抑制することができる。 The coating liquid is preferably a coating liquid containing a resin component dissolved or dispersed in water. The resin component dissolved or dispersed in water means a resin dissolved in water at room temperature (25 ° C.) or a resin soluble in water dissolved in an aqueous solvent. When the coating liquid is an aqueous or water-dispersed system, when the damaged portion is present on the surface of the polarizer 1, the surface of the polarizer 1 is swollen so that the coating liquid is adapted to the damaged portion, which is advantageous. It is. That is, when the coating liquid is an aqueous system or an aqueous dispersion system, the orientation of the polyvinyl alcohol molecules around the damaged part constituting the polarizer is partially relaxed and the boric acid content around the damaged part is reduced. Therefore, even if the thickness of the transparent resin layer 4 is small (for example, even if it is less than 3 μm, preferably 2 μm or less), the expansion of the damaged portion can be effectively suppressed.
　水に溶解又は分散することができる樹脂成分の代表例としては、例えば、ポリビニルアルコール系樹脂、ポリ（メタ）アクリル酸、ポリアクリルアミド、メチロール化メラミン樹脂、メチロール化ユリア樹脂、レゾール型フェノール樹脂、ポリエチレンオキシド、カルボキシメチルセルロース等が挙げられる。これは単独で用いても良いし、複数を組み合わせて用いても良い。前記樹脂成分としてはポリビニルアルコール系樹脂、ポリ（メタ）アクリル酸、メチロール化メラミンが好適に用いられる。特に、偏光子を構成するポリビニルアルコール系樹脂との密着性の観点から前記樹脂成分としてはポリビニルアルコール系樹脂が好適である。以下では、ポリビニルアルコール系樹脂を用いた場合を説明する。 Representative examples of the resin component that can be dissolved or dispersed in water include, for example, polyvinyl alcohol resin, poly (meth) acrylic acid, polyacrylamide, methylolated melamine resin, methylolated urea resin, resol type phenolic resin, poly Examples thereof include ethylene oxide and carboxymethyl cellulose. These may be used alone or in combination. As the resin component, polyvinyl alcohol resin, poly (meth) acrylic acid, and methylolated melamine are preferably used. In particular, a polyvinyl alcohol resin is suitable as the resin component from the viewpoint of adhesion to the polyvinyl alcohol resin constituting the polarizer. Below, the case where a polyvinyl alcohol-type resin is used is demonstrated.
　透明樹脂層４は、ポリビニルアルコール系樹脂を含有する形成材（塗工液）から形成することが好ましい。透明樹脂層を形成するポリビニルアルコール系樹脂は、「ポリビニルアルコール系樹脂」である限り、偏光子が含有するポリビニルアルコール系樹脂と同一でも異なっていてもよい。 The transparent resin layer 4 is preferably formed from a forming material (coating liquid) containing a polyvinyl alcohol resin. The polyvinyl alcohol resin forming the transparent resin layer may be the same as or different from the polyvinyl alcohol resin contained in the polarizer as long as it is a “polyvinyl alcohol resin”.
　前記ポリビニルアルコール系樹脂としては、例えば、ポリビニルアルコールが挙げられる。ポリビニルアルコールは、ポリ酢酸ビニルをケン化することにより得られる。また、ポリビニルアルコール系樹脂としては、酢酸ビニルと共重合性を有する単量体との共重合体のケン化物が挙げられる。前記共重合性を有する単量体がエチレンの場合には、エチレン－ビニルアルコール共重合体が得られる。また、前記共重合性を有する単量体としては、（無水）マレイン酸、フマール酸、クロトン酸、イタコン酸、（メタ）アクリル酸等の不飽和カルボン酸及びそのエステル類；エチレン、プロピレン等のα－オレフィン、（メタ）アリルスルホン酸（ソーダ）、スルホン酸ソーダ（モノアルキルマレート）、ジスルホン酸ソーダアルキルマレート、Ｎ－メチロールアクリルアミド、アクリルアミドアルキルスルホン酸アルカリ塩、Ｎ－ビニルピロリドン、Ｎ－ビニルピロリドン誘導体等が挙げられる。これらポリビニルアルコール系樹脂は一種を単独で又は二種以上を併用することができる。 Examples of the polyvinyl alcohol resin include polyvinyl alcohol. Polyvinyl alcohol is obtained by saponifying polyvinyl acetate. Examples of the polyvinyl alcohol-based resin include a saponified product of a copolymer of vinyl acetate and a monomer having copolymerizability. When the copolymerizable monomer is ethylene, an ethylene-vinyl alcohol copolymer is obtained. Examples of the copolymerizable monomer include unsaturated carboxylic acids such as (anhydrous) maleic acid, fumaric acid, crotonic acid, itaconic acid, (meth) acrylic acid, and esters thereof; ethylene, propylene, etc. α-olefin, (meth) allylsulfonic acid (soda), sulfonic acid soda (monoalkylmalate), disulfonic acid soda alkylmalate, N-methylolacrylamide, acrylamide alkylsulfonic acid alkali salt, N-vinylpyrrolidone, N- Examples include vinyl pyrrolidone derivatives. These polyvinyl alcohol resins can be used alone or in combination of two or more.
　前記ポリビニルアルコール系樹脂のケン化度は、例えば、９５モル％以上のものを用いることができるが、耐湿熱性や耐水性を満足させる観点からは、ケン化度は９９モル％以上が好ましく、さらには９９．７モル％以上が好ましい。ケン化度は、ケン化によりビニルアルコール単位に変換され得る単位の中で、実際にビニルアルコール単位にケン化されている単位の割合を表したものであり、残基はビニルエステル単位である。ケン化度は、ＪＩＳ－Ｋ６７２６－１９９４に準じて求めることができる。 The saponification degree of the polyvinyl alcohol-based resin can be, for example, 95 mol% or more, but from the viewpoint of satisfying moisture heat resistance and water resistance, the saponification degree is preferably 99 mol% or more, Is preferably 99.7 mol% or more. The degree of saponification represents the proportion of units that are actually saponified to vinyl alcohol units among the units that can be converted to vinyl alcohol units by saponification, and the residue is a vinyl ester unit. The degree of saponification can be determined according to JIS-K6726-1994.
　前記ポリビニルアルコール系樹脂の平均重合度は、例えば、５００以上のものを用いることができるが、耐湿熱性や耐水性を満足させる観点からは、平均重合度は、１０００以上が好ましく、１５００以上がより好ましく、２０００以上がさらに好ましい。ポリビニルアルコール系樹脂の平均重合度は、ＪＩＳ－Ｋ６７２６に準じて測定される。 The average degree of polymerization of the polyvinyl alcohol-based resin can be, for example, 500 or more, but from the viewpoint of satisfying moisture and heat resistance and water resistance, the average degree of polymerization is preferably 1000 or more, more preferably 1500 or more. Preferably, 2000 or more is more preferable. The average degree of polymerization of the polyvinyl alcohol resin is measured according to JIS-K6726.
　また、前記ポリビニルアルコール系樹脂としては、前記ポリビニルアルコール又はその共重合体の側鎖に親水性の官能基を有する変性ポリビニルアルコール系樹脂を用いることができる。前記親水性の官能基としては、例えば、アセトアセチル基、カルボニル基等が挙げられる。その他、ポリビニルアルコール系樹脂をアセタール化、ウレタン化、エーテル化、グラフト化、リン酸エステル化等した変性ポリビニルアルコールを用いることができる。 As the polyvinyl alcohol resin, a modified polyvinyl alcohol resin having a hydrophilic functional group in the side chain of the polyvinyl alcohol or a copolymer thereof can be used. Examples of the hydrophilic functional group include an acetoacetyl group and a carbonyl group. In addition, modified polyvinyl alcohol obtained by acetalization, urethanization, etherification, grafting, phosphoric esterification or the like of a polyvinyl alcohol resin can be used.
　透明樹脂層４又は塗工液（固形分）中のポリビニルアルコール系樹脂の割合は、８０重量％以上であるのが好ましく、９０重量％以上がより好ましく、９５重量％以上がさらに好ましい。 The ratio of the polyvinyl alcohol resin in the transparent resin layer 4 or the coating liquid (solid content) is preferably 80% by weight or more, more preferably 90% by weight or more, and further preferably 95% by weight or more.
　前記塗工液は、前記ポリビニルアルコール系樹脂を溶媒に溶解させた溶液として調整される。溶媒としては、例えば、水、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセト、アミドＮ－メチルピロリドン、各種グリコール類、トリメチロールプロパン等の多価アルコール類、エチレンジアミン、ジエチレントリアミン等のアミン類が挙げられる。これらは単独で、又は、二種以上組み合わせて用いることができる。これらの中でも、溶剤として水を用いた水溶液として用いるのが好ましい。前記形成材（例えば、水溶液）における、前記ポリビニルアルコール系樹脂の濃度は、特に制限はないが、塗工性や放置安定性等を考慮すれば、０．１～１５重量％が好ましく、０．５～１０重量％がより好ましい。 The coating liquid is prepared as a solution in which the polyvinyl alcohol resin is dissolved in a solvent. Examples of the solvent include water, dimethyl sulfoxide, dimethylformamide, dimethylacetate, amide N-methylpyrrolidone, various glycols, polyhydric alcohols such as trimethylolpropane, and amines such as ethylenediamine and diethylenetriamine. These may be used alone or in combination of two or more. Among these, it is preferable to use it as an aqueous solution using water as a solvent. The concentration of the polyvinyl alcohol-based resin in the forming material (for example, an aqueous solution) is not particularly limited, but is preferably 0.1 to 15% by weight in consideration of coating properties, storage stability, and the like. 5 to 10% by weight is more preferable.
　なお、前記塗工液（例えば、水溶液）には、添加剤を添加することができる。前記添加剤としては、例えば、可塑剤、界面活性剤等が挙げられる。可塑剤としては、例えば、エチレングリコールやグリセリン等の多価アルコールが挙げられる。界面活性剤としては、例えば、非イオン界面活性剤が挙げられる。さらにシランカップリング剤、チタンカップリング剤等のカップリング剤、各種粘着付与剤、紫外線吸収剤、酸化防止剤、耐熱安定剤、耐加水分解安定剤等の安定剤等を配合することもできる。 In addition, an additive can be added to the coating liquid (for example, an aqueous solution). Examples of the additive include a plasticizer and a surfactant. Examples of the plasticizer include polyhydric alcohols such as ethylene glycol and glycerin. Examples of the surfactant include nonionic surfactants. Furthermore, a coupling agent such as a silane coupling agent and a titanium coupling agent, various tackifiers, an ultraviolet absorber, an antioxidant, a heat stabilizer, a hydrolysis stabilizer, and the like can also be blended.
　次いで、前記透明樹脂層４の形成にあたり、透明樹脂層を構成することができる硬化性成分を含む塗工液を用いる場合について説明する。硬化性成分としては、電子線硬化型、紫外線硬化型、可視光線硬化型等の活性エネルギー線硬化型と熱硬化型に大別することができる。さらには、紫外線硬化型、可視光線硬化型は、ラジカル重合硬化型とカチオン重合硬化型に区分出来る。本発明において、波長範囲１０ｎｍ～３８０ｎｍ未満の活性エネルギー線を紫外線、波長範囲３８０ｎｍ～８００ｎｍの活性エネルギー線を可視光線として表記する。前記ラジカル重合硬化型の硬化性成分は、熱硬化型の硬化性成分として用いることができる。 Next, in the formation of the transparent resin layer 4, a case where a coating liquid containing a curable component that can constitute the transparent resin layer is used will be described. The curable component can be roughly classified into an active energy ray curable type such as an electron beam curable type, an ultraviolet ray curable type, and a visible light curable type, and a thermosetting type. Furthermore, the ultraviolet curable type and the visible light curable type can be classified into a radical polymerization curable type and a cationic polymerization curable type. In the present invention, an active energy ray having a wavelength range of 10 nm to less than 380 nm is expressed as ultraviolet light, and an active energy ray having a wavelength range of 380 nm to 800 nm is expressed as visible light. The radical polymerization curable component can be used as a thermosetting curable component.
　（ラジカル重合硬化型形成材）
　前記硬化性成分としては、例えば、ラジカル重合性化合物が挙げられる。ラジカル重合性化合物は、（メタ）アクリロイル基、ビニル基等の炭素－炭素二重結合のラジカル重合性の官能基を有する化合物が挙げられる。これら硬化性成分は、単官能ラジカル重合性化合物又は二官能以上の多官能ラジカル重合性化合物のいずれも用いることができる。また、これらラジカル重合性化合物は、１種を単独で、又は２種以上を組み合わせて用いることができる。これらラジカル重合性化合物としては、例えば、（メタ）アクリロイル基を有する化合物が好適である。なお、本発明において、（メタ）アクリロイルとは、アクリロイル基及び／又はメタクリロイル基を意味し、「（メタ）」は以下同様の意味である。 (Radical polymerization curable forming material)
Examples of the curable component include a radical polymerizable compound. Examples of the radical polymerizable compound include compounds having a radical polymerizable functional group of a carbon-carbon double bond such as a (meth) acryloyl group and a vinyl group. As these curable components, either a monofunctional radical polymerizable compound or a bifunctional or higher polyfunctional radical polymerizable compound can be used. Moreover, these radically polymerizable compounds can be used individually by 1 type or in combination of 2 or more types. As these radically polymerizable compounds, for example, compounds having a (meth) acryloyl group are suitable. In the present invention, (meth) acryloyl means an acryloyl group and / or methacryloyl group, and “(meth)” has the same meaning hereinafter.
　（単官能ラジカル重合性化合物）
　単官能ラジカル重合性化合物としては、例えば、（メタ）アクリルアミド基を有する（メタ）アクリルアミド誘導体が挙げられる。（メタ）アクリルアミド誘導体は、偏光子との密着性を確保するうえで、また、重合速度が速く生産性に優れる点で好ましい。（メタ）アクリルアミド誘導体の具体例としては、例えば、Ｎ－メチル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、Ｎ－ブチル（メタ）アクリルアミド、Ｎ－ヘキシル（メタ）アクリルアミド等のＮ－アルキル基含有（メタ）アクリルアミド誘導体；Ｎ－メチロール（メタ）アクリルアミド、Ｎ－ヒドロキシエチル（メタ）アクリルアミド、Ｎ－メチロール－Ｎ－プロパン（メタ）アクリルアミド等のＮ－ヒドロキシアルキル基含有（メタ）アクリルアミド誘導体；アミノメチル（メタ）アクリルアミド、アミノエチル（メタ）アクリルアミド等のＮ－アミノアルキル基含有（メタ）アクリルアミド誘導体；Ｎ－メトキシメチルアクリルアミド、Ｎ－エトキシメチルアクリルアミド等のＮ－アルコキシ基含有（メタ）アクリルアミド誘導体；メルカプトメチル（メタ）アクリルアミド、メルカプトエチル（メタ）アクリルアミド等のＮ－メルカプトアルキル基含有（メタ）アクリルアミド誘導体；等が挙げられる。また、（メタ）アクリルアミド基の窒素原子が複素環を形成している複素環含有（メタ）アクリルアミド誘導体としては、例えば、Ｎ－アクリロイルモルホリン、Ｎ－アクリロイルピペリジン、Ｎ－メタクリロイルピペリジン、Ｎ－アクリロイルピロリジン等が挙げられる。 (Monofunctional radical polymerizable compound)
Examples of the monofunctional radical polymerizable compound include (meth) acrylamide derivatives having a (meth) acrylamide group. The (meth) acrylamide derivative is preferable in terms of ensuring adhesion with the polarizer and having a high polymerization rate and excellent productivity. Specific examples of (meth) acrylamide derivatives include, for example, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N N-alkyl group-containing (meth) acrylamide derivatives such as butyl (meth) acrylamide and N-hexyl (meth) acrylamide; N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylol-N— N-hydroxyalkyl group-containing (meth) acrylamide derivatives such as propane (meth) acrylamide; N-aminoalkyl group-containing (meth) acrylamide derivatives such as aminomethyl (meth) acrylamide and aminoethyl (meth) acrylamide; N-methoxymethyl N-alkoxy group-containing (meth) acrylamide derivatives such as acrylamide and N-ethoxymethylacrylamide; N-mercaptoalkyl group-containing (meth) acrylamide derivatives such as mercaptomethyl (meth) acrylamide and mercaptoethyl (meth) acrylamide; It is done. Examples of the heterocyclic-containing (meth) acrylamide derivative in which the nitrogen atom of the (meth) acrylamide group forms a heterocyclic ring include, for example, N-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine. Etc.
　前記（メタ）アクリルアミド誘導体の中でも、偏光子との密着性の点から、Ｎ－ヒドロキシアルキル基含有（メタ）アクリルアミド誘導体が好ましく、特に、Ｎ－ヒドロキシエチル（メタ）アクリルアミドが好ましい。 Among the (meth) acrylamide derivatives, N-hydroxyalkyl group-containing (meth) acrylamide derivatives are preferable from the viewpoint of adhesion to a polarizer, and N-hydroxyethyl (meth) acrylamide is particularly preferable.
　また、単官能ラジカル重合性化合物としては、例えば、（メタ）アクリロイルオキシ基を有する各種の（メタ）アクリル酸誘導体が挙げられる。具体的には、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、２－メチル－２－ニトロプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ｎ－ペンチル（メタ）アクリレート、ｔ－ペンチル（メタ）アクリレート、３－ペンチル（メタ）アクリレート、２，２－ジメチルブチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、セチル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、４－メチル－２－プロピルペンチル（メタ）アクリレート、ｎ－オクタデシル（メタ）アクリレート等の（メタ）アクリル酸（炭素数１～２０）アルキルエステル類が挙げられる。 In addition, examples of the monofunctional radical polymerizable compound include various (meth) acrylic acid derivatives having a (meth) acryloyloxy group. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-methyl-2-nitropropyl (meth) acrylate, n-butyl ( (Meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, t-pentyl (meth) acrylate, 3-pentyl (meth) acrylate, 2,2-dimethylbutyl (meth) acrylate, n-hexyl (meth) acrylate, cetyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 4-methyl-2-propylpentyl ( (Meth) acrylate, n-o Tadeshiru (meth) acrylate (meth) acrylic acid (1-20 carbon atoms) alkyl esters and the like.
　また、前記（メタ）アクリル酸誘導体としては、例えば、シクロヘキシル（メタ）アクリレート、シクロペンチル（メタ）アクリレート等のシクロアルキル（メタ）アクリレート；
　ベンジル（メタ）アクリレート等のアラルキル（メタ）アクリレート；
　２－イソボルニル（メタ）アクリレート、２－ノルボルニルメチル（メタ）アクリレート、５－ノルボルネン－２－イル－メチル（メタ）アクリレート、３－メチル－２－ノルボルニルメチル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレ－ト、ジシクロペンテニルオキシエチル（メタ）アクリレ－ト、ジシクロペンタニル（メタ）アクリレ－ト、等の多環式（メタ）アクリレート；
　２－メトキシエチル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、２－メトキシメトキシエチル（メタ）アクリレート、３－メトキシブチル（メタ）アクリレート、エチルカルビトール（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、アルキルフェノキシポリエチレングリコール（メタ）アクリレート等のアルコキシ基又はフェノキシ基含有（メタ）アクリレート；等が挙げられる。 Examples of the (meth) acrylic acid derivative include cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and cyclopentyl (meth) acrylate;
Aralkyl (meth) acrylates such as benzyl (meth) acrylate;
2-isobornyl (meth) acrylate, 2-norbornylmethyl (meth) acrylate, 5-norbornen-2-yl-methyl (meth) acrylate, 3-methyl-2-norbornylmethyl (meth) acrylate, dicyclo Polycyclic (meth) acrylates such as pentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxymethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) Examples thereof include alkoxy groups such as acrylates and alkylphenoxypolyethylene glycol (meth) acrylates or phenoxy group-containing (meth) acrylates.
　また、前記（メタ）アクリル酸誘導体としては、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレート、１０－ヒドロキシデシル（メタ）アクリレート、１２－ヒドロキシラウリル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレートや、［４－（ヒドロキシメチル）シクロヘキシル］メチルアクリレート、シクロヘキサンジメタノールモノ（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート等の水酸基含有（メタ）アクリレート；
　グリシジル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートグリシジルエーテル等のエポキシ基含有（メタ）アクリレート；
　２，２，２－トリフルオロエチル（メタ）アクリレート、２，２，２－トリフルオロエチルエチル（メタ）アクリレート、テトラフルオロプロピル（メタ）アクリレート、ヘキサフルオロプロピル（メタ）アクリレート、オクタフルオロペンチル（メタ）アクリレート、ヘプタデカフルオロデシル（メタ）アクリレート、３－クロロ－２－ヒドロキシプロピル（メタ）アクリレート等のハロゲン含有（メタ）アクリレート；
　ジメチルアミノエチル（メタ）アクリレート等のアルキルアミノアルキル（メタ）アクリレート；
　３－オキセタニルメチル（メタ）アクリレート、３－メチル－オキセタニルメチル（メタ）アクリレート、３－エチル－オキセタニルメチル（メタ）アクリレート、３－ブチル－オキセタニルメチル（メタ）アクリレート、３－ヘキシル－オキセタニルメチル（メタ）アクリレート等のオキセタン基含有（メタ）アクリレート；
　テトラヒドロフルフリル（メタ）アクリレート、ブチロラクトン（メタ）アクリレート、等の複素環を有する（メタ）アクリレートや、ヒドロキシピバリン酸ネオペンチルグリコール（メタ）アクリル酸付加物、ｐ－フェニルフェノール（メタ）アクリレート等が挙げられる。 Examples of the (meth) acrylic acid derivative include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, etc. And hydroxyl groups such as [4- (hydroxymethyl) cyclohexyl] methyl acrylate, cyclohexanedimethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc. Meth) acrylate;
Epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether;
2,2,2-trifluoroethyl (meth) acrylate, 2,2,2-trifluoroethylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) ) Halogen-containing (meth) acrylates such as acrylate, heptadecafluorodecyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate;
Alkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate;
3-oxetanylmethyl (meth) acrylate, 3-methyl-oxetanylmethyl (meth) acrylate, 3-ethyl-oxetanylmethyl (meth) acrylate, 3-butyl-oxetanylmethyl (meth) acrylate, 3-hexyl-oxetanylmethyl (meta) ) Oxetane group-containing (meth) acrylates such as acrylates;
(Meth) acrylate having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate, butyrolactone (meth) acrylate, hydroxypivalate neopentyl glycol (meth) acrylic acid adduct, p-phenylphenol (meth) acrylate, etc. Can be mentioned.
　また、単官能ラジカル重合性化合物としては、（メタ）アクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸等のカルボキシル基含有モノマーが挙げられる。 Also, examples of the monofunctional radically polymerizable compound include carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
　また、単官能ラジカル重合性化合物としては、例えば、Ｎ－ビニルピロリドン、Ｎ－ビニル－ε－カプロラクタム、メチルビニルピロリドン等のラクタム系ビニルモノマー；ビニルピリジン、ビニルピペリドン、ビニルピリミジン、ビニルピペラジン、ビニルピラジン、ビニルピロール、ビニルイミダゾール、ビニルオキサゾール、ビニルモルホリン等の窒素含有複素環を有するビニル系モノマー等が挙げられる。 Examples of the monofunctional radical polymerizable compound include lactam vinyl monomers such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and methylvinylpyrrolidone; vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, Examples thereof include vinyl monomers having a nitrogen-containing heterocyclic ring such as vinyl pyrrole, vinyl imidazole, vinyl oxazole and vinyl morpholine.
　また、単官能ラジカル重合性化合物としては、活性メチレン基を有するラジカル重合性化合物を用いることができる。活性メチレン基を有するラジカル重合性化合物は、末端又は分子中に（メタ）アクリル基等の活性二重結合基を有し、かつ活性メチレン基を有する化合物である。活性メチレン基としては、例えば、アセトアセチル基、アルコキシマロニル基、又はシアノアセチル基等が挙げられる。前記活性メチレン基がアセトアセチル基であることが好ましい。活性メチレン基を有するラジカル重合性化合物の具体例としては、例えば、２－アセトアセトキシエチル（メタ）アクリレート、２－アセトアセトキシプロピル（メタ）アクリレート、２－アセトアセトキシ－１－メチルエチル（メタ）アクリレート等のアセトアセトキシアルキル（メタ）アクリレート；２－エトキシマロニルオキシエチル（メタ）アクリレート、２－シアノアセトキシエチル（メタ）アクリレート、Ｎ－（２－シアノアセトキシエチル）アクリルアミド、Ｎ－（２－プロピオニルアセトキシブチル）アクリルアミド、Ｎ－（４－アセトアセトキシメチルベンジル）アクリルアミド、Ｎ－（２－アセトアセチルアミノエチル）アクリルアミド等が挙げられる。活性メチレン基を有するラジカル重合性化合物は、アセトアセトキシアルキル（メタ）アクリレートであることが好ましい。 Also, as the monofunctional radically polymerizable compound, a radically polymerizable compound having an active methylene group can be used. The radically polymerizable compound having an active methylene group is a compound having an active methylene group having an active double bond group such as a (meth) acryl group in the terminal or in the molecule. Examples of the active methylene group include an acetoacetyl group, an alkoxymalonyl group, and a cyanoacetyl group. The active methylene group is preferably an acetoacetyl group. Specific examples of the radical polymerizable compound having an active methylene group include, for example, 2-acetoacetoxyethyl (meth) acrylate, 2-acetoacetoxypropyl (meth) acrylate, 2-acetoacetoxy-1-methylethyl (meth) acrylate Acetoacetoxyalkyl (meth) acrylate such as 2-ethoxymalonyloxyethyl (meth) acrylate, 2-cyanoacetoxyethyl (meth) acrylate, N- (2-cyanoacetoxyethyl) acrylamide, N- (2-propionylacetoxybutyl) ) Acrylamide, N- (4-acetoacetoxymethylbenzyl) acrylamide, N- (2-acetoacetylaminoethyl) acrylamide and the like. The radical polymerizable compound having an active methylene group is preferably acetoacetoxyalkyl (meth) acrylate.
　（多官能ラジカル重合性化合物）
　また、二官能以上の多官能ラジカル重合性化合物としては、例えば、トリプロピレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジアクリレート、２－エチル－２－ブチルプロパンジオールジ（メタ）アクリレート、ビスフェノールＡジ（メタ）アクリレート、ビスフェノールＡエチレンオキサイド付加物ジ（メタ）アクリレート、ビスフェノールＡプロピレンオキサイド付加物ジ（メタ）アクリレート、ビスフェノールＡジグリシジルエーテルジ（メタ）アクリレート、ネオぺンチルグリコールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリート、環状トリメチロールプロパンフォルマル（メタ）アクリレート、ジオキサングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ＥＯ変性ジグリセリンテトラ（メタ）アクリレート等の（メタ）アクリル酸と多価アルコールとのエステル化物、９，９－ビス［４－（２－（メタ）アクリロイルオキシエトキシ）フェニル］フルオレンが挙げられる。具体例としては、アロニックスＭ－２２０、Ｍ－３０６（東亞合成（株）製）、ライトアクリレート１，９ＮＤ－Ａ（共栄社化学（株）製）、ライトアクリレートＤＧＥ－４Ａ（共栄社化学（株）製）、ライトアクリレートＤＣＰ－Ａ（共栄社化学（株）製）、ＳＲ－５３１（Ｓａｒｔｏｍｅｒ社製）、ＣＤ－５３６（Ｓａｒｔｏｍｅｒ社製）等が挙げられる。また必要に応じて、各種のエポキシ（メタ）アクリレート、ウレタン（メタ）アクリレート、ポリエステル（メタ）アクリレートや、各種の（メタ）アクリレート系モノマー等が挙げられる。 (Polyfunctional radical polymerizable compound)
Examples of the bifunctional or higher polyfunctional radical polymerizable compound include tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 -Nonanediol di (meth) acrylate, 1,10-decanediol diacrylate, 2-ethyl-2-butylpropanediol di (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) ) Acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) Acryte, cyclic trimethylolpropane formal (meth) acrylate, dioxane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta Esterified products of (meth) acrylic acid and polyhydric alcohols such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO-modified diglycerin tetra (meth) acrylate, 9,9-bis [4- (2- (Meth) acryloyloxyethoxy) phenyl] fluorene. Specific examples include Aronix M-220 and M-306 (manufactured by Toagosei Co., Ltd.), light acrylate 1,9ND-A (manufactured by Kyoeisha Chemical Co., Ltd.), light acrylate DGE-4A (manufactured by Kyoeisha Chemical Co., Ltd.). ), Light acrylate DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.), SR-531 (manufactured by Sartomer), CD-536 (manufactured by Sartomer) and the like. Moreover, various epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, various (meth) acrylate monomers, and the like are included as necessary.
　ラジカル重合性化合物は、偏光子との密着性と光学耐久性を両立させる観点から、単官能ラジカル重合性化合物と多官能ラジカル重合性化合物を併用することが好ましい。通常は、ラジカル重合性化合物１００重量％に対して、単官能ラジカル重合性化合物３～８０重量％と多官能ラジカル重合性化合物２０～９７重量％の割合で併用することが好ましい。 The radical polymerizable compound is preferably used in combination with a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound from the viewpoint of achieving both adhesion to the polarizer and optical durability. Usually, it is preferable to use a combination of 3 to 80% by weight of the monofunctional radical polymerizable compound and 20 to 97% by weight of the polyfunctional radical polymerizable compound with respect to 100% by weight of the radical polymerizable compound.
　（ラジカル重合硬化型形成材の態様）
　ラジカル重合硬化型形成材は、活性エネルギー線硬化型又は熱硬化型の形成材として用いることができる。活性エネルギー線に電子線等を用いる場合には、当該活性エネルギー線硬化型形成材は光重合開始剤を含有することは必要ではないが、活性エネルギー線に紫外線又は可視光線を用いる場合には、光重合開始剤を含有するのが好ましい。一方、前記硬化性成分を熱硬化性成分として用いる場合には、当該形成材は熱重合開始剤を含有するのが好ましい。 (Mode of radical polymerization curable forming material)
The radical polymerization curable forming material can be used as an active energy ray curable forming material or a thermosetting forming material. When using an electron beam or the like for the active energy ray, the active energy ray curable forming material does not need to contain a photopolymerization initiator, but when using an ultraviolet ray or visible light for the active energy ray, It preferably contains a photopolymerization initiator. On the other hand, when the curable component is used as a thermosetting component, the forming material preferably contains a thermal polymerization initiator.
　（光重合開始剤）
　ラジカル重合性化合物を用いる場合の光重合開始剤は、活性エネルギー線によって適宜に選択される。紫外線又は可視光線により硬化させる場合には紫外線又は可視光線開裂の光重合開始剤が用いられる。前記光重合開始剤としては、例えば、ベンジル、ベンゾフェノン、ベンゾイル安息香酸、３，３′－ジメチル－４－メトキシベンゾフェノン等のベンゾフェノン系化合物；４－（２－ヒドロキシエトキシ）フェニル（２－ヒドロキシ－２－プロピル）ケトン、α－ヒドロキシ－α，α´－ジメチルアセトフェノン、２－メチル－２－ヒドロキシプロピオフェノン、α－ヒドロキシシクロヘキシルフェニルケトン等の芳香族ケトン化合物；メトキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフエノン、２，２－ジエトキシアセトフェノン、２－メチル－１－［４－（メチルチオ）－フェニル］－２－モルホリノプロパン－１等のアセトフェノン系化合物；べンゾインメチルエーテル、べンゾインエチルエーテル、ベンゾインイソプロピルエーテル、べンゾインブチルエーテル、アニソインメチルエーテル等のベンゾインエーテル系化合物；ベンジルジメチルケタール等の芳香族ケタール系化合物；２－ナフタレンスルホニルクロリド等の芳香族スルホニルクロリド系化合物；１－フェノン－１，２―プロパンジオン－２－（Ｏ－エトキシカルボニル）オキシム等の光活性オキシム系化合物；チオキサンソン、２－クロロチオキサンソン、２－メチルチオキサンソン、２，４－ジメチルチオキサンソン、イソプロピルチオキサンソン、２，４－ジクロロチオキサンソン、２，４－ジエチルチオキサンソン、２，４－ジイソプロピルチオキサンソン、ドデシルチオキサントン等のチオキサンソン系化合物；カンファーキノン；ハロゲン化ケトン；アシルホスフィノキシド；アシルホスフォナート等が挙げられる。 (Photopolymerization initiator)
The photopolymerization initiator in the case of using the radical polymerizable compound is appropriately selected depending on the active energy ray. In the case of curing with ultraviolet light or visible light, a photopolymerization initiator for ultraviolet light or visible light cleavage is used. Examples of the photopolymerization initiator include benzophenone compounds such as benzyl, benzophenone, benzoylbenzoic acid, and 3,3′-dimethyl-4-methoxybenzophenone; 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2 -Propyl) ketone, aromatic ketone compounds such as α-hydroxy-α, α′-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, α-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy- Acetophenone compounds such as 2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) -phenyl] -2-morpholinopropane-1; benzoin methyl ether; Benzoin ethyl ether, benzoin isop Benzoin ether compounds such as propyl ether, benzoin butyl ether and anisoin methyl ether; aromatic ketal compounds such as benzyldimethyl ketal; aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride; 1-phenone-1, Photoactive oxime compounds such as 2-propanedione-2- (O-ethoxycarbonyl) oxime; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone Thioxanthone compounds such as 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone; camphorquinone; halogenated ketone; acyl phosphinoxide; Ruhosufonato, and the like.
　前記光重合開始剤の配合量は、硬化性成分（ラジカル重合性化合物）の全量１００重量部に対して、２０重量部以下である。光重合開始剤の配合量は、０．０１～２０重量部であるのが好ましく、０．０５～１０重量部がより好ましく、０．１～５重量部がさらに好ましい。 The blending amount of the photopolymerization initiator is 20 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component (radical polymerizable compound). The blending amount of the photopolymerization initiator is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, and further preferably 0.1 to 5 parts by weight.
　また、硬化性成分としてラジカル重合性化合物を含有する可視光線硬化型で用いる場合には、特に３８０ｎｍ以上の光に対して高感度な光重合開始剤を用いることが好ましい。３８０ｎｍ以上の光に対して高感度な光重合開始剤については後述する。 Also, when using a visible light curable type containing a radical polymerizable compound as a curable component, it is preferable to use a photopolymerization initiator that is particularly sensitive to light of 380 nm or more. A photopolymerization initiator that is highly sensitive to light of 380 nm or more will be described later.
　前記光重合開始剤としては、下記一般式（１）で表される化合物；
Figure JPOXMLDOC01-appb-C000001
 （式中、Ｒ１及びＲ２は－Ｈ、－ＣＨ２ＣＨ３、－ｉＰｒ又はＣｌを示し、Ｒ１及びＲ２は同一又は異なっても良い）を単独で使用するか、あるいは一般式（１）で表される化合物と後述する３８０ｎｍ以上の光に対して高感度な光重合開始剤とを併用することが好ましい。一般式（１）で表される化合物を使用した場合、３８０ｎｍ以上の光に対して高感度な光重合開始剤を単独で使用した場合に比べて密着性に優れる。一般式（１）で表される化合物の中でも、Ｒ１及びＲ２が－ＣＨ２ＣＨ３であるジエチルチオキサントンが特に好ましい。当該形成材（塗工液）中の一般式（１）で表される化合物の組成比率は、硬化性成分の全量１００重量部に対して、０．１～５重量部であることが好ましく、０．５～４重量部であることがより好ましく、０．９～３重量部であることがさらに好ましい。 As said photoinitiator, the compound represented by following General formula (1);
Figure JPOXMLDOC01-appb-C000001
 (Wherein R 1 and R 2 represent —H, —CH 2 CH 3 , —iPr or Cl, and R 1 and R 2 may be the same or different), respectively, or a general formula ( It is preferable to use together the compound represented by 1) and a photopolymerization initiator that is highly sensitive to light of 380 nm or more, which will be described later. When the compound represented by the general formula (1) is used, the adhesion is excellent as compared with the case where a photopolymerization initiator having high sensitivity to light of 380 nm or more is used alone. Among the compounds represented by the general formula (1), diethylthioxanthone in which R 1 and R 2 are —CH 2 CH 3 is particularly preferable. The composition ratio of the compound represented by the general formula (1) in the forming material (coating liquid) is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable component, The amount is more preferably 0.5 to 4 parts by weight, and further preferably 0.9 to 3 parts by weight.
　また、必要に応じて重合開始助剤を添加することが好ましい。重合開始助剤としては、トリエチルアミン、ジエチルアミン、Ｎ－メチルジエタノールアミン、エタノールアミン、４－ジメチルアミノ安息香酸、４－ジメチルアミノ安息香酸メチル、４－ジメチルアミノ安息香酸エチル、４－ジメチルアミノ安息香酸イソアミル等が挙げられ、４－ジメチルアミノ安息香酸エチルが特に好ましい。重合開始助剤を使用する場合、その添加量は、硬化性成分の全量１００重量部に対して、通常０～５重量部、好ましくは０～４重量部、最も好ましくは０～３重量部である。 Further, it is preferable to add a polymerization initiation assistant as necessary. Examples of polymerization initiators include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and the like. Among them, ethyl 4-dimethylaminobenzoate is particularly preferable. When a polymerization initiation assistant is used, its addition amount is usually 0 to 5 parts by weight, preferably 0 to 4 parts by weight, most preferably 0 to 3 parts by weight, based on 100 parts by weight of the total amount of the curable component. is there.
　また、必要に応じて公知の光重合開始剤を併用することができる。ＵＶ吸収能を有する保護フィルムは、３８０ｎｍ以下の光を透過しないため、光重合開始剤としては、３８０ｎｍ以上の光に対して高感度な光重合開始剤を使用することが好ましい。具体的には、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド、ビス（η５－２，４－シクロペンタジエン－１－イル）－ビス（２，６－ジフルオロ－３－（１Ｈ－ピロール－１－イル）－フェニル）チタニウム等が挙げられる。 Further, a known photopolymerization initiator can be used in combination as necessary. Since the protective film having UV absorbing ability does not transmit light of 380 nm or less, it is preferable to use a photopolymerization initiator that is highly sensitive to light of 380 nm or more as the photopolymerization initiator. Specifically, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine Oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) 1-yl) -phenyl) titanium and the like.
　特に、光重合開始剤として、一般式（１）の光重合開始剤に加えて、さらに下記一般式
（２）で表される化合物；
Figure JPOXMLDOC01-appb-C000002
 （式中、Ｒ３、Ｒ４及びＲ５は－Ｈ、－ＣＨ３、－ＣＨ２ＣＨ３、－ｉＰｒ又はＣｌを示し、Ｒ３、Ｒ４及びＲ５は同一又は異なっても良い）を使用することが好ましい。一般式（２）で表される化合物としては、市販品でもある２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン（商品名：ＩＲＧＡＣＵＲＥ９０７、ＢＡＳＦ社製）が好適に使用可能である。その他、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１（商品名：ＩＲＧＡＣＵＲＥ３６９、ＢＡＳＦ社製）、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン（商品名：ＩＲＧＡＣＵＲＥ３７９、ＢＡＳＦ社製）が感度が高いため好ましい。 In particular, as a photopolymerization initiator, in addition to the photopolymerization initiator of the general formula (1), a compound represented by the following general formula (2);
Figure JPOXMLDOC01-appb-C000002
 (Wherein R 3 , R 4 and R 5 represent —H, —CH 3 , —CH 2 CH 3 , —iPr or Cl, and R 3 , R 4 and R 5 may be the same or different). It is preferable to use it. Examples of the compound represented by the general formula (2) include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: IRGACURE907, manufactured by BASF) which is a commercially available product. It can be suitably used. In addition, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE369, manufactured by BASF), 2- (dimethylamino) -2-[(4-methylphenyl ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE379, manufactured by BASF) is preferred because of its high sensitivity.
　（熱重合開始剤）
　熱重合開始剤としては、熱開裂によって重合が開始しないものが好ましい。例えば、熱重合開始剤としては、１０時間半減期温度が６５℃以上、さらには７５～９０℃であるものが好ましい。なお、半減期とは、重合開始剤の分解速度を表す指標であり、重合開始剤の残存量が半分になるまでの時間をいう。任意の時間で半減期を得るための分解温度や、任意の温度での半減期時間に関しては、メーカーカタログ等に記載されており、例えば、日本油脂（株）の「有機過酸化物カタログ第９版（２００３年５月）」等に記載されている。 (Thermal polymerization initiator)
As the thermal polymerization initiator, those in which polymerization does not start by thermal cleavage are preferable. For example, as the thermal polymerization initiator, those having a 10-hour half-life temperature of 65 ° C. or higher, more preferably 75 to 90 ° C. are preferable. The half-life is an index representing the decomposition rate of the polymerization initiator, and means the time until the remaining amount of the polymerization initiator is halved. The decomposition temperature for obtaining a half-life at an arbitrary time and the half-life time at an arbitrary temperature are described in the manufacturer catalog, for example, “Organic Peroxide Catalog No. 9 of Nippon Oil & Fats Co., Ltd.” Edition (May 2003) ".
　熱重合開始剤としては、例えば、過酸化ラウロイル（１０時間半減期温度：６４℃）、過酸化ベンゾイル（１０時間半減期温度：７３℃）、１，１－ビス（ｔ－ブチルペルオキシ）－３，３，５－トリメチルシクロへキサン（１０時間半減期温度：９０℃）、ジ（２－エチルヘキシル）パーオキシジカーボネート（１０時間半減期温度：４９℃）、ジ（４－ｔ－ブチルシクロヘキシル）パーオキシジカーボネート、ジ－ｓｅｃ－ブチルパーオキシジカーボネート（１０時間半減期温度：５１℃）、ｔ－ブチルパーオキシネオデカノエート（１０時間半減期温度：４８℃）、ｔ－ヘキシルパーオキシピバレート、ｔ－ブチルパーオキシピバレート、ジラウロイルパーオキシド（１０時間半減期温度：６４℃）、ジ－ｎ－オクタノイルパーオキシド、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエート（１０時間半減期温度：６６℃）、ジ（４－メチルベンゾイル）パーオキシド、ジベンゾイルパーオキシド（１０時間半減期温度：７３℃）、ｔ－ブチルパーオキシイソブチレート（１０時間半減期温度：８１℃）、１，１－ジ（ｔ－ヘキシルパーオキシ）シクロヘキサン等の有機系過酸化物が挙げられる。 Examples of the thermal polymerization initiator include lauroyl peroxide (10 hour half-life temperature: 64 ° C.), benzoyl peroxide (10 hour half-life temperature: 73 ° C.), 1,1-bis (t-butylperoxy) -3. , 3,5-trimethylcyclohexane (10-hour half-life temperature: 90 ° C.), di (2-ethylhexyl) peroxydicarbonate (10-hour half-life temperature: 49 ° C.), di (4-t-butylcyclohexyl) Peroxydicarbonate, di-sec-butylperoxydicarbonate (10-hour half-life temperature: 51 ° C.), t-butyl peroxyneodecanoate (10-hour half-life temperature: 48 ° C.), t-hexyl peroxy Pivalate, t-butylperoxypivalate, dilauroyl peroxide (10 hour half-life temperature: 64 ° C.), di-n-octanoyl peroxide 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (10-hour half-life temperature: 66 ° C.), di (4-methylbenzoyl) peroxide, dibenzoyl peroxide (half-hour 10 hours) Organic peroxides such as t-butyl peroxyisobutyrate (10-hour half-life temperature: 81 ° C.), 1,1-di (t-hexylperoxy) cyclohexane, and the like.
　また、熱重合開始剤としては、例えば、２，２’－アゾビスイソブチロニトリル（１０時間半減期温度：６７℃）、２，２’－アゾビス（２－メチルブチロニトリル）（１０時間半減期温度：６７℃）、１，１－アゾビス－シクロへキサン－１－カルボニトリル（１０時間半減期温度：８７℃）等のアゾ系化合物が挙げられる。 Examples of the thermal polymerization initiator include 2,2′-azobisisobutyronitrile (10 hour half-life temperature: 67 ° C.), 2,2′-azobis (2-methylbutyronitrile) (10 hours). And azo compounds such as 1,1-azobis-cyclohexane-1-carbonitrile (10 hour half-life temperature: 87 ° C.).
　熱重合開始剤の配合量は、硬化性成分（ラジカル重合性化合物）の全量１００重量部に対して、０．０１～２０重量部である。熱重合開始剤の配合量は、さらには０．０５～１０重量部、さらには０．１～３重量部であるのが好ましい。 The blending amount of the thermal polymerization initiator is 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of the curable component (radical polymerizable compound). The blending amount of the thermal polymerization initiator is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 3 parts by weight.
　（カチオン重合硬化型形成材）
　カチオン重合硬化型形成材の硬化性成分としては、エポキシ基やオキセタニル基を有する化合物が挙げられる。エポキシ基を有する化合物は、分子内に少なくとも２個のエポキシ基を有するものであれば特に限定されず、一般に知られている各種の硬化性エポキシ化合物を用いることができる。好ましいエポキシ化合物として、分子内に少なくとも２個のエポキシ基と少なくとも１個の芳香環を有する化合物（芳香族系エポキシ化合物）や、分子内に少なくとも２個のエポキシ基を有し、そのうちの少なくとも１個は脂環式環を構成する隣り合う２個の炭素原子との間で形成されている化合物（脂環式エポキシ化合物）等が例として挙げられる。 (Cationic polymerization curable forming material)
Examples of the curable component of the cationic polymerization curable forming material include compounds having an epoxy group or an oxetanyl group. The compound having an epoxy group is not particularly limited as long as it has at least two epoxy groups in the molecule, and various generally known curable epoxy compounds can be used. As a preferable epoxy compound, a compound having at least two epoxy groups and at least one aromatic ring in the molecule (aromatic epoxy compound), or at least two epoxy groups in the molecule, at least one of them. Examples thereof include a compound (alicyclic epoxy compound) formed between two adjacent carbon atoms constituting an alicyclic ring.
　（光カチオン重合開始剤）
　カチオン重合硬化型形成材は、硬化性成分として以上で説明したエポキシ化合物及びオキセタン化合物を含有し、これらはいずれもカチオン重合により硬化するものであることから、光カチオン重合開始剤が配合される。この光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、カチオン種又はルイス酸を発生し、エポキシ基やオキセタニル基の重合反応を開始する。 (Photocationic polymerization initiator)
The cationic polymerization curable forming material contains the epoxy compound and the oxetane compound described above as curable components, and these are cured by cationic polymerization, and therefore, a photocationic polymerization initiator is blended therein. This cationic photopolymerization 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 starts a polymerization reaction of an epoxy group or an oxetanyl group.
　１－２．固化又は硬化工程
　本発明の製造方法は、得られた塗布膜を固化又は硬化する工程を含む。塗布膜を固化又は硬化することで、透明樹脂層４を形成することができる。 1-2. Solidification or hardening process The manufacturing method of this invention includes the process of solidifying or hardening the obtained coating film. The transparent resin layer 4 can be formed by solidifying or curing the coating film.
　前記塗工液が、樹脂成分を含む塗工液の場合、前記透明樹脂層４の形成にあたり、前記塗工液を塗布した後には、当該樹脂成分に種類に応じて固化させる。前記樹脂成分を含む塗工液は、前記樹脂成分を溶剤に溶解した溶液又は分散させた分散液であり、例えば、水系の溶液、水分散系の分散液、又は溶剤系の溶液として用いられる。前記固化は、前記塗工液中から溶剤を除去することにより透明樹脂層４を形成することをいう。例えば、前記樹脂成分がポリビニルアルコール系樹脂の場合には、前記塗工液は水溶液として用いることができ、加熱（乾燥）等により固化を施すことができる。また、前記樹脂成分が水溶性アクリルの場合も同様に固化を施すことができる。 When the coating liquid is a coating liquid containing a resin component, after forming the transparent resin layer 4, after applying the coating liquid, the resin component is solidified according to the type. The coating liquid containing the resin component is a solution obtained by dissolving or dispersing the resin component in a solvent, and is used as, for example, an aqueous solution, an aqueous dispersion, or a solvent solution. The solidification means forming the transparent resin layer 4 by removing the solvent from the coating liquid. For example, when the resin component is a polyvinyl alcohol-based resin, the coating liquid can be used as an aqueous solution and can be solidified by heating (drying) or the like. Further, when the resin component is water-soluble acrylic, it can be solidified similarly.
　乾燥温度は、特に限定されるものではなく、通常、６０～２００℃程度であるが、本発明においては、カール抑制の観点から、１２０℃以下であることが好ましく、１００℃以下がより好ましい。乾燥時間は１８０秒以内であるのが好ましく、１２０秒以内がより好ましく、６０秒以内がさらに好ましい。 The drying temperature is not particularly limited and is usually about 60 to 200 ° C., but in the present invention, it is preferably 120 ° C. or less and more preferably 100 ° C. or less from the viewpoint of curling suppression. The drying time is preferably within 180 seconds, more preferably within 120 seconds, and even more preferably within 60 seconds.
　一方、前記透明樹脂層４の形成にあたり、透明樹脂層を構成することができる硬化性成分を含む塗工液を塗布した後には、当該硬化性成分の種類に応じて、当該硬化性成分が透明樹脂層を形成することができる硬化を施す。前記樹脂を構成することができる硬化性成分を含む塗工液は、前記硬化性成分が塗工液を呈するものであれば、無溶剤系で用いることができる。また、前記塗工液は、前記硬化性成分を溶剤に溶解した溶液を用いることができる。なお、前記硬化性成分が塗工液を呈する場合にも溶液として用いることができる。前記溶剤としは、用いる硬化性成分に応じて適宜に選択することができる。例えば、前記硬化性成分として、アクリル系樹脂を形成するアクリル系モノマーを用いる場合、エポキシ樹脂を形成するエポキシ系モノマーを用いる場合には、前記硬化性成分を含む塗工液に活性エネルギー線照射（紫外線照射）等による硬化を施すことができる。 On the other hand, in forming the transparent resin layer 4, after applying a coating liquid containing a curable component capable of constituting the transparent resin layer, the curable component is transparent according to the type of the curable component. Curing that can form a resin layer is performed. The coating liquid containing a curable component that can constitute the resin can be used in a solventless system as long as the curable component exhibits a coating liquid. Moreover, the said coating liquid can use the solution which melt | dissolved the said sclerosing | hardenable component in the solvent. The curable component can also be used as a solution when presenting a coating solution. The solvent can be appropriately selected according to the curable component to be used. For example, when an acrylic monomer that forms an acrylic resin is used as the curable component, or when an epoxy monomer that forms an epoxy resin is used, the coating liquid containing the curable component is irradiated with active energy rays ( Curing by ultraviolet irradiation or the like can be performed.
　前記硬化型形成材（塗工液）による透明樹脂層４の形成は、偏光子の面に、硬化型形成材を塗工し、その後、硬化することにより行う。 The formation of the transparent resin layer 4 with the curable forming material (coating liquid) is performed by coating the curable forming material on the surface of the polarizer and then curing.
　偏光子１は、上記硬化型形成材を塗工する前に、表面改質処理を行ってもよい。具体的な処理としては、コロナ処理、プラズマ処理、ケン化処理による処理等が挙げられる。 The polarizer 1 may be subjected to a surface modification treatment before coating the curable forming material. Specific examples of the treatment include corona treatment, plasma treatment, and saponification treatment.
　前記硬化型形成材は、活性エネルギー線硬化型形成材又は熱硬化型形成材として用いられる。活性エネルギー線硬化型形成材では、電子線硬化型、紫外線硬化型、可視光線硬化型の態様で用いることができる。前記硬化型形成材の態様は生産性の観点から熱硬化型形成材よりも、活性エネルギー線硬化型形成材が好ましく、さらには活性エネルギー線硬化型形成材としては、可視光線硬化型形成材が生産性の観点から好ましい。 The curable forming material is used as an active energy ray curable forming material or a thermosetting forming material. The active energy ray curable forming material can be used in an electron beam curable type, an ultraviolet curable type, or a visible light curable type. The aspect of the curable forming material is preferably an active energy ray curable forming material rather than a thermosetting forming material from the viewpoint of productivity, and moreover, the active energy ray curable forming material is a visible light curable forming material. It is preferable from the viewpoint of productivity.
　（活性エネルギー線硬化型）
　活性エネルギー線硬化型形成材では、偏光子に活性エネルギー線硬化型形成材を塗工した後、活性エネルギー線（電子線、紫外線、可視光線等）を照射し、活性エネルギー線硬化型形成材を硬化して透明樹脂層４を形成する。活性エネルギー線（電子線、紫外線、可視光線等）の照射方向は、任意の適切な方向から照射することができる。好ましくは、透明樹脂層４側から照射する。 (Active energy ray curable type)
In the active energy ray curable forming material, the active energy ray curable forming material is applied to the polarizer, and then the active energy ray (electron beam, ultraviolet ray, visible light, etc.) is applied to the active energy ray curable forming material. The transparent resin layer 4 is formed by curing. The irradiation direction of active energy rays (electron beam, ultraviolet ray, visible light, etc.) can be irradiated from any appropriate direction. Preferably, it irradiates from the transparent resin layer 4 side.
　（電子線硬化型）
　電子線硬化型において、電子線の照射条件は、上記活性エネルギー線硬化型形成材を硬化しうる条件であれば、任意の適切な条件を採用できる。例えば、電子線照射は、加速電圧が、好ましくは５ｋＶ～３００ｋＶであり、さらに好ましくは１０ｋＶ～２５０ｋＶである。加速電圧が５ｋＶ未満の場合、電子線が透明樹脂層４最深部まで届かず硬化不足となるおそれがあり、加速電圧が３００ｋＶを超えると、試料を通る浸透力が強すぎて、保護フィルム２や偏光子１にダメージを与えるおそれがある。照射線量としては、５～１００ｋＧｙ、さらに好ましくは１０～７５ｋＧｙである。照射線量が５ｋＧｙ未満の場合は、透明樹脂層４が硬化不足となり、１００ｋＧｙを超えると、保護フィルムや偏光子にダメージを与え、機械的強度の低下や黄変を生じ、所定の光学特性を得ることができない。 (Electron beam curing type)
In the electron beam curable type, any appropriate condition can be adopted as the electron beam irradiation condition as long as the active energy ray curable forming material can be cured. For example, in the electron beam irradiation, the acceleration voltage is preferably 5 kV to 300 kV, more preferably 10 kV to 250 kV. If the acceleration voltage is less than 5 kV, the electron beam may not reach the deepest portion of the transparent resin layer 4 and may be insufficiently cured. If the acceleration voltage exceeds 300 kV, the penetration force through the sample is too strong, and the protective film 2 or There is a risk of damaging the polarizer 1. The irradiation dose is 5 to 100 kGy, more preferably 10 to 75 kGy. When the irradiation dose is less than 5 kGy, the transparent resin layer 4 becomes insufficiently cured, and when it exceeds 100 kGy, the protective film and the polarizer are damaged, resulting in a decrease in mechanical strength and yellowing, thereby obtaining predetermined optical characteristics. I can't.
　電子線照射は、通常、不活性ガス中で照射を行うが、必要であれば大気中や酸素を少し導入した条件で行ってもよい。 The electron beam irradiation is usually performed in an inert gas, but if necessary, it may be performed in the atmosphere or under a condition where a little oxygen is introduced.
　（紫外線硬化型、可視光線硬化型）
　本発明の製造方法では、活性エネルギー線として、波長範囲３８０ｎｍ～４５０ｎｍの可視光線を含むもの、特には波長範囲３８０ｎｍ～４５０ｎｍの可視光線の照射量が最も多い活性エネルギー線を使用することが好ましい。本発明に係る活性エネルギー線としては、ガリウム封入メタルハライドランプ、波長範囲３８０～４４０ｎｍを発光するＬＥＤ光源が好ましい。あるいは、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、白熱電球、キセノンランプ、ハロゲンランプ、カーボンアーク灯、メタルハライドランプ、蛍光灯、タングステンランプ、ガリウムランプ、エキシマレーザー又は太陽光等の紫外線と可視光線を含む光源を使用することができ、バンドパスフィルターを用いて３８０ｎｍより短波長の紫外線を遮断して用いることもできる。 (UV curing type, visible light curing type)
In the production method of the present invention, it is preferable to use an active energy ray containing visible light having a wavelength range of 380 nm to 450 nm, particularly an active energy ray having the largest irradiation amount of visible light having a wavelength range of 380 nm to 450 nm. As the active energy ray according to the present invention, a gallium-encapsulated metal halide lamp and an LED light source that emits light in the wavelength range of 380 to 440 nm are preferable. Or low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, incandescent lamp, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, gallium lamp, excimer laser, or ultraviolet rays such as sunlight A light source including visible light can be used, and ultraviolet light having a wavelength shorter than 380 nm can be blocked using a band pass filter.
　（熱硬化型）
　一方、熱硬化型形成材では、加熱することにより、熱重合開始剤により重合を開始して、硬化物層を形成する。加熱温度は、熱重合開始剤に応じて設定されるが、６０～２００℃程度、好ましくは８０～１５０℃である。 (Thermosetting type)
On the other hand, in the thermosetting type forming material, by heating, polymerization is started by a thermal polymerization initiator to form a cured product layer. The heating temperature is set according to the thermal polymerization initiator, but is about 60 to 200 ° C., preferably 80 to 150 ° C.
　２．粘着剤層付偏光フィルムの製造方法
　本発明の粘着剤層付偏光フィルムの製造方法は、前記製造方法により得られた透明樹脂層付の片保護偏光フィルムの透明樹脂層４上に粘着剤層を形成する工程を含むことを特徴とする。 2. The manufacturing method of the polarizing film with an adhesive layer The manufacturing method of the polarizing film with an adhesive layer of this invention puts an adhesive layer on the transparent resin layer 4 of the piece protection polarizing film with a transparent resin layer obtained by the said manufacturing method. A step of forming.
　（１）粘着剤層
　粘着剤層の形成には、適宜な粘着剤を用いることができ、その種類について特に制限はない。粘着剤としては、ゴム系粘着剤、アクリル系粘着剤、シリコーン系粘着剤、ウレタン系粘着剤、ビニルアルキルエーテル系粘着剤、ポリビニルアルコール系粘着剤、ポリビニルピロリドン系粘着剤、ポリアクリルアミド系粘着剤、セルロース系粘着剤等が挙げられる。 (1) Pressure-sensitive adhesive layer An appropriate pressure-sensitive adhesive can be used for forming the pressure-sensitive adhesive layer, and the type thereof is not particularly limited. Adhesives include rubber adhesives, acrylic adhesives, silicone adhesives, urethane adhesives, vinyl alkyl ether adhesives, polyvinyl alcohol adhesives, polyvinyl pyrrolidone adhesives, polyacrylamide adhesives, Examples thereof include cellulose-based pressure-sensitive adhesives.
　これら粘着剤の中でも、光学的透明性に優れ、適宜な濡れ性と凝集性と接着性の粘着特性を示して、耐候性や耐熱性等に優れるものが好ましく使用される。このような特徴を示すものとしてアクリル系粘着剤が好ましく使用される。 Of these pressure-sensitive adhesives, those having excellent optical transparency, suitable wettability, cohesiveness, and adhesive pressure characteristics, and excellent weather resistance, heat resistance and the like are preferably used. An acrylic pressure-sensitive adhesive is preferably used as one exhibiting such characteristics.
　粘着剤層を形成する方法としては、例えば、前記粘着剤を剥離処理したセパレータ等に塗布し、重合溶剤等を乾燥除去して粘着剤層を形成した後に、透明樹脂層４上に転写する方法又は透明樹脂層４に前記粘着剤を塗布し、重合溶剤等を乾燥除去して粘着剤層を透明樹脂層４上に形成する方法等により作製される。なお、粘着剤の塗布にあたっては、適宜に、重合溶剤以外の一種以上の溶剤を新たに加えてもよい。 As a method for forming the pressure-sensitive adhesive layer, for example, a method of applying the pressure-sensitive adhesive to a separator or the like that has been subjected to a release treatment, drying and removing the polymerization solvent or the like to form a pressure-sensitive adhesive layer, and then transferring it onto the transparent resin layer 4 Alternatively, the pressure-sensitive adhesive is prepared by a method of applying the pressure-sensitive adhesive to the transparent resin layer 4 and drying and removing the polymerization solvent to form the pressure-sensitive adhesive layer on the transparent resin layer 4. In applying the pressure-sensitive adhesive, one or more solvents other than the polymerization solvent may be added as appropriate.
　剥離処理したセパレータとしては、シリコーン剥離ライナーが好ましく用いられる。このようなライナー上に粘着剤を塗布、乾燥させて粘着剤層を形成する工程において、粘着剤を乾燥させる方法としては、目的に応じて、適宜、適切な方法が採用され得る。好ましくは、上記塗布膜を加熱乾燥する方法が用いられる。加熱乾燥温度は、４０℃～２００℃であることが好ましく、５０℃～１８０℃がより好ましく、７０℃～１７０℃がさらに好ましい。加熱温度を上記の範囲とすることによって、優れた粘着特性を有する粘着剤を得ることができる。 A silicone release liner is preferably used as the release-treated separator. In the step of forming a pressure-sensitive adhesive layer by applying and drying a pressure-sensitive adhesive on such a liner, an appropriate method can be appropriately employed as a method for drying the pressure-sensitive adhesive according to the purpose. Preferably, a method of heating and drying the coating film is used. The heating and drying temperature is preferably 40 ° C to 200 ° C, more preferably 50 ° C to 180 ° C, and further preferably 70 ° C to 170 ° C. By setting the heating temperature within the above range, an adhesive having excellent adhesive properties can be obtained.
　乾燥時間は、適宜、適切な時間が採用され得る。上記乾燥時間は、５秒～２０分が好ましく、５秒～１０分がより好ましく、１０秒～５分がさらに好ましい。 Appropriate time can be adopted as the drying time. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and even more preferably 10 seconds to 5 minutes.
　粘着剤層の形成方法としては、各種方法が用いられる。具体的には、例えば、ロールコート、キスロールコート、グラビアコート、リバースコート、ロールブラッシュ、スプレーコート、ディップロールコート、バーコート、ナイフコート、エアーナイフコート、カーテンコート、リップコート、ダイコーター等による押出しコート法等の方法が挙げられる。 Various methods are used as a method for forming the pressure-sensitive adhesive layer. Specifically, for example, by roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples thereof include an extrusion coating method.
　粘着剤層の厚さは、特に制限されず、例えば、１～１００μｍ程度であり、２～５０μｍが好ましく、２～４０μｍがより好ましく、５～３５μｍがさらに好ましい。 The thickness of the pressure-sensitive adhesive layer is not particularly limited, and is, for example, about 1 to 100 μm, preferably 2 to 50 μm, more preferably 2 to 40 μm, and further preferably 5 to 35 μm.
　前記粘着剤層が露出する場合には、実用に供されるまで剥離処理したシート（セパレータ）で粘着剤層を保護してもよい。 When the pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a peeled sheet (separator) until practical use.
　セパレータの構成材料としては、例えば、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリエステルフィルム等のプラスチックフィルム、紙、布、不織布等の多孔質材料、ネット、発泡シート、金属箔、及びこれらのラミネート体等の適宜な薄葉体等を挙げることができるが、表面平滑性に優れる点からプラスチックフィルムが好適に用いられる。 Examples of the constituent material of the separator include, for example, plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof. Although a thin leaf body etc. can be mentioned, a plastic film is used suitably from the point which is excellent in surface smoothness.
　そのプラスチックフィルムとしては、前記粘着剤層を保護し得るフィルムであれば特に限定されず、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフイルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン－酢酸ビニル共重合体フィルム等が挙げられる。 The plastic film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer. For example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, and a vinyl chloride co-polymer are used. Examples thereof include a polymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
　前記セパレータの厚みは、通常５～２００μｍ程度であり、５～１００μｍ程度が好ましい。前記セパレータには、必要に応じて、シリコーン系、フッ素系、長鎖アルキル系もしくは脂肪酸アミド系の離型剤、シリカ粉等による離型及び防汚処理や、塗布型、練り込み型、蒸着型等の帯電防止処理もすることもできる。特に、前記セパレータの表面にシリコーン処理、長鎖アルキル処理、フッ素処理等の剥離処理を適宜おこなうことにより、前記粘着剤層からの剥離性をより高めることができる。 The thickness of the separator is usually about 5 to 200 μm, preferably about 5 to 100 μm. For the separator, silicone type, fluorine type, long chain alkyl type or fatty acid amide type release agent, release by a silica powder and antifouling treatment, coating type, kneading type, vapor deposition type, if necessary It is also possible to perform antistatic treatment such as. In particular, the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, and fluorine treatment on the surface of the separator.
　（２）表面保護フィルム
　本発明の偏光フィルム（片保護偏光フィルム、粘着剤層付偏光フィルムを含む）には、表面保護フィルムを設けることができる。表面保護フィルムは、通常、基材フィルム及び粘着剤層を有し、当該粘着剤層を介して偏光フィルムを保護する。 (2) Surface protective film A surface protective film can be provided in the polarizing film of the present invention (including a piece protective polarizing film and a polarizing film with an adhesive layer). The surface protective film usually has a base film and a pressure-sensitive adhesive layer, and protects the polarizing film via the pressure-sensitive adhesive layer.
　表面保護フィルムの基材フィルムとしては、検査性や管理性等の観点から、等方性を有する又は等方性に近いフィルム材料が選択される。そのフィルム材料としては、例えば、ポリエチレンテレフタレートフィルム等のポリエステル系樹脂、セルロース系樹脂、アセテート系樹脂、ポリエーテルサルホン系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリオレフィン系樹脂、アクリル系樹脂のような透明なポリマーが挙げられる。これらの中でも、ポリエステル系樹脂が好ましい。基材フィルムは、１種又は２種以上のフィルム材料のラミネート体として用いることもでき、また前記フィルムの延伸物を用いることもできる。基材フィルムの厚さは、一般的には、５００μｍ以下、好ましくは１０～２００μｍである。 As the base film of the surface protective film, a film material having isotropic property or close to isotropic property is selected from the viewpoints of inspection property and manageability. Examples of film materials include polyester resins such as polyethylene terephthalate film, cellulose resins, acetate resins, polyether sulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, acrylic resins, and the like. Examples thereof include transparent polymers such as resins. Among these, a polyester resin is preferable. The base film can be used as a laminate of one kind or two or more kinds of film materials, and a stretched product of the film can also be used. The thickness of the base film is generally 500 μm or less, preferably 10 to 200 μm.
　表面保護フィルムの粘着剤層を形成する粘着剤としては、（メタ）アクリル系ポリマー、シリコーン系ポリマー、ポリエステル、ポリウレタン、ポリアミド、ポリエーテル、フッ素系やゴム系等のポリマーをベースポリマーとする粘着剤を適宜に選択して用いることができる。透明性、耐候性、耐熱性等の観点から、アクリル系ポリマーをベースポリマーとするアクリル系粘着剤が好ましい。粘着剤層の厚さ（乾燥膜厚）は、必要とされる粘着力に応じて決定される。通常１～１００μｍ程度、好ましくは５～５０μｍである。 As the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer of the surface protective film, a pressure-sensitive adhesive based on a (meth) acrylic polymer, silicone-based polymer, polyester, polyurethane, polyamide, polyether, fluorine-based or rubber-based polymer, etc. Can be appropriately selected and used. From the viewpoints of transparency, weather resistance, heat resistance and the like, an acrylic pressure-sensitive adhesive having an acrylic polymer as a base polymer is preferable. The thickness (dry film thickness) of the pressure-sensitive adhesive layer is determined according to the required adhesive force. Usually, it is about 1 to 100 μm, preferably 5 to 50 μm.
　なお、表面保護フィルムには、基材フィルムにおける粘着剤層を設けた面の反対面に、シリコーン処理、長鎖アルキル処理、フッ素処理等の低接着性材料により、剥離処理層を設けることができる。 The surface protective film can be provided with a release treatment layer on the surface opposite to the surface on which the pressure-sensitive adhesive layer is provided on the base film, using a low adhesive material such as silicone treatment, long-chain alkyl treatment, or fluorine treatment. .
３．光学積層体の製造方法
　本発明の光学積層体の製造方法は、前記製造方法により得られた粘着剤層付偏光フィルムを巻き取ることなく、前記粘着剤層を介して光学部材に貼り合せる工程を含むことを特徴とする。 3. Method for Producing Optical Laminate The method for producing an optical laminate of the present invention comprises the step of bonding to an optical member via the pressure-sensitive adhesive layer without winding up the polarizing film with the pressure-sensitive adhesive layer obtained by the production method. It is characterized by including.
　本発明の製造方法により得られた透明樹脂層付の片保護偏光フィルムや、当該透明樹脂層付の片保護偏光フィルムを用いた粘着剤層付偏光フィルムは、カールが抑制されているため、当該フィルムをロール等に巻き取ることなく、そのまま次の工程で使用することができるすなわち、粘着剤層を介して光学部材に貼り合せることで、光学積層体を製造することができる。従来の製造方法により（透明樹脂層付の）片保護偏光フィルムを製造すると、フィルムの端部においてカールが発生する場合があり、カールが発生すると、次工程への搬送の際にフィルム端部に折れやシワによるフィルムの破断が発生したりするため、そのまま次工程に使用することが困難であった。 Since the curl is suppressed in the piece protective polarizing film with a transparent resin layer obtained by the production method of the present invention and the piece protective polarizing film with the transparent resin layer, curling is suppressed, The film can be used as it is in the next step without being wound on a roll or the like, that is, an optical laminate can be produced by being bonded to an optical member via an adhesive layer. When a piece-protecting polarizing film (with a transparent resin layer) is manufactured by a conventional manufacturing method, curling may occur at the end of the film. When curling occurs, it may be transferred to the film end during transport to the next process. Since the film breaks due to creases or wrinkles, it is difficult to use it in the next process as it is.
　前記光学部材としては、特に限定されるものではないが、例えば、反射板や半透過板、位相差板（１／２や１／４等の波長板を含む）、視角補償フィルム等の液晶表示装置等の形成に用いられることがあるものを１層又は２層以上用いることができる。光学積層体としては、特に、本発明の製造方法により得られた粘着剤層付偏光フィルムに、さらに、反射板又は半透過反射板が積層されてなる反射型偏光フィルム又は半透過型偏光フィルム、本発明の製造方法により得られた粘着剤層付偏光フィルムに、さらに、位相差板が積層されてなる楕円偏光フィルム又は円偏光フィルム、本発明の製造方法により得られた粘着剤層付偏光フィルムに、さらに、視角補償フィルムが積層されてなる広視野角偏光フィルム、あるいは、本発明の製造方法により得られた粘着剤層付偏光フィルムに、さらに、輝度向上フィルムが積層されてなる偏光フィルムが好ましい。 The optical member is not particularly limited. For example, a liquid crystal display such as a reflection plate, a semi-transmission plate, a retardation plate (including a wavelength plate such as 1/2 or 1/4), a viewing angle compensation film, and the like. One layer or two or more layers that may be used for forming a device or the like can be used. As an optical laminate, in particular, a reflective polarizing film or a transflective polarizing film in which a polarizing plate with a pressure-sensitive adhesive layer obtained by the production method of the present invention is further laminated with a reflective plate or a semi-transmissive reflective plate, The polarizing film with the pressure-sensitive adhesive layer obtained by the production method of the present invention, an elliptically polarizing film or a circularly polarizing film obtained by further laminating a retardation plate, and the polarizing film with a pressure-sensitive adhesive layer obtained by the production method of the present invention Furthermore, a polarizing film in which a viewing angle compensation film is laminated, or a polarizing film in which a brightness enhancement film is further laminated on a polarizing film with an adhesive layer obtained by the production method of the present invention. preferable.
　本発明の粘着剤層付偏光フィルムに上記光学部材を積層した光学積層体は、液晶表示装置等の製造過程で順次別個に積層する方式にても形成することができるが、予め積層して光学積層体としたものは、品質の安定性や組立作業等に優れていて液晶表示装置等の製造工程を向上させ得る利点がある。光学部材を２層以上積層する場合には、粘着剤層等の適宜な接着手段を用いることができる。前記粘着剤層付偏光フィルムの接着に際し、それらの光学軸は目的とする位相差特性等に応じて適宜な配置角度とすることができる。 The optical laminate in which the optical member is laminated on the polarizing film with the pressure-sensitive adhesive layer of the present invention can be formed by a method of sequentially laminating separately in the manufacturing process of a liquid crystal display device or the like. What was made into the laminated body is excellent in the stability of quality, assembly work, etc., and has an advantage which can improve the manufacturing process of a liquid crystal display device etc. When two or more optical members are stacked, an appropriate adhesive means such as a pressure-sensitive adhesive layer can be used. When adhering the polarizing film with the pressure-sensitive adhesive layer, the optical axes thereof can be set at an appropriate arrangement angle in accordance with the target retardation characteristics and the like.
　本発明の製造方法により得られた透明樹脂層付の片保護偏光フィルム、粘着剤層付偏光フィルム、又は光学積層体は、液晶表示装置等の各種装置の形成等に好ましく用いることができる。液晶表示装置の形成は、従来に準じて行いうる。すなわち液晶表示装置は一般に、液晶セルと透明樹脂層付の片保護偏光フィルム又は光学フィルム、及び必要に応じての照明システム等の構成部品を適宜に組立てて駆動回路を組込むこと等により形成されるが、本発明においては、本発明の製造方法により得られた透明樹脂層付の片保護偏光フィルム、粘着剤層付偏光フィルム、又は光学積層体を用いる点を除いては、特に限定はなく、従来に準じうる。液晶セルについても、例えば、ＩＰＳ型、ＶＡ型等の任意なタイプのものを用いうるが、特にＩＰＳ型に好適である。 The piece protective polarizing film with a transparent resin layer, the polarizing film with an adhesive layer, or the optical laminate obtained by the production method of the present invention can be preferably used for forming various devices such as a liquid crystal display device. The liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device is generally formed by assembling components such as a liquid crystal cell, a single protective polarizing film or an optical film with a transparent resin layer, and an illumination system as necessary, and incorporating a drive circuit. However, in the present invention, there is no particular limitation except that a piece protective polarizing film with a transparent resin layer obtained by the production method of the present invention, a polarizing film with an adhesive layer, or an optical laminate is used. It can conform to the conventional method. As the liquid crystal cell, for example, an arbitrary type such as an IPS type or a VA type can be used, but it is particularly suitable for the IPS type.
　液晶セルの片側又は両側に、本発明の製造方法により得られた透明樹脂層付の片保護偏光フィルム、粘着剤層付偏光フィルム、又は光学積層体を配置した液晶表示装置や、照明システムにバックライトあるいは反射板を用いたもの等の適宜な液晶表示装置を形成することができる。その場合、本発明の製造方法により得られた透明樹脂層付の片保護偏光フィルム、粘着剤層付偏光フィルム、又は光学積層体は、液晶セルの片側又は両側に設置することができる。両側に本発明の製造方法により得られた透明樹脂層付の片保護偏光フィルム、粘着剤層付偏光フィルム、又は光学積層体を設ける場合、それらは同じものであってもよいし、異なるものであってもよい。さらに、液晶表示装置の形成に際しては、例えば、拡散板、アンチグレア層、反射防止膜、保護板、プリズムアレイ、レンズアレイシート、光拡散板、バックライト等の適宜な部品を適宜な位置に１層又は２層以上配置することができる。 Backed by a liquid crystal display device or lighting system in which a single protective polarizing film with a transparent resin layer, a polarizing film with a pressure-sensitive adhesive layer, or an optical laminate obtained by the production method of the present invention is disposed on one or both sides of a liquid crystal cell. An appropriate liquid crystal display device such as one using a light or a reflector can be formed. In that case, the piece protective polarizing film with a transparent resin layer, the polarizing film with an adhesive layer, or the optical laminate obtained by the production method of the present invention can be installed on one side or both sides of the liquid crystal cell. In the case where a transparent protective layer-provided piece protective polarizing film, a pressure-sensitive adhesive layer-attached polarizing film, or an optical laminate obtained by the production method of the present invention is provided on both sides, they may be the same or different. There may be. Further, when forming a liquid crystal display device, for example, a single layer of appropriate parts such as a diffusion plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusion plate, and a backlight are provided at appropriate positions. Alternatively, two or more layers can be arranged.
　以下に、本発明を、実施例を挙げて説明するが、本発明は、以下に示した実施例に制限されるものではない。なお、各例中の部及び％はいずれも重量基準である。以下に特に規定のない室温放置条件は全て２３℃、６５％Ｒ．Ｈ．である。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the examples shown below. In addition, all the parts and% in each example are based on weight. The room temperature standing conditions not specifically specified below are all 23 ° C. and 65% R.S. H. It is.
　製造例１（偏光子の作製）
　吸水率０．７５％、ガラス転移温度（Ｔｇ）７５℃の非晶質のイソフタル酸共重合ポリエチレンテレフタレート（ＩＰＡ共重合ＰＥＴ）フィルム（厚み：１００μｍ）基材の片面に、コロナ処理を施し、このコロナ処理面に、ポリビニルアルコール（重合度：４２００、ケン化度：９９．２モル％）及びアセトアセチル変性ＰＶＡ（商品名：ゴーセファイマーＺ２００、重合度：１２００、アセトアセチル変性度：４．６％、ケン化度：９９．０モル％以上、日本合成化学工業（株）製）を９：１の比で含む水溶液を２５℃で塗布及び乾燥して、厚み１１μｍのＰＶＡ系樹脂層を形成し、積層体を作製した。
　得られた積層体を、１２０℃のオーブン内で周速の異なるロール間で縦方向（長手方向）に２．０倍に自由端一軸延伸した（空中補助延伸処理）。
　次いで、積層体を、液温３０℃の不溶化浴（水１００重量部に対して、ホウ酸を４重量部配合して得られたホウ酸水溶液）に３０秒間浸漬させた（不溶化処理）。
　次いで、液温３０℃の染色浴に、偏光板が所定の透過率となるようにヨウ素濃度、浸漬時間を調整しながら浸漬させた。本実施例では、水１００重量部に対して、ヨウ素を０．２重量部配合し、ヨウ化カリウムを１．０重量部配合して得られたヨウ素水溶液に６０秒間浸漬させた（染色処理）。
　次いで、液温３０℃の架橋浴（水１００重量部に対して、ヨウ化カリウムを３重量部配合し、ホウ酸を３重量部配合して得られたホウ酸水溶液）に３０秒間浸漬させた（架橋処理）。
　その後、積層体を、液温７０℃のホウ酸水溶液（水１００重量部に対して、ホウ酸を４重量部配合し、ヨウ化カリウムを５重量部配合して得られた水溶液）に浸漬させながら、周速の異なるロール間で縦方向（長手方向）に総延伸倍率が５．５倍となるように一軸延伸を行った（水中延伸処理）。
　その後、積層体を液温３０℃の洗浄浴（水１００重量部に対して、ヨウ化カリウムを４重量部配合して得られた水溶液）に浸漬させた（洗浄処理）。
　以上により、厚み５μｍの偏光子を含む光学フィルム積層体を得た。 Production Example 1 (Production of Polarizer)
One side of an amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA copolymerized PET) film (thickness: 100 μm) having a water absorption of 0.75% and a glass transition temperature (Tg) of 75 ° C. is subjected to corona treatment. On the corona-treated surface, polyvinyl alcohol (degree of polymerization: 4200, degree of saponification: 99.2 mol%) and acetoacetyl-modified PVA (trade name: Goosefimer Z200, degree of polymerization: 1200, degree of acetoacetyl modification: 4.6) %, Degree of saponification: 99.0 mol% or more, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) is applied and dried at 25 ° C. to form a PVA resin layer having a thickness of 11 μm. Thus, a laminate was produced.
The obtained laminate was uniaxially stretched in the longitudinal direction (longitudinal direction) 2.0 times between rolls having different peripheral speeds in an oven at 120 ° C. (air-assisted stretching process).
Next, the laminate was immersed in an insolubilization bath (a boric acid aqueous solution obtained by blending 4 parts by weight of boric acid with respect to 100 parts by weight of water) for 30 seconds (insolubilization treatment).
Subsequently, it was immersed in a dyeing bath having a liquid temperature of 30 ° C. while adjusting the iodine concentration and the immersion time so that the polarizing plate had a predetermined transmittance. In this example, 0.2 parts by weight of iodine was blended with 100 parts by weight of water, and immersed in an aqueous iodine solution obtained by blending 1.0 part by weight of potassium iodide (dyeing treatment). .
Subsequently, it was immersed for 30 seconds in a crosslinking bath having a liquid temperature of 30 ° C. (a boric acid aqueous solution obtained by blending 3 parts by weight of potassium iodide and 3 parts by weight of boric acid with respect to 100 parts by weight of water). (Crosslinking treatment).
Thereafter, the laminate was immersed in a boric acid aqueous solution (an aqueous solution obtained by blending 4 parts by weight of boric acid and 5 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 70 ° C. However, uniaxial stretching was performed between rolls having different peripheral speeds in the longitudinal direction (longitudinal direction) so that the total stretching ratio was 5.5 times (in-water stretching treatment).
Thereafter, the laminate was immersed in a cleaning bath (an aqueous solution obtained by blending 4 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 30 ° C. (cleaning treatment).
As a result, an optical film laminate including a polarizer having a thickness of 5 μm was obtained.
　製造例２（片保護偏光フィルムの作製）
　厚み４０μｍのラクトン環構造を有する（メタ）アクリル樹脂フィルムの易接着処理面にコロナ処理を施したものと保護フィルムとして用いた。 Production Example 2 (Production of a single protective polarizing film)
A (meth) acrylic resin film having a lactone ring structure having a thickness of 40 μm and subjected to corona treatment on the easily adhesive-treated surface was used as a protective film.
　Ｎ－ヒドロキシエチルアクリルアミド（ＨＥＡＡ）４０重量部とアクリロイルモルホリン（ＡＣＭＯ）６０重量部と光開始剤（商品名：ＩＲＧＡＣＵＲＥ　８１９、ＢＡＳＦ社製）３重量部を混合し、紫外線硬化型接着剤を調製した。これを保護フィルム用接着剤とした。 An ultraviolet curable adhesive was prepared by mixing 40 parts by weight of N-hydroxyethylacrylamide (HEAA), 60 parts by weight of acryloylmorpholine (ACMO) and 3 parts by weight of a photoinitiator (trade name: IRGACURE 819, manufactured by BASF). . This was made into the adhesive for protective films.
　製造例１で得られた光学フィルム積層体の偏光子の表面に、上記紫外線硬化型接着剤を硬化後の接着剤層の厚みが１μｍとなるように塗布しながら、上記保護フィルムを貼合せたのち、活性エネルギー線として、紫外線を照射し、接着剤を硬化させた。紫外線照射は、ガリウム封入メタルハライドランプ（照射装置：Ｆｕｓｉｏｎ　ＵＶ　Ｓｙｓｔｅｍｓ，Ｉｎｃ社製のＬｉｇｈｔ　ＨＡＭＭＥＲ１０、バルブ：Ｖバルブ、ピーク照度：１６００ｍＷ／ｃｍ２、積算照射量：１０００／ｍＪ／ｃｍ２（波長３８０～４４０ｎｍ））を使用し、紫外線の照度は、Ｓｏｌａｔｅｌｌ社製のＳｏｌａ－Ｃｈｅｃｋシステムを使用して測定した。次いで、非晶性ＰＥＴ基材を剥離し、薄型偏光子を用いた片保護偏光フィルム（総厚み４６μｍ）作製した。
　得られた片保護偏光フィルムの光学特性は単体透過率４２．８％、偏光度９９．９９％であった。 The protective film was bonded to the surface of the polarizer of the optical film laminate obtained in Production Example 1 while applying the ultraviolet curable adhesive so that the thickness of the adhesive layer after curing was 1 μm. After that, ultraviolet rays were applied as active energy rays to cure the adhesive. Ultraviolet irradiation is carried out using a gallium-filled metal halide lamp (irradiation device: Fusion UV Systems, Inc., Light HAMMER 10, Inc., bulb: V bulb, peak illuminance: 1600 mW / cm 2 , integrated irradiation amount: 1000 / mJ / cm 2 (wavelength 380˜ 440 nm)), and the illuminance of ultraviolet rays was measured using a Sola-Check system manufactured by Solatell. Subsequently, the amorphous PET base material was peeled off, and a piece protective polarizing film (total thickness 46 μm) using a thin polarizer was produced.
The optical properties of the obtained piece-protecting polarizing film were a single transmittance of 42.8% and a degree of polarization of 99.99%.
　＜単体透過率Ｔ及び偏光度Ｐ＞
　得られた片保護偏光フィルムの単体透過率Ｔ及び偏光度Ｐを、積分球付き分光透過率測定器（（株）村上色彩技術研究所のＤｏｔ－３ｃ）を用いて測定した。
　なお、偏光度Ｐは、２枚の同じ偏光フィルムを両者の透過軸が平行となるように重ね合わせた場合の透過率（平行透過率：Ｔｐ）及び、両者の透過軸が直交するように重ね合わせた場合の透過率（直交透過率：Ｔｃ）を以下の式に適用することにより求められるものである。
　　　偏光度Ｐ（％）＝｛（Ｔｐ－Ｔｃ）／（Ｔｐ＋Ｔｃ）｝１／２×１００
　各透過率は、グランテラープリズム偏光子を通して得られた完全偏光を１００％として、ＪＩＳ　Ｚ８７０１の２度視野（Ｃ光源）により視感度補整したＹ値で示したものである。 <Single transmittance T and degree of polarization P>
The single transmittance T and polarization degree P of the obtained piece-protecting polarizing film were measured using a spectral transmittance measuring device with an integrating sphere (Dot-3c, Murakami Color Research Laboratory Co., Ltd.).
The degree of polarization P is the transmittance when two identical polarizing films are overlapped so that their transmission axes are parallel (parallel transmittance: Tp), and they are overlapped so that their transmission axes are orthogonal to each other. It is calculated | required by applying the transmittance | permeability (orthogonal transmittance | permeability: Tc) at the time of combining to the following formula | equation.
Polarization degree P (%) = {(Tp−Tc) / (Tp + Tc)} 1/2 × 100
Each transmittance is represented by a Y value obtained by correcting visibility with a two-degree field of view (C light source) of JIS Z8701, with 100% of the completely polarized light obtained through the Granteller prism polarizer.
　製造例３（透明樹脂層を形成する塗工液の製造）
　重合度２５００、ケン化度９９．７モル％のポリビニルアルコール樹脂を純水に溶解し、固形分濃度４重量％、粘度６０ｍＰａ・ｓ（２５℃）の水溶液（塗工液）を調製した。 Production Example 3 (Manufacture of a coating solution for forming a transparent resin layer)
A polyvinyl alcohol resin having a polymerization degree of 2500 and a saponification degree of 99.7 mol% was dissolved in pure water to prepare an aqueous solution (coating liquid) having a solid content concentration of 4% by weight and a viscosity of 60 mPa · s (25 ° C.).
　＜粘度測定＞
　塗工液の粘度は、ＶＩＳＣＯＭＥＴＥＲ　Ｒ８５型粘度計　ＲＥ８５Ｌ（東機産業（株）製）を用いて下記の条件で測定した。
　測定温度：２５℃
　回転数：０．５～１００ｒｐｍ
　コーンローター：１°３４’×Ｒ２４ <Viscosity measurement>
The viscosity of the coating solution was measured under the following conditions using a VISCOMETER R85 viscometer RE85L (manufactured by Toki Sangyo Co., Ltd.).
Measurement temperature: 25 ° C
Rotation speed: 0.5-100rpm
Cone rotor: 1 ° 34 '× R24
　実施例１（透明樹脂層付の片保護偏光フィルムの作製）
　製造例２で得られた片保護偏光フィルムの偏光子の面（保護フィルムが設けられていない偏光子面）に、製造例３で得られた塗工液（透明樹脂層の形成材）を、グラビアロールを用いて厚みが２５μｍになるように塗布した。塗布は、片保護偏光フィルムの幅方向において全面に行った。塗布後、フローティング方式オーブンを用いて、９５℃で３０秒間熱風乾燥して、厚さ１μｍの透明樹脂層を形成し、透明樹脂層付の片保護偏光フィルムを作製した。 Example 1 (Production of a piece protective polarizing film with a transparent resin layer)
On the surface of the polarizer of the piece protective polarizing film obtained in Production Example 2 (polarizer surface on which no protective film is provided), the coating liquid obtained in Production Example 3 (the material for forming the transparent resin layer) It applied so that thickness might be set to 25 micrometers using a gravure roll. The coating was performed on the entire surface in the width direction of the single protective polarizing film. After the application, it was dried with hot air at 95 ° C. for 30 seconds using a floating oven to form a transparent resin layer having a thickness of 1 μm, and a piece protective polarizing film with a transparent resin layer was produced.
　実施例２、比較例１
　実施例１において、片保護偏光フィルムの幅方向の両端から内側に向かって、表１に記載の未塗布部分を設けたこと以外は、実施例１と同様にして、透明樹脂層付の片保護偏光フィルムを作製した。 Example 2 and Comparative Example 1
In Example 1, the piece protection with a transparent resin layer was carried out in the same manner as in Example 1 except that the uncoated portions listed in Table 1 were provided from both ends in the width direction of the piece protective polarizing film to the inside. A polarizing film was produced.
　実施例、比較例で得られた透明樹脂層付の片保護偏光フィルムを用いて、以下の評価を行った。評価結果は表１に示す。 The following evaluation was performed using the piece protective polarizing film with a transparent resin layer obtained in Examples and Comparative Examples. The evaluation results are shown in Table 1.
　＜カールの発生＞
　得られた透明樹脂層付の片保護偏光フィルムを、透明樹脂層を上に向けた状態で２３℃、５５％Ｒ．Ｈ．の条件下で巻取り直後の偏光板フィルムのカール量を評価した。カール測定は、塗工端部箇所が含まれるように、吸収軸に対して４５度、一片を１５０ｍｍのひし形にサンプルカットしたのち、水平卓上に透明樹脂層側が上になるようにサンプルをセットした。セットしたサンプルの塗工端部箇所のカールをものさしにて測定し、以下の評価基準により評価した。
　Ａ：１０ｍｍ以下
　Ｂ：１０ｍｍを超え３０ｍｍ以下
　Ｃ：３０ｍｍを超える <Occurrence of curls>
The obtained piece-protecting polarizing film with a transparent resin layer was placed at 23 ° C. and 55% R.D. with the transparent resin layer facing upward. H. The curl amount of the polarizing film immediately after winding was evaluated under the above conditions. For curl measurement, after cutting the sample into a diamond of 45 mm and a piece of 45 mm with respect to the absorption axis so that the coating end portion is included, the sample was set so that the transparent resin layer side was on the horizontal tabletop . The curl at the coating end portion of the set sample was measured with a ruler and evaluated according to the following evaluation criteria.
A: 10 mm or less B: Over 10 mm and 30 mm or less C: Over 30 mm
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　実施例の透明樹脂層付の片保護偏光フィルムは、いずれもカール発生が抑制されていた。一方、比較例１の透明樹脂層付の片保護偏光フィルムでは、保護フィルム側が凸状、透明樹脂層側が凹状になるように、カールが発生した。 In all of the piece protective polarizing films with a transparent resin layer in Examples, curling was suppressed. On the other hand, in the single protective polarizing film with a transparent resin layer of Comparative Example 1, curling occurred so that the protective film side was convex and the transparent resin layer side was concave.
　　１　　　偏光子
　　２　　　保護フィルム
　　３　　　片保護偏光フィルム
　　４　　　透明樹脂層
　　５　　　未塗布部分
　１０　　　透明樹脂層付の片保護偏光フィルム
　　Ａ　　　偏光フィルムの幅方向
  DESCRIPTION OF SYMBOLS 1 Polarizer 2 Protective film 3 Single piece protective polarizing film 4 Transparent resin layer 5 Uncoated part 10 Single piece protective polarizing film with a transparent resin layer A Width direction of a polarizing film

Claims (9)

  1. 　偏光子の片面にのみ保護フィルムを有する片保護偏光フィルム、及び、前記片保護偏光フィルムの偏光子の他の面に設けられた透明樹脂層を有する透明樹脂層付の片保護偏光フィルムの製造方法であって、
    　前記偏光子は、ポリビニルアルコール系樹脂を含み、厚みが１０μｍ以下であり、
    　前記透明樹脂層は、前記偏光子に、樹脂成分又は透明樹脂層を構成することができる硬化性成分を含む塗工液を塗布する工程、及び、得られた塗布膜を固化又は硬化する工程により形成され、
    　前記塗工液の塗布工程において、前記偏光子の幅方向の両端から内側にそれぞれ２０ｍｍ未満の領域において前記塗工液を塗布しない未塗布部分を有するか、又は、前記偏光子の幅方向全体にわたって塗工液を塗布することを特徴とする透明樹脂層付の片保護偏光フィルムの製造方法。     Method for producing a piece protective polarizing film with a transparent resin layer having a piece of protective protective film having a protective film only on one side of the polarizer and a transparent resin layer provided on the other side of the polarizer of the piece protective polarizing film Because
    The polarizer includes a polyvinyl alcohol resin and has a thickness of 10 μm or less,
    The transparent resin layer is formed by applying a coating liquid containing a curable component capable of constituting a resin component or a transparent resin layer to the polarizer, and a step of solidifying or curing the obtained coating film. Formed,
    In the application step of the coating liquid, it has an uncoated part where the coating liquid is not applied in a region less than 20 mm inward from both ends in the width direction of the polarizer, or over the entire width direction of the polarizer. The manufacturing method of the piece protection polarizing film with a transparent resin layer characterized by apply | coating a coating liquid.
  2. 　前記塗工液の塗布が、前記偏光子の幅方向全体にわたって塗工液を塗布することにより行われることを特徴とする請求項１に記載の透明樹脂層付の片保護偏光フィルムの製造方法。 The method for producing a piece protective polarizing film with a transparent resin layer according to claim 1, wherein the coating liquid is applied by coating the coating liquid over the entire width direction of the polarizer.
  3. 　前記偏光子の幅が、１１００～２０００ｍｍであることを特徴とする請求項１又は２に記載の透明樹脂層付の片保護偏光フィルムの製造方法。 The method for producing a piece protective polarizing film with a transparent resin layer according to claim 1 or 2, wherein the polarizer has a width of 1100 to 2000 mm.
  4. 　前記透明樹脂層が、前記塗布膜を固化することにより形成されるものであって、当該固化が乾燥により行われることを特徴とする請求項１～３のいずれかに記載の透明樹脂層付の片保護偏光フィルムの製造方法。 The transparent resin layer with a transparent resin layer according to claim 1, wherein the transparent resin layer is formed by solidifying the coating film, and the solidification is performed by drying. A method for producing a single protective polarizing film.
  5. 　前記乾燥温度が、１２０℃以下であることを特徴とする請求項４に記載の透明樹脂層付の片保護偏光フィルムの製造方法。 The method for producing a piece protective polarizing film with a transparent resin layer according to claim 4, wherein the drying temperature is 120 ° C. or lower.
  6. 　前記乾燥時間が、１８０秒以内であることを特徴とする請求項４又は５に記載の透明樹脂層付の片保護偏光フィルムの製造方法。 The method for producing a piece protective polarizing film with a transparent resin layer according to claim 4 or 5, wherein the drying time is within 180 seconds.
  7. 　前記塗工液が、樹脂成分を含む塗工液であって、前記樹脂成分が、ポリビニルアルコール系樹脂であることを特徴とする請求項１～６のいずれかに記載の透明樹脂層付の片保護偏光フィルムの製造方法。 The strip with a transparent resin layer according to any one of claims 1 to 6, wherein the coating liquid is a coating liquid containing a resin component, and the resin component is a polyvinyl alcohol resin. A method for producing a protective polarizing film.
  8. 　請求項１～７のいずれかに記載の製造方法により得られた透明樹脂層付の片保護偏光フィルムの透明樹脂層上に粘着剤層を形成する工程を含むことを特徴とする粘着剤層付偏光フィルムの製造方法。 A process for forming a pressure-sensitive adhesive layer on a transparent resin layer of a piece-protecting polarizing film with a transparent resin layer obtained by the production method according to any one of claims 1 to 7, comprising a pressure-sensitive adhesive layer A method for producing a polarizing film.
  9. 　請求項８の製造方法により得られた粘着剤層付偏光フィルムを巻き取ることなく、前記粘着剤層を介して光学部材に貼り合せる工程を含むことを特徴とする光学積層体の製造方法。 A method for producing an optical laminate, comprising the step of bonding the optical film with the adhesive layer through the pressure-sensitive adhesive layer without winding up the polarizing film with the pressure-sensitive adhesive layer obtained by the production method according to claim 8.
PCT/JP2017/008984 2016-03-17 2017-03-07 Method for producing one-side-protected polarizing film having transparent resin layer, method for producing polarizing film having adhesive layer, and method for producing optical laminate WO2017159454A1 (en)

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