WO2017159454A1 - Procédé de production de film polarisant protégé sur un côté ayant une couche de résine transparente, procédé de production de film polarisant ayant une couche adhésive, et procédé de production de stratifié optique - Google Patents

Procédé de production de film polarisant protégé sur un côté ayant une couche de résine transparente, procédé de production de film polarisant ayant une couche adhésive, et procédé de production de stratifié optique 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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English (en)
Japanese (ja)
Inventor
友徳 上野
聡司 三田
健太郎 池嶋
岸　敦史
佑輔 茂手木
Original Assignee
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/zh
Priority to KR1020187024097A priority patent/KR102166983B1/ko
Publication of WO2017159454A1 publication Critical patent/WO2017159454A1/fr

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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.

Abstract

La présente invention propose un procédé pour produire un film polarisant protégé sur un côté ayant une couche de résine transparente, le film polarisant protégé sur un côté ayant un film polarisant protégé sur un côté qui comprend un film protecteur sur une seule surface d'un polariseur et une couche de résine transparente disposée sur l'autre surface du polariseur du film polarisant protégé sur un côté, le procédé étant caractérisé en ce que: le polariseur comprend une résine d'alcool polyvinylique, et a une épaisseur de 10 μm ou moins ; la couche de résine transparente est formée par une étape consistant à appliquer, sur le polariseur, un liquide de revêtement qui comprend un composé de résine ou un composé durcissable qui est apte à constituer une couche de résine transparente, et une étape consistant à solidifier ou durcir le film de revêtement résultant ; et dans l'étape d'application du liquide de revêtement, il y a une partie non appliquée dans laquelle le liquide de revêtement n'est pas appliqué dans une région inférieure à 20 mm vers l'intérieur à partir de chacune des deux extrémités dans le sens de la largeur du polariseur, ou le liquide de revêtement est appliqué sur l'ensemble du polariseur le long du sens de la largeur. Le procédé de production permet de supprimer l'enroulement du film polarisant protégé sur un côté ayant une couche de résine transparente.
PCT/JP2017/008984 2016-03-17 2017-03-07 Procédé de production de film polarisant protégé sur un côté ayant une couche de résine transparente, procédé de production de film polarisant ayant une couche adhésive, et procédé de production de stratifié optique WO2017159454A1 (fr)

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CN201780016889.4A CN108780179B (zh) 2016-03-17 2017-03-07 带透明树脂层的单侧保护偏振膜的制造方法、带粘合剂层的偏振膜的制造方法、光学层叠体的制造方法
KR1020187024097A KR102166983B1 (ko) 2016-03-17 2017-03-07 투명 수지층 부착 편보호 편광 필름의 제조 방법, 점착제층 부착 편광 필름의 제조 방법, 광학 적층체의 제조 방법

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JP2016-054127 2016-03-17

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KR20210075166A (ko) * 2018-11-28 2021-06-22 후지필름 가부시키가이샤 광학 적층 필름롤의 제조 방법, 및 광학 적층 필름롤
JPWO2020138329A1 (ja) * 2018-12-27 2021-10-14 日東電工株式会社 偏光板および偏光板ロール
JPWO2020209224A1 (ja) * 2019-04-09 2021-11-18 日東電工株式会社 偏光板
JP2021076806A (ja) * 2019-11-13 2021-05-20 日東電工株式会社 積層偏光フィルムの製造方法
CN117042961A (zh) * 2021-04-30 2023-11-10 日东电工株式会社 层叠光学膜

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