WO2017164066A1 - 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、及び画像表示装置の製造方法 - Google Patents
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、及び画像表示装置の製造方法 Download PDFInfo
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- WO2017164066A1 WO2017164066A1 PCT/JP2017/010681 JP2017010681W WO2017164066A1 WO 2017164066 A1 WO2017164066 A1 WO 2017164066A1 JP 2017010681 W JP2017010681 W JP 2017010681W WO 2017164066 A1 WO2017164066 A1 WO 2017164066A1
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- WIPO (PCT)
- Prior art keywords
- polarizing film
- film
- polarizer
- resin layer
- transparent resin
- Prior art date
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/14—Corona, ionisation, electrical discharge, plasma treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
Definitions
- This invention relates to the manufacturing method of the piece protection polarizing film with a transparent resin layer. Moreover, this invention relates to the manufacturing method of the polarizing film with an adhesive layer containing the piece protection polarizing film with the said transparent resin layer, and an adhesive layer. In addition, the present invention relates to an image display device such as a liquid crystal display device (LCD) or an organic EL display device using the transparent protective layer-attached piece protective polarizing film or the pressure-sensitive adhesive layer-containing polarizing film obtained by the manufacturing method. It relates to a manufacturing method.
- LCD liquid crystal display device
- organic EL display device using the transparent protective layer-attached piece protective polarizing film or the pressure-sensitive adhesive layer-containing polarizing film obtained by the manufacturing method. It relates to a manufacturing method.
- 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.
- the durability of the piece protective polarizing film can be improved by forming a transparent resin layer on the polarizer.
- a transparent resin layer is formed on a polarizer of a piece protective polarizing film using a thin polarizer having a thickness of 10 ⁇ m or less
- a transparent resin layer is formed on a polarizer of a piece protective polarizing film using a thin polarizer having a thickness of 10 ⁇ m or less
- a transparent resin layer is formed on a polarizer of a piece protective polarizing film using a thin polarizer having a thickness of 10 ⁇ m or less
- uneven appearance is easily visible when a single protective polarizing film with a transparent resin layer after a humidification test is attached to both sides of an image display panel or the like so that the absorption axes are orthogonal.
- the present invention provides a strip with a transparent resin layer that can suppress the occurrence of uneven appearance even when the strip protective polarizing film with a transparent resin layer using a thin polarizer is exposed to a humidified environment. It aims at providing the manufacturing method of a protective polarizing film.
- the present invention provides a method for producing a polarizing film with a pressure-sensitive adhesive layer using the piece-protecting polarizing film with a transparent resin layer, an image using the piece-protecting polarizing film with a transparent resin layer and a polarizing film with a pressure-sensitive adhesive layer. It is another object of the present invention to provide a method for manufacturing a display device.
- 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 relates to 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 polarizer side of the piece protective polarizing film.
- a manufacturing method of A step (1) of preparing a single protective polarizing film having a protective film only on one side of the polarizer; A step (2) of applying an aqueous coating solution containing a resin component to the polarizer surface of the piece protective polarizing film, and a step (3) of drying the obtained coating film to form a transparent resin layer.
- the polarizer includes a polyvinyl alcohol resin and has a thickness of 10 ⁇ m or less
- the present invention relates to a method for producing a piece-protecting polarizing film with a transparent resin layer, wherein the variation of the water contact angle of the surface forming the transparent resin layer of the polarizer is in the range of an average water contact angle of ⁇ 20 °.
- step (2) of applying the aqueous coating solution Bonding a surface protective film to the polarizer surface of the piece protective polarizing film, and then peeling the surface protective film from the piece protective polarizing film; and A step of performing activation treatment on the surface protective film peeling surface of the piece protective polarizing film can be included in this order.
- a step of applying an activation treatment to the polarizer surface of the piece protective polarizing film; and A step of attaching a surface protective film to the activated surface of the piece protective polarizing film and then peeling the surface protective film from the piece protective polarizing film can be included in this order.
- the activation treatment is a corona treatment and / or a plasma treatment.
- the variation in the water contact angle is within a range of an average water contact angle of ⁇ 15 °.
- the average water contact angle is preferably 90 ° or less.
- this invention has 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 polarizing film with an adhesive layer characterized by the above-mentioned It relates to a manufacturing method.
- the present invention is an image display device formed by using a piece-protective polarizing film with a transparent resin layer obtained by the production method or a polarizing film with an adhesive layer obtained by the production method. It relates to the manufacturing method.
- the method for producing a single-protective polarizing film with a transparent resin layer of the present invention is capable of suppressing the occurrence of uneven appearance even when exposed to a humidified environment, despite the use of a thin polarizer.
- a piece protective polarizing film with a resin layer can be provided.
- the ratio of the component that exudes into the transparent resin layer is large with respect to the total amount of the polarizer, and the thickness of the transparent resin layer varies, the transparent resin layer from the polarizer is caused thereby. Since the amount of the component that oozes out varies, it is considered that it is easily visible as uneven appearance.
- the image display device of the present invention since the single protective polarizing film with a transparent resin layer and the polarizing film with an adhesive layer obtained by the manufacturing method of the present invention are used, the image display device with high reliability is used. Can be provided.
- the method for producing a piece protective polarizing film with a transparent resin layer of the present invention comprises a piece protective polarizing film having a protective film only on one side of a polarizer, and the piece protective polarizing film.
- a method for producing a piece protective polarizing film with a transparent resin layer having a transparent resin layer provided on a polarizer surface of the film A step (1) of preparing a single protective polarizing film having a protective film only on one side of the polarizer; A step (2) of applying an aqueous coating solution containing a resin component to the polarizer surface of the piece protective polarizing film, and a step (3) of drying the obtained coating film to form a transparent resin layer.
- the polarizer includes a polyvinyl alcohol resin and has a thickness of 10 ⁇ m or less, The variation in the water contact angle of the surface on which the transparent resin layer of the polarizer is formed is within an average water contact angle of ⁇ 20 °.
- 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).
- the piece protective polarizing film 10 with a transparent resin layer obtained by the production method of the present invention has a transparent resin layer 4 on the polarizer surface of the piece protective polarizing film 3 (the surface not having the protective film 2 of the polarizer 1). It is what has.
- Step of preparing a piece protective polarizing film (1) a piece protective polarizing film 3 having a protective film 2 only on one side of the polarizer 1 is prepared.
- a polarizer 1 having a thickness of 10 ⁇ m or less is used as the polarizer 1.
- the thickness of the polarizer 1 is preferably 8 ⁇ m or less, more preferably 7 ⁇ m or less, and further 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 1 has little thickness unevenness, excellent visibility, and little 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 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.
- 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 the protective film 2 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, and 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.
- the piece protection polarizing film 3 used by this invention can be prepared with the manufacturing method which laminates
- the laminate (protective film 2 / polarizer 1 / transport film) obtained in the step (1-2) may be formed by a production method including the step (1-3) of peeling the transport film. preferable.
- each process of the said preferable manufacturing method is demonstrated.
- the laminate (a) includes, for example, at least a laminate (a ′) having a transport film and a polyvinyl alcohol resin (hereinafter also referred to as PVA resin) layer formed on one surface of the transport film. It is obtained by performing a stretching process and a dyeing process.
- the transport film can form a long PVA resin layer by using a long material, which is advantageous for continuous production.
- thermoplastic resin films can be used as the transport film.
- the material for forming the thermoplastic resin film include ester resins such as polyethylene terephthalate resins, cycloolefin resins such as norbornene resins, olefin resins such as polyethylene and polypropylene, polyamide rheo resins, polycarbonate resins, and the like. And a copolymer resin.
- ester resins are preferable from the viewpoint of ease of production and cost reduction.
- an amorphous ester-based thermoplastic resin film or a crystalline ester-based thermoplastic resin film can be used as the ester-based thermoplastic resin film.
- the thickness of the thermoplastic resin film is preferably thicker from the viewpoint of avoiding breakage in the stretching step and easy transport of the laminate (a). Usually, the thickness before the stretching step is 20 to 200 ⁇ m. The thickness is preferably 30 to 150 ⁇ m.
- thermoplastic resin film a film provided with a peelable adhesive layer on the thermoplastic resin film can be used.
- adhesive layer the thing similar to what is used for the surface protection film etc. which are mentioned later can be used.
- the polarizer in the laminate (a) contains a polyvinyl alcohol resin and has a thickness of 10 ⁇ m or less.
- the preferable range of the thickness of the polarizer and the polyvinyl alcohol-based resin are as described above.
- Such a thin polarizer 1 is prone to defects on the surface of the thin polarizer 1 when the transport film is peeled from the laminate (a) in the step (1-3). 1 may cause unevenness in the surface state of the surface on which the transparent resin layer 4 is formed.
- the thin polarizer described in the publication 2014/077636 pamphlet etc., or the thin polarizer obtained from the manufacturing method described in these can be mentioned.
- the thin-type polarizer among the production methods including a stretching step and a dyeing step in the state of the laminate (a ′), it can be stretched at a high magnification and can improve polarization performance.
- Patent Nos. 4,751,481 and 4,815,544, and those obtained by a production method including a step of stretching in an aqueous boric acid solution are preferable, and particularly, patents 4,751,481, and 4,815,544. What is obtained by the manufacturing method including the process of extending
- These thin polarizers can be obtained by a production method including a step of stretching and dyeing a polyvinyl alcohol-based resin layer and a film for stretching in the state of a laminate. If it is this manufacturing method, even if a PVA-type resin layer is thin, it will become possible to extend
- the laminate (a ′) can be formed, for example, by applying an aqueous solution of PVA-based resin to a transport film and then drying.
- the PVA-type resin layer in the said laminated body (a ') can be formed on a film for conveyance by extrusion molding.
- the PVA-based resin layer can be formed by laminating a PVA-based resin film prepared in advance on a transport film. The thickness of the PVA-based resin layer is appropriately determined in consideration of the draw ratio and the like so that the thickness of the polarizer obtained after stretching is 10 ⁇ m or less.
- the PVA-type resin film is dyed, the dyeing process performed to a laminated body (a ') can be skipped.
- the stretching step applied to the laminate (a ′) is preferably performed, for example, so that the total stretching ratio of the PVA-based resin layer is in the range of 3 to 10 times in terms of the total stretching ratio.
- the total draw ratio is preferably 4 to 8 times, more preferably 5 to 7 times.
- the total draw ratio is desirably 5 times or more.
- the stretching process can also be performed in the dyeing process and other processes.
- the total stretching ratio refers to a cumulative stretching ratio including stretching in those processes when stretching is performed in a process other than the stretching process.
- the dyeing step applied to the laminate (a ′) is performed by adsorbing and orienting a dichroic dye or iodine on the PVA resin layer.
- the dyeing process can be performed together with the stretching process.
- a dyeing process is generally performed by, for example, immersing the laminate (a ′) in an iodine solution for an arbitrary time.
- an iodine aqueous solution used as the iodine solution an aqueous solution containing iodine ions with iodine and an iodide compound which is a dissolution aid is used.
- Examples of the iodide compound include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and iodide. Titanium or the like is used.
- potassium iodide is preferred.
- the iodide compound used in the present invention is the same as described above when used in other steps.
- the iodine concentration in the iodine solution is about 0.01 to 10% by weight, preferably 0.02 to 5% by weight, and more preferably 0.02 to 0.5% by weight.
- the concentration of the iodide compound is about 0.1 to 10% by weight, preferably 0.2 to 8% by weight.
- the temperature of the iodine solution is usually about 20 to 50 ° C. and preferably 25 to 40 ° C.
- the immersion time is usually about 10 to 300 seconds, and preferably in the range of 20 to 240 seconds.
- the laminate (a ′) can be subjected to, for example, an insolubilization step, a crosslinking step, a drying (adjustment of moisture content) step, and the like in addition to the above steps.
- a boron compound is used as a crosslinking agent.
- the order of these steps is not particularly limited.
- the crosslinking step can be performed together with the dyeing step and the stretching step.
- the insolubilization step and the crosslinking step can be performed a plurality of times.
- the boron compound include boric acid and borax.
- the boron compound is generally used in the form of an aqueous solution or a water-organic solvent mixed solution. Usually, an aqueous boric acid solution is used.
- the boric acid concentration in the boric acid aqueous solution is about 1 to 10% by weight, preferably 2 to 7% by weight.
- the boric acid concentration is preferably used.
- the boric acid aqueous solution or the like can contain an iodide compound such as potassium iodide.
- the iodide compound concentration is about 0.1 to 10% by weight, preferably 0.5 to 8% by weight.
- Step of forming protective film (1-2) In the step (1-2), a protective film 2 is formed on the polarizer 1 side of the obtained laminate (a). By the step (1-2), a piece protective polarizing film A ′ with a transport film having the protective film 2 only on one side of the polarizer 1 is obtained. About the intervening layer used when laminating
- Step (1-3) Step of peeling the transport film (1-3)
- the transport film is peeled from the piece protective polarizing film A ′ with the transport film.
- the method for peeling the transport film There is no particular limitation on the method for peeling the transport film.
- an angle may be given to the polarizer 1 (or the piece-protecting polarizing film) side, or an angle may be given to the film side for conveyance. Moreover, you may peel at an angle on both sides. In any case, the thin polarizer 1 is likely to be damaged by peeling of the transport film.
- the angle at the time of peeling the film for conveyance is arbitrarily set. When peeling the film for conveyance, there exists an angle at which the peeling force becomes weakest. The angle at which the peeling force becomes weak depends on the configuration, the peeling speed, the humidity at the time of peeling, and the rigidity of the film to be peeled, and can be determined as appropriate.
- Step (2) Step of applying an aqueous coating solution containing a resin component (2)
- an aqueous coating solution containing a resin component is applied to the surface of the polarizer 1 of the piece protective polarizing film 3 having the protective film 2 only on one side of the polarizer 1 prepared in the step (1).
- the surface of the polarizer 1 forming the transparent resin layer 4 is the surface from which the transport film of the piece protective polarizing film 3 obtained in the step (1) is peeled off.
- the variation of the water contact angle of the surface of the polarizer 1 on which the transparent resin layer 4 is formed is in the range of an average water contact angle of ⁇ 20 °.
- the variation in the water contact angle means a deflection width with respect to the average water contact angle of each water contact angle measured at a plurality of locations in an arbitrary location of the polarizer 1.
- water contact angles at 25 points in the width direction of the polarizer 1 and 5 points in the stretching direction (conveying direction) of the polarizer 1 are measured at an arbitrary location of the polarizer 1, and an average value thereof ( (Mean water contact angle) is calculated and means that each measured water contact angle is within ⁇ 20 ° of the average water contact angle. Therefore, for example, when the average value of the water contact angle measured in the width direction is 90 ° at an arbitrary position of the polarizer 1, each water contact angle measured in the width direction is 90 ° ⁇ 20 ° (70 to 110). °) within the range.
- This operation is performed at a plurality of arbitrary locations on the polarizer 1.
- the width direction of the polarizer 1 means a direction orthogonal to the extending direction (conveying direction) of the polarizer 1.
- the variation in the water contact angle is within the range of the average water contact angle ⁇ 20 °, preferably within the range of the average water contact angle ⁇ 15 °, and within the range of the average water contact angle ⁇ 10 °. Is more preferable.
- the variation in the water contact angle of the surface of the polarizer 1 on which the transparent resin layer 4 is formed is within the above range, whereby the polarizer 1 Since the occurrence of unevenness in the thickness of the transparent resin layer 4 formed thereon is suppressed, it is possible to suppress the appearance unevenness from being visually recognized even when exposed to a humidified environment.
- the average water contact angle of the surface of the polarizer 1 on which the transparent resin layer 4 is formed is not particularly limited, but is preferably 90 ° or less from the viewpoint of affinity with the aqueous coating solution, More preferably, it is 60 ° or less, and further preferably 60 ° or less.
- Control of the water contact angle of the surface of the polarizer 1 on which the transparent resin layer 4 is formed can be appropriately performed by the material of the polarizer 1, various treatments, and the like. Various processes will be described later.
- the aqueous coating solution used in the present invention contains a resin component, and the transparent resin layer 4 is formed from the aqueous coating solution.
- aqueous coating liquid examples include 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.
- an aqueous coating solution aqueous or aqueous dispersion
- the affinity with the surface of the polarizer 1 in which the variation in the water contact angle is controlled is excellent.
- the surface of the polarizer 1 swells to the damaged portion.
- the water-based coating solution is compatible. That is, by using the aqueous coating liquid, the orientation of the polyvinyl alcohol molecules around the damaged part constituting the polarizer 1 can be partially relaxed, and the boric acid content around the damaged part can be 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 include, for example, polyvinyl alcohol (PVA) resin, poly (meth) acrylic acid, polyacrylamide, methylol melamine resin, methylol urea resin, resol type phenol resin, polyethylene oxide, carboxymethyl cellulose, and the like. Is mentioned. These may be used alone or in combination.
- PVA polyvinyl alcohol
- 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 proportion of the polyvinyl alcohol resin in the transparent resin layer 4 or the aqueous 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 water coating solution is prepared as a solution obtained by dissolving the polyvinyl alcohol resin in an aqueous solvent.
- the aqueous solvent examples include water or a mixed solvent composed of water and a water-soluble organic solvent. Among these, an aqueous solvent composed only of water is preferable. Examples of water include distilled water, ion exchange water, and ultrapure water. Examples of the water-soluble organic solvent include methanol, ethanol, acetone, 1-propanol, 2-propanol and the like. When the aqueous solvent contains a water-soluble organic solvent, the content of the water-soluble organic solvent in the aqueous solvent is preferably 40% by weight or less, more preferably 20% by weight or less, and more preferably 10% by weight or less. More preferably.
- 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 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 aqueous coating liquid is applied to the surface of the polarizer 1 of the piece protective polarizing film 3 so that the thickness of the dried coating film (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.
- Step (3) Step of forming a transparent resin layer (3)
- the coating film obtained in the step (2) is dried to form the transparent resin layer 4.
- the drying temperature is not particularly limited, and is usually about 60 to 150 ° C., preferably 80 to 120 ° C., and more preferably 90 to 120 ° C.
- the drying time is preferably 10 to 500 seconds, more preferably 20 to 400 seconds.
- the aqueous coating liquid is applied on the surface of the polarizer 1.
- the film thickness unevenness of the transparent resin layer 4 obtained by forming and drying the coating film can be suppressed, and the appearance unevenness can be suppressed from occurring in a humidified environment.
- the surface protection film usually has a base film and an adhesive layer, and protects the single-protective polarizing film 3 via the adhesive layer.
- the said surface protective film protects the piece protection polarizing film with an adhesive layer temporarily, and is peeled in the case of actual use.
- 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 surface protective film As the surface protective film, a commercially available one can also be preferably used. For example, Toraytec 7832C # 30 manufactured by Toray Film Processing Co., Ltd. can be preferably used.
- the time until the surface protective film is bonded and the surface protective film is peeled off is not particularly limited, but is preferably 1 hour or longer, and more preferably 12 hours or longer.
- the water contact angle of the surface of the polarizer 1 on which the transparent resin layer 4 is formed varies by sticking and peeling the surface protective film on the surface of the polarizer 1 (surface on which the transparent resin layer 4 is formed) of the piece protective polarizing film 3. Can be suppressed.
- the activation treatment may include corona treatment and / or plasma treatment.
- the corona treatment include a method in which discharge is performed in normal pressure air using a corona treatment machine.
- the plasma treatment for example, a method of discharging in a normal pressure air by a plasma discharge machine can be mentioned.
- the corona output in the corona treatment is not particularly limited, but is preferably about 0.5 to 8.0 kW, more preferably about 0.5 to 7.0 kW, and more preferably 0.5 to 6 More preferably, it is about 0.0 kW.
- the treatment speed in the corona treatment is preferably about 5 to 100 m / min, more preferably about 5 to 90 m / min, and further preferably about 5 to 80 m / min.
- the plasma output in the plasma treatment is not particularly limited, but is preferably about 0.5 to 5.0 kW, more preferably about 0.5 to 3.0 kW, and more preferably 0.5 to 1. More preferably, it is about 5 W.
- the treatment speed in the plasma treatment is preferably about 5 to 100 m / min, more preferably about 5 to 90 m / min, and further preferably about 5 to 80 m / min.
- the treatment may be performed once, but the treatment is more preferably performed twice or more. Further, both corona treatment and plasma treatment may be performed.
- the surface of the polarizer 1 (the surface on which the transparent resin layer 4 is formed) of the piece protective polarizing film 3 is subjected to corona treatment, and then subjected to plasma treatment, and the aqueous coating liquid is applied to the treated surface. be able to.
- the hydrophilicity of the one surface of the polarizer (the surface on which the transparent resin layer 4 is formed) of the piece protective polarizing film 3 is increased by the corona treatment or the plasma treatment. For this reason, the affinity between the polarizer 1 surface (transparent resin layer 4 forming surface) of the piece protective polarizing film 3 and the aqueous coating liquid is improved, and the polarizer 1 surface (transparent resin layer) of the piece protective polarizing film 3 is improved. (4 forming surface) wettability of the aqueous coating solution is improved.
- the corona treatment and the plasma treatment can suppress variations in the water contact angle of one surface of the polarizer (the surface on which the transparent resin layer 4 is formed).
- the manufacturing method of polarizing film with a pressure-sensitive adhesive layer according to the present invention is a method in which a transparent resin layer of a piece-protecting polarizing film with a transparent resin layer obtained by any one of the manufacturing methods described above It has the process of forming an agent layer.
- the pressure-sensitive adhesive layer-attached polarizing film 11 obtained by the production method of the present invention further has a pressure-sensitive adhesive layer 5 on the transparent resin layer 4 of the piece-protecting polarizing film 10 with the transparent resin layer. It is characterized by having.
- 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.
- the polarizing film of the present invention (including a piece protective polarizing film with a transparent resin layer and a polarizing film with an adhesive layer) can be provided with a surface protective film.
- Examples of the surface protective film include those described above.
- the manufacturing method of the image display device of the present invention uses a piece-protecting polarizing film with a transparent resin layer obtained by the manufacturing method, or a polarizing film with an adhesive layer obtained by the manufacturing method. It is characterized by forming.
- 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 laminate in which this is laminated with an optical member, as a liquid crystal display device (LCD), An image display device such as an organic EL display device can be formed.
- LCD liquid crystal display device
- 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.
- One layer or two or more layers that may be used for forming a device or the like can be used.
- a reflective polarizing film or a semi-transmissive film obtained by further laminating a reflective plate or a semi-transmissive reflective plate on the transparent protective layer-provided transparent protective film or pressure-sensitive adhesive layer-coated polarizing film of the present invention.
- a polarizing film obtained by further laminating a brightness enhancement film on the film is preferable.
- An optical laminate in which the optical member is laminated on a transparent protective layer-provided transparent protective film or a pressure-sensitive adhesive layer-carrying film obtained by the production method of the present invention is sequentially laminated separately in the production process of a liquid crystal display device or the like.
- the optical layered body that has been laminated in advance is excellent in quality stability, assembly work, and the like, and has an advantage that the manufacturing process of the liquid crystal display device and the like can be improved.
- an appropriate adhesive means such as a pressure-sensitive adhesive layer can be used.
- the optical axes thereof can be set to 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 manufacturing method of a liquid crystal display device can be performed according to the conventional method.
- a liquid crystal display device is generally formed by assembling components such as a liquid crystal cell, a polarizing film or an optical film, and an illumination system as necessary, and incorporating a drive circuit.
- the piece protection polarizing film with a transparent resin layer of this invention the polarizing film with an adhesive layer, or an optical laminated body, and it can apply according to the former.
- 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 with a transparent resin layer, a polarizing film with an adhesive layer obtained by the production method of the present invention, or an optical laminate on one side or both sides of a liquid crystal cell, or a lighting system 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 a pressure-sensitive 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.
- the polarizing film with an adhesive layer, or an optical laminated body on both sides they may be the same and may differ.
- 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 3 (Production of a single protective polarizing film) A (meth) acrylic resin film having a lactone ring structure with a thickness of 40 ⁇ m and subjected to corona treatment on the easy adhesion 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. The amorphous IPA copolymerized PET film substrate did not peel and was left as it was.
- the total thickness of the single protective polarizing film using a thin polarizer (excluding the amorphous IPA copolymerized PET film substrate) was 46 ⁇ m.
- 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 4 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 amorphous IPA copolymerized PET film substrate was peeled from the piece-protecting polarizing film obtained in Production Example 3, and a surface protective film (trade name: Toraytec 7832C # 30, Toray Processing Co., Ltd.) was exposed on the exposed polarizer. Film).
- the surface protective film was peeled off, and the coating liquid (transparent resin layer of the transparent resin layer) obtained in Production Example 4 was applied to the surface of the polarizer (polarizer surface provided with no protective film).
- the forming material was applied using a gravure roll so that the thickness was 25 ⁇ m. 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 In Example 1, after removing the amorphous IPA copolymerized PET film substrate from the piece protective polarizing film obtained in Production Example 3, the exposed polarizer surface was subjected to corona treatment (discharge amount: 0.038 W). Min / m 2 , output: 2.0 kW, processing speed: 25 m / min). Thereafter, a surface protective film (trade name: Tretec 7832C # 30, manufactured by Toray Industries Film Co., Ltd.) was bonded. Other than that was carried out similarly to Example 1, and produced the piece protection polarizing film with a transparent resin layer.
- Example 3 In Example 1, after the surface protective film was peeled off, the exposed polarizer surface was subjected to corona treatment (discharge amount: 0.038 W ⁇ min / m 2 , output: 2.0 kW, treatment speed: 25 m / min). gave. Thereafter, a surface protective film (trade name: Tretec 7832C # 30, manufactured by Toray Industries Film Co., Ltd.) was bonded. Furthermore, the surface protective film is peeled off, and plasma treatment (discharge amount: 0.024 W ⁇ min / m 2 , output: 1.0 kW, treatment on the surface of the polarizer (polarizer surface on which no protective film is provided). Speed: 20 m / min), and a piece protective polarizing film with a transparent resin layer was produced in the same manner as in Example 1.
- corona treatment discharge amount: 0.038 W ⁇ min / m 2 , output: 2.0 kW, treatment speed: 25 m / min.
- a surface protective film (trade name: Tretec
- Example 4 In Example 1, the surface protective film was peeled off, and plasma treatment (discharge amount: 0.024 W ⁇ min / m 2 , output: 1. on the surface of the polarizer (the surface of the polarizer not provided with the protective film). 0 kW, treatment speed: 20 m / min), and a piece protective polarizing film with a transparent resin layer was produced in the same manner as in Example 1.
- Example 1 After removing the amorphous IPA copolymerized PET film substrate from the piece protective polarizing film obtained in Production Example 3, the exposed polarizer surface was subjected to plasma treatment (discharge amount: 0.048 W). Min / m 2 , output: 2.0 kW, processing speed: 20 m / min), and a piece protective polarizing film with a transparent resin layer was produced in the same manner as in Example 1.
- Example 2 In Example 1, after removing the amorphous IPA copolymerized PET film base material from the piece protective polarizing film obtained in Production Example 3, the coated polarizer obtained in Production Example 4 was applied to the exposed polarizer surface. A piece protective polarizing film with a transparent resin layer was produced in the same manner as in Example 1 except that the coating liquid (formation material for the transparent resin layer) was applied.
- Reference example 1 A piece protective polarizing film was produced in the same manner as in Production Example 3 except that the polarizer obtained in Production Example 2 was used.
- a piece protective polarizing film with a transparent resin layer was produced in the same manner as in Example 1 except that the piece protective polarizing film was used.
- the contact angle of water on the transparent resin layer forming surface of the polarizer used in the examples and comparative examples is DM-501 manufactured by Kyowa Interface Chemical Co., Ltd. It was measured as 1000 ms.
- the water contact angle is 25 points in the width direction of the polarizer and 5 points in the stretching direction (conveying direction), and the water contact angle is measured at an arbitrary plurality of locations of the polarizer, and the average in the width direction is measured.
- the water contact angle and the variation in water contact angle were evaluated. Since the water contact angle changes with time, the water contact angle was measured immediately after the plasma treatment or corona treatment (specifically, within 5 minutes).
- the film thickness of the coating film formed by coating the aqueous coating solution is optical spectroscope (USB2000 + manufactured by Ocean optics, light source: HL-2000, optical fiber) : ZFQ-12796 (200 ⁇ m reflective fiber)).
- the measurement conditions were as follows, and the measurement was performed by measuring 25 points in the width direction of the polarizer and 5 points in the stretching direction (conveying direction), and obtaining the average value.
- Transparent resin layer refractive index 1.51
- the coating film formed by applying an aqueous coating solution was measured for optical film thickness variation (USB2000 + manufactured by Ocean Optics, light source: HL-2000, Measurement was performed using an optical fiber: ZFQ-12796 (200 ⁇ m reflective fiber). Samples with a size of 1200 mm ⁇ 100 mm were measured at a pitch of 1 mm, and the film thickness variation was evaluated. 3 (a), (b), and (c) are 100 mm (absorption axis direction, vertical direction in the figure) ⁇ 100 mm (transmission axis direction, horizontal direction in the figure) for Examples 1 and 3 and Comparative Example 1, respectively. The result of in-plane film thickness variation is shown. (Measurement condition) Measurement wavelength: 450nm to 800nm Transparent resin layer refractive index: 1.51
- ⁇ Humidification environment test (visual appearance irregularity confirmation)>
- the piece protective polarizing film with a transparent resin layer obtained in Examples and Comparative Examples was cut into a size of 300 mm (absorption axis direction) ⁇ 300 mm (transmission axis direction).
- Two pieces of the piece-protecting polarizing film (sample) were prepared and attached to both surfaces of non-alkali glass so that their absorption axes were in an orthogonal state, thereby preparing a humidified environment test sample.
- the obtained humidified environment test sample was put in a humidified environment (60 ° C./90% RH environment) for 300 hours.
- the variation of the water contact angle of the transparent resin layer forming surface of the polarizer is an average water contact angle of ⁇ 20 °, and the variation of the water contact angle is small.
- the variation in thickness was small, and the appearance unevenness after the humidified environment test was suppressed.
- Comparative Examples 1 and 2 in which the water contact angle on the transparent resin layer-forming surface of the polarizer was large, the obtained transparent resin layer had a large film thickness variation, and uneven appearance occurred after the humidified environment test.
- the thickness of the polarizer was 12 ⁇ m, even when the water contact angle varied greatly, the appearance unevenness was not visually recognized after the humidified environment test.
Abstract
Description
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を準備する工程(1)、
前記片保護偏光フィルムの偏光子面に、樹脂成分を含む水系塗工液を塗布する工程(2)、及び
得られた塗布膜を乾燥して、透明樹脂層を形成する工程(3)、をこの順に含み、
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、
前記偏光子の透明樹脂層を形成する面の水接触角のバラつきが、平均水接触角±20°の範囲内であ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。
前記片保護偏光フィルムの偏光子面に、表面保護フィルムを貼り合せ、その後、当該表面保護フィルムを前記片保護偏光フィルムから剥離する工程、及び、
前記片保護偏光フィルムの表面保護フィルム剥離面に、活性化処理を施す工程をこの順に含むことができる。
前記片保護偏光フィルムの偏光子面に、活性化処理を施す工程、及び、
前記片保護偏光フィルムの活性化処理された面に、表面保護フィルムを貼り合せ、その後、当該表面保護フィルムを前記片保護偏光フィルムから剥離する工程、をこの順に含むことができる。
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、
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を準備する工程(1)、
前記片保護偏光フィルムの偏光子面に、樹脂成分を含む水系塗工液を塗布する工程(2)、及び
得られた塗布膜を乾燥して、透明樹脂層を形成する工程(3)、をこの順に含み、
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、
前記偏光子の透明樹脂層を形成する面の水接触角のバラつきが、平均水接触角±20°の範囲内であることを特徴とする。
工程(1)では、偏光子1の片面にのみ保護フィルム2を有する片保護偏光フィルム3を準備する。
搬送用フィルムと、当該搬送用フィルムの片面に形成されたポリビニルアルコール系樹脂を含有する厚み10μm以下の偏光子1を有する積層体(a)を形成する工程(1-1)、
前記工程(1-1)で得られた積層体(a)の偏光子1の側に、保護フィルム2を形成する工程(1-2)、及び、
前記工程(1-2)で得られた積層体(保護フィルム2/偏光子1/搬送用フィルム)から、搬送用フィルムを剥離する工程(1-3)を含む製造方法により形成されることが好ましい。以下、前記好ましい製造方法の各工程について説明する。
前記積層体(a)は、例えば、搬送用フィルムと当該搬送用フィルムの片面に形成されたポリビニルアルコール系樹脂(以下、PVA系樹脂ともいう)層とを有する積層体(a´)に、少なくとも延伸工程、及び染色工程を施すことにより得られる。前記搬送用フィルムは、長尺物を用いることにより、長尺のPVA系樹脂層を形成することができ、連続生産に有利である。
前記工程(1-2)では、前記得られた積層体(a)の偏光子1の側に、保護フィルム2を形成する。当該工程(1-2)により、偏光子1の片側にのみ保護フィルム2を有する搬送用フィルム付きの片保護偏光フィルムA´が得られる。保護フィルム2及び保護フィルム2を積層する際に用いられる介在層については、前述のものを用いることができる。
前記工程(1-3)では、前記搬送用フィルム付き片保護偏光フィルムA´から、前記搬送用フィルムを剥離する。搬送用フィルムの剥離方法は特に制限はない。搬送用フィルムの剥離に際しては、偏光子1(又は片保護偏光フィルム)側に角度をつけてもよいし、搬送用フィルム側に角度をつけて剥離してもよい。また、両側に角度をつけて剥離してもよい。いずれの場合でも、薄型の偏光子1には、搬送用フィルムの剥離により損傷が発生しやすい。搬送用フィルムを剥離する際の角度は任意に設定される。搬送用フィルムを剥離する際には、最も剥離力が弱くなる角度が存在する。剥離力が弱くなる角度は、構成や剥離速度、剥離する際の湿度、剥離するフィルムの剛性に左右されるため、適宜に決定することができる。
工程(2)では、前記工程(1)で準備された、偏光子1の片面にのみ保護フィルム2を有する片保護偏光フィルム3の偏光子1面に、樹脂成分を含む水系塗工液を塗布する。透明樹脂層4を形成する前記偏光子1面は、前記工程(1)で得られた片保護偏光フィルム3の搬送用フィルムを剥離した面である。
工程(3)では、工程(2)で得られた塗布膜を乾燥して、透明樹脂層4を形成する。
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においては、前記水系塗工液を塗布する工程(2)の前に、
前記片保護偏光フィルムの偏光子面に、
表面保護フィルムを貼り合せ、その後、当該表面保護フィルムを前記片保護偏光フィルムから剥離する工程、及び、
活性化処理を施す工程、からなる群から選択される1つ以上の工程を含むことが、前記偏光子1の透明樹脂層4を形成する面の水接触角のバラつきを制御できるため好ましい。
前記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片保護偏光フィルム3を保護する。当該表面保護フィルムは、一時的に粘着剤層付片保護偏光フィルムを保護するものであって、実際の使用の際には剥離されるものである。
前記活性化処理としては、コロナ処理及び/又はプラズマ処理を挙げることができる。前記コロナ処理としては、例えば、コロナ処理機により常圧空気中で放電する方式が挙げられる。プラズマ処理は、例えば、プラズマ放電機により常圧空気中で放電する方式が挙げられる。
(組み合わせ1)前記片保護偏光フィルム3の偏光子1面に、表面保護フィルムを貼り合せ、その後、当該表面保護フィルムを前記片保護偏光フィルム3から剥離し、その後、前記片保護偏光フィルム3の表面保護フィルム剥離面に、活性化処理を施す方法や、
(組み合わせ2)前記片保護偏光フィルム3の偏光子1面に、活性化処理を施し、その後、前記片保護偏光フィルム3の活性化処理された面に、表面保護フィルムを貼り合せ、その後、当該表面保護フィルムを前記片保護偏光フィルム3から剥離する方法等を挙げることができる。
本発明の粘着剤層付偏光フィルムの製造方法は、前記いずれか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有することを特徴とする。
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。
本発明の偏光フィルム(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、前述のものを挙げることができる。
本発明の画像表示装置の製造方法は、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、又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用いて形成することを特徴とする。
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。
平均重合度2400、ケン化度99.9モル%の厚み30μmのポリビニルアルコールフィルムを、30℃の温水中に60秒間浸漬し膨潤させた。次いで、ヨウ素/ヨウ化カリウム(重量比=0.5/8)の濃度0.3%の水溶液に浸漬し、3.5倍まで延伸させながらフィルムを染色した。その後、65℃のホウ酸エステル水溶液中で、総延伸倍率が6倍となるように延伸を行った。延伸後に、40℃のオーブンにて3分間乾燥を行い、PVA系偏光子を得た。得られた偏光子の厚みは12μmであった。
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を保護フィルムとして用いた。
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。
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。
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
製造例3で得られた片保護偏光フィルムから、非晶質IPA共重合PETフィルム基材を剥離し、剥き出しになった偏光子上に、表面保護フィルム(商品名:トレテック 7832C #30、東レ加工フィルム社製)を貼り合せた。その状態で、24時間放置後、表面保護フィルムを剥離し、当該偏光子の面(保護フィルムが設けられていない偏光子面)に、製造例4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。
実施例1において、製造例3で得られた片保護偏光フィルムから、非晶質IPA共重合PETフィルム基材を剥離した後、剥き出しになった偏光子面にコロナ処理(放電量:0.038W・min/m2、出力:2.0kW、処理速度:25m/min)を施した。その後、表面保護フィルム(商品名:トレテック 7832C #30、東レ加工フィルム(株)製)を貼り合せた。それ以外は、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。
実施例1において、表面保護フィルムを剥離した後、剥き出しになった偏光子面にコロナ処理(放電量:0.038W・min/m2、出力:2.0kW、処理速度:25m/min)を施した。その後、表面保護フィルム(商品名:トレテック 7832C #30、東レ加工フィルム(株)製)を貼り合せた。さらに、表面保護フィルムを剥離し、当該偏光子の面(保護フィルムが設けられていない偏光子面)に、プラズマ処理(放電量:0.024W・min/m2、出力:1.0kW、処理速度:20m/min)を施し、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。
実施例1において、表面保護フィルムを剥離し、当該偏光子の面(保護フィルムが設けられていない偏光子面)に、プラズマ処理(放電量:0.024W・min/m2、出力:1.0kW、処理速度:20m/min)を施し、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。
実施例1において、製造例3で得られた片保護偏光フィルムから、非晶質IPA共重合PETフィルム基材を剥離した後、剥き出しになった偏光子面にプラズマ処理(放電量:0.048W・min/m2、出力:2.0kW、処理速度:20m/min)を施し、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。
実施例1において、製造例3で得られた片保護偏光フィルムから、非晶質IPA共重合PETフィルム基材を剥離した後、剥き出しになった偏光子面に、製造例4で得られた塗工液(透明樹脂層の形成材)を塗工した以外は、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。
製造例2で得られた偏光子を使用した以外は、製造例3と同様にして、片保護偏光フィルムを作製した。
前記片保護偏光フィルムを用いた以外は、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。
実施例、比較例で用いた偏光子の透明樹脂層形成面の水の接触角は、共和界面化学(株)製のDM-501を用いて、作製液量が3μL、測定までの待ち時間が1000msとして測定した。
また、前記水の接触角は、偏光子の任意の複数の箇所において、偏光子の幅方向に25点かつ延伸方向(搬送方向)に5点、水接触角を測定し、幅方向での平均水接触角、及び水接触角のバラつきを評価した。なお、水接触角は時間の経過と共に変化するため、プラズマ処理やコロナ処理の直後(具体的には5分以内)に測定した。
実施例、比較例において、水系塗工液(透明樹脂層の形成材)を塗工して形成した塗布膜の膜厚は光学分光器(Ocean optics社製のUSB2000+、光源:HL-2000、光ファイバー:ZFQ-12796(200μm反射ファイバー))を用いて測定した。測定条件は、以下の通りであり、測定は、偏光子の幅方向に25点かつ延伸方向(搬送方向)に5点測定し、その平均値を求めた。
(測定条件)
測定波長:450nm~800nm
透明樹脂層屈折率:1.51
実施例、比較例において、水系塗工液(透明樹脂層の形成材)を塗工して形成した塗布膜の膜厚バラつきを光学分光器(Ocean optics社製のUSB2000+、光源:HL-2000、光ファイバー:ZFQ-12796(200μm反射ファイバー))を用いて測定した。1200mm×100mmサイズのサンプルを1mmピッチで測定し、膜厚バラつきを評価した。図3(a)、(b)、(c)は、それぞれ実施例1、3、比較例1について、100mm(吸収軸方向、図の縦方向)×100mm(透過軸方向、図の横方向)の面内膜厚バラつきの結果を示す。
(測定条件)
測定波長:450nm~800nm
透明樹脂層屈折率:1.51
実施例及び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300mm(吸収軸方向)×300mm(透過軸方向)のサイズに裁断した。当該片保護偏光フィルム(サンプル)を2枚準備し、これらの吸収軸が直交状態になるように、無アルカリガラスの両面に貼りつけ、加湿環境試験用サンプルを作製した。得られた加湿環境試験用サンプルを、加湿環境(60℃/90%RHの環境)下に300時間投入した。その後、バックライトユニット(均一発光面照明、TWNシリーズ、アイテックシステム社製)の上に、加湿環境試験用サンプルを置き、外観ムラの視認性を確認した。図4(a)、(b)、(c)は、それぞれ実施例1、3、比較例1において、外観ムラの視認性を観察した写真である。
〇:外観ムラが視認されない。
×:外観ムラ視認される。
2 保護フィルム
3 片保護偏光フィルム
4 透明樹脂層
5 粘着剤層
10 透明樹脂層付の片保護偏光フィルム
11 粘着剤層付偏光フィルム
A 偏光フィルムの幅方向
Claims (8)
- 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、
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を準備する工程(1)、
前記片保護偏光フィルムの偏光子面に、樹脂成分を含む水系塗工液を塗布する工程(2)、及び
得られた塗布膜を乾燥して、透明樹脂層を形成する工程(3)、をこの順に含み、
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、
前記偏光子の透明樹脂層を形成する面の水接触角のバラつきが、平均水接触角±20°の範囲内であ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。 - 前記水系塗工液を塗布する工程(2)の前に、
前記片保護偏光フィルムの偏光子面に、表面保護フィルムを貼り合せ、その後、当該表面保護フィルムを前記片保護偏光フィルムから剥離する工程、及び、
前記片保護偏光フィルムの表面保護フィルム剥離面に、活性化処理を施す工程をこの順に含む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。 - 前記水系塗工液を塗布する工程(2)の前に、
前記片保護偏光フィルムの偏光子面に、活性化処理を施す工程、及び、
前記片保護偏光フィルムの活性化処理された面に、表面保護フィルムを貼り合せ、その後、当該表面保護フィルムを前記片保護偏光フィルムから剥離する工程、をこの順に含む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。 - 前記活性化処理が、コロナ処理及び/又はプラズマ処理であることを特徴とする請求項1~3のいずれかの記載の透明樹脂層付の片保護偏光フィルムの製造方法。
- 前記水接触角のバラつきが、平均水接触角±15°の範囲内であることを特徴とする請求項1~4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。
- 前記平均水接触角が、90°以下であることを特徴とする請求項1~5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。
- 請求項1~6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有することを特徴とする粘着剤層付偏光フィルムの製造方法。
- 請求項1~6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、又は請求項7の製造方法により得られた粘着剤層付偏光フィルムを用いて形成することを特徴とする画像表示装置の製造方法。
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