WO2016052540A1 - Polarizing film, adhesive-layer-equipped polarizing film, and image display device - Google Patents
Polarizing film, adhesive-layer-equipped polarizing film, and image display device Download PDFInfo
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- WO2016052540A1 WO2016052540A1 PCT/JP2015/077580 JP2015077580W WO2016052540A1 WO 2016052540 A1 WO2016052540 A1 WO 2016052540A1 JP 2015077580 W JP2015077580 W JP 2015077580W WO 2016052540 A1 WO2016052540 A1 WO 2016052540A1
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- polarizer
- polarizing film
- layer
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- thickness
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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
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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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
Definitions
- the present invention relates to a polarizing film. Moreover, this invention relates to the polarizing film with an adhesive layer using the said polarizing film.
- the polarizing film or the polarizing film with the pressure-sensitive adhesive layer can form an image display device such as a liquid crystal display device (LCD) or an organic EL display device alone or as an optical film in which the polarizing film is laminated.
- LCD liquid crystal display device
- organic EL display device alone or as an optical film in which the polarizing film is laminated.
- polarizing films In a liquid crystal display device, it is indispensable to dispose polarizing films on both sides of a glass substrate that forms the surface of a liquid crystal panel because of its image forming method.
- a polarizing film in which a protective film is bonded to one or both sides of a polarizer made of a dichroic material such as a polyvinyl alcohol film and iodine with a polyvinyl alcohol adhesive or the like is used. .
- the polarizing film is prone to cracks in the entire absorption axis direction of the polarizer due to a change in the contraction stress of the polarizer under a severe environment of thermal shock (for example, a high temperature test at 95 ° C. for 250 hours). There is. That is, the polarizing film did not have sufficient crack resistance due to thermal shock in the harsh environment.
- a polarizing film with an adhesive layer in which a protective layer having a tensile modulus of 100 MPa or more is provided on a single protective polarizing film and an adhesive layer is further provided on the protective layer has been proposed.
- Patent Document 1 Moreover, it has a protective layer made of a cured product of the curable resin composition on one side of a polarizer having a thickness of 25 ⁇ m or less, a protective film on the other side of the polarizer, and an adhesive layer outside the protective layer
- Patent Document 2 proposes a polarizing film with a pressure-sensitive adhesive layer.
- Patent Document 3 The polarizing film with the pressure-sensitive adhesive layer described in Patent Documents 1 and 2 is effective from the viewpoint of suppressing the occurrence of cracks.
- a protective layer made of a water-soluble film-forming composition (polyvinyl alcohol-based resin composition) is provided on at least one surface of the polarizer from the viewpoint of thinning and weight reduction. It has been proposed (Patent Document 3).
- the protective layer can suppress the contraction of the polarizer in the absorption axis direction to some extent, and the generation of the cracks can be suppressed.
- the protective layer sufficiently suppresses the dimensional change due to the contraction stress of the polarizer.
- the polarizer has, for example, a polyvinyl alcohol film stretching process, even if it is a thin polarizer, the polarizer obtained in the stretching process is manufactured in a state having a residual stress inside.
- various protective films and the like are usually bonded to one or both sides of a polarizer.
- the residual stress of the various protective films and the residual stress of the polarizer in the thermal shock test. are expressed in a combined form, and the behavior of the polarizing film shrinking as a whole is exhibited.
- the dimensional change due to the contraction stress of the polarizer is sufficiently observed particularly in the vicinity of Tg of the polyvinyl alcohol resin used for forming the polarizer and in a high temperature test (for example, 85 ° C. or more). It was not able to be suppressed.
- the present invention is a polarizing film having a transparent layer on at least one side of a polarizer, which suppresses the generation of cracks in a high temperature environment of 85 ° C. or higher and suppresses the change in the dimensions of the polarizer.
- the purpose is to provide.
- this invention aims at providing the polarizing film with an adhesive layer using the said polarizing film.
- this invention relates to the image display apparatus which has the said polarizing film or a polarizing film with an adhesive layer.
- the present invention is a polarizing film having a transparent layer on at least one side of a polarizer
- the polarizer contains a polyvinyl alcohol resin and has a thickness of 15 ⁇ m or less
- On the side of the transparent layer in the polarizer it has a compatible layer with the transparent layer
- the thickness A of the polarizer and the thickness B of the compatible layer relate to a polarizing film characterized by satisfying the general formula: (100 ⁇ B / A) ⁇ 1.
- the compatible layer preferably has a lower boric acid concentration than the portion other than the compatible layer in the polarizer.
- the present invention is also a polarizing film having a transparent layer on at least one side of the polarizer,
- the polarizer contains a polyvinyl alcohol-based resin and has a thickness of 15 ⁇ m or less.
- On the side of the transparent layer in the polarizer it has a boric acid low-concentration layer in which the boric acid concentration is relatively lower than other parts of the polarizer,
- the thickness A of the polarizer and the thickness C of the low concentration layer of boric acid relate to a polarizing film characterized by satisfying the general formula: (100 ⁇ C / A) ⁇ 1.
- the transparent layer preferably has a thickness of 0.2 ⁇ m or more.
- the transparent layer preferably has a thickness of 6 ⁇ m or less.
- the transparent layer preferably has an orientation index of 0.05 or less.
- the transparent layer is preferably formed of a forming material containing a polyvinyl alcohol-based resin.
- the polyvinyl alcohol resin preferably has a saponification degree of 99 mol% or more and an average polymerization degree of 2000 or more.
- the polarizer has an optical property represented by the following formula: P> ⁇ (10 0.929T-42.4 ⁇ 1) ⁇ 100 (where T ⁇ 42.3) or It is preferably in the range represented by P ⁇ 99.9 (however, T ⁇ 42.3).
- the polarizing film can have a protective film.
- this invention relates to the polarizing film with an adhesive layer characterized by having the said polarizing film and an adhesive layer.
- the present invention also relates to an image display device having the polarizing film or the polarizing film with an adhesive layer.
- the polarizing film of the present invention the occurrence of cracks in a high temperature environment of 85 ° C. or higher can be suppressed by providing the polarizer with the transparent layer.
- the polarizing film of this invention has a compatible layer with the said transparent layer in the said transparent layer side in the said polarizer.
- the compatible layer is formed in the vicinity of the polarizer surface as a part of the material forming the transparent layer soaks into the polarizer and the component in the vicinity of the polarizer surface leaks out.
- Such a compatible layer can be formed by forming a transparent layer on the surface of the polarizer using a material that penetrates into the polarizer.
- a typical polarizer is produced by, for example, subjecting a polyvinyl alcohol resin (film) to a stretching process, so that the resin molecules in the obtained polarizer are oriented with a certain degree of regularity. It has become.
- the transparent layer formed on the surface of the polarizer is formed, for example, by coating. Therefore, the transparent layer is not subjected to a stretching step, and the molecules forming the transparent layer are not regularly oriented.
- the compatible layer of the present invention is formed by the transparent layer forming component soaking into the polarizer. When the transparent layer is formed, the components of the transparent layer soaked in the polarizer have a function of partially relaxing the molecular orientation in the polarizer. It is presumed that this function leads to relaxation of the residual stress of the polarizer and suppresses the dimensional change of the polarizer. Note that the present invention is not limited to this estimation mechanism.
- the polarizing film of the present invention uses a thin polarizer having a thickness of 15 ⁇ m or less.
- the thin polarizer has a small change in the contraction stress of the polarizer, but the polarizer itself has been thinned, so that the crack resistance is not sufficient.
- the crack resistance can be improved because it has a transparent layer despite the use of a thin polarizer.
- the polarizing films 10 and 11 of the present invention will be described with reference to FIGS. 1 and 2.
- the polarizing films 10 and 11 have a polarizer 1 and a transparent layer 2.
- the polarizing films 10 and 11 of this invention have the compatible layer X with the said transparent layer 2 in the side of the said transparent layer 2 in the said polarizer 1, as shown in FIG. 1, FIG. Yes.
- FIG. 1 (A) only the polarizer 1, the compatible layer X, and the transparent layer 2 are shown, but as shown in FIG. 1 (B), on the side of the polarizer 1 in FIG. 1 (A).
- the resin base material 3 may be provided.
- As the resin base material 3, for example, a resin base material used when the thin polarizer 1 is manufactured may be mentioned.
- the protective film 4 is provided in the polarizing film 10 of FIG. 1 (A).
- the protective film 4 can be provided on one side or both sides of the polarizing film of the polarizing film 10 in FIG.
- the protective film 4 is provided only on the polarizer 1 side, but the protective film 4 may be provided only on the transparent layer 2 side.
- protective films 4 are provided on both sides of the polarizing film 10 of FIG.
- the protective film 4 can also be laminated
- FIG. 2C shows a case where two protective films 4 are laminated on one side of the polarizer 1.
- the polarizer 1 or the transparent layer 2 and the protective film 4 are laminated via intervening layers such as an adhesive layer, an adhesive layer, and an undercoat layer (primer layer).
- an adhesive layer such as an adhesive layer, an adhesive layer, and an undercoat layer (primer layer).
- an undercoat layer such as an adhesive layer, an adhesive layer, and an undercoat layer (primer layer).
- the easy-adhesion layer and the adhesive layer can be laminated by providing the protective film 4 with an easy-adhesion layer or applying an activation treatment.
- the polarizing films 10 and 11 of the present invention can be provided with an adhesive layer. Furthermore, a separator can be provided in the pressure-sensitive adhesive layer. Moreover, a surface protective film can be provided in the polarizing films 10 and 11 (especially when it has the protective film 4) of this invention.
- the compatible layer X is a layer formed by the component forming the transparent layer 2 soaking into the inside from the surface of the polarizer 1. 1 residual stress can be relaxed. As a result, the dimensional change of the polarizer can be suppressed. From this viewpoint, in the present invention, the thickness A of the polarizer 1 and the thickness B of the compatible layer are adjusted so as to satisfy the general formula: (100 ⁇ B / A) ⁇ 1. The thickness B of the compatible layer X is adjusted in relation to the thickness A of the polarizer 1.
- the value of (100 ⁇ B / A) is preferably 2 or more from the viewpoint of alleviating the residual stress of the polarizer, more preferably 2.5 or more, further 3 or more, further 4 or more, and further 5 The above is preferable.
- the value of (100 ⁇ B / A) is preferably 10 or less, and more preferably 7 or less.
- the thickness B of the compatible layer X can be measured by the method described in Examples.
- the polarizer is not particularly limited, and various types can be used.
- polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
- hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
- examples thereof include polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products.
- a polarizer composed of a polyvinyl alcohol film and a dichroic material 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 a polyvinyl alcohol film by immersing it in an aqueous solution of iodine 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 such as potassium iodide. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing.
- 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 such as boric acid or potassium iodide or in a water bath.
- a thin polarizer having a thickness of 15 ⁇ m or less is used as the polarizer.
- the thickness of the polarizer is preferably 12 ⁇ m from the viewpoint of thinning and crack resistance due to thermal shock, more preferably 10 ⁇ m or less, further 8 ⁇ m or less, further 7 ⁇ m or less, and further 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 preferably contains boric acid from the viewpoint of stretching stability and optical durability.
- the boric acid content contained in the polarizer 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 cracks such as through cracks. It is preferably 18% by weight or less, more 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.
- Patent No. 4751486 Japanese Patent No. 4751481, Patent No. 4815544, Patent No. 5048120, Japanese Patent No. 5587517, International Publication No. 2014/077599 pamphlet, International Publication No. 2014/077636 Pamphlet, And the thin polarizers obtained from the production methods described therein.
- the polarizer 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 preferably 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 and dyeing a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin base material in a laminated state.
- PVA-based resin polyvinyl alcohol-based resin
- a stretching resin base material in a laminated state.
- thermoplastic resin substrate an amorphous ester-based thermoplastic resin substrate or a crystalline ester-based thermoplastic resin substrate can be used.
- a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is preferable.
- 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 mentioned as examples of the polymer forming the protective film.
- thermoplastic resin in the protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight.
- content of the said thermoplastic resin in a protective film is 50 weight% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.
- a retardation film As the protective film, a retardation film, a brightness enhancement film, a diffusion film, and 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 can be determined as appropriate, but is generally about 1 to 500 ⁇ m from the viewpoints of workability such as strength and handleability, and thin layer properties. In particular, it is preferably 1 to 300 ⁇ m, more preferably 5 to 200 ⁇ m, and further preferably 5 to 150 ⁇ m, particularly 20 to 100 ⁇ m.
- 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 on which the polarizer is not adhered (particularly, the embodiment shown in FIG. 1).
- 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 itself, or can be provided separately from the protective film. it can.
- the protective film and the polarizer are laminated via an intervening layer such as an adhesive layer, an 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 such as an adhesive layer, an adhesive layer, and an undercoat layer (primer layer).
- the adhesive layer is formed with 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 or ultraviolet rays (radical curable type, cationic curable type), for example, in an electron beam curable type or an ultraviolet curable type. Can be used.
- an active energy ray such as an electron beam or ultraviolet rays (radical curable type, cationic curable type), for example, in an electron beam curable type or an ultraviolet curable type.
- an active energy ray curable adhesive for example, 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 dapping method can be appropriately used.
- the adhesive is preferably applied so that the finally formed adhesive layer has a thickness of 30 to 300 nm.
- the thickness of the adhesive layer is more preferably 60 to 250 nm.
- the thickness of the adhesive layer is preferably 0.1 to 200 ⁇ m. More preferably, it is 0.5 to 50 ⁇ m, and still more preferably 0.5 to 10 ⁇ 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. Specifically, a stabilizer such as a tackifier, an ultraviolet absorber, an antioxidant, and a heat resistance stabilizer may be used.
- 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 and the smoothness of coating.
- 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 and heat resistance.
- the undercoat layer (primer layer) is formed to improve the adhesion between the polarizer and the protective film.
- 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 base film and the polyvinyl alcohol-based resin layer.
- a thermoplastic resin excellent in transparency, thermal stability, stretchability, etc. is used.
- the thermoplastic resin include an acrylic resin, a polyolefin resin, a polyester resin, a polyvinyl alcohol resin, or a mixture thereof.
- the transparent layer can be formed from various forming materials.
- the material for forming the transparent layer include polyester resins, polyether resins, polycarbonate resins, polyurethane resins, silicone resins, polyamide resins, polyimide resins, PVA resins, and acrylic resins. Can do. These resin materials can be used alone or in combination of two or more. Among these, one or more selected from the group consisting of polyurethane resins and PVA resins are preferable, and PVA resins are more preferable. preferable.
- the form of the resin may be either water-based or solvent-based.
- the resin is preferably a water-based resin, and is preferably a PVA-based resin.
- As the water-based resin an acrylic resin aqueous solution or a urethane resin aqueous solution can be used.
- the thickness of the transparent layer is preferably 0.2 ⁇ m or more.
- the generation of cracks can be suppressed by the transparent layer having the thickness.
- the thickness of the transparent layer is preferably 0.5 ⁇ m or more, and more preferably 0.7 ⁇ m or more.
- the thickness of the transparent layer is generally 8 ⁇ m or less, preferably 6 ⁇ m or less, and more preferably 5 ⁇ m or less. And more preferably 3 ⁇ m or less.
- the thickness of the transparent layer is the thickness formed on the compatible layer.
- the transparent layer preferably has a low orientation index in terms of crack resistance.
- the orientation index is preferably controlled to be 0.05 or less, more preferably 0.02 or less, and most preferably non-orientation (orientation index is 0.01 or less).
- the orientation index of the transparent layer can be measured by the method described in Examples.
- the material forming the transparent layer is preferably one that penetrates into the polarizer.
- a material for forming the transparent layer for example, a forming material mainly composed of a water-soluble polyvinyl alcohol resin is preferable.
- 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, and the like.
- ⁇ -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. From the viewpoint of satisfying the heat and moisture resistance and water resistance, polyvinyl alcohol obtained by saponifying polyvinyl acetate is preferable.
- 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 K 6726-1994.
- the average degree of polymerization of the polyvinyl alcohol-based resin can be, for example, 500 or more. From the viewpoint of satisfying the heat and moisture resistance and water resistance, the average degree of polymerization is preferably 1000 or more, and more preferably 1500 or more. Is preferable, and 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 transparent layer can be formed from a forming material that does not contain a curable component.
- it can be formed from a forming material containing the polyvinyl alcohol resin (PVA resin) as a main component.
- PVA resin polyvinyl alcohol resin
- the polyvinyl alcohol resin forming the transparent 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”.
- the forming material containing the polyvinyl alcohol-based resin as a main component can contain a curable component (crosslinking agent) and the like.
- the ratio of the polyvinyl alcohol resin in the transparent layer or the forming material (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 forming material does not contain a curable component (crosslinking agent).
- a compound having at least two functional groups having reactivity with the polyvinyl alcohol resin can be used.
- alkylenediamine having two alkylene groups and two amino groups such as ethylenediamine, triethylenediamine, hexamethylenediamine; tolylene diisocyanate, hydrogenated tolylene diisocyanate, trimethylolpropane tolylene diisocyanate adduct, triphenylmethane triisocyanate, methylene bis (4-Phenylmethane triisocyanate, isophorone diisocyanate and isocyanates such as ketoxime block product or phenol block product thereof; ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin di or triglycidyl ether, 1,6-hexane Diol diglycidyl ether, trimethylolpropane triglycidyl ether, di Epoxies
- hardenable component crosslinking agent
- the ratio is 20 weight part or less, 10 weight part or less, 5 weight part with respect to 100 weight part of polyvinyl alcohol-type resin. It is preferable that:
- the forming material is prepared as a solution in which the polyvinyl alcohol resin is dissolved in a solvent.
- the solvent include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide 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 0.1 to 15% by weight, preferably 0.5%, in consideration of coating properties and storage stability. ⁇ 10% by weight.
- an additive suitably to the said forming material (for example, 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.
- coupling agents such as silane coupling agents and titanium coupling agents, various tackifiers, ultraviolet absorbers, antioxidants, heat stabilizers, hydrolysis stabilizers, and other stabilizers can be added.
- the transparent layer can be formed by applying and drying the forming material on the other side of the polarizer (the side having no protective film).
- the forming material is preferably applied such that the thickness after drying is 0.2 ⁇ m or more.
- the application operation is not particularly limited, and any appropriate method can be adopted. For example, various means such as a roll coating method, a spin coating method, a wire bar coating method, a dip coating method, a die coating method, a curtain coating method, a spray coating method, a knife coating method (comma coating method, etc.) can be employed.
- the drying temperature is usually preferably 60 to 120 ° C, and more preferably 70 to 100 ° C.
- the drying time is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
- the polarizing film can be used as a polarizing film with an adhesive layer by providing an adhesive layer.
- the pressure-sensitive adhesive layer can be provided on the transparent layer or polarizer side of the polarizing film, or in the case of having a protective film.
- a separator can be provided in the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer.
- an appropriate pressure-sensitive adhesive can be used, 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 and heat resistance are preferably used.
- An acrylic pressure-sensitive adhesive is preferably used as one exhibiting such characteristics.
- the pressure-sensitive adhesive is applied to a separator having been subjected to a release treatment, and after the polymerization solvent and the like are removed by drying to form a pressure-sensitive adhesive layer
- FIGS. In the embodiment of FIG. 2, a method of transferring to a transparent layer or a protective film (or a protective film in the embodiment of FIG. 2C), or in the embodiments of FIGS. ), The pressure-sensitive adhesive is applied to the protective film), and the polymerization solvent is dried and removed to form a pressure-sensitive adhesive layer on the polarizer.
- 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 may be adopted as appropriate 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 particularly preferably 70 ° C to 170 ° C.
- the drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.
- Various methods are used as a method for forming the pressure-sensitive adhesive layer. Specifically, for example, 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.
- the thickness is preferably 2 to 50 ⁇ m, more preferably 2 to 40 ⁇ m, and still more 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 thin film can be used, but a plastic film is preferably used because of its excellent 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.
- mold release and antifouling treatment with a silicone type, fluorine type, long chain alkyl type or fatty acid amide type release agent, silica powder, etc., coating type, kneading type, vapor deposition type It is also possible to carry out 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, or fluorine treatment on the surface of the separator.
- a surface protective film can be provided on the polarizing film.
- the surface protective film usually has a base film and an adhesive layer, and protects the polarizer via the 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. Examples thereof include transparent polymers such as resins. Of these, polyester resins are preferred.
- 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.
- the pressure-sensitive adhesive that forms the pressure-sensitive adhesive layer of the surface protective film includes a (meth) acrylic polymer, a silicone-based polymer, a polyester, a polyurethane, a polyamide, a polyether, a fluorine-based or a rubber-based pressure-sensitive adhesive. 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 adhesion material such as silicone treatment, long-chain alkyl treatment, or fluorine treatment. .
- the polarizing film of the present invention can be used as an optical film laminated with another optical layer in practical use.
- the optical layer is not particularly limited.
- a liquid crystal display device such as a reflection plate, a semi-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), and a viewing angle compensation film.
- One or more optical layers that may be used can be used.
- a reflective polarizing film or semi-transmissive polarizing film in which a polarizing plate or a semi-transmissive reflecting plate is further laminated on the polarizing film of the present invention an elliptical polarizing film or circularly polarizing film in which a retardation film is further laminated on a polarizing film.
- a wide viewing angle polarizing film obtained by further laminating a viewing angle compensation film on a film or a polarizing film, or a polarizing film obtained by further laminating a brightness enhancement film on the polarizing film is preferred.
- An optical film obtained by laminating the above optical layer on a polarizing film can be formed by a method of sequentially laminating separately in the manufacturing process of a liquid crystal display device or the like. It is excellent in stability and assembly work, and has the advantage of improving the manufacturing process of a liquid crystal display device and the like.
- an appropriate adhesive means such as a pressure-sensitive adhesive layer can be used.
- their optical axes can be set at an appropriate arrangement angle in accordance with the target retardation characteristics.
- the polarizing film or optical film 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 appropriately 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. There is no limitation in particular except the point which uses a polarizing film or an optical film by invention, and it can apply according to the former.
- As the liquid crystal cell an arbitrary type such as an IPS type or a VA type can be used, but is particularly suitable for the IPS type.
- liquid crystal display devices such as a liquid crystal display device in which a polarizing film or an optical film is disposed on one side or both sides of a liquid crystal cell, or a backlight or a reflector used in an illumination system can be formed.
- the polarizing film or optical film by this invention can be installed in the one side or both sides of a liquid crystal cell.
- polarizing film or an optical film on both sides they may be the same or different.
- a single layer or a suitable part such as a diffusing plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusing plate, a backlight, etc.
- a diffusing plate for example, a diffusing plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusing plate, a backlight, etc.
- a protective plate such as a prism array, a lens array sheet, a light diffusing plate, a backlight, etc.
- a prism array such as a prism array, a lens array sheet, a light diffusing plate, a backlight, etc.
- IPA copolymerized PET amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA copolymerized PET) film (thickness: 100 ⁇ m) having a water absorption of 0.75% and Tg of 75 ° C. is subjected to corona treatment.
- Alcohol polymerization degree 4200, saponification degree 99.2 mol%) and acetoacetyl-modified PVA (polymerization degree 1200, acetoacetyl modification degree 4.6%, saponification degree 99.0 mol% or more, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
- aqueous solution containing 9: 1 ratio of the trade name “Gosefimer Z200”) was applied and dried at 25 ° C. to form a PVA-based resin layer having a thickness of 11 ⁇ m, thereby preparing a laminate.
- the obtained laminate was uniaxially stretched in the longitudinal direction (longitudinal direction) 2.0 times between rolls having different peripheral speeds in an oven at 120 ° C. (air-assisted stretching process).
- 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).
- boric acid aqueous solution obtained by blending 3 parts by weight of potassium iodide and 3 parts by weight of boric acid with respect to 100 parts by weight of water.
- Crosslinking treatment Thereafter, the laminate was immersed in a boric acid aqueous solution (an aqueous solution obtained by blending 4 parts by weight of boric acid and 5 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 70 ° C.
- uniaxial stretching was performed between rolls having different peripheral speeds in the longitudinal direction (longitudinal direction) so that the total stretching ratio was 5.5 times (in-water stretching treatment).
- an optical film laminate A0 including a polarizer having a thickness of 5 ⁇ m was obtained.
- the optical film laminate A1 was prepared in the same manner as the production method of the optical film laminate A0 except that boric acid blended in the boric acid aqueous solution in the underwater stretching treatment was changed to 3.5 parts by weight. Got. The thickness of the obtained polarizer was 5 ⁇ m.
- the optical film laminate A2 was produced in the same manner as the production method of the optical film laminate A0 except that boric acid blended in the boric acid aqueous solution in the underwater stretching treatment was changed to 4.5 parts by weight. Got. The thickness of the obtained polarizer was 5 ⁇ m.
- optical film laminate D In the production of the optical film laminate A0, an optical film laminate D was obtained in the same manner as the production method of the optical film laminate A0 except that a PVA resin layer having a thickness of 15 ⁇ m was formed. The thickness of the obtained polarizer was 7 ⁇ m.
- Protective film A (meth) acrylic resin film having a lactone ring structure with a thickness of 40 ⁇ m was subjected to corona treatment on the easy adhesion treated surface.
- 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 “IRGACURE 819” (manufactured by BASF).
- HEAA N-hydroxyethylacrylamide
- ACMO acryloylmorpholine
- UVGACURE 819 a photoinitiator
- Polyvinyl alcohol-based forming material A A polyvinyl alcohol resin having a polymerization degree of 2500 and a saponification degree of 99.0 mol% was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight.
- Polyvinyl alcohol-based forming material B A polyvinyl alcohol resin having a polymerization degree of 500 and a saponification degree of 99.0 mol% was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight.
- Polyvinyl alcohol-based forming material C A polyvinyl alcohol resin having a polymerization degree of 2500 and a saponification degree of 89.0 mol% was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight.
- Polyvinyl alcohol-based forming material D 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 having a solid content concentration of 4% by weight.
- Polyvinyl alcohol-based forming material E 100 parts of a polyvinyl alcohol resin having a polymerization degree of 2500 and a saponification degree of 99.7 mol% and 5 parts of methylol melamine (trade name “Watersol: S-695” manufactured by DIC) as an additive were dissolved in pure water. An aqueous solution having a solid content concentration of 4% by weight was prepared.
- composition of acrylic forming material A N-hydroxyethylacrylamide (trade name “HEAA” manufactured by Kojin Co., Ltd.) 20 parts Urethane acrylate (trade name “UV-1700B” manufactured by Nippon Synthetic Chemical Co., Ltd.) 80 parts Photoradical polymerization initiator (2-methyl-1- (4-Methylthiophenyl) -2-morpholinopropan-1-one, manufactured by BASF, trade name “IRGACURE907”) 3 parts Photosensitizer (diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd., trade name “KAYACURE DETX-S” ]) 2 parts
- active energy ray irradiation As an active energy ray, visible light (gallium filled metal halide lamp) Irradiation device: Fusion UV Systems, Inc. Light HAMMER10 bulb: V bulb Peak illuminance: 1600 mW / cm 2 , integrated irradiation amount 1000 / mJ / cm 2 (wavelength 380 ⁇ 440 nm) was used. The illuminance of visible light was measured using a Sola-Check system manufactured by Solatell.
- Reference example 1 ⁇ Preparation of single protective polarizing film A> After applying the protective film to the surface of the polarizer of the optical film laminate A0 while applying the UV curable adhesive so that the thickness of the adhesive layer after curing is 0.5 ⁇ m, Energy rays were irradiated to cure the adhesive. Subsequently, the amorphous PET base material was peeled off to produce a piece protective polarizing film A0 using a thin polarizer. The optical properties of the obtained piece-protecting polarizing film A0 were a transmittance of 42.8% and a degree of polarization of 99.99%.
- Reference examples 2-4 ⁇ Production of single-protective polarizing films A1, A2, D>
- the piece protective polarizing film A1, A2 or D was obtained.
- the optical properties of the obtained piece-protecting polarizing film A1, A2 or D were a transmittance of 42.8% and a polarization degree of 99.99%.
- Reference Example 5 ⁇ Preparation of single protective polarizing film E> While applying the UV curable adhesive to the surface of one side of the polarizer E so that the thickness of the adhesive layer after curing is 0.5 ⁇ m, the protective film is pasted and then irradiated with active energy rays. The adhesive was cured to obtain a piece protective polarizing film E.
- the optical properties of the obtained piece-protecting polarizing film E were a transmittance of 42.8% and a degree of polarization of 99.99%.
- Reference Example 6 Preparation of single protective polarizing film F>
- a piece protective polarizing film F was obtained in the same manner as Reference Example 5 except that the polarizer F was used instead of the polarizer E.
- the optical properties of the obtained piece-protecting polarizing film F were a transmittance of 42.8% and a degree of polarization of 99.99%.
- Example 1 ⁇ Preparation of transparent protective single-sided polarizing film A0: corresponding to FIG. 2 (A)>
- the polyvinyl alcohol-based forming material A adjusted to 25 ° C. on the surface of the polarizer of the piece protective polarizing film A0 obtained in Reference Example 1 (the surface of the polarizer not provided with a protective film) is a wire bar coater. After coating so that the thickness after drying (not including the compatible layer) was 0.8 ⁇ m, it was dried with hot air at 80 ° C. for 30 seconds to prepare a piece-protecting polarizing film A0 with a transparent layer.
- Example 2 Comparative Examples 2 and 3
- the transparent layer in the comparative example 2 is as follows. After applying the active energy ray-curable forming material (acrylic forming material A) to a thickness of 1 ⁇ m using a wire bar coater, the active energy ray is irradiated in a nitrogen atmosphere to provide a transparent layer. A piece protective polarizing film A0 was prepared. The optical properties of the obtained piece-protecting polarizing film A0 with a transparent layer were a transmittance of 42.8% and a degree of polarization of 99.99%.
- the active energy ray-curable forming material (acrylic forming material A)
- Example 11 Comparative Examples 4 and 5 ⁇ Preparation of transparent protective film D to F with a transparent layer>
- a piece with a transparent layer was prepared in the same manner as in Example 1 except that the type of the piece protective polarizing film, the type of the transparent layer forming material, and the thickness of the transparent layer were changed as shown in Table 1.
- Protective polarizing films D to F were produced.
- the optical properties of the obtained piece-protecting polarizing films D to F with a transparent layer were a transmittance of 42.8% and a degree of polarization of 99.99%.
- Comparative Example 1 Polyvinyl alcohol-based resin containing acetoacetyl group (average polymerization degree: 1200, saponification degree: 98.5 mol%, acetoacetylation degree: 5 mol%) to 100 parts, Under temperature conditions, an aqueous solution dissolved in pure water and adjusted to a solid content concentration of 3.7% was prepared. To 100 parts of the aqueous solution, 18 parts of an alumina colloid aqueous solution (average particle diameter 15 nm, solid content concentration 10%, positive charge) was added to prepare an aqueous adhesive.
- IPA copolymerized PET amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA copolymerized PET) film (thickness: 100 ⁇ m) having a water absorption of 0.75% and Tg of 75 ° C. is subjected to corona treatment.
- the water-based adhesive is applied to the surface of the polarizer of the single protective polarizing film A0 (the surface of the polarizer not provided with the protective film) so that the film thickness becomes 0.1 ⁇ m, and the PVA resin layer surface of the laminate And then dried at 60 ° C. for 1 minute. Then, the piece protection polarizing film with a transparent layer was produced by peeling the PET film of a base material.
- Reference Example 7 ⁇ Preparation of single protective polarizing film (lamination) B>
- the protective film was bonded to the surface of the polarizer of the optical film laminate A0 while applying the ultraviolet curable adhesive so that the thickness of the adhesive layer after curing was 0.5 ⁇ m. Furthermore, after applying the protective film on the surface of the protective film while applying the ultraviolet curable adhesive so that the thickness of the adhesive layer after curing is 0.5 ⁇ m, as an active energy ray, The adhesive was cured by irradiating with ultraviolet rays. Subsequently, the amorphous PET base material was peeled off, and a single protective polarizing film (lamination) B using a thin polarizer was produced.
- the optical properties of the obtained piece-protecting polarizing film (laminate) B were a transmittance of 42.8% and a polarization degree of 99.99%.
- Example 13 Manufacturing a single protective polarizing film (lamination) with a transparent layer: corresponding to FIG.
- the polyvinyl alcohol-based forming material A adjusted to 25 ° C. is wired on the surface of the polarizer of the piece protective polarizing film (laminated) B obtained in Reference Example 7 (the surface of the polarizer provided with no protective film). After coating with a bar coater such that the thickness after drying was 0.7 ⁇ m, it was dried with hot air at 60 ° C. for 1 minute to produce a single protective polarizing film (laminated) B with a transparent layer.
- the optical properties of the obtained piece-protecting polarizing film (lamination) B with a transparent layer were a transmittance of 42.8% and a degree of polarization of 99.99%.
- Example 14 ⁇ Preparation of both protective polarizing films C with a transparent layer: corresponding to FIG. 2 (C)>
- the protective film is laminated on the surface of the transparent layer of the transparent protective film A0 with the transparent layer while applying the UV curable adhesive so that the thickness of the adhesive layer after curing is 0.5 ⁇ m. Thereafter, ultraviolet rays were applied as active energy rays to cure the adhesive.
- the optical properties of the obtained both protective polarizing films C with a transparent layer were a transmittance of 42.8% and a degree of polarization of 99.99%.
- Reference Example 8 ⁇ Preparation of both protective polarizing films C>
- the thickness of the adhesive layer after curing the ultraviolet curable adhesive on the surface of the polarizer of the piece protective polarizing film A0 obtained in Reference Example 1 (the surface of the polarizer provided with no protective film) is 0.
- the adhesive film was cured by applying ultraviolet rays as active energy rays after laminating the protective film while coating to a thickness of 5 ⁇ m.
- the optical properties of the obtained both protective polarizing films C were a transmittance of 42.8% and a degree of polarization of 99.99%.
- FTIR Fourier transform infrared spectrophotometer
- SPECTRUM2000 the total reflection attenuation spectroscopy using the polarized light as the measurement light for the polarizers obtained in the examples and comparative examples
- the intensity of the boric acid peak (665 cm ⁇ 1 ) and the intensity of the reference peak (2941 cm ⁇ 1 ) were measured by ATR) measurement.
- the boric acid content index was calculated from the obtained boric acid peak intensity and the reference peak intensity by the following formula, and the boric acid content (% by weight) was determined from the calculated boric acid index by the following formula.
- the acrylic pressure-sensitive adhesive solution is uniformly applied to the surface of a polyethylene terephthalate film (separator film) treated with a silicone-based release agent with a fountain coater and dried in an air circulation type thermostatic oven at 155 ° C. for 2 minutes. Then, an adhesive layer having a thickness of 20 ⁇ m was formed on the surface of the separator film.
- the thickness of the compatible layer was measured by TOF-SIMS equipped with a gas cluster ion gun.
- FT-IR Fourier transform infrared spectrophotometer
- ATR total reflection attenuation
- the orientation function was calculated according to the following procedure. The measurement was carried out with the measured polarized light at 0 ° and 90 ° with respect to the stretching direction of the polarizer. Using the intensity of 2941 cm ⁇ 1 of the obtained spectrum, calculation was performed according to the following (formula).
- the peak at 2941 cm ⁇ 1 is said to be absorption due to vibration of “—CH 2 —”. When there is no “—CH 2 —” in the main chain of the material used for the transparent layer, it can be evaluated by replacing with a spectrum caused by vibration of the main chain.
- the obtained polarizing film with a pressure-sensitive adhesive layer has a longitudinal absorption axis direction, is cut into a size of 100 mm ⁇ 100 mm in length, and is pasted on a non-alkali glass having a thickness of 1.3 mm, and then in an environment of 85 ° C. for 500 hours. I put it in. Thereafter, the size of the polarizing film was measured. From the obtained results, the dimensional change rate% in the absorption axis direction was calculated by the following formula.
- the rate of dimensional change was determined based on the criteria shown below with respect to the case where a transparent layer was not provided (Reference Examples 1 to 8), in the polarizing film having the same configuration.
- the dimensional change suppression effect was calculated by the following formula. 100- ⁇ (dimensional change rate) / (standard change rate) ⁇ 100 ⁇ (%) X: The effect of suppressing dimensional change is less than 10%.
- ⁇ The effect of suppressing dimensional change is 10% or more and less than 15%.
- ⁇ Suppression effect of dimensional change is 15% or more and less than 20%.
- ⁇ Crack resistance> The obtained polarizing film with a pressure-sensitive adhesive layer was cut into a size of 400 mm long ⁇ 708 mm wide (absorption axis direction is 400 mm) and 708 mm long ⁇ 400 mm wide (absorption axis direction is 708 mm), 402 mm long ⁇ 710 mm wide ⁇
- a sample was prepared by pasting both sides of a non-alkali glass having a thickness of 1.3 mm in the crossed Nicols direction. The sample was put into an oven at 95 ° C. for 250 hours, and then taken out, and it was visually confirmed whether or not a crack was generated in the polarizing film with the pressure-sensitive adhesive layer.
- the number of cracks generated is 6 or more.
- ⁇ 3 to 5 cracks were generated.
- ⁇ The number of cracks generated is 1-2. (Double-circle): There is no crack generation.
- 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 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.
- Table 1 describes the rate of change in the degree of polarization, and the rate of change was determined according to the following criteria.
- WS indicates methylolmelamine: watersol S-695 (manufactured by DIC)).
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Abstract
Description
前記偏光子はポリビニルアルコール系樹脂を含有し、厚みが15μm以下であって、
前記偏光子における前記透明層の側には、前記透明層との相溶層を有しており、
前記偏光子の厚みAと前記相溶層の厚みBは、一般式:(100×B/A)≧1、を満たすことを特徴とする偏光フィルム、に関する。 That is, the present invention is a polarizing film having a transparent layer on at least one side of a polarizer,
The polarizer contains a polyvinyl alcohol resin and has a thickness of 15 μm or less,
On the side of the transparent layer in the polarizer, it has a compatible layer with the transparent layer,
The thickness A of the polarizer and the thickness B of the compatible layer relate to a polarizing film characterized by satisfying the general formula: (100 × B / A) ≧ 1.
前記偏光子は、ポリビニルアルコール系樹脂を含有し、厚みが15μm以下であり、
前記偏光子における前記透明層の側には、前記偏光子の他の部分よりもホウ酸濃度が相対的に低いホウ酸低濃度層を有しており、
前記偏光子の厚みAと前記ホウ酸低濃度層の厚みCは、一般式:(100×C/A)≧1、を満たすことを特徴とする偏光フィルム、に関する。 The present invention is also a polarizing film having a transparent layer on at least one side of the polarizer,
The polarizer contains a polyvinyl alcohol-based resin and has a thickness of 15 μm or less.
On the side of the transparent layer in the polarizer, it has a boric acid low-concentration layer in which the boric acid concentration is relatively lower than other parts of the polarizer,
The thickness A of the polarizer and the thickness C of the low concentration layer of boric acid relate to a polarizing film characterized by satisfying the general formula: (100 × C / A) ≧ 1.
P>-(100.929T-42.4-1)×100(ただし、T<42.3)、又は、
P≧99.9(ただし、T≧42.3)表される範囲にあることが好ましい。 In the polarizing film, the polarizer has an optical property represented by the following formula: P> − (10 0.929T-42.4 −1) × 100 (where T < 42.3) or
It is preferably in the range represented by P ≧ 99.9 (however, T ≧ 42.3).
偏光子は、特に限定されず、各種のものを使用できる。偏光子としては、例えば、ポリビニルアルコール系フィルム、部分ホルマール化ポリビニルアルコール系フィルム、エチレン・酢酸ビニル共重合体系部分ケン化フィルム等の親水性高分子フィルムに、ヨウ素や二色性染料の二色性物質を吸着させて一軸延伸したもの、ポリビニルアルコールの脱水処理物やポリ塩化ビニルの脱塩酸処理物等ポリエン系配向フィルム等が挙げられる。これらの中でも、ポリビニルアルコール系フィルムとヨウ素などの二色性物質からなる偏光子が好適である。 <Polarizer>
The polarizer is not particularly limited, and various types can be used. Examples of polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films. Examples thereof include polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products. Among these, a polarizer composed of a polyvinyl alcohol film and a dichroic material such as iodine is preferable.
特許第4751486号明細書、
特許第4751481号明細書、
特許第4815544号明細書、
特許第5048120号明細書、
特許第5587517号明細書、
国際公開第2014/077599号パンフレット、
国際公開第2014/077636号パンフレット、
等に記載されている薄型偏光子またはこれらに記載の製造方法から得られる薄型偏光子を挙げることができる。 As a thin polarizer having a thickness of 15 μm or less, typically,
Patent No. 4751486,
Japanese Patent No. 4751481,
Patent No. 4815544,
Patent No. 5048120,
Japanese Patent No. 5587517,
International Publication No. 2014/077599 pamphlet,
International Publication No. 2014/077636 Pamphlet,
And the thin polarizers obtained from the production methods described therein.
P>-(100.929T-42.4-1)×100(ただし、T<42.3)、又は、
P≧99.9(ただし、T≧42.3)の条件を満足するように構成されたことが好ましい。前記条件を満足するように構成された偏光子は、一義的には、大型表示素子を用いた液晶テレビ用のディスプレイとして求められる性能を有する。具体的にはコントラスト比1000:1以上かつ最大輝度500cd/m2以上である。他の用途としては、例えば有機EL表示装置の視認側に貼り合される。 The polarizer 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 preferably 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.
なお、図1(B)に示した樹脂基材(延伸用樹脂基材)は、前記薄型偏光子の製造に適用されたものを用いることができる。樹脂基材の形成材料としては、各種の熱可塑性樹脂を用いることができる。熱可塑性樹脂としては、例えば、ポリエチレンテレフタレート系樹脂等のエステル系樹脂、ノルボルネン系樹脂等のシクロオレフィン系樹脂、ポリプロピレン等のオレフィン系樹脂、ポリアミドレオ樹脂、ポリカーボネート系樹脂、これらの共重合樹脂等が挙げられる。これらのなかでも製造のしやすさ及びコスト軽減の点から、エステル系樹脂が好ましい。エステル系熱可塑性樹脂基材は、非晶性エステル系熱可塑性樹脂基材または結晶性エステル系熱可塑性樹脂基材を用いることができる。 <Resin substrate>
In addition, what was applied to manufacture of the said thin polarizer can be used for the resin base material (resin base material for extending | stretching) shown to FIG. 1 (B). Various thermoplastic resins can be used as the material for forming the resin base material. Examples of the thermoplastic resin include ester resins such as polyethylene terephthalate resins, cycloolefin resins such as norbornene resins, olefin resins such as polypropylene, polyamide rheo resins, polycarbonate resins, and copolymer resins thereof. Can be mentioned. Of these, ester resins are preferred from the viewpoint of ease of production and cost reduction. As the ester-based thermoplastic resin substrate, an amorphous ester-based thermoplastic resin substrate or a crystalline ester-based thermoplastic resin substrate can be used.
前記保護フィルムを構成する材料としては、透明性、機械的強度、熱安定性、水分遮断性、等方性などに優れるものが好ましい。例えば、ポリエチレンテレフタレートやポリエチレンナフタレートなどのポリエステル系ポリマー、ジアセチルセルロースやトリアセチルセルロースなどのセルロース系ポリマー、ポリメチルメタクリレートなどのアクリル系ポリマー、ポリスチレンやアクリロニトリル・スチレン共重合体(AS樹脂)などのスチレン系ポリマー、ポリカーボネート系ポリマー等が挙げられる。また、ポリエチレン、ポリプロピレン、シクロ系ないしはノルボルネン構造を有するポリオレフィン、エチレン・プロピレン共重合体の如きポリオレフィン系ポリマー、塩化ビニル系ポリマー、ナイロンや芳香族ポリアミドなどのアミド系ポリマー、イミド系ポリマー、スルホン系ポリマー、ポリエーテルスルホン系ポリマー、ポリエーテルエーテルケトン系ポリマー、ポリフェニレンスルフィド系ポリマー、ビニルアルコール系ポリマー、塩化ビニリデン系ポリマー、ビニルブチラール系ポリマー、アリレート系ポリマー、ポリオキシメチレン系ポリマー、エポキシ系ポリマー、または上記ポリマーのブレンド物なども上記保護フィルムを形成するポリマーの例として挙げられる。 <Protective film>
As the material constituting the protective film, a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is preferable. For example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin) And polymers based on polycarbonate and polycarbonate. In addition, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or the above Polymer blends and the like can also be mentioned as examples of the polymer forming the protective film.
前記保護フィルムと偏光子は接着剤層、粘着剤層、下塗り層(プライマー層)などの介在層を介して積層される。この際、介在層により両者を空気間隙なく積層することが望ましい。 <Intervening layer>
The protective film and the polarizer are laminated via an intervening layer such as an adhesive layer, an 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.
透明層は、各種の形成材から形成することができる。透明層の形成材料としては、例えば、ポリエステル系樹脂、ポリエーテル系樹脂、ポリカーボネート系樹脂、ポリウレタン系樹脂、シリコーン系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、PVA系樹脂、アクリル系樹脂等を挙げることができる。これら樹脂材料は1種を単独で又は2種以上を組み合わせて用いることができるが、これらの中でもポリウレタン系樹脂、PVA系樹脂からなる群から選択される1種以上が好ましく、PVA系樹脂がより好ましい。また、前記樹脂の形態は、水系、溶剤系のいずれでもよい。前記樹脂の形態は、水系樹脂が好ましく、PVA系樹脂が好ましい。また、水系樹脂としては、アクリル樹脂水溶液やウレタン樹脂水溶液を用いることができる。 <Transparent layer>
The transparent layer can be formed from various forming materials. Examples of the material for forming the transparent layer include polyester resins, polyether resins, polycarbonate resins, polyurethane resins, silicone resins, polyamide resins, polyimide resins, PVA resins, and acrylic resins. Can do. These resin materials can be used alone or in combination of two or more. Among these, one or more selected from the group consisting of polyurethane resins and PVA resins are preferable, and PVA resins are more preferable. preferable. The form of the resin may be either water-based or solvent-based. The resin is preferably a water-based resin, and is preferably a PVA-based resin. As the water-based resin, an acrylic resin aqueous solution or a urethane resin aqueous solution can be used.
前記偏光フィルムには粘着剤層を設けて、粘着剤層付偏光フィルムとして用いることができる。粘着剤層は、偏光フィルムの透明層または偏光子の側に、また、保護フィルムを有する場合には保護フィルムに設けることができる。粘着剤層付偏光フィルムの粘着剤層にはセパレータを設けることができる。 <Adhesive layer>
The polarizing film can be used as a polarizing film with an adhesive layer by providing an adhesive layer. The pressure-sensitive adhesive layer can be provided on the transparent layer or polarizer side of the polarizing film, or in the case of having a protective film. A separator can be provided in the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer.
偏光フィルムには、表面保護フィルムを設けることができる。表面保護フィルムは、通常、基材フィルムおよび粘着剤層を有し、当該粘着剤層を介して偏光子を保護する。 <Surface protection film>
A surface protective film can be provided on the polarizing film. The surface protective film usually has a base film and an adhesive layer, and protects the polarizer via the adhesive layer.
本発明の偏光フィルムは、実用に際して他の光学層と積層した光学フィルムとして用いることができる。その光学層については特に限定はないが、例えば反射板や半透過板、位相差板(1/2や1/4などの波長板を含む)、視角補償フィルムなどの液晶表示装置などの形成に用いられることのある光学層を1層または2層以上用いることができる。特に、本発明の偏光フィルムに更に反射板または半透過反射板が積層されてなる反射型偏光フィルムまたは半透過型偏光フィルム、偏光フィルムに更に位相差板が積層されてなる楕円偏光フィルムまたは円偏光フィルム、偏光フィルムに更に視角補償フィルムが積層されてなる広視野角偏光フィルム、あるいは偏光フィルムに更に輝度向上フィルムが積層されてなる偏光フィルムが好ましい。 <Other optical layers>
The polarizing film of the present invention can be used as an optical film laminated with another optical layer in practical use. The optical layer is not particularly limited. For example, for forming a liquid crystal display device such as a reflection plate, a semi-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), and a viewing angle compensation film. One or more optical layers that may be used can be used. In particular, a reflective polarizing film or semi-transmissive polarizing film in which a polarizing plate or a semi-transmissive reflecting plate is further laminated on the polarizing film of the present invention, an elliptical polarizing film or circularly polarizing film in which a retardation film is further laminated on a polarizing film. A wide viewing angle polarizing film obtained by further laminating a viewing angle compensation film on a film or a polarizing film, or a polarizing film obtained by further laminating a brightness enhancement film on the polarizing film is preferred.
吸水率0.75%、Tg75℃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%)およびアセトアセチル変性PVA(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、日本合成化学工業社製、商品名「ゴーセファイマーZ200」)を9:1の比で含む水溶液を25℃で塗布および乾燥して、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A0を得た。 <Preparation of optical film laminate A0>
One side of an amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA copolymerized PET) film (thickness: 100 μm) having a water absorption of 0.75% and Tg of 75 ° C. is subjected to corona treatment. Alcohol (polymerization degree 4200, saponification degree 99.2 mol%) and acetoacetyl-modified PVA (polymerization degree 1200, acetoacetyl modification degree 4.6%, saponification degree 99.0 mol% or more, manufactured by Nippon Synthetic Chemical Industry Co., Ltd. An aqueous solution containing 9: 1 ratio of the trade name “Gosefimer Z200”) was applied and dried at 25 ° C. to form a PVA-based resin layer having a thickness of 11 μm, thereby preparing a laminate.
The obtained laminate was uniaxially stretched in the longitudinal direction (longitudinal direction) 2.0 times between rolls having different peripheral speeds in an oven at 120 ° C. (air-assisted stretching process).
Next, the laminate was immersed in an insolubilization bath (a boric acid aqueous solution obtained by blending 4 parts by weight of boric acid with respect to 100 parts by weight of water) for 30 seconds (insolubilization treatment).
Subsequently, it was immersed in a dyeing bath having a liquid temperature of 30 ° C. while adjusting the iodine concentration and the immersion time so that the polarizing plate had a predetermined transmittance. In this example, 0.2 parts by weight of iodine was blended with 100 parts by weight of water, and immersed in an aqueous iodine solution obtained by blending 1.0 part by weight of potassium iodide (dyeing treatment). .
Subsequently, it was immersed for 30 seconds in a crosslinking bath having a liquid temperature of 30 ° C. (a boric acid aqueous solution obtained by blending 3 parts by weight of potassium iodide and 3 parts by weight of boric acid with respect to 100 parts by weight of water). (Crosslinking treatment).
Thereafter, the laminate was immersed in a boric acid aqueous solution (an aqueous solution obtained by blending 4 parts by weight of boric acid and 5 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 70 ° C. However, uniaxial stretching was performed between rolls having different peripheral speeds in the longitudinal direction (longitudinal direction) so that the total stretching ratio was 5.5 times (in-water stretching treatment).
Thereafter, the laminate was immersed in a cleaning bath (an aqueous solution obtained by blending 4 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 30 ° C. (cleaning treatment).
Thus, an optical film laminate A0 including a polarizer having a thickness of 5 μm was obtained.
光学フィルム積層体A0の作製において、水中延伸処理におけるホウ酸水溶液に配合したホウ酸を3.5重量部に変えたこと以外は光学フィルム積層体A0の作製方法と同様にして光学フィルム積層体A1を得た。得られた偏光子の厚みは5μmであった。 <Preparation of optical film laminate A1>
In the production of the optical film laminate A0, the optical film laminate A1 was prepared in the same manner as the production method of the optical film laminate A0 except that boric acid blended in the boric acid aqueous solution in the underwater stretching treatment was changed to 3.5 parts by weight. Got. The thickness of the obtained polarizer was 5 μm.
光学フィルム積層体A0の作製において、水中延伸処理におけるホウ酸水溶液に配合したホウ酸を4.5重量部に変えたこと以外は光学フィルム積層体A0の作製方法と同様にして光学フィルム積層体A2を得た。得られた偏光子の厚みは5μmであった。 <Preparation of optical film laminate A2>
In the production of the optical film laminate A0, the optical film laminate A2 was produced in the same manner as the production method of the optical film laminate A0 except that boric acid blended in the boric acid aqueous solution in the underwater stretching treatment was changed to 4.5 parts by weight. Got. The thickness of the obtained polarizer was 5 μm.
光学フィルム積層体A0の作製において、厚み15μmのPVA系樹脂層を形成したこと以外は光学フィルム積層体A0の作製方法と同様にして光学フィルム積層体Dを得た。得られた偏光子の厚みは7μmであった。 <Preparation of optical film laminate D>
In the production of the optical film laminate A0, an optical film laminate D was obtained in the same manner as the production method of the optical film laminate A0 except that a PVA resin layer having a thickness of 15 μm was formed. The thickness of the obtained polarizer was 7 μm.
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Eを得た。得られた偏光子の厚みは12μmであった。 <Production of Polarizer E>
A polyvinyl alcohol film having an average polymerization degree of 2400 and a saponification degree of 99.9 mol% and a thickness of 30 μm was immersed in warm water at 30 ° C. for 60 seconds to swell. Next, the film was dyed while being immersed in an aqueous solution of 0.3% concentration of iodine / potassium iodide (weight ratio = 0.5 / 8) and stretched to 3.5 times. Then, it extended | stretched so that the total draw ratio might be 6 time in 65 degreeC borate ester aqueous solution. After extending | stretching, it dried for 3 minutes in 40 degreeC oven, and obtained the PVA-type polarizer E. FIG. The thickness of the obtained polarizer was 12 μm.
平均重合度2400、ケン化度99.9モル%の厚み75μm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Fを得た。得られた偏光子の厚みは23μmであった。 <Preparation of polarizer F>
A polyvinyl alcohol film having an average polymerization degree of 2400 and a saponification degree of 99.9 mol% and a thickness of 75 μm was immersed in warm water at 30 ° C. for 60 seconds to swell. Next, the film was dyed while being immersed in an aqueous solution of 0.3% concentration of iodine / potassium iodide (weight ratio = 0.5 / 8) and stretched to 3.5 times. Then, it extended | stretched so that the total draw ratio might be 6 time in 65 degreeC borate ester aqueous solution. After stretching, drying was performed in an oven at 40 ° C. for 3 minutes to obtain a PVA polarizer F. The thickness of the obtained polarizer was 23 μm.
保護フィルム: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て用いた。 (Preparation of protective film)
Protective film: A (meth) acrylic resin film having a lactone ring structure with a thickness of 40 μm was subjected to corona treatment on the easy adhesion treated surface.
N-ヒドロキシエチルアクリルアミド(HEAA)40重量部とアクリロイルモルホリン(ACMO)60重量部と光開始剤「IRGACURE 819」(BASF社製)3重量部を混合し、紫外線硬化型接着剤を調製した。 (Production of adhesive to be applied to 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 “IRGACURE 819” (manufactured by BASF).
重合度2500、ケン化度99.0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%の水溶液を調製した。 (Polyvinyl alcohol-based forming material A)
A polyvinyl alcohol resin having a polymerization degree of 2500 and a saponification degree of 99.0 mol% was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight.
重合度500、ケン化度99.0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%の水溶液を調製した。 (Polyvinyl alcohol-based forming material B)
A polyvinyl alcohol resin having a polymerization degree of 500 and a saponification degree of 99.0 mol% was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight.
重合度2500、ケン化度89.0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%の水溶液を調製した。 (Polyvinyl alcohol-based forming material C)
A polyvinyl alcohol resin having a polymerization degree of 2500 and a saponification degree of 89.0 mol% was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight.
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%の水溶液を調製した。 (Polyvinyl alcohol-based forming material D)
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 having a solid content concentration of 4% by weight.
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100部と、添加剤としてメチロールメラミン(DIC社製、商品名「ウォーターゾル:S-695」)5部とを純水に溶解し、固形分濃度4重量%の水溶液を調製した。 (Polyvinyl alcohol-based forming material E)
100 parts of a polyvinyl alcohol resin having a polymerization degree of 2500 and a saponification degree of 99.7 mol% and 5 parts of methylol melamine (trade name “Watersol: S-695” manufactured by DIC) as an additive were dissolved in pure water. An aqueous solution having a solid content concentration of 4% by weight was prepared.
N-ヒドロキシエチルアクリルアミド(興人社製、商品名「HEAA」) 20部
ウレタンアクリレート(日本合成化学社製、商品名「UV-1700B」) 80部
光ラジカル重合開始剤(2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン、BASF社製、商品名「IRGACURE907」) 3部
光増感剤(ジエチルチオキサントン、日本化薬社製、商品名「KAYACURE DETX-S」) 2部 (Composition of acrylic forming material A)
N-hydroxyethylacrylamide (trade name “HEAA” manufactured by Kojin Co., Ltd.) 20 parts Urethane acrylate (trade name “UV-1700B” manufactured by Nippon Synthetic Chemical Co., Ltd.) 80 parts Photoradical polymerization initiator (2-methyl-1- (4-Methylthiophenyl) -2-morpholinopropan-1-one, manufactured by BASF, trade name “IRGACURE907”) 3 parts Photosensitizer (diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd., trade name “KAYACURE DETX-S” ]) 2 parts
上記アクリル系形成材を混合して50℃で1時間撹拌して、各種の活性エネルギー線硬化型形成材を調製した。 (Preparation of active energy ray-curable forming material)
The acrylic forming material was mixed and stirred at 50 ° C. for 1 hour to prepare various active energy ray-curable forming materials.
活性エネルギー線として、可視光線(ガリウム封入メタルハライドランプ) 照射装置:Fusion UV Systems,Inc社製Light HAMMER10 バルブ:Vバルブ ピーク照度:1600mW/cm2、積算照射量1000/mJ/cm2(波長380~440nm)を使用した。なお、可視光線の照度は、Solatell社製Sola-Checkシステムを使用して測定した。 (Active energy ray irradiation)
As an active energy ray, visible light (gallium filled metal halide lamp) Irradiation device: Fusion UV Systems, Inc. Light HAMMER10 bulb: V bulb Peak illuminance: 1600 mW / cm 2 , integrated irradiation amount 1000 / mJ / cm 2 (wavelength 380˜ 440 nm) was used. The illuminance of visible light was measured using a Sola-Check system manufactured by Solatell.
<片保護偏光フィルムAの作製>
上記光学フィルム積層体A0の偏光子の表面に、上記紫外線硬化型接着剤を硬化後の接着剤層の厚みが0.5μmとなるように塗布しながら、上記保護フィルムを貼合せたのち、活性エネルギー線を照射し、接着剤を硬化させた。次いで、非晶性PET基材を剥離し、薄型偏光子を用いた片保護偏光フィルムA0を作製した。得られた片保護偏光フィルムA0の光学特性は、透過率42.8%、偏光度99.99%であった。 Reference example 1
<Preparation of single protective polarizing film A>
After applying the protective film to the surface of the polarizer of the optical film laminate A0 while applying the UV curable adhesive so that the thickness of the adhesive layer after curing is 0.5 μm, Energy rays were irradiated to cure the adhesive. Subsequently, the amorphous PET base material was peeled off to produce a piece protective polarizing film A0 using a thin polarizer. The optical properties of the obtained piece-protecting polarizing film A0 were a transmittance of 42.8% and a degree of polarization of 99.99%.
<片保護偏光フィルムA1、A2、Dの作製>
参考例1において、光学フィルム積層体A0の代わりに、光学フィルム積層体A1、A2またはDを用いたこと以外は、片保護偏光フィルムA0の作製方法と同様にして片保護偏光フィルムA1、A2またはDを得た。得られた片保護偏光フィルムA1、A2またはDの光学特性は、透過率42.8%、偏光度99.99%であった。 Reference examples 2-4
<Production of single-protective polarizing films A1, A2, D>
In Reference Example 1, except that the optical film laminate A1, A2 or D was used instead of the optical film laminate A0, the piece protective polarizing film A1, A2 or D was obtained. The optical properties of the obtained piece-protecting polarizing film A1, A2 or D were a transmittance of 42.8% and a polarization degree of 99.99%.
<片保護偏光フィルムEの作製>
偏光子Eの片側表面に、上記紫外線硬化型接着剤を硬化後の接着剤層の厚みが0.5μmとなるように塗布しながら、上記保護フィルムを貼合せたのち、活性エネルギー線を照射し、接着剤を硬化させ片保護偏光フィルムEを得た。得られた片保護偏光フィルムEの光学特性は、透過率42.8%、偏光度99.99%であった。 Reference Example 5
<Preparation of single protective polarizing film E>
While applying the UV curable adhesive to the surface of one side of the polarizer E so that the thickness of the adhesive layer after curing is 0.5 μm, the protective film is pasted and then irradiated with active energy rays. The adhesive was cured to obtain a piece protective polarizing film E. The optical properties of the obtained piece-protecting polarizing film E were a transmittance of 42.8% and a degree of polarization of 99.99%.
<片保護偏光フィルムFの作製>
参考例5において、偏光子Eの代わりに、偏光子Fを用いたこと以外は参考例5と同様にして、片保護偏光フィルムFを得た。得られた片保護偏光フィルムFの光学特性は、透過率42.8%、偏光度99.99%であった。 Reference Example 6
<Preparation of single protective polarizing film F>
In Reference Example 5, a piece protective polarizing film F was obtained in the same manner as Reference Example 5 except that the polarizer F was used instead of the polarizer E. The optical properties of the obtained piece-protecting polarizing film F were a transmittance of 42.8% and a degree of polarization of 99.99%.
<透明層付の片保護偏光フィルムA0の作製:図2(A)に対応>
参考例1で得られた、上記片保護偏光フィルムA0の偏光子の面(保護フィルムが設けられていない偏光子面)に、25℃に調整した上記ポリビニルアルコール系形成材Aをワイヤーバーコーターで乾燥後の厚み(相溶層を含まない)が0.8μmになるように塗布した後、80℃で30秒間熱風乾燥して、透明層付の片保護偏光フィルムA0を作製した。 Example 1
<Preparation of transparent protective single-sided polarizing film A0: corresponding to FIG. 2 (A)>
The polyvinyl alcohol-based forming material A adjusted to 25 ° C. on the surface of the polarizer of the piece protective polarizing film A0 obtained in Reference Example 1 (the surface of the polarizer not provided with a protective film) is a wire bar coater. After coating so that the thickness after drying (not including the compatible layer) was 0.8 μm, it was dried with hot air at 80 ° C. for 30 seconds to prepare a piece-protecting polarizing film A0 with a transparent layer.
実施例1において、透明層の形成材の種類、透明層の厚みを表1に示すように変えたこと以外は、実施例1と同様にして、透明層付の片保護偏光フィルムA0、A1またはA2を作製した。
なお、比較例2における透明層は下記のとおりである。
上記活性エネルギー線硬化型形成材(アクリル系形成材A)をワイヤーバーコーターを用いて、厚み1μmになるように塗工した後、窒素雰囲気下で活性エネルギー線を照射することで、透明層付の片保護偏光フィルムA0を作製した。得られた透明層付の片保護偏光フィルムA0の光学特性は、いずれも透過率42.8%、偏光度99.99%であった。 Examples 2 to 10, Comparative Examples 2 and 3
In Example 1, except that the type of the transparent layer forming material and the thickness of the transparent layer were changed as shown in Table 1, in the same manner as in Example 1, the piece-protecting polarizing film A0, A1 with a transparent layer or A2 was produced.
In addition, the transparent layer in the comparative example 2 is as follows.
After applying the active energy ray-curable forming material (acrylic forming material A) to a thickness of 1 μm using a wire bar coater, the active energy ray is irradiated in a nitrogen atmosphere to provide a transparent layer. A piece protective polarizing film A0 was prepared. The optical properties of the obtained piece-protecting polarizing film A0 with a transparent layer were a transmittance of 42.8% and a degree of polarization of 99.99%.
<透明層付の片保護偏光フィルムD乃至Fの作製>
実施例1において、片保護偏光フィルムの種類、透明層の形成材の種類、透明層の厚みを表1に示すように変えたこと以外は、実施例1と同様にして、透明層付の片保護偏光フィルムD乃至Fを作製した。得られた透明層付の片保護偏光フィルムD乃至Fの光学特性は、透過率42.8%、偏光度99.99%であった。 Examples 11 and 12, Comparative Examples 4 and 5
<Preparation of transparent protective film D to F with a transparent layer>
In Example 1, a piece with a transparent layer was prepared in the same manner as in Example 1 except that the type of the piece protective polarizing film, the type of the transparent layer forming material, and the thickness of the transparent layer were changed as shown in Table 1. Protective polarizing films D to F were produced. The optical properties of the obtained piece-protecting polarizing films D to F with a transparent layer were a transmittance of 42.8% and a degree of polarization of 99.99%.
(水系接着剤の作製)
アセトアセチル基を含有するポリビニルアルコール系樹脂(平均重合度:1200,ケン化度:98.5モル%,アセトアセチル化度:5モル%)100部に対し、メチロールメラミン50部を、30℃の温度条件下に、純水に溶解し、固形分濃度3.7%に調整した水溶液を調製した。前記水溶液100部に対し、アルミナコロイド水溶液(平均粒子径15nm,固形分濃度10%,正電荷)18部を加えて水系接着剤を調製した。 Comparative Example 1
(Production of water-based adhesive)
Polyvinyl alcohol-based resin containing acetoacetyl group (average polymerization degree: 1200, saponification degree: 98.5 mol%, acetoacetylation degree: 5 mol%) to 100 parts, Under temperature conditions, an aqueous solution dissolved in pure water and adjusted to a solid content concentration of 3.7% was prepared. To 100 parts of the aqueous solution, 18 parts of an alumina colloid aqueous solution (average particle diameter 15 nm,
吸水率0.75%、Tg75℃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2500,ケン化度99.0モル%)を含む水溶液を25℃で塗布および乾燥して、厚み1μmのPVA樹脂層を形成し、積層体を作製した。次いで片保護偏光フィルムA0の偏光子の面(保護フィルムが設けられていない偏光子面)に上記水系接着剤を膜厚が0.1μmとなるように塗工し、上記積層体のPVA樹脂層面に貼り合せた後、60℃で1分間乾燥した。その後、基材のPETフィルムを剥離することで、透明層付の片保護偏光フィルムを作製した。 (Preparation of polarizing film)
One side of an amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA copolymerized PET) film (thickness: 100 μm) having a water absorption of 0.75% and Tg of 75 ° C. is subjected to corona treatment. An aqueous solution containing alcohol (polymerization degree 2500, saponification degree 99.0 mol%) was applied and dried at 25 ° C. to form a PVA resin layer having a thickness of 1 μm, thereby producing a laminate. Next, the water-based adhesive is applied to the surface of the polarizer of the single protective polarizing film A0 (the surface of the polarizer not provided with the protective film) so that the film thickness becomes 0.1 μm, and the PVA resin layer surface of the laminate And then dried at 60 ° C. for 1 minute. Then, the piece protection polarizing film with a transparent layer was produced by peeling the PET film of a base material.
<片保護偏光フィルム(積層)Bの作製>
上記光学フィルム積層体A0の偏光子の表面に、上記紫外線硬化型接着剤を硬化後の接着剤層の厚みが0.5μmとなるように塗布しながら、上記保護フィルムを貼合せた。さらに、前記保護フィルムの表面に、上記紫外線硬化型接着剤を硬化後の接着剤層の厚みが0.5μmとなるように塗布しながら、上記保護フィルムを貼合せた後、活性エネルギー線として、紫外線を照射し、接着剤を硬化させた。
次いで、非晶性PET基材を剥離し、薄型偏光子を用いた片保護偏光フィルム(積層)Bを作製した。得られた片保護偏光フィルム(積層)Bの光学特性は、透過率42.8%、偏光度99.99%であった。 Reference Example 7
<Preparation of single protective polarizing film (lamination) B>
The protective film was bonded to the surface of the polarizer of the optical film laminate A0 while applying the ultraviolet curable adhesive so that the thickness of the adhesive layer after curing was 0.5 μm. Furthermore, after applying the protective film on the surface of the protective film while applying the ultraviolet curable adhesive so that the thickness of the adhesive layer after curing is 0.5 μm, as an active energy ray, The adhesive was cured by irradiating with ultraviolet rays.
Subsequently, the amorphous PET base material was peeled off, and a single protective polarizing film (lamination) B using a thin polarizer was produced. The optical properties of the obtained piece-protecting polarizing film (laminate) B were a transmittance of 42.8% and a polarization degree of 99.99%.
<透明層付の片保護偏光フィルム(積層)を作製:図2(B)に対応>
参考例7で得られた、上記片保護偏光フィルム(積層)Bの偏光子の面(保護フィルムが設けられていない偏光子面)に、25℃に調整した上記ポリビニルアルコール系形成材Aをワイヤーバーコーターで乾燥後の厚みが0.7μmになるように塗布した後、60℃で1分間熱風乾燥して、透明層付の片保護偏光フィルム(積層)Bを作製した。得られた透明層付の片保護偏光フィルム(積層)Bの光学特性は、いずれも透過率42.8%、偏光度99.99%であった。 Example 13
<Manufacturing a single protective polarizing film (lamination) with a transparent layer: corresponding to FIG.
The polyvinyl alcohol-based forming material A adjusted to 25 ° C. is wired on the surface of the polarizer of the piece protective polarizing film (laminated) B obtained in Reference Example 7 (the surface of the polarizer provided with no protective film). After coating with a bar coater such that the thickness after drying was 0.7 μm, it was dried with hot air at 60 ° C. for 1 minute to produce a single protective polarizing film (laminated) B with a transparent layer. The optical properties of the obtained piece-protecting polarizing film (lamination) B with a transparent layer were a transmittance of 42.8% and a degree of polarization of 99.99%.
<透明層付の両保護偏光フィルムCの作製:図2(C)に対応>
参考例1で得られた、上記片保護偏光フィルムA0の偏光子の面(保護フィルムが設けられていない偏光子面)に、25℃に調整した上記ポリビニルアルコール系形成材Aをワイヤーバーコーターで乾燥後の厚みが0.7μmになるように塗布した後、60℃で1分間熱風乾燥して、透明層付の片保護偏光フィルムA0を作製した。
上記透明層付の片保護偏光フィルムA0の透明層の表面に、上記紫外線硬化型接着剤を硬化後の接着剤層の厚みが0.5μmとなるように塗布しながら、上記保護フィルムを貼合せ後、活性エネルギー線として、紫外線を照射し、接着剤を硬化させた。得られた透明層付の両保護偏光フィルムCの光学特性は、透過率42.8%、偏光度99.99%であった。 Example 14
<Preparation of both protective polarizing films C with a transparent layer: corresponding to FIG. 2 (C)>
The polyvinyl alcohol-based forming material A adjusted to 25 ° C. on the surface of the polarizer of the piece protective polarizing film A0 obtained in Reference Example 1 (the surface of the polarizer not provided with a protective film) is a wire bar coater. After apply | coating so that the thickness after drying might be set to 0.7 micrometer, it dried with hot air for 1 minute at 60 degreeC, and produced the piece protection polarizing film A0 with a transparent layer.
The protective film is laminated on the surface of the transparent layer of the transparent protective film A0 with the transparent layer while applying the UV curable adhesive so that the thickness of the adhesive layer after curing is 0.5 μm. Thereafter, ultraviolet rays were applied as active energy rays to cure the adhesive. The optical properties of the obtained both protective polarizing films C with a transparent layer were a transmittance of 42.8% and a degree of polarization of 99.99%.
<両保護偏光フィルムCの作製>
参考例1で得られた、上記片保護偏光フィルムA0の偏光子の面(保護フィルムが設けられていない偏光子面)に、上記紫外線硬化型接着剤を硬化後の接着剤層の厚みが0.5μmとなるように塗布しながら、上記保護フィルムを貼合せ後、活性エネルギー線として、紫外線を照射し、接着剤を硬化させた。得られた両保護偏光フィルムCの光学特性は、透過率42.8%、偏光度99.99%であった。 Reference Example 8
<Preparation of both protective polarizing films C>
The thickness of the adhesive layer after curing the ultraviolet curable adhesive on the surface of the polarizer of the piece protective polarizing film A0 obtained in Reference Example 1 (the surface of the polarizer provided with no protective film) is 0. The adhesive film was cured by applying ultraviolet rays as active energy rays after laminating the protective film while coating to a thickness of 5 μm. The optical properties of the obtained both protective polarizing films C were a transmittance of 42.8% and a degree of polarization of 99.99%.
実施例および比較例で得られた偏光子について、フーリエ変換赤外分光光度計(FTIR)(Perkin Elmer社製、商品名「SPECTRUM2000」)を用いて、偏光を測定光とする全反射減衰分光(ATR)測定によりホウ酸ピーク(665cm-1)の強度および参照ピーク(2941cm-1)の強度を測定した。得られたホウ酸ピーク強度および参照ピーク強度からホウ酸量指数を下記式により算出し、さらに、算出したホウ酸量指数から下記式によりホウ酸含有量(重量%)を決定した。
(ホウ酸量指数)=(ホウ酸ピーク665cm-1の強度)/(参照ピーク2941cm-1の強度)
(ホウ酸含有量(重量%))=(ホウ酸量指数)×5.54+4.1 <Measurement of boric acid content in polarizer>
Using the Fourier transform infrared spectrophotometer (FTIR) (manufactured by Perkin Elmer, trade name “SPECTRUM2000”), the total reflection attenuation spectroscopy using the polarized light as the measurement light for the polarizers obtained in the examples and comparative examples ( The intensity of the boric acid peak (665 cm −1 ) and the intensity of the reference peak (2941 cm −1 ) were measured by ATR) measurement. The boric acid content index was calculated from the obtained boric acid peak intensity and the reference peak intensity by the following formula, and the boric acid content (% by weight) was determined from the calculated boric acid index by the following formula.
(Boric acid amount index) = (Intensity of boric acid peak 665 cm −1 ) / (Intensity of reference peak 2941 cm −1 )
(Boric acid content (% by weight)) = (Boric acid content index) × 5.54 + 4.1
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに、ブチルアクリレート99部およびアクリル酸4-ヒドロキシブチル1部を含有するモノマー混合物を仕込んだ。さらに、前記モノマー混合物(固形分)100部に対して、重合開始剤として2,2´-アゾビスイソブチロニトリル0.1部を酢酸エチルと共に仕込み、緩やかに攪拌しながら窒素ガスを導入して窒素置換した後、フラスコ内の液温を60℃付近に保って7時間重合反応を行った。その後、得られた反応液に、酢酸エチルを加えて、固形分濃度30%に調整した、重量平均分子量140万のアクリル系ポリマーの溶液を調製した。 <Preparation of acrylic polymer>
A monomer mixture containing 99 parts of butyl acrylate and 1 part of 4-hydroxybutyl acrylate was charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser. Furthermore, 0.1 part of 2,2′-azobisisobutyronitrile as a polymerization initiator was charged with ethyl acetate to 100 parts of the monomer mixture (solid content), and nitrogen gas was introduced while gently stirring. Then, the temperature of the liquid in the flask was kept at around 60 ° C., and a polymerization reaction was carried out for 7 hours. Then, ethyl acetate was added to the resulting reaction solution to prepare a solution of an acrylic polymer having a weight average molecular weight of 1,400,000 adjusted to a solid content concentration of 30%.
上記アクリル系ポリマー溶液の固形分100部に対して、トリメチロールプロパンキシリレンジイソシアネート(三井化学社製:タケネートD110N)0.1部と、ジベンゾイルパーオキサイド0.3部と、γ-グリシドキシプロピルメトキシシラン(信越化学工業社製:KBM-403)0.075部を配合して、アクリル系粘着剤溶液を調製した。 (Preparation of adhesive composition)
For 100 parts of the solid content of the acrylic polymer solution, 0.1 part of trimethylolpropane xylylene diisocyanate (manufactured by Mitsui Chemicals: Takenate D110N), 0.3 part of dibenzoyl peroxide, and γ-glycidoxy An acrylic pressure-sensitive adhesive solution was prepared by blending 0.075 part of propylmethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-403).
次いで、上記アクリル系粘着剤溶液を、シリコーン系剥離剤で処理されたポリエチレンテレフタレートフィルム(セパレータフィルム)の表面に、ファウンテンコータで均一に塗工し、155℃の空気循環式恒温オーブンで2分間乾燥し、セパレータフィルムの表面に厚さ20μmの粘着剤層を形成した。 (Formation of adhesive layer)
Next, the acrylic pressure-sensitive adhesive solution is uniformly applied to the surface of a polyethylene terephthalate film (separator film) treated with a silicone-based release agent with a fountain coater and dried in an air circulation type thermostatic oven at 155 ° C. for 2 minutes. Then, an adhesive layer having a thickness of 20 μm was formed on the surface of the separator film.
次いで、各例で得られた偏光フィルムの透明層(但し、参考例1~7では偏光子側、参考例8では一方の保護フィルム)に、上記離型シート(セパレータ)の剥離処理面に形成した粘着剤層を貼り合わせて、粘着剤層付偏光フィルムを作製した。 <Preparation of polarizing film with adhesive layer>
Next, the transparent layer of the polarizing film obtained in each example (however, on the polarizer side in Reference Examples 1 to 7 and one protective film in Reference Example 8) is formed on the release treatment surface of the release sheet (separator). The obtained pressure-sensitive adhesive layer was bonded to produce a polarizing film with a pressure-sensitive adhesive layer.
相溶層の厚みは、ガスクラスターイオン銃搭載のTOF-SIMSによって測定した。偏光フィルム(サンプル)の透明層(相溶層を含まない)の膜厚は予め走査型電子顕微鏡で正確な膜厚を算出した数値を使用した。偏光フィルム(サンプル)の透明層側から偏光子側に向かってアルゴンクラスターでエッチングしながらデプスプロファイルを観察し、偏光子由来の「BO2 -イオン」(イオン強度)を抽出した。透明層側からの深さ(nm)と「BO2 -イオン」(イオン強度)について、図3に示すようなグラフを作成した。電子顕微鏡から得られた透明層の膜厚を「B」、偏光子側から透明層側に向かって「BO2 -イオン」が減少し始めるところを「A」とし、「A-B間距離」を相溶層の厚みとした。実施例1に関して走査型電子顕微鏡にて膜厚を計測したところ、偏光子の厚みが5.0μmであるのに対して透明層の厚みは0.8μmであった。また、TOF-SIMSによって透明層側からエッチングしながらイオン強度を測定した結果、図3に示すようなグラフが得られた。図3の透明層中の「BO2 -イオン」強度は0.8であったのに対して、偏光子中の「BO2 -イオン」強度は3.5であった。また図3に示すようにA-B間には「BO2 -イオン」強度の勾配が出来ていた。「A-B間距離」をアルゴンクラスターのエッチングレートから換算すると、相溶層の厚みは0.12μmであった。また、透明層側の「BO2 -イオン」強度0.8の部分を実施例に記載のFTIRを用いたホウ酸含有量測定を行うと、ホウ酸含有量は4%であった。一方で、TOF-SIMSにおける「BO2 -イオン」強度が3.5であった偏光子中のホウ酸含有量は、透明層を形成する前にFTIRによって求められ、ホウ酸含有量は16%であった。このことから、偏光子中の相溶層ではホウ酸が勾配を持って存在していること(相溶層が偏光子の他の部分よりもホウ酸濃度が相対的に低いホウ酸低濃度層に該当すること)が示された。 <Confirmation of compatible layer thickness>
The thickness of the compatible layer was measured by TOF-SIMS equipped with a gas cluster ion gun. As the film thickness of the transparent layer (not including the compatible layer) of the polarizing film (sample), a numerical value obtained by calculating an accurate film thickness with a scanning electron microscope in advance was used. From the transparent layer side of the polarizing film (sample) toward the polarizer side to observe the depth profile while etching with argon clusters, from the polarizer - it was extracted "BO 2 ion" (ionic strength). Depth from the transparent layer side (nm) and - for "BO 2 ion" (ionic strength) were generated graph shown in Figure 3. The thickness of the obtained transparent layer from the electron microscope "B", towards the transparent layer side from the polarizer side - and "BO 2 ion""A" where begins to decrease, "inter A-B distance" Was the thickness of the compatible layer. When the film thickness was measured with a scanning electron microscope with respect to Example 1, the thickness of the polarizer was 5.0 μm, whereas the thickness of the transparent layer was 0.8 μm. Further, as a result of measuring the ionic strength while etching from the transparent layer side by TOF-SIMS, a graph as shown in FIG. 3 was obtained. The transparent layer of 3 "BO 2 - ion" strength whereas was 0.8, in the polarizer "BO 2 - ion" strength was 3.5. Also between A-B as shown in FIG. 3 - was able gradient of "BO 2 ion" strength. When the “A-B distance” was converted from the etching rate of the argon cluster, the thickness of the compatible layer was 0.12 μm. Further, the transparent layer side - Doing boric acid content measured using FTIR according to the "BO 2 ions" portions of the strength 0.8 Example, boric acid content was 4%. Meanwhile, in the TOF-SIMS - boric acid content in the polarizer "BO 2 ions" strength was 3.5, determined by FTIR before forming the transparent layer, boric acid content 16% Met. Therefore, boric acid is present with a gradient in the compatible layer in the polarizer (the boric acid low-concentration layer in which the boric acid concentration is relatively lower than the other parts of the polarizer). This is the case.
測定装置は、フーリエ変換赤外分光光度計(FT-IR)(Perkin Elmer社製、商品名:「SPECTRUM2000」)を用いた。偏光を測定光として、全反射減衰分光(ATR:attenuated total reflection)測定により、透明層表面の評価を行った。配向関数の算出は以下の手順で行った。測定偏光を偏光子の延伸方向に対して0°と90°にした状態で測定を実施した。得られたスペクトルの2941cm-1の強度を用いて、以下に記した(式)に従い算出した。また、下記強度Iは3330cm-1を参照ピークとして、2941cm-1/3330cm-1の値を用いた。なお、f=1のとき完全配向、f=0のときランダムとなる。また、2941cm-1のピークは、「-CH2-」の振動起因の吸収といわれている。透明層に使用している材料の主鎖中に、「-CH2-」が無い場合には、主鎖の振動起因のスペクトルに置き換えて評価することができる。
(式)f=(3<cos2θ>-1)/2
=(1-D)/[c(2D+1)]
但し、
c=(3cos2β-1)/2
β=90deg⇒f=-2×(1-D)/(2D+1)
θ:分子鎖・延伸方向
β:分子鎖・遷移双極子モーメント
D=(I⊥)/(I//)
(PVAが配向するほどDの値が大きくなる。)
I⊥:偏光を延伸方向と垂直方向に入射して測定したときの強度
I//:偏光を延伸方向と平行方向に入射して測定したときの強度 <Orientation index of transparent layer>
As a measuring apparatus, a Fourier transform infrared spectrophotometer (FT-IR) (manufactured by Perkin Elmer, trade name: “SPECTRUM2000”) was used. The surface of the transparent layer was evaluated by measuring total reflection attenuation (ATR) using polarized light as measurement light. The orientation function was calculated according to the following procedure. The measurement was carried out with the measured polarized light at 0 ° and 90 ° with respect to the stretching direction of the polarizer. Using the intensity of 2941 cm −1 of the obtained spectrum, calculation was performed according to the following (formula). The following intensity I as a reference peak to 3330cm -1, using the value of 2941cm -1 / 3330cm -1. Note that perfect orientation is obtained when f = 1, and random orientation when f = 0. The peak at 2941 cm −1 is said to be absorption due to vibration of “—CH 2 —”. When there is no “—CH 2 —” in the main chain of the material used for the transparent layer, it can be evaluated by replacing with a spectrum caused by vibration of the main chain.
(Formula) f = (3 <cos 2 θ> −1) / 2
= (1-D) / [c (2D + 1)]
However,
c = (3cos 2 β-1) / 2
β = 90deg => f = -2 × (1-D) / (2D + 1)
theta: molecular chain-extending direction beta: = molecular chain, the transition dipole moment D (I ⊥) / (I //)
(The value of D increases as PVA is oriented.)
I 強度 : Intensity when measured with polarized light incident in a direction perpendicular to the stretching direction I // : Intensity when measured with polarized light incident in a direction parallel to the stretching direction
得られた粘着剤層付偏光フィルムの吸収軸方向を縦とし、縦100mm×100mmの大きさにカットし、厚み1.3mmの無アルカリガラスに貼りつけた後、85℃の環境下に500時間投入した。その後、偏光フィルムの大きさを測定した。得られた結果から、吸収軸方向の寸法変化率%を下記式により算出した。
{(投入後の長さ)-(投入前の長さ)}/(投入前の長さ)×100(%)
寸法変化率は、透明層を設けていない場合(参考例1~8)を基準として、同じ構成の偏光フィルムにおいて、寸法変化率が減少している割合を以下に示す基準により判断した。寸法変化抑制効果は、下記式により算出した。
100―{(寸法変化率)/(基準の寸法変化率)×100}(%)
基準に対して
×:寸法変化の抑制効果が10%未満である。
△:寸法変化の抑制効果が10%以上15%未満である。
○:寸法変化の抑制効果が15%以上20%未満である。
◎:寸法変化の抑制効果が20%以上である。 <Dimensional change rate>
The obtained polarizing film with a pressure-sensitive adhesive layer has a longitudinal absorption axis direction, is cut into a size of 100 mm × 100 mm in length, and is pasted on a non-alkali glass having a thickness of 1.3 mm, and then in an environment of 85 ° C. for 500 hours. I put it in. Thereafter, the size of the polarizing film was measured. From the obtained results, the dimensional change rate% in the absorption axis direction was calculated by the following formula.
{(Length after loading)-(Length before loading)} / (Length before loading) × 100 (%)
The rate of dimensional change was determined based on the criteria shown below with respect to the case where a transparent layer was not provided (Reference Examples 1 to 8), in the polarizing film having the same configuration. The dimensional change suppression effect was calculated by the following formula.
100-{(dimensional change rate) / (standard change rate) × 100} (%)
X: The effect of suppressing dimensional change is less than 10%.
Δ: The effect of suppressing dimensional change is 10% or more and less than 15%.
○: Suppression effect of dimensional change is 15% or more and less than 20%.
A: The dimensional change suppression effect is 20% or more.
得られた粘着剤層付偏光フィルムを、縦400mm×横708mmのサイズ(吸収軸方向が400mm)と縦708mm×横400mmのサイズ(吸収軸方向が708mm)に裁断し、縦402mm×横710mm×厚み1.3mmの無アルカリガラスの両面にクロスニコルの方向に貼り合せてサンプルを作成した。当該サンプルを、95℃のオーブンに250時間投入した後に、取り出して粘着剤層付偏光フィルムにクラックが発生しているか否かを目視にて確認した。この試験を1サンプルにつき10枚行い、クラックが発生したサンプルの枚数をカウントし、以下の判断基準で判断を行った。
×:クラック発生枚数が6枚以上。
△:クラック発生枚数が3~5枚。
○:クラック発生枚数が1~2枚。
◎:クラック発生無し。 <Crack resistance>
The obtained polarizing film with a pressure-sensitive adhesive layer was cut into a size of 400 mm long × 708 mm wide (absorption axis direction is 400 mm) and 708 mm long × 400 mm wide (absorption axis direction is 708 mm), 402 mm long × 710 mm wide × A sample was prepared by pasting both sides of a non-alkali glass having a thickness of 1.3 mm in the crossed Nicols direction. The sample was put into an oven at 95 ° C. for 250 hours, and then taken out, and it was visually confirmed whether or not a crack was generated in the polarizing film with the pressure-sensitive adhesive layer. This test was performed 10 samples per sample, the number of samples with cracks was counted, and the determination was made according to the following criteria.
X: The number of cracks generated is 6 or more.
Δ: 3 to 5 cracks were generated.
○: The number of cracks generated is 1-2.
(Double-circle): There is no crack generation.
得られた粘着剤層付偏光フィルムを25mm×50mmのサイズ(吸収軸方向が50mm)に裁断した。当該片保護偏光フィルム(サンプル)を、85℃/85%RHの恒温恒湿機に150時間投入した。投入前と投入後の片保護偏光フィルムの偏光度を、積分球付き分光透過率測定器(村上色彩技術研究所のDot-3c)を用いて測定し、
偏光度の変化率(%)=(1-(投入後の偏光度/投入前の偏光度))、を求めた。
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)および、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。
表1には、偏光度の変化率を記載するとともに、当該変化率を下記の基準で判断した。
〇:偏光度の変化率が0.5%以下。
△:偏光度の変化率が0.5%超5.0%以下。
×:偏光度の変化率が5.0%超。 <Heat and heat resistance: Change rate of polarization degree (optical reliability test)>
The obtained polarizing film with an adhesive layer was cut into a size of 25 mm × 50 mm (absorption axis direction was 50 mm). The piece protective polarizing film (sample) was put into a constant temperature and humidity machine of 85 ° C./85% RH for 150 hours. Measure the degree of polarization of the single-protective polarizing film before and after loading using a spectral transmittance meter with integrating sphere (Dot-3c from Murakami Color Research Laboratory)
Change rate of polarization degree (%) = (1− (polarization degree after injection / polarization degree before injection)).
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 overlapped so that their transmission axes are orthogonal to each other. It is calculated | required by applying the transmittance | permeability (orthogonal transmittance | permeability: Tc) at the time of combining to the following formula | equation. Polarization degree P (%) = {(Tp−Tc) / (Tp + Tc)} 1/2 × 100
Each transmittance is represented by a Y value obtained by correcting visibility with a two-degree field of view (C light source) of JIS Z8701, with 100% of the completely polarized light obtained through the Granteller prism polarizer.
Table 1 describes the rate of change in the degree of polarization, and the rate of change was determined according to the following criteria.
A: Change rate of polarization degree is 0.5% or less.
(Triangle | delta): The change rate of a polarization degree exceeds 0.5% and 5.0% or less.
X: Change rate of polarization degree is over 5.0%.
2 透明層
3 樹脂基材
4 保護フィルム
10 偏光フィルム
11 偏光フィルム
X 相溶層
A 偏光子の厚み
B 相溶層の厚み DESCRIPTION OF SYMBOLS 1
Claims (12)
- 偏光子の少なくとも片面に透明層を有する偏光フィルムであって、
前記偏光子は、ポリビニルアルコール系樹脂を含有し、厚みが15μm以下であり、
前記偏光子における前記透明層の側には、前記透明層との相溶層を有しており、
前記偏光子の厚みAと前記相溶層の厚みBは、一般式:(100×B/A)≧1、を満たすことを特徴とする偏光フィルム。 A polarizing film having a transparent layer on at least one side of a polarizer,
The polarizer contains a polyvinyl alcohol-based resin and has a thickness of 15 μm or less.
On the side of the transparent layer in the polarizer, it has a compatible layer with the transparent layer,
The polarizing film is characterized in that a thickness A of the polarizer and a thickness B of the compatible layer satisfy a general formula: (100 × B / A) ≧ 1. - 前記相溶層は、前記偏光子における前記相溶層以外の部分よりもホウ酸濃度が低いことを特徴とする請求項1記載の偏光フィルム。 The polarizing film according to claim 1, wherein the compatible layer has a lower boric acid concentration than a portion of the polarizer other than the compatible layer.
- 偏光子の少なくとも片面に透明層を有する偏光フィルムであって、
前記偏光子は、ポリビニルアルコール系樹脂を含有し、厚みが15μm以下であり、
前記偏光子における前記透明層の側には、前記偏光子の他の部分よりもホウ酸濃度が相対的に低いホウ酸低濃度層を有しており、
前記偏光子の厚みAと前記ホウ酸低濃度層の厚みCは、一般式:(100×C/A)≧1、を満たすことを特徴とする偏光フィルム。 A polarizing film having a transparent layer on at least one side of a polarizer,
The polarizer contains a polyvinyl alcohol-based resin and has a thickness of 15 μm or less.
On the side of the transparent layer in the polarizer, it has a boric acid low-concentration layer in which the boric acid concentration is relatively lower than other parts of the polarizer,
The polarizing film is characterized in that a thickness A of the polarizer and a thickness C of the boric acid low concentration layer satisfy a general formula: (100 × C / A) ≧ 1. - 前記透明層は、厚みが0.2μm以上であることを特徴とする請求項1~3のいずれかに記載の偏光フィルム。 4. The polarizing film according to claim 1, wherein the transparent layer has a thickness of 0.2 μm or more.
- 前記透明層は、厚みが6μm以下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偏光フィルム。 5. The polarizing film according to claim 1, wherein the transparent layer has a thickness of 6 μm or less.
- 前記透明層は、配向性指数が0.05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偏光フィルム。 The polarizing film according to any one of claims 1 to 5, wherein the transparent layer has an orientation index of 0.05 or less.
- 前記透明層は、ポリビニルアルコール系樹脂を含有する形成材の形成物であることを特徴とする請求項1~6のいずれかに記載の偏光フィルム。 The polarizing film according to any one of claims 1 to 6, wherein the transparent layer is formed of a forming material containing a polyvinyl alcohol-based resin.
- 前記ポリビニルアルコール系樹脂は、ケン化度が99モル%以上、平均重合度が2000以上であることを特徴とする請求項7記載の偏光フィルム。 The polarizing film according to claim 7, wherein the polyvinyl alcohol-based resin has a saponification degree of 99 mol% or more and an average polymerization degree of 2000 or more.
- 前記偏光子は、単体透過率T及び偏光度Pによって表される光学特性が、下記式
P>-(100.929T-42.4-1)×100(ただし、T<42.3)、又は、
P≧99.9(ただし、T≧42.3)の条件を満足するように構成されたことを特徴とする請求項1~8のいずれかに記載の偏光フィルム。 The polarizer has an optical characteristic represented by the following formula: P> − (10 0.929T-42.4 −1) × 100 (where T <42.3) Or
9. The polarizing film according to claim 1, wherein the polarizing film is configured to satisfy a condition of P ≧ 99.9 (however, T ≧ 42.3). - 保護フィルムを有することを特徴とする請求項1~9のいずれかに記載の偏光フィルム。 10. The polarizing film according to claim 1, further comprising a protective film.
- 請求項1~10のいずれかに記載の偏光フィルム、および粘着剤層を有することを特徴とする粘着剤層付偏光フィルム。 11. A polarizing film with a pressure-sensitive adhesive layer, comprising the polarizing film according to claim 1 and a pressure-sensitive adhesive layer.
- 請求項1~10のいずれかに記載の偏光フィルムまたは請求項11記載の粘着剤層付偏光フィルムを有する画像表示装置。
An image display device comprising the polarizing film according to any one of claims 1 to 10 or the polarizing film with an adhesive layer according to claim 11.
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