WO2022209340A1 - 偏光子および偏光子の製造方法 - Google Patents
偏光子および偏光子の製造方法 Download PDFInfo
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- WO2022209340A1 WO2022209340A1 PCT/JP2022/005332 JP2022005332W WO2022209340A1 WO 2022209340 A1 WO2022209340 A1 WO 2022209340A1 JP 2022005332 W JP2022005332 W JP 2022005332W WO 2022209340 A1 WO2022209340 A1 WO 2022209340A1
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- Prior art keywords
- polarizer
- layer
- chemically modified
- main surface
- liquid crystal
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Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/126—Halogenation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
Definitions
- the present invention relates to a polarizer and a method for manufacturing a polarizer.
- Image display devices represented by liquid crystal display devices and electroluminescence (EL) display devices are rapidly spreading.
- a polarizing plate is typically used for an image display panel mounted in an image display device.
- a polarizing plate with a retardation layer, in which a polarizing plate and a retardation plate are integrated, is widely used (for example, Patent Document 1).
- the polarizer included in the polarizing plate may deteriorate in polarizing performance when the image display device is used for a long time or placed in a harsh environment (for example, high temperature and high humidity environment).
- decolorization loss of color
- the present invention has been made to solve the above problems, and its main purpose is to provide a polarizer in which deterioration of polarization performance is suppressed.
- a polarizer contains iodine and is composed of a resin film having a first principal surface and a second principal surface facing each other, and at least the first principal surface has a chemically modified portion in which the resin film is chemically modified. , the chemically modified portion is more hydrophobic than other portions that are not chemically modified.
- the chemical modifier comprises a fluorine-containing group.
- the fluorine containing group comprises a trifluoroacetyl group.
- the chemically modified portion is chemically modified with trifluoroacetic anhydride.
- the polarizer has a fluorine content of 20 ⁇ g/g or more.
- the chemically modified portion has a contact angle of 90° or more.
- the thickness of the polarizer is 8 ⁇ m or less.
- a method for manufacturing the polarizer contains iodine and includes chemically modifying at least the first main surface of a resin film having a first main surface and a second main surface facing each other.
- the chemical modification increases the contact angle of the first main surface by 5° or more.
- a polarizer is provided. This polarizing plate has the polarizer and at least one of a protective layer and a retardation layer.
- FIG. 1 is a schematic cross-sectional view of a polarizer according to one embodiment of the invention
- FIG. 1 is a schematic cross-sectional view showing a schematic configuration of a laminate used for manufacturing a polarizer in one embodiment of the present invention
- FIG. 1 is a schematic cross-sectional view of a polarizing plate according to one embodiment of the invention
- FIG. 1 is a schematic cross-sectional view of a polarizing plate according to one embodiment of the invention
- refractive index (nx, ny, nz) is the refractive index in the direction in which the in-plane refractive index is maximum (i.e., slow axis direction), and "ny” is the in-plane direction orthogonal to the slow axis (i.e., fast axis direction) and "nz” is the refractive index in the thickness direction.
- In-plane retardation (Re) “Re( ⁇ )” is an in-plane retardation measured at 23° C. with light having a wavelength of ⁇ nm.
- Re(550) is the in-plane retardation measured with light having a wavelength of 550 nm at 23°C.
- Thickness direction retardation (Rth) is the retardation in the thickness direction measured at 23° C. with light having a wavelength of ⁇ nm.
- Rth(550) is the retardation in the thickness direction measured at 23° C. with light having a wavelength of 550 nm.
- FIG. 1 is a schematic cross-sectional view of a polarizer according to one embodiment of the invention. In addition, in FIG. 1, hatching is omitted from the cross section of the polarizer in order to make the drawing easier to see.
- the polarizer 10 is composed of a resin film having a first major surface 10a and a second major surface 10b facing each other.
- a first main surface 10a of the polarizer 10 has a chemically modified portion in which a resin film is chemically modified.
- the chemically modified portion may be formed on at least a portion of the first main surface 10a, and the formation region is not particularly limited, but for example, it is formed over the entire first main surface 10a.
- the polarizer is composed of a resin film containing iodine.
- resin film for example, hydrophilic polymer films such as polyvinyl alcohol (PVA) films, partially formalized PVA films, and partially saponified ethylene/vinyl acetate copolymer films are used.
- PVA polyvinyl alcohol
- partially formalized PVA films partially saponified ethylene/vinyl acetate copolymer films are used.
- the thickness of the polarizer 10 is preferably 15 ⁇ m or less, may be 12 ⁇ m or less, may be 10 ⁇ m or less, or may be 8 ⁇ m or less. On the other hand, the thickness of the polarizer is preferably 1 ⁇ m or more.
- the polarizer 10 preferably exhibits absorption dichroism at any wavelength from 380 nm to 780 nm.
- the single transmittance (Ts) of the polarizer 10 is preferably 41.0% or higher, more preferably 42.0% or higher, and even more preferably 42.5% or higher. On the other hand, the single transmittance of the polarizer 10 is, for example, 44.2% or less.
- the degree of polarization (P) of the polarizer 10 is preferably 99.95% or higher, more preferably 99.98% or higher, even more preferably 99.99% or higher. On the other hand, the degree of polarization of the polarizer 10 is, for example, 99.996% or less.
- the single transmittance is typically a Y value measured using an ultraviolet-visible spectrophotometer and subjected to visibility correction.
- the degree of polarization is typically obtained by the following formula based on the parallel transmittance Tp and the orthogonal transmittance Tc measured using an ultraviolet-visible spectrophotometer and subjected to visibility correction.
- Degree of polarization (%) ⁇ (Tp-Tc)/(Tp+Tc) ⁇ 1/2 ⁇ 100
- the chemically modified part is more hydrophobic than other parts that are not chemically modified.
- a chemically modified portion By forming such a chemically modified portion, it is possible to obtain a polarizer (polarizing plate) in which the intrusion of moisture into the polarizer (resin film) is suppressed and the deterioration of the polarizing performance is suppressed.
- the other parts include not only the surface of the resin film but also the inside of the resin film.
- the chemically modified portion may be formed on at least one main surface (first main surface 10a), and may be formed on each of the first main surface 10a and the second main surface 10b.
- a chemically modified portion is formed only on one main surface.
- chemically modified portions are formed on both main surfaces.
- the chemically modified portion may or may not be formed on the end face 10c.
- the chemically modified portion can be formed by chemically modifying the resin film.
- it can be formed by a modification reaction of the hydroxy groups of the resin film.
- Modification reactions of hydroxy groups in resin films include, for example, methyl ether, substituted methyl ether, substituted ethyl ether, methoxy-substituted benzyl ether, silyl ether, ester (formate, acetyl, benzoyl), micellized ester, sulfonate, and sulfenate.
- modifying groups such as acid esters, sulfinic acid esters, carbonates, carbamates, cyclic acetals, cyclic ketals, cyclic orthoesters, silyl derivative groups, cyclic carbonates, cyclic borate esters and the like can be mentioned.
- the conditions for the modification reaction appropriate conditions can be appropriately adopted depending on the type of modification group and the like.
- the resin film and the chloride of the modifying group to be substituted are brought into contact with each other at 0° C. to 100° C. for 1 minute to 20 hours in the presence of a catalyst, if necessary, for modification reaction.
- the above-mentioned chemical modification part is a modification having groups such as alkyl groups, halogeno groups, halogenated alkyl groups, aryl groups, acyl groups, and silyl groups (groups that improve hydrophobicity) on the hydroxy groups of the resin film. It can be formed by reacting agents. Chemical modification is performed by, for example, alkylation, halogenation, acylation (eg, acetylation, esterification), silylation, etherification, and the like. These may be used alone or in combination of two or more.
- acylating agents used for the above acylation include carboxylic acid anhydrides, carboxylic acid halides, benzoyl halides, esters, amides, and ketene. Specific examples include trifluoroacetic anhydride, acetic anhydride, acetyl chloride, chloroacetic anhydride, chloroacetyl chloride, dichloroacetic anhydride, trichloroacetic anhydride, and benzoyl chloride.
- silylating agent used for the silylation examples include chlorotrimethylsilane, chlorotriethylsilane, chlorotriisopropylsilane, chlorotriphenylsilane, tert-butyldimethylchlorosilane, dichlorodimethylsilane, dichlorodiethylsilane, dichlorodiisopropylsilane, and the like. chlorosilanes of.
- amide-based silylating agents such as N,O-bis(trimethylsilyl)acetamide and N,O-bis(trimethylsilyl)trifluoroacetamide, and amine-based silylating agents such as N-trimethylsilylimidazole are also used. be able to.
- etherification agent used for the etherification examples include benzyl bromide, 4-methoxybenzyl chloride, chloromethyl methyl ether, and trityl chloride.
- the chemical modification moiety has a fluorine-containing group.
- Groups containing fluorine include, for example, fluoroalkyl groups having one or more fluoro groups, and fluoroacyl groups (eg, trifluoroacetyl group).
- the chemically modified portion is chemically modified with trifluoroacetic anhydride.
- the fluorine content of the polarizer is preferably 20 ⁇ g/g or more, more preferably 30 ⁇ g/g or more, still more preferably 40 ⁇ g/g or more.
- the fluorine content of the polarizer may be, for example, 100 ⁇ g/g or more, 200 ⁇ g/g or more, or 300 ⁇ g/g or more.
- the fluorine content of the polarizer is, for example, 800 ⁇ g/g or less.
- the fluorine content of the polarizer is preferably 0.01 ⁇ g/cm 2 or more, more preferably 0.02 ⁇ g/cm 2 or more, still more preferably 0.03 ⁇ g/cm 2 or more.
- the fluorine content of the polarizer may be, for example, 0.1 ⁇ g/cm 2 or more, 0.2 ⁇ g/cm 2 or more, or 0.3 ⁇ g/cm 2 or more.
- the fluorine content of the polarizer is, for example, 0.5 ⁇ g/cm 2 or less.
- the fluorine content can be determined by ion chromatography (IC).
- the chemically modified portion (main surface having the chemically modified portion) preferably has a ratio of absorbance at 1787 cm -1 to absorbance at 2940 cm -1 exceeding 0.2, more preferably 0, in the FT-IR spectrum measured by ATR. 0.25 or more, more preferably 0.3 or more.
- the ratio of absorbance at 1787 cm -1 to absorbance at 2940 cm -1 is less than one, for example.
- the absorption peak near 2940 cm ⁇ 1 is derived from the C—H stretching vibration of the resin film
- the absorption peak near 1787 cm ⁇ 1 is derived from the C ⁇ O stretching vibration of the trifluoroacetyl group.
- the contact angle of the chemically modified portion (main surface having the chemically modified portion) is preferably 90° or more, more preferably 92° or more, and still more preferably 94° or more.
- the contact angle of the chemically modified portion is, for example, 115° or less, and may be 110° or less.
- the contact angle of the other sites not chemically modified is, for example, 86° or less.
- the polarizer contains iodine and can be obtained by chemically modifying at least one main surface (first main surface) of a resin film having a first main surface and a second main surface facing each other.
- first main surface of the resin film is chemically modified while the protective material is placed on the second main surface of the resin film.
- a laminate of a resin film and a protective material is prepared, and the first main surface of the resin film of this laminate is chemically modified.
- FIG. 2 is a schematic cross-sectional view showing a schematic configuration of a laminate used for manufacturing a polarizer in one embodiment of the present invention.
- a laminate 100 has a resin film 10 and a protective material 1 .
- the resin film 10 has a first main surface 10a and a second main surface 10b facing each other, and the protective material 1 is arranged on the second main surface 10b of the resin film 10 .
- the resin film contained in the laminate can be produced by any appropriate method.
- hydrophilic polymer films such as polyvinyl alcohol (PVA) films, partially formalized PVA films, and partially saponified ethylene/vinyl acetate copolymer films are added with iodine, dichroic dyes, and the like. It is produced by a method including dyeing with a dichroic material and stretching. The method may further include an insolubilization treatment, a swelling treatment, a cross-linking treatment, and the like. Since such a manufacturing method is well known and commonly used in the industry, detailed description thereof will be omitted.
- the resin film contained in the laminate is produced using a laminate of a resin substrate and a resin layer (typically, a PVA-based resin layer).
- a PVA-based resin solution is applied to a resin substrate and dried to form a PVA-based resin layer on the resin substrate to obtain a laminate of the resin substrate and the PVA-based resin layer; stretching and dyeing;
- a PVA-based resin layer containing a halide and a PVA-based resin is formed on one side of the resin substrate.
- Stretching typically includes immersing the laminate in an aqueous boric acid solution for stretching.
- stretching may further include stretching the laminate in air at a high temperature (eg, 95° C.
- the laminate is preferably subjected to drying shrinkage treatment in which the laminate is heated while being conveyed in the longitudinal direction to shrink the laminate by 2% or more in the width direction.
- the manufacturing method of the present embodiment includes subjecting the laminate to an in-air auxiliary stretching treatment, a dyeing treatment, an underwater stretching treatment, and a drying shrinkage treatment in this order.
- the resin substrate may be used as it is as a protective layer of the resulting polarizer, or may be peeled off from the laminate of the resin substrate/PVA-based resin layer. Details of the method for producing such a resin film (polarizer) are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580 and Japanese Patent No. 6470455. These publications are incorporated herein by reference in their entireties.
- any appropriate member for example, film, layer
- the resin base material can be used as a protective material.
- the protective material at least one of a protective layer of a polarizer and a retardation layer, which will be described later, may be used.
- the protective material can be laminated to the resin film via an adhesive or adhesive.
- the chemical modification can be carried out by any appropriate method depending on, for example, the properties of the modifying agent used.
- a gas phase reaction Specifically, it can be carried out by placing the resin film (laminate) in an atmosphere containing a vaporized modifier.
- the reaction time is, for example, 30 seconds to 60 minutes.
- a liquid phase reaction Specifically, a reaction liquid containing a modifying agent may be applied to the main surface (first main surface 10a) of the resin film, or the resin film (laminate) may be coated on the reaction liquid containing the modifying agent. may be immersed.
- the immersion time is, for example, 10 seconds to 5 minutes.
- the contact angle of the treated surface (first main surface) it is preferable to increase the contact angle of the treated surface (first main surface) by 5° or more, more preferably 7° or more, and still more preferably 10° or more by chemical modification.
- By performing such a treatment it is possible to effectively suppress the intrusion of moisture into the obtained polarizer, and to obtain a polarizer (polarizing plate) in which deterioration of polarizing performance is suppressed.
- Polarizing Plate A polarizing plate according to an embodiment of the present invention has the polarizer described above. Typically, it has the polarizer and at least one of a protective layer and a retardation layer. Polarizing plates according to embodiments of the present invention are typically used in image display panels. Specifically, it is arranged on the viewing side of the image display panel main body.
- FIG. 3 is a schematic cross-sectional view of a polarizing plate according to one embodiment of the present invention.
- the polarizing plate 200 includes a polarizer 10, a first protective layer 21 arranged on the first main surface 10a side (viewing side) of the polarizer 10, and an adhesive layer 21 arranged on the second main surface 10b side of the polarizer 10. It has an agent layer 40 and a release film 50 . At least the first main surface 10a of the polarizer 10 is formed with the chemically modified portion. In the image display panel, by arranging the first main surface 10a having the chemically modified portion on the viewing side, it is possible to effectively suppress deterioration of the polarization performance due to the influence of the external environment.
- the adhesive layer 40 and the release film 50 are arranged on the first main surface 10a side having the chemically modified portion, and the first protective layer 21 is arranged on the second main surface 10b side (viewing side). may have been
- the release film 50 is detachably attached to the adhesive layer 40 and can protect the adhesive layer 40 .
- the polarizing plate 200 can be formed into a roll. Practically, the polarizing plate 200 can be attached to the image display panel main body by the adhesive layer 40 .
- the release film 50 can function as a separator that is temporarily attached until the polarizing plate 200 is ready for use.
- a second protective layer may be arranged between the polarizer 10 and the adhesive layer 40.
- the polarizing plate may have a retardation layer. Specifically, it may be a polarizing plate with a retardation layer. A retardation layer is arranged, for example, between the polarizer 10 and the adhesive layer 40 .
- Each member constituting the polarizing plate can be laminated via any appropriate adhesive layer (some of which are not shown).
- Specific examples of the adhesive layer include an adhesive layer and an adhesive layer.
- the polarizing plate may be elongated or sheet-shaped.
- the term "elongated” refers to an elongated shape whose length is sufficiently longer than its width, for example, an elongated shape whose length is 10 times or more, preferably 20 times or more, its width.
- the elongated retardation layer polarizing plate can be wound into a roll.
- the protective layer can be formed of any suitable film that can be used as a protective layer for a polarizer.
- the material that is the main component of the film include cellulose-based resins such as triacetyl cellulose (TAC), polyester-based, polyvinyl alcohol-based, polycarbonate-based, polyamide-based, polyimide-based, polyethersulfone-based, and polysulfone-based resins.
- TAC triacetyl cellulose
- polyester-based polyvinyl alcohol-based
- polycarbonate-based polyamide-based
- polyimide-based polyimide-based
- polyethersulfone-based polysulfone-based resins.
- polystyrene cycloolefin such as polynorbornene, polyolefin, (meth)acrylic, and acetate.
- the polarizing plate is typically arranged on the viewing side of the image display device, and the first protective layer 21 is arranged on the viewing side. Therefore, the first protective layer 21 may be subjected to surface treatment such as hard coat (HC) treatment, anti-reflection treatment, anti-sticking treatment, anti-glare treatment, etc., if necessary.
- surface treatment such as hard coat (HC) treatment, anti-reflection treatment, anti-sticking treatment, anti-glare treatment, etc.
- the thickness of the protective layer is preferably 5 ⁇ m to 80 ⁇ m, more preferably 10 ⁇ m to 40 ⁇ m, still more preferably 15 ⁇ m to 35 ⁇ m.
- the thickness of the 1st protective layer 21 is thickness including the thickness of a surface treatment layer.
- the second protective layer is preferably optically isotropic in one embodiment.
- “optically isotropic” means that the in-plane retardation Re (550) is 0 nm to 10 nm and the thickness direction retardation Rth (550) is ⁇ 10 nm to +10 nm.
- the thickness of the second protective layer is preferably 5 ⁇ m to 80 ⁇ m, more preferably 10 ⁇ m to 40 ⁇ m, still more preferably 10 ⁇ m to 30 ⁇ m.
- the thickness of the adhesive layer 40 is preferably 10 ⁇ m to 20 ⁇ m. Any appropriate configuration can be adopted as the adhesive that constitutes the adhesive layer 40 . Specific examples include acrylic adhesives, rubber adhesives, silicone adhesives, polyester adhesives, urethane adhesives, epoxy adhesives, and polyether adhesives. By adjusting the type, number, combination and compounding ratio of the monomers forming the base resin of the adhesive, as well as the compounding amount of the cross-linking agent, the reaction temperature, the reaction time, etc., an adhesive having desired properties according to the purpose. can be prepared.
- the base resin of the adhesive may be used alone or in combination of two or more.
- the base resin is preferably an acrylic resin (specifically, the pressure-sensitive adhesive layer is preferably composed of an acrylic pressure-sensitive adhesive).
- the release film may be composed of any suitable plastic film.
- plastic films include polyethylene terephthalate (PET) films, polyethylene films, and polypropylene films.
- PET polyethylene terephthalate
- a release film can function as a separator.
- a plastic film whose surface is coated with a release agent is preferably used as the release film.
- release agents include silicone-based release agents, fluorine-based release agents, and long-chain alkyl acrylate-based release agents.
- the thickness of the release film is preferably 20 ⁇ m to 80 ⁇ m, more preferably 35 ⁇ m to 55 ⁇ m.
- the retardation layer may have a laminated structure of two or more layers, or may be a single layer.
- the thickness of the retardation layer is, for example, 1 ⁇ m or more and 50 ⁇ m or less, depending on its configuration (whether it is a single layer or has a laminated structure). In one embodiment, the thickness of the retardation layer is preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less, and even more preferably 6 ⁇ m or less.
- the "thickness of the retardation layer” means the total thickness of each retardation layer. Specifically, the "thickness of the retardation layer" does not include the thickness of the adhesive layer.
- an alignment fixed layer (liquid crystal alignment fixed layer) of a liquid crystal compound is preferably used.
- a liquid crystal compound for example, the difference between nx and ny in the resulting retardation layer can be significantly increased compared to a non-liquid crystal material. thickness can be significantly reduced. Therefore, it is possible to realize a remarkable thinning of the polarizing plate with the retardation layer.
- the term "fixed alignment layer” refers to a layer in which a liquid crystal compound is aligned in a predetermined direction and the alignment state is fixed.
- the "alignment fixed layer” is a concept including an alignment cured layer obtained by curing a liquid crystal monomer as described later.
- rod-shaped liquid crystal compounds are typically aligned in the slow axis direction of the retardation layer (homogeneous alignment).
- the liquid crystal alignment fixed layer is formed by subjecting the surface of a predetermined base material to an alignment treatment, coating the surface with a coating liquid containing a liquid crystal compound, and orienting the liquid crystal compound in a direction corresponding to the alignment treatment. It can be formed by fixing the orientation state. Any appropriate orientation treatment can be adopted as the orientation treatment. Specific examples include mechanical orientation treatment, physical orientation treatment, and chemical orientation treatment. Specific examples of mechanical orientation treatment include rubbing treatment and stretching treatment. Specific examples of physical orientation treatment include magnetic orientation treatment and electric field orientation treatment. Specific examples of chemical alignment treatment include oblique vapor deposition and photo-alignment treatment. Arbitrary appropriate conditions can be adopted as the processing conditions for various alignment treatments depending on the purpose.
- the alignment of the liquid crystal compound is performed by processing at a temperature that exhibits a liquid crystal phase depending on the type of liquid crystal compound. By performing such a temperature treatment, the liquid crystal compound assumes a liquid crystal state, and the liquid crystal compound is aligned in accordance with the orientation treatment direction of the surface of the base material.
- the alignment state is fixed by cooling the liquid crystal compound aligned as described above.
- the orientation state is fixed by subjecting the liquid crystal compound oriented as described above to a polymerization treatment or a crosslinking treatment.
- liquid crystal compound and details of the method for forming the alignment fixed layer are described in JP-A-2006-163343. The description of the publication is incorporated herein by reference.
- the retardation layer can function as a ⁇ /4 plate.
- Re(550) of the retardation layer is preferably 100 nm to 180 nm, more preferably 110 nm to 170 nm, still more preferably 110 nm to 160 nm.
- the thickness of the retardation layer can be adjusted so as to obtain the desired in-plane retardation of the ⁇ /4 plate.
- the retardation layer is the liquid crystal alignment fixing layer described above, its thickness is, for example, 1.0 ⁇ m to 2.5 ⁇ m.
- the angle formed by the slow axis of the retardation layer and the absorption axis of the polarizer is preferably 40 ° to 50 °, more preferably 42 ° to 48 °, still more preferably 44 ° to 46°.
- the retardation layer preferably exhibits reverse dispersion wavelength characteristics in which the retardation value increases according to the wavelength of the measurement light.
- the retardation layer can function as a ⁇ /2 plate.
- Re(550) of the retardation layer is preferably 200 nm to 300 nm, more preferably 230 nm to 290 nm, still more preferably 230 nm to 280 nm.
- the thickness of the retardation layer can be adjusted so as to obtain the desired in-plane retardation of the ⁇ /2 plate.
- the retardation layer is the liquid crystal alignment fixed layer described above, its thickness is, for example, 2.0 ⁇ m to 4.0 ⁇ m.
- the angle formed by the slow axis of the retardation layer and the absorption axis of the polarizer is preferably 10 ° to 20 °, more preferably 12 ° to 18 °, still more preferably 12 ° to 16°.
- the retardation layer has a laminated structure
- the retardation layer has a first retardation layer (H layer) and a second retardation layer (Q layer) arranged in this order from the polarizer side. It also has a two-layer laminated structure.
- the H layer can typically function as a ⁇ /2 plate and the Q layer can typically function as a ⁇ /4 plate.
- Re(550) of the H layer is preferably 200 nm to 300 nm, more preferably 220 nm to 290 nm, still more preferably 230 nm to 280 nm;
- Re(550) of the Q layer is preferably It is 100 nm to 180 nm, more preferably 110 nm to 170 nm, even more preferably 110 nm to 150 nm.
- the thickness of the H layer can be adjusted to obtain the desired in-plane retardation of the ⁇ /2 plate.
- the H layer is the liquid crystal alignment fixing layer described above, its thickness is, for example, 2.0 ⁇ m to 4.0 ⁇ m.
- the thickness of the Q layer can be adjusted to obtain the desired in-plane retardation of the ⁇ /4 plate.
- the Q layer is the liquid crystal alignment fixing layer described above, its thickness is, for example, 1.0 ⁇ m to 2.5 ⁇ m.
- the angle between the slow axis of the H layer and the absorption axis of the polarizer is preferably 10° to 20°, more preferably 12° to 18°, still more preferably 12°. ⁇ 16°; the angle formed by the slow axis of the Q layer and the absorption axis of the polarizer is preferably 70° to 80°, more preferably 72° to 78°, still more preferably 72° ⁇ 76°.
- each layer (for example, the H layer and the Q layer) may exhibit an inverse dispersion wavelength characteristic in which the retardation value increases according to the wavelength of the measurement light, and the retardation value increases according to the wavelength of the measurement light. It may exhibit a small positive wavelength dispersion characteristic, or may exhibit a flat wavelength dispersion characteristic in which the retardation value hardly changes even with the wavelength of the measurement light.
- the Nz coefficient of the retardation layer is preferably 0.9 to 1.5, more preferably 0.9 to 1.3.
- the retardation layer is preferably a liquid crystal alignment fixed layer.
- the liquid crystal compound include a liquid crystal compound having a nematic liquid crystal phase (nematic liquid crystal).
- a liquid crystal compound for example, a liquid crystal polymer or a liquid crystal monomer can be used. Either lyotropic or thermotropic mechanism may be used to develop the liquid crystallinity of the liquid crystal compound.
- the liquid crystal polymer and liquid crystal monomer may be used alone or in combination.
- the liquid crystal monomer is preferably a polymerizable monomer and a crosslinkable monomer.
- the alignment state of the liquid crystal monomer can be fixed by polymerizing or cross-linking (that is, curing) the liquid crystal monomer. After aligning the liquid crystal monomers, for example, the alignment state can be fixed by polymerizing or cross-linking the liquid crystal monomers.
- a polymer is formed by polymerization and a three-dimensional network structure is formed by cross-linking, but these are non-liquid crystalline. Therefore, the formed retardation layer does not undergo a transition to a liquid crystal phase, a glass phase, or a crystal phase due to a change in temperature, which is peculiar to liquid crystalline compounds. As a result, the retardation layer becomes a highly stable retardation layer that is not affected by temperature changes.
- the temperature range in which the liquid crystal monomer exhibits liquid crystallinity differs depending on the type. Specifically, the temperature range is preferably 40°C to 120°C, more preferably 50°C to 100°C, and most preferably 60°C to 90°C.
- liquid crystal monomer Any appropriate liquid crystal monomer can be adopted as the liquid crystal monomer.
- polymerizable mesogenic compounds described in JP-T-2002-533742 WO00/37585
- EP358208 US5211877
- EP66137 US4388453
- WO93/22397 EP0261712, DE19504224, DE4408171, and GB2280445
- Specific examples of such polymerizable mesogenic compounds include LC242 (trade name) available from BASF, E7 (trade name) available from Merck, and LC-Sillicon-CC3767 (trade name) available from Wacker-Chem.
- a nematic liquid crystal monomer is preferable as the liquid crystal monomer.
- the details of the ⁇ /4 plate are as described above.
- the angle between the slow axis of the first retardation layer and the absorption axis of the polarizer is preferably 40° to 50°, more preferably 42° to 48°, still more preferably is 44° to 46°.
- the first retardation layer preferably exhibits reverse dispersion wavelength characteristics in which the retardation value increases according to the wavelength of the measurement light.
- the thickness direction retardation Rth (550) of the positive C plate is preferably ⁇ 50 nm to ⁇ 300 nm, more preferably ⁇ 70 nm to ⁇ 250 nm, still more preferably ⁇ 90 nm to ⁇ 200 nm, and particularly preferably is -100 nm to -180 nm.
- the in-plane retardation Re(550) of the positive C plate is, for example, less than 10 nm.
- a liquid crystal material (liquid crystal compound) capable of homeotropic alignment may be a liquid crystal monomer or a liquid crystal polymer.
- Specific examples of the liquid crystal compound and the method for forming the retardation layer include the liquid crystal compound and the method for forming the retardation layer described in [0020] to [0028] of JP-A-2002-333642.
- the thickness of the second retardation layer is preferably 0.5 ⁇ m to 5 ⁇ m.
- a polarizing plate according to an embodiment of the present invention can be obtained by laminating each layer on the polarizer. Lamination of each layer is performed, for example, while being transported by rolls (so-called roll-to-roll). Lamination of the protective layer is performed using, for example, an adhesive. Lamination of the retardation layer is typically carried out by transferring the liquid crystal alignment solidified layer formed on the substrate. When the retardation layer has a laminated structure, the respective retardation layers may be sequentially laminated (transferred) to the resin film, or the laminate of the retardation layers may be laminated (transferred) to the resin film. Transfer is performed using, for example, an active energy ray-curable adhesive.
- the thickness of the active energy ray-curable adhesive after curing is preferably 0.4 ⁇ m or more, more preferably 0.4 ⁇ m to 3.0 ⁇ m, and still more preferably 0.6 ⁇ m to 1.5 ⁇ m.
- thickness is the value measured by the following measuring method.
- parts and “%” in Examples and Comparative Examples are by weight.
- ⁇ Thickness> The thickness of 10 ⁇ m or less was measured using a scanning electron microscope (manufactured by JEOL Ltd., product name “JSM-7100F”). A thickness exceeding 10 ⁇ m was measured using a digital micrometer (manufactured by Anritsu Co., Ltd., product name “KC-351C”).
- Example 1 (Production of laminate) As a thermoplastic resin substrate, a long amorphous isophthalic copolymerized polyethylene terephthalate film (thickness: 100 ⁇ m) having a Tg of about 75° C. was used, and one side of this resin substrate was subjected to corona treatment. .
- Polyvinyl alcohol degree of polymerization: 4,200, degree of saponification: 99.2 mol%) and acetoacetyl-modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "GOSEFIMER”) were mixed at a ratio of 9:1, and 100 parts by weight of PVA-based resin.
- aqueous PVA solution (coating solution).
- the above PVA aqueous solution was applied to the corona-treated surface of the resin base material and dried at 60° C. to form a PVA-based resin layer having a thickness of 13 ⁇ m, thereby producing a laminate.
- the resulting laminate was uniaxially stretched 2.4 times in the machine direction (longitudinal direction) in an oven at 130° C. (in-air auxiliary stretching treatment).
- the laminate was immersed in an insolubilizing bath (an aqueous boric acid solution obtained by mixing 4 parts by weight of boric acid with 100 parts by weight of water) at a liquid temperature of 40° C.
- the finally obtained polarizer is added to a dyeing bath (iodine aqueous solution obtained by blending iodine and potassium iodide at a weight ratio of 1:7 with respect to 100 parts by weight of water) at a liquid temperature of 30 ° C. It was immersed for 60 seconds while adjusting the concentration so that the single transmittance (Ts) was a desired value (dyeing treatment). Next, it was immersed for 30 seconds in a cross-linking bath at a liquid temperature of 40°C (an aqueous solution of boric acid obtained by blending 3 parts by weight of potassium iodide and 5 parts by weight of boric acid with respect to 100 parts by weight of water).
- crosslinking treatment After that, while immersing the laminate in an aqueous solution of boric acid (boric acid concentration: 4% by weight, potassium iodide concentration: 5% by weight) at a liquid temperature of 70° C., the laminate was moved vertically (longitudinally) between rolls with different peripheral speeds. Uniaxial stretching was performed so that the stretching ratio was 5.5 times (underwater stretching treatment). After that, the laminate was immersed in a washing bath (aqueous solution obtained by blending 4 parts by weight of potassium iodide with 100 parts by weight of water) at a liquid temperature of 20° C. (washing treatment).
- a washing bath aqueous solution obtained by blending 4 parts by weight of potassium iodide with 100 parts by weight of water
- HC-TAC film (thickness: 32 ⁇ m) was attached as a first protective layer to the chemically modified surface of the resin film (polarizer) via an ultraviolet curable adhesive.
- the HC-TAC film is a film in which a hard coat (HC) layer (7 ⁇ m in thickness) is formed on a TAC film (25 ⁇ m in thickness), and the TAC film is attached to the resin film side.
- the resin substrate is peeled off from the resin film, a 20 ⁇ m-thick pressure-sensitive adhesive layer (higher moisture permeability than the HC-TAC film) is formed on the peeled surface, and a separator (PET film, thickness 38 ⁇ m) is attached. rice field.
- a polarizing plate was obtained.
- polarizing plate B A pressure-sensitive adhesive layer having a thickness of 23 ⁇ m was formed on the chemically modified surface of the resin film (polarizer), and a separator (PET film, thickness of 38 ⁇ m) was attached.
- the resin substrate was peeled off from the resin film, and an HC-TAC film (thickness: 32 ⁇ m) was attached as a first protective layer to the peeled surface via an ultraviolet curable adhesive.
- the HC-TAC film is a film in which a hard coat (HC) layer (7 ⁇ m in thickness) is formed on a TAC film (25 ⁇ m in thickness), and the TAC film is attached to the resin film side.
- Example 2 A polarizing plate A and a polarizing plate B were obtained in the same manner as in Example 1, except that the laminate was treated according to the following procedure for the chemical modification.
- Example 3 In the chemical modification, polarizing plate A and polarizing plate B were obtained in the same manner as in Example 2, except that the standing time was set to 30 minutes.
- Example 1 A polarizing plate was obtained in the same manner as in Example 1, except that the resulting laminate was not chemically modified.
- Table 1 The values shown in Table 1 are the average values of three measurements. 2. Fluorine content
- a test piece of 2 cm ⁇ 4 cm (8 cm 2 ) was cut out from the resin film (polarizer) after chemical modification, placed on a ceramic board and weighed, and then a combustion improver was added. . Next, it was combusted using an automatic sample combustor, and the generated gas was collected in 10 mL of the absorbent. The absorption liquid after collection was adjusted to 15 mL with ultrapure water, and the fluorine content was determined by performing an analysis by ion chromatography.
- the analyzer and measurement conditions are as follows.
- a polarizer according to an embodiment of the present invention is used, for example, in image display devices such as liquid crystal display devices, organic EL display devices, and inorganic EL display devices.
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Abstract
Description
1つの実施形態においては、上記化学修飾部はフッ素を含む基を含む。
1つの実施形態においては、上記フッ素を含む基はトリフルオロアセチル基を含む。
1つの実施形態においては、上記化学修飾部は無水トリフルオロ酢酸により化学修飾されている。
1つの実施形態においては、上記偏光子のフッ素含有量は20μg/g以上である。
1つの実施形態においては、上記化学修飾部の接触角は90°以上である。
1つの実施形態においては、上記偏光子の厚みは8μm以下である。
本発明の別の実施形態によれば、上記偏光子の製造方法が提供される。この製造方法は、ヨウ素を含み、互いに対向する第一主面および第二主面を有する樹脂フィルムの少なくとも前記第一主面を化学修飾することを含む。
1つの実施形態においては、上記化学修飾により上記第一主面の接触角を5°以上上昇させる。
本発明のさらに別の実施形態によれば、偏光板が提供される。この偏光板は、上記偏光子と、保護層または位相差層の少なくとも一つと、を有する。
本明細書における用語および記号の定義は下記の通りである。
(1)屈折率(nx、ny、nz)
「nx」は面内の屈折率が最大になる方向(すなわち、遅相軸方向)の屈折率であり、「ny」は面内で遅相軸と直交する方向(すなわち、進相軸方向)の屈折率であり、「nz」は厚み方向の屈折率である。
(2)面内位相差(Re)
「Re(λ)」は、23℃における波長λnmの光で測定した面内位相差である。例えば、「Re(550)」は、23℃における波長550nmの光で測定した面内位相差である。Re(λ)は、層(フィルム)の厚みをd(nm)としたとき、式:Re(λ)=(nx-ny)×dによって求められる。
(3)厚み方向の位相差(Rth)
「Rth(λ)」は、23℃における波長λnmの光で測定した厚み方向の位相差である。例えば、「Rth(550)」は、23℃における波長550nmの光で測定した厚み方向の位相差である。Rth(λ)は、層(フィルム)の厚みをd(nm)としたとき、式:Rth(λ)=(nx-nz)×dによって求められる。
(4)Nz係数
Nz係数は、Nz=Rth/Reによって求められる。
(5)角度
本明細書において角度に言及するときは、当該角度は基準方向に対して時計回りおよび反時計回りの両方を包含する。したがって、例えば「45°」は±45°を意味する。
図1は、本発明の1つの実施形態による偏光子の模式的な断面図である。なお、図1では、図を見やすくするために偏光子の断面は、ハッチングを省略している。偏光子10は、互いに対向する第一主面10aおよび第二主面10bを有する樹脂フィルムから構成される。偏光子10の第一主面10aは、樹脂フィルムが化学修飾された化学修飾部を有する。化学修飾部は、第一主面10aの少なくとも一部に形成されていればよく、形成領域は特に限定されないが、例えば、第一主面10aの全体に亘って形成される。
偏光度(%)={(Tp-Tc)/(Tp+Tc)}1/2×100
上記偏光子は、ヨウ素を含み、互いに対向する第一主面および第二主面を有する樹脂フィルムの少なくとも一方の主面(第一主面)を化学修飾することにより得ることができる。1つの実施形態においては、樹脂フィルムの第二主面に保護材が配置された状態で、樹脂フィルムの第一主面を化学修飾する。具体的には、樹脂フィルムと保護材との積層物を準備し、この積層物の樹脂フィルムの第一主面を化学修飾する。
図2は、本発明の1つの実施形態における偏光子の製造に用いられる積層物の概略の構成を示す模式的な断面図である。積層物100は、樹脂フィルム10と保護材1を有する。樹脂フィルム10は互いに対向する第一主面10aおよび第二主面10bを有し、樹脂フィルム10の第二主面10bに保護材1が配置される。
上記化学修飾は、例えば、用いる修飾化剤の性質に応じて、任意の適切な方法により行うことができる。例えば、気相反応により行うことができる。具体的には、気化した修飾化剤を含む雰囲気下に上記樹脂フィルム(積層物)を置くことにより行うことができる。気相反応を採用する場合、反応時間は、例えば、30秒~60分である。別の例としては、液相反応により行うことができる。具体的には、上記樹脂フィルムの主面(第一主面10a)に修飾化剤を含む反応液を塗工してもよいし、修飾化剤を含む反応液に上記樹脂フィルム(積層物)を浸漬してもよい。浸漬による液相反応を採用する場合、浸漬時間は、例えば、10秒~5分である。
本発明の実施形態による偏光板は、上記偏光子を有する。代表的には、上記偏光子と、保護層または位相差層の少なくとも一つとを有する。本発明の実施形態による偏光板は、代表的には、画像表示パネルに用いられる。具体的には、画像表示パネル本体の視認側に配置される。
上記保護層は、偏光子の保護層として使用できる任意の適切なフィルムで形成され得る。当該フィルムの主成分となる材料の具体例としては、トリアセチルセルロース(TAC)等のセルロース系樹脂や、ポリエステル系、ポリビニルアルコール系、ポリカーボネート系、ポリアミド系、ポリイミド系、ポリエーテルスルホン系、ポリスルホン系、ポリスチレン系、ポリノルボルネン等のシクロオレフィン系、ポリオレフィン系、(メタ)アクリル系、アセテート系等の透明樹脂が挙げられる。
粘着剤層40の厚みは、好ましくは10μm~20μmである。粘着剤層40を構成する粘着剤としては、任意の適切な構成が採用され得る。具体例としては、アクリル系粘着剤、ゴム系粘着剤、シリコーン系粘着剤、ポリエステル系粘着剤、ウレタン系粘着剤、エポキシ系粘着剤、およびポリエーテル系粘着剤が挙げられる。粘着剤のベース樹脂を形成するモノマーの種類、数、組み合わせおよび配合比、ならびに、架橋剤の配合量、反応温度、反応時間等を調整することにより、目的に応じた所望の特性を有する粘着剤を調製することができる。粘着剤のベース樹脂は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。ベース樹脂は、好ましくはアクリル樹脂である(具体的には、粘着剤層は、好ましくはアクリル系粘着剤で構成される)。
上記剥離フィルムは、任意の適切なプラスチックフィルムで構成され得る。プラスチックフィルムの具体例としては、ポリエチレンテレフタレート(PET)フィルム、ポリエチレンフィルム、ポリプロピレンフィルムが挙げられる。剥離フィルムは、セパレーターとして機能し得る。具体的には、剥離フィルムとして、表面が剥離剤でコートされたプラスチックフィルムが好ましく用いられる。剥離剤の具体例としては、シリコーン系剥離剤、フッ素系剥離剤、長鎖アルキルアクリレート系剥離剤が挙げられる。
上記位相差層は、二層以上の積層構造を有していてもよいし、単一層とされていてもよい。位相差層の厚みは、その構成(単一層であるか積層構造を有するか)にもよるが、例えば1μm以上50μm以下である。1つの実施形態においては、位相差層の厚みは、好ましくは10μm以下であり、より好ましくは8μm以下であり、さらに好ましくは6μm以下である。なお、位相差層が積層構造である場合、「位相差層の厚み」は、各位相差層の厚みの合計を意味する。具体的には、「位相差層の厚み」には接着層の厚みは含まれない。
本発明の実施形態による偏光板は、上記偏光子に各層を積層することにより得ることができる。各層の積層は、例えば、ロール搬送しながら(いわゆるロールトゥロールにより)行われる。上記保護層の積層は、例えば、接着剤を用いて行われる。上記位相差層の積層は、代表的には、基材に形成された液晶配向固化層を転写することにより行われる。位相差層が積層構造を有する場合には、それぞれの位相差層を樹脂フィルムに順次積層(転写)してもよく、位相差層の積層物を樹脂フィルムに積層(転写)してもよい。転写は、例えば、活性エネルギー線硬化型接着剤を用いて行われる。活性エネルギー線硬化型接着剤の硬化後の厚み(接着剤層の厚み)は、好ましくは0.4μm以上であり、より好ましくは0.4μm~3.0μmであり、さらに好ましくは0.6μm~1.5μmである。
<厚み>
10μm以下の厚みは、走査型電子顕微鏡(日本電子社製、製品名「JSM-7100F」)を用いて測定した。10μmを超える厚みは、デジタルマイクロメーター(アンリツ社製、製品名「KC-351C」)を用いて測定した。
(積層物の作製)
熱可塑性樹脂基材として、長尺状で、Tg約75℃である、非晶質のイソフタル共重合ポリエチレンテレフタレートフィルム(厚み:100μm)を用い、この樹脂基材の片面に、コロナ処理を施した。
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(日本合成化学工業社製、商品名「ゴーセファイマー」)を9:1で混合したPVA系樹脂100重量部に、ヨウ化カリウム13重量部を添加したものを水に溶かし、PVA水溶液(塗布液)を調製した。
樹脂基材のコロナ処理面に、上記PVA水溶液を塗布して60℃で乾燥することにより、厚み13μm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、130℃のオーブン内で縦方向(長手方向)に2.4倍に一軸延伸した(空中補助延伸処理)。
次いで、積層体を、液温40℃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(水100重量部に対して、ヨウ素とヨウ化カリウムを1:7の重量比で配合して得られたヨウ素水溶液)に、最終的に得られる偏光子の単体透過率(Ts)が所望の値となるように濃度を調整しながら60秒間浸漬させた(染色処理)。
次いで、液温40℃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5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(ホウ酸濃度4重量%、ヨウ化カリウム濃度5重量%)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20℃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)。
その後、約90℃に保たれたオーブン中で乾燥しながら、表面温度が約75℃に保たれたSUS製の加熱ロールに接触させた(乾燥収縮処理)。
このようにして、樹脂基材上に厚み約5μmの樹脂フィルムを形成し、樹脂基材/樹脂フィルムの構成を有する積層物を得た。
室温下で、得られた積層物の樹脂フィルムの露出面に、無水トリフルオロ酢酸(富士フイルム和光純薬株式会社製、純度98.0%以上)を塗工した。
上記樹脂フィルム(偏光子)の化学修飾を施した面に、紫外線硬化型接着剤を介して、HC-TACフィルム(厚み32μm)を第一保護層として貼り合わせた。HC-TACフィルムは、TACフィルム(厚み25μm)にハードコート(HC)層(厚み7μm)が形成されたフィルムであり、TACフィルムが樹脂フィルム側となるようにして貼り合わせた。次いで、樹脂フィルムから樹脂基材を剥がし、この剥離面に、厚み20μmの粘着剤層(HC-TACフィルムよりも透湿度が高い)を形成し、セパレーター(PET系フィルム、厚み38μm)を貼り合わせた。こうして、偏光板を得た。
上記樹脂フィルム(偏光子)の化学修飾を施した面に、厚み23μmの粘着剤層を形成し、セパレーター(PET系フィルム、厚み38μm)を貼り合わせた。次いで、樹脂フィルムから樹脂基材を剥がし、この剥離面に、紫外線硬化型接着剤を介して、HC-TACフィルム(厚み32μm)を第一保護層として貼り合わせた。HC-TACフィルムは、TACフィルム(厚み25μm)にハードコート(HC)層(厚み7μm)が形成されたフィルムであり、TACフィルムが樹脂フィルム側となるようにして貼り合わせた。こうして、偏光板を得た。
化学修飾に際し、上記積層物に対する処理を下記の手順で行ったこと以外は実施例1と同様にして、偏光板Aおよび偏光板Bを得た。
長尺状の積層物を長手方向および幅方向に沿って切断して得られた200mm×150mmの枚葉状の積層物および4mlの無水トリフルオロ酢酸を入れた容器(カップ)を、内部を窒素で満たしたポリエチレン製の袋(旭化成ホームプロダクツ株式会社製、ジップロック(登録商標)フリーザーバッグ、268mm×273mm)に入れて密封し、室温下に5分間静置した。
化学修飾に際し、上記静置時間を30分としたこと以外は実施例2と同様にして、偏光板Aおよび偏光板Bを得た。
得られた積層物に対し化学修飾を行わなかったこと以外は実施例1と同様にして、偏光板を得た。
各実施例および比較例について、下記の評価を行った。評価結果を表1にまとめる。
1.接触角
各実施例および比較例において、化学修飾後の樹脂フィルム(偏光子)の化学修飾面の水接触角を測定した。具体的には、23℃、50%RHの環境下において、接触角計(協和界面科学社製、商品名「DMo-501型」、コントロールボックス「DMC-2」、制御・解析ソフト「FAMAS(バージョン5.0.30)」)を用いて液滴法により測定した。蒸留水の滴下量は2μLとし、滴下5秒後の画像からθ/2法により接触角を算出した。
なお、表1に記載の値は、測定3回の平均値である。
2.フッ素含有量
各実施例および比較例において、化学修飾後の樹脂フィルム(偏光子)から2cm×4cm(8cm2)の試験片を切り出し、これをセラミックボードに入れて秤量後、助燃剤を添加した。次に、自動試料燃焼装置を用いて燃焼させ、発生したガスを吸収液10mLに捕集した。捕集後の吸収液を超純水で15mLとし、イオンクロマトグラフィーによる分析を行うことによりフッ素含有量を求めた。
なお、分析装置・測定条件は以下のとおりである。
〇分析装置
(1)自動試料燃焼装置:日東精工アナリテック社製、「AQF-2100H」
(2)イオンクロマトグラフィー装置:Thermo Fisher Scientific社製、「ICS-3000」
〇測定条件
(1)自動試料燃焼装置
Inlet温度:1000℃
Outlet温度:1100℃
ガス流量O2:400mL/min
ガス流量Ar:200mL/min
Ar送液ユニット:100mL/min
(2)イオンクロマトグラフィー装置
分離カラム:Dionex IonPac AS18-fast(4mm×150mm)
ガードカラム:Dionex IonPac AS18-fast(4mm×30mm)
除去システム:Dionex ADRS-600(エクスターナルモード)
検出器:電気伝導度検出器
溶離液:KOH水溶液(溶離液ジェネレーターEGCIIIを使用)
溶離液流量:1.2mL/min
試料注入量:250μL
なお、表1に記載の値は、測定2回(実施例1のみ3回)の平均値である。
3.耐久性
実施例および比較例で得られた偏光板からセパレーターを剥がし、無アルカリガラス板に貼り合わせた。この状態で85℃、85%RHのオーブン内に24時間静置した後、湿熱試験前後の偏光板の単体透過率を測定し、湿熱試験による単体透過率の変化を算出した。単体透過率Tsは、紫外可視分光光度計(日本分光社製、V-7100)を用いて測定した。なお、Tsは、JIS Z8701の2度視野(C光源)により測定して視感度補正を行なったY値である。
なお、表1に記載の値は、湿熱試験前の単体透過率から湿熱試験後の単体透過率を引いた値を示している。
10 偏光子(樹脂フィルム)
21 第一保護層
40 粘着剤層
50 剥離フィルム
100 積層物
200 偏光板
Claims (10)
- ヨウ素を含み、互いに対向する第一主面および第二主面を有する樹脂フィルムから構成され、
少なくとも前記第一主面に前記樹脂フィルムが化学修飾された化学修飾部を有し、
前記化学修飾部は、化学修飾されていない他の部位よりも疎水性が高い、
偏光子。 - 前記化学修飾部はフッ素を含む基を含む、請求項1に記載の偏光子。
- 前記フッ素を含む基はトリフルオロアセチル基を含む、請求項2に記載の偏光子。
- 前記化学修飾部は無水トリフルオロ酢酸により化学修飾されている、請求項1から3のいずれかに記載の偏光子。
- フッ素含有量が20μg/g以上である、請求項1から4のいずれかに記載の偏光子。
- 前記化学修飾部の接触角が90°以上である、請求項1から5のいずれかに記載の偏光子。
- 厚みが8μm以下である、請求項1から6のいずれかに記載の偏光子。
- ヨウ素を含み、互いに対向する第一主面および第二主面を有する樹脂フィルムの少なくとも前記第一主面を化学修飾することを含む、
請求項1から7のいずれかに記載の偏光子の製造方法。 - 前記化学修飾により前記第一主面の接触角を5°以上上昇させる、請求項8に記載の製造方法。
- 請求項1から7のいずれかに記載の偏光子と、
保護層または位相差層の少なくとも一つと、
を有する、偏光板。
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JP2004258165A (ja) * | 2003-02-25 | 2004-09-16 | Nitto Denko Corp | 光学部材、その製造方法、粘着型光学部材および画像表示装置 |
JP2006293188A (ja) * | 2005-04-14 | 2006-10-26 | Nippon Kayaku Co Ltd | 偏光素膜、偏光板、及びその製造法 |
WO2015056801A1 (ja) * | 2013-10-17 | 2015-04-23 | ホヤ レンズ タイランド リミテッド | 偏光レンズ、アイウエア、および偏光レンズの製造方法 |
CN109181186A (zh) * | 2018-11-12 | 2019-01-11 | 洪春 | 一种可生物降解疏水性pva树脂复合材料 |
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JP2004258165A (ja) * | 2003-02-25 | 2004-09-16 | Nitto Denko Corp | 光学部材、その製造方法、粘着型光学部材および画像表示装置 |
JP2006293188A (ja) * | 2005-04-14 | 2006-10-26 | Nippon Kayaku Co Ltd | 偏光素膜、偏光板、及びその製造法 |
WO2015056801A1 (ja) * | 2013-10-17 | 2015-04-23 | ホヤ レンズ タイランド リミテッド | 偏光レンズ、アイウエア、および偏光レンズの製造方法 |
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