WO2021177046A1 - 位相差層付偏光板の製造方法 - Google Patents

位相差層付偏光板の製造方法 Download PDF

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Publication number
WO2021177046A1
WO2021177046A1 PCT/JP2021/006077 JP2021006077W WO2021177046A1 WO 2021177046 A1 WO2021177046 A1 WO 2021177046A1 JP 2021006077 W JP2021006077 W JP 2021006077W WO 2021177046 A1 WO2021177046 A1 WO 2021177046A1
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Prior art keywords
layer
retardation layer
liquid crystal
polarizing plate
group
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PCT/JP2021/006077
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English (en)
French (fr)
Japanese (ja)
Inventor
中西　貞裕
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日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020227026792A priority Critical patent/KR20220145332A/ko
Priority to JP2022505116A priority patent/JP7707146B2/ja
Priority to CN202180018408.XA priority patent/CN115244435A/zh
Publication of WO2021177046A1 publication Critical patent/WO2021177046A1/ja

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/03—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers with respect to the orientation of features
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • 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
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8793—Arrangements for polarized light emission

Definitions

  • the present invention relates to a method for manufacturing a polarizing plate with a retardation layer.
  • image display devices represented by liquid crystal displays and electroluminescence (EL) display devices for example, organic EL display devices and inorganic EL display devices
  • EL electroluminescence
  • a polarizing plate and a retardation plate are typically used in the 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).
  • image display devices such as liquid crystal display devices and organic EL display devices are required to have higher durability. Therefore, the optical members constituting the image display device are required to have a small change in optical characteristics even when exposed to a high temperature environment for a long time.
  • the oriented liquid crystal film that is photocured after the liquid crystal molecules are oriented the molecules are fixed in the oriented state, and no phase transition occurs even when heated. Therefore, it is considered to have high heating durability and is used as a retardation layer.
  • a polarizing plate with a retardation layer in which a retardation layer made of an oriented liquid crystal film is laminated via an adhesive layer has a problem that the optical characteristics change.
  • the present invention has been made to solve the above-mentioned conventional problems, and its main purpose is to have a small change in optical characteristics even when exposed to a high temperature environment for a long time, and a phase difference having excellent heating durability.
  • An object of the present invention is to provide a method for manufacturing a layered polarizing plate.
  • the present invention provides a method for producing a polarizing plate with a retardation layer, which comprises a protective layer, a polarizing element, an adhesive layer, and a retardation layer which is an orientation-solidifying layer of a liquid crystal compound in this order.
  • the method for manufacturing a polarizing plate with a retardation layer includes a step of laminating the polarizer and the retardation layer via an adhesive layer, and after the laminating step, a polarizer, a retardation layer, and an adhesive. Includes a step of heating the laminate containing the layers.
  • a protective layer in another aspect of the present invention, a protective layer, a polarizing element, a first adhesive layer, a first retardation layer which is an orientation-solidifying layer of a liquid crystal compound, a second adhesive layer, and a second.
  • a method for manufacturing a polarizing plate with a retardation layer which comprises two retardation layers in this order.
  • the method for manufacturing the polarizing plate with a retardation layer includes a step of laminating the first retardation layer and the second retardation layer via a second adhesive layer, and after the laminating step, a second step. It includes a step of heating a laminate including a retardation layer (1), a second retardation layer, and a second adhesive layer.
  • the method for manufacturing a polarizing plate with a retardation layer includes a step of laminating the polarizer and the first retardation layer via a first adhesive layer, and a step of laminating the lamination step. Later, it comprises a step of heating the laminate containing the polarizer, the first retardation layer, and the first adhesive layer. In one embodiment, the heating time in the step of heating the laminate exceeds 1 hour. In one embodiment, the heating temperature in the step of heating the laminate is 90 ° C. to 110 ° C.
  • a method for manufacturing a polarizing plate with a retardation layer which has a small change in optical characteristics even when exposed to a high temperature environment for a long time and has excellent heating durability.
  • the method for producing a polarizing plate with a retardation layer of the present invention after a step of laminating a polarizer and a retardation layer and / or a first retardation layer and a second retardation layer via an adhesive layer, It includes a step of heating the laminated body laminated via the adhesive layer.
  • Refractive index (nx, ny, nz) “Nx” is the refractive index in the direction in which the in-plane refractive index is maximized (that is, the slow-phase axis direction), and “ny” is the in-plane direction orthogonal to the slow-phase axis (that is, the phase-advance axis direction). Is the refractive index of, and "nz” is the refractive index in the thickness direction.
  • In-plane phase difference (Re) “Re ( ⁇ )” is an in-plane phase difference measured with light having a wavelength of ⁇ nm at 23 ° C.
  • Re (550) is an in-plane phase difference measured with light having a wavelength of 550 nm at 23 ° C.
  • Phase difference in the thickness direction (Rth) is a phase difference in the thickness direction measured with light having a wavelength of ⁇ nm at 23 ° C.
  • Rth (550) is a phase difference in the thickness direction measured with light having a wavelength of 550 nm at 23 ° C.
  • FIG. 1 is a schematic cross-sectional view of the polarizing plate with a retardation layer according to one embodiment of the present invention.
  • the polarizing plate with a retardation layer 100 of the present embodiment has a protective layer 10, a polarizer 20, an adhesive layer 30, and a retardation layer 40 which is an orientation-solidifying layer of a liquid crystal compound (hereinafter, the first Also called a polarizing plate with a retardation layer).
  • the adhesive layer 30 comprises a UV curable adhesive.
  • the retardation layer 40 may be a single layer of the orientation solidification layer, or may have a laminated structure of the first orientation solidification layer 21 and the second orientation solidification layer 22.
  • FIG. 2 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to another embodiment of the present invention.
  • the polarizing plate 101 with a retardation layer according to another embodiment includes a protective layer 10, a polarizer 20, a first adhesive layer 31, a first retardation layer 41, and a second adhesive layer 32.
  • a second retardation layer 42 is provided in this order (hereinafter, also referred to as a second polarizing plate with a retardation layer).
  • the first adhesive layer and / or the second adhesive layer comprises a UV curable adhesive.
  • the first retardation layer 41 and the second retardation layer 42 may be a single layer of the orientation solidification layer, and have a laminated structure of the first orientation solidification layer 21 and the second orientation solidification layer 22. You may.
  • the polarizing plate with a retardation layer according to the embodiment of the present invention may further include other retardation layers.
  • the optical characteristics for example, refractive index characteristics, in-plane retardation, Nz coefficient, photoelastic coefficient
  • thickness, arrangement position, and the like of other retardation layers can be appropriately set according to the purpose.
  • the total thickness of the polarizing plate with a retardation layer can be set to an arbitrary appropriate value according to the components included.
  • the total thickness of the first polarizing plate with a retardation layer is preferably 10 ⁇ m to 200 ⁇ m, more preferably 20 ⁇ m to 150 ⁇ m, and even more preferably 30 ⁇ m to 120 ⁇ m.
  • the total thickness of the second polarizing plate with a retardation layer is preferably 10 ⁇ m to 200 ⁇ m, more preferably 20 ⁇ m to 150 ⁇ m, and even more preferably 30 ⁇ m to 120 ⁇ m.
  • any suitable polarizer can be used.
  • a hydrophilic polymer film such as a polyvinyl alcohol (hereinafter, also referred to as PVA) film, a partially formalized polyvinyl alcohol film, an ethylene / vinyl acetate copolymerization system partially saponified film, and iodine or a bicolor dye are used.
  • PVA polyvinyl alcohol
  • a partially formalized polyvinyl alcohol film an ethylene / vinyl acetate copolymerization system partially saponified film
  • iodine or a bicolor dye examples thereof include those obtained by adsorbing a bicolor material and uniaxially stretching, and polyene-based oriented films such as a dehydrated product of polyvinyl alcohol and a dehydrogenated product of polyvinyl chloride.
  • a PVA-based film and a polarizer composed of a dichroic substance such as iodine are used.
  • a polarizer composed of a PVA-based film and a dichroic substance such as iodine can be obtained by any suitable method. Specifically, it can be produced by dyeing a PVA-based film by immersing it in an aqueous solution of iodine and stretching it to 3 to 7 times the original length. If necessary, the PVA-based film may be immersed in an aqueous solution such as boric acid and potassium iodide. Further, if necessary, the PVA-based film may be immersed in water and washed with water before dyeing. By washing the PVA-based film with water, stains on the surface of the PVA-based film and anti-blocking agents can be washed.
  • Stretching may be performed after dyeing with iodine, stretching may be performed while dyeing, or the stretched PVA-based film may be dyed with iodine. Stretching may be carried out in an aqueous solution such as boric acid and potassium iodide or in a water bath.
  • the thickness of the polarizer is preferably 2 ⁇ m to 30 ⁇ m, more preferably 4 ⁇ m to 20 ⁇ m, and further preferably 5 ⁇ m to 15 ⁇ m.
  • the thickness of the polarizer is within the above range, the optical durability is excellent, the dimensional change in a high temperature and high humidity environment is suppressed, and the occurrence of display unevenness can be prevented.
  • the thickness of the polarizer is preferably 10 ⁇ m or less.
  • the composition (curable resin composition) for forming the adhesive layer which will be described later, is used in combination with a polarizing element having a thickness of 10 ⁇ m or less to obtain optical durability of the polarizing plate obtained in a harsh environment such as high temperature and high humidity. Can be improved.
  • a polarizer having a thickness of 10 ⁇ m or less is more affected by moisture than a polarizer having a thickness of more than 10 ⁇ m, and its optical durability is not sufficient in an environment of high temperature and high humidity, so that the transmittance increases and the degree of polarization decreases. May be more likely to occur.
  • the thickness of the polarizer is more preferably 1 ⁇ m to 7 ⁇ m from the viewpoint of thinning. When the thickness of the polarizer is within the above range, a polarizing plate having less uneven thickness and excellent visibility can be obtained. Further, the dimensional change of the polarizer is small, and the thickness of the polarizer can be reduced.
  • Polarizers having a thickness of 10 ⁇ m or less are, for example, JP-A-51-069644, JP-A-2000-338329, WO2010 / 100917 Pamphlet, PCT / JP2010 / 00146, and Japanese Patent Application No. 2010-269002.
  • the book, Japanese Patent Application No. 2010-263692, is described. The entire description of these publications is incorporated herein by reference.
  • These polarizers can be obtained by a production method including a step of stretching a laminate of a PVA-based resin layer and a stretching resin base material and a step of dyeing the PVA-based resin layer.
  • the polarizing element having a thickness of 10 ⁇ m or less can be stretched at a high magnification even in a manufacturing method including a step of stretching in the state of the laminated body and a step of dyeing a PVA-based resin layer, thereby improving the polarization performance. Therefore, preferably, one obtained by a production method further including a step of stretching the laminate in an aqueous boric acid solution is used.
  • a manufacturing method is disclosed in WO2010 / 100917 pamphlet, PCT / JP2010 / 00146, or Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692. The entire description of these publications is incorporated herein by reference.
  • a polarizer obtained by a production method including a step of auxiliary stretching in the air before stretching in an aqueous boric acid solution can be mentioned.
  • Such a manufacturing method is disclosed in Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692. The entire description of these publications is incorporated herein by reference.
  • the first polarizing plate with a retardation layer 100 includes a retardation layer 40 which is an orientation-solidified layer of a liquid crystal compound.
  • the second polarizing plate with a retardation layer 101 includes a first retardation layer 41 which is an orientation-solidified layer of a liquid crystal compound.
  • Orientation of liquid crystal compound In the retardation layer, which is a solidified layer, a liquid crystal composition is applied on a support substrate, the liquid crystal composition is heated to orient the liquid crystal compound in a predetermined direction, and the liquid crystal compound is irradiated with light. Is obtained by polymerizing or cross-linking.
  • the second retardation layer 42 is an orientation-solidified layer of a liquid crystal compound.
  • the liquid crystal compound is a thermotropic liquid crystal that develops liquid crystal properties by heating.
  • the thermotropic liquid crystal undergoes a phase transition of a crystal phase, a liquid crystal phase, and an isotropic phase as the temperature changes.
  • the liquid crystal compound may be a nematic liquid crystal, a smectic liquid crystal, or a cholesteric liquid crystal.
  • a chiral agent may be added to the nematic liquid crystal to give it cholesteric orientation.
  • the liquid crystal composition contains at least one photopolymerizable liquid crystal monomer.
  • the photopolymerizable liquid crystal monomer has a mesogen group and at least one photopolymerizable functional group in one molecule.
  • the temperature at which the photopolymerizable liquid crystal monomer exhibits liquid crystallinity is preferably 40 ° C. to 200 ° C., more preferably 50 ° C. to 150 ° C., and even more preferably 55 ° C. to 100 ° C. ..
  • any suitable liquid crystal monomer can be adopted as the photopolymerizable liquid crystal monomer.
  • the liquid crystal composition may contain a compound that controls the orientation of the photopolymerizable liquid crystal monomer in a predetermined direction (hereinafter, also referred to as an orientation control compound). Since the liquid crystal composition contains the orientation control compound, it is possible to form a liquid crystal layer in which the liquid crystal molecules are oriented in a predetermined direction even when a support substrate without an alignment film is used.
  • an orientation control compound a compound that controls the orientation of the photopolymerizable liquid crystal monomer in a predetermined direction
  • the orientation control compound may be a polymer or a low molecular weight compound.
  • the liquid crystal composition contains a side chain type liquid crystal polymer.
  • the polymer has a liquid crystal fragment in the side chain, liquid crystallinity is exhibited, and when the liquid crystal composition is heated to a predetermined temperature, the orientation of the polymer in a predetermined direction can be promoted.
  • the liquid crystal composition may contain a photopolymerization initiator.
  • the liquid crystal composition When the liquid crystal monomer is cured by ultraviolet irradiation, the liquid crystal composition preferably contains a photopolymerization initiator (photoradical generator) that generates radicals by light irradiation in order to promote photocuring.
  • a photopolymerization initiator photoradical generator
  • a photocation generator or a photoanion generator may be used.
  • the photopolymerization initiator can be used in any suitable amount. The amount of the photopolymerization initiator used is, for example, 0.01 parts by weight to 10 parts by weight with respect to 100 parts by weight of the liquid crystal monomer. Further, a sensitizer or the like may be used.
  • a liquid crystal composition can be prepared by mixing a photopolymerizable liquid crystal monomer, an arbitrary orientation control agent, a photopolymerization initiator and the like, and a solvent.
  • a solvent any suitable solvent can be used, and a solvent that can dissolve the photopolymerizable liquid crystal monomer and does not erode the substrate or has low erosion resistance can be preferably used.
  • halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene and orthodichlorobenzene; phenols such as phenol and parachlorophenol; benzene, toluene, xylene, methoxybenzene, etc.
  • Aromatic hydrocarbons such as 1,2-dimethoxybenzene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-pyrrolidone, N-methyl-2-pyrrolidone; ethyl acetate, butyl acetate Ester-based solvents such as t-butyl alcohol, glycerin, ethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol and other alcohol solvents.
  • ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-pyrrolidone, N-methyl-2-pyrrolidone
  • Amid solvents such as dimethylformamide and dimethylacetamide; nitrile solvents such as acetonitrile and butyronitrile; ether solvents such as diethyl ether, dibutyl ether and tetrahydrofuran; ethyl cellsolve, butyl cellsolve and the like can be mentioned. Only one type of solvent may be used, or two or more types may be used in combination.
  • the solid content concentration of the liquid crystal composition is usually 5% by weight to 60% by weight.
  • the liquid crystal composition may further contain other additives such as surfactants and leveling agents.
  • any suitable substrate can be used as the support substrate on which the liquid crystal composition is applied.
  • a glass plate, a metal plate, a metal belt, a resin film substrate and the like can be mentioned.
  • the support substrate has a first main surface and a second main surface, and the liquid crystal composition is applied onto the first main surface.
  • a resin film substrate is preferably used as the support substrate.
  • a series of steps from coating the liquid crystal composition onto the substrate, photocuring the liquid crystal monomer, and subsequent heat treatment can be carried out by roll-to-roll, and the phase difference can be obtained. Layer productivity can be improved.
  • a resin that is insoluble in the solvent used for the liquid crystal composition and has heat resistance during heating for orienting the liquid crystal composition is preferably used.
  • polyesters such as polyethylene terephthalate and polyethylene naphthalate; polyolefins such as polyethylene and polypropylene; cyclic polyolefins such as norbornene-based polymers; cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose; acrylic polymers; styrene-based polymers; polycarbonate and polyamide.
  • polyesters such as polyethylene terephthalate and polyethylene naphthalate
  • polyolefins such as polyethylene and polypropylene
  • cyclic polyolefins such as norbornene-based polymers
  • cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose
  • acrylic polymers styrene-based polymers
  • polycarbonate and polyamide polyamide
  • the support substrate may have an orientation ability for orienting liquid crystal molecules in a predetermined direction.
  • liquid crystal molecules can be homogenically oriented along the stretching direction.
  • the stretch ratio of the stretched film may be such that it can exhibit the orientation ability. For example, it is stretched 1.1 to 5 times.
  • the stretched film may be a biaxially stretched film. Even if the biaxially stretched film is used, the liquid crystal molecules can be oriented along the direction in which the stretching ratio is large by using a film having different stretching ratios in the vertical direction and the horizontal direction.
  • the support substrate may have an orientation model on the first main surface.
  • the alignment film any appropriate one may be selected depending on the type of liquid crystal monomer, the material of the substrate, and the like.
  • a polyimide-based film or a polyvinyl alcohol-based film alignment film that has been subjected to rubbing treatment is preferably used.
  • a photoalignment film may be used.
  • the resin film as the support substrate may be subjected to a rubbing treatment without providing the alignment film.
  • the support substrate may include an alignment film for homeotropic alignment of liquid crystal molecules.
  • an orienting agent for forming a homeotopic pick-oriented alignment film vertical alignment film
  • lecithin lecithin
  • stearic acid hexadecyltrimethylammonium bromide
  • octadecylamine hydroxychloride monobasic carboxylic acid chromium complex
  • silane coupling examples thereof include organic silanes such as agents and siloxane compounds, perfluorodimethylcyclohexane, tetrafluoroethylene, and polytetrafluoroethylene.
  • liquid crystal composition contains an orientation control compound
  • a homeotropically oriented liquid crystal film can be formed even when a substrate without an alignment film is used.
  • the versatility of the support substrate can be enhanced, the process can be simplified, and the manufacturing cost can be reduced.
  • the retardation layer which is the orientation solidification layer of the liquid crystal compound, is formed by applying the liquid crystal composition to the support substrate and then heating the liquid crystal compound to orient the liquid crystal compound in a liquid crystal state.
  • Any suitable method can be used as the method for applying the liquid crystal composition. For example, spin coat, die coat, kiss roll coat, gravure coat, reverse coat, spray coat, Meyer bar coat, knife roll coat, air knife coat and the like can be mentioned.
  • the solvent is removed to form a liquid crystal composition layer on the support substrate.
  • the coating thickness can be set to any suitable thickness.
  • the thickness of the liquid crystal composition layer (thickness of the oriented liquid crystal film) after drying and removing the solvent can be adjusted to be about 0.1 ⁇ m to 20 ⁇ m.
  • the liquid crystal compound can be oriented by heating the coating film of the liquid crystal composition coated on the support substrate to form a liquid crystal phase.
  • the heating temperature at which the liquid crystal compound is oriented in a predetermined direction can be set to an arbitrary appropriate value depending on the type of the liquid crystal composition. Usually, the heating temperature is 40 ° C. to 200 ° C. If the heating temperature is too low, the transition to the liquid crystal phase may be insufficient. Further, if the heating temperature is too high, orientation defects may increase.
  • the heating time may be adjusted so that the liquid crystal phase domain grows sufficiently. Usually, the heating time is 30 seconds to 30 minutes.
  • the liquid crystal compound is cooled to a temperature equal to or lower than the glass transition temperature. Any suitable cooling method can be used as the cooling method. For example, it may be taken out from a heating atmosphere to room temperature and left to stand, or it may be forcibly cooled by air cooling or water cooling.
  • the photopolymerizable liquid crystal monomer can be solidified (photocured) in a state of having liquid crystal regularity.
  • the irradiation light any appropriate irradiation light is used so that the photopolymerizable liquid crystal monomer can be polymerized.
  • ultraviolet light or visible light having a wavelength of 250 nm to 450 nm is used.
  • the liquid crystal composition contains a photopolymerization initiator, light of an arbitrary appropriate wavelength may be used according to the photopolymerization initiator.
  • any appropriate light source can be used, and examples thereof include a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a xenon lamp, an LED, a black light, and a chemical lamp.
  • light irradiation is preferably performed in an atmosphere of an inert gas such as nitrogen gas.
  • the irradiation intensity can be set to an arbitrary appropriate value depending on the composition of the liquid crystal composition, the amount of the photopolymerization initiator added, and the like.
  • Irradiation energy integrated light quantity
  • light irradiation may be carried out under heating conditions in order to promote the photocuring reaction.
  • the polymer after photo-curing the liquid crystal monomer by light irradiation is non-liquid crystal, and the transition of the liquid crystal phase, the glass phase, and the crystal phase does not occur due to the temperature change. Therefore, the liquid crystal layer photo-cured with the liquid crystal monomer oriented in a predetermined direction is unlikely to change in molecular orientation due to a temperature change. Further, since the oriented liquid crystal film has a remarkably large birefringence as compared with a film made of a non-liquid crystal material, the thickness of the optically anisotropic element having a desired retardation can be remarkably reduced.
  • the thickness of the oriented liquid crystal film may be set according to a target retardation value or the like, and is, for example, 0.1 ⁇ m to 20 ⁇ m, preferably 0.2 ⁇ m to 10 ⁇ m, and more preferably 0. It is .5 ⁇ m to 7 ⁇ m.
  • the first retardation layer is typically provided to impart antireflection characteristics to the polarizing plate, and functions as a ⁇ / 4 plate when the first retardation layer is a single layer of an orientation solidification layer. Can be done.
  • the in-plane retardation Re (550) of the first retardation layer is preferably 100 nm to 190 nm, more preferably 110 nm to 170 nm, and even more preferably 130 nm to 160 nm.
  • the Nz coefficient of the first retardation layer is preferably 0.9 to 1.5, and more preferably 0.9 to 1.3. By satisfying such a relationship, a very excellent reflected hue can be achieved when the obtained polarizing plate with a retardation layer is used in an image display device.
  • the first retardation layer may exhibit a reverse dispersion wavelength characteristic in which the retardation value increases according to the wavelength of the measurement light, and a positive wavelength dispersion characteristic in which the retardation value decreases according to the wavelength of the measurement light. It may be shown, or may show a flat wavelength dispersion characteristic in which the phase difference value hardly changes with the wavelength of the measurement light.
  • the first retardation layer exhibits inverse dispersion wavelength characteristics.
  • the Re (450) / Re (550) of the retardation layer is preferably 0.8 or more and less than 1, and more preferably 0.8 or more and 0.95 or less. With such a configuration, very excellent antireflection characteristics can be realized.
  • the angle ⁇ formed by 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 °, and even more preferably about 45 °. Is. If the angle ⁇ is in such a range, by using the ⁇ / 4 plate as the first retardation layer as described above, very excellent circularly polarized light characteristics (as a result, very excellent antireflection characteristics). A polarizing plate with a retardation layer having the above can be obtained.
  • the first retardation layer may have a laminated structure of a first oriented solidified layer and a second oriented solidified layer.
  • either one of the first oriented solidified layer and the second oriented solidified layer may function as a ⁇ / 4 plate, and the other may function as a ⁇ / 2 plate. Therefore, the thicknesses of the first oriented solidified layer and the second oriented solidified layer can be adjusted so as to obtain the desired in-plane retardation of the ⁇ / 4 plate or the ⁇ / 2 plate.
  • the angle formed by the slow axis of the first oriented solidification layer and the absorption axis of the polarizer is preferably 10 ° to 20 °, more preferably 12 ° to 18 °, and even more preferably about 15 °. be.
  • the angle formed by the slow axis of the second oriented solidification layer and the absorption axis of the polarizer is preferably 70 ° to 80 °, more preferably 72 ° to 78 °, and even more preferably about 75 °. be.
  • liquid crystal compounds constituting the first oriented solidified layer and the second oriented solidified layer are described above with respect to the single oriented solidified layer. As explained in.
  • the retardation Rth (550) in the thickness direction of the second retardation layer 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. It is -100 nm to -180 nm.
  • the second retardation layer preferably consists of a film containing a liquid crystal material fixed in a homeotropic orientation.
  • the liquid crystal material (liquid crystal compound) that can be homeotropically oriented 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 compounds described in [0020] to [0028] of JP-A-2002-333642 and the method for forming the retardation layer.
  • the thickness of the second retardation layer is preferably 0.5 ⁇ m to 10 ⁇ m, more preferably 0.5 ⁇ m to 8 ⁇ m, and even more preferably 0.5 ⁇ m to 5 ⁇ m.
  • any suitable resin film can be used.
  • the material forming the protective layer include polyester polymers such as polyethylene terephthalate and polyethylene naphthalate; cellulose polymers such as diacetyl cellulose and triacetyl cellulose; acrylic polymers such as polymethyl methacrylate; polystyrene, both acrylonitrile and styrene.
  • Polystyrene-based polymers such as polymers (AS resins); polycarbonate-based polymers and the like can be mentioned.
  • polyolefin-based polymers such as polyethylene, polypropylene, cycloolefin-based or norbornene-structured polyolefins, ethylene-propylene copolymers; vinyl chloride-based polymers; amide-based polymers such as nylon and aromatic polyamides; imide-based polymers; Polymers; polyether sulfone-based polymers; polyether ether ketone-based polymers; polyphenylene sulfide-based polymers; vinyl alcohol-based polymers; vinylidene chloride-based polymers; vinyl butyral-based polymers; allylate-based polymers; polyoxymethylene-based polymers; epoxy-based polymers; or A blend of the above polymers is also used.
  • the film forming the protective layer may contain one or more kinds of arbitrary suitable additives.
  • suitable additives include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a mold release agent, a color retardant, a flame retardant, a nucleating agent, an antistatic agent, a pigment, a colorant and the like. These additives are used in any suitable amount.
  • the film forming the protective layer examples include a polymer film described in JP-A-2001-343529 (WO01 / 37007), for example, a thermoplastic resin having a substituted and / or unsubstituted imide group in the side chain, and a side chain.
  • a thermoplastic resin having a substituted and / or unsubstituted imide group in the side chain examples thereof include resin compositions containing a substituted and / or unsubstituted phenyl and a thermoplastic resin having a nitrile group.
  • Specific examples thereof include a film of a resin composition containing an alternating copolymer composed of isobutylene and N-methylmaleimide and an acrylonitrile / styrene copolymer.
  • the thickness of the protective layer can be set to any appropriate value. From the viewpoint of workability such as strength and handleability, thin layer property, etc., it is preferably 5 ⁇ m to 100 ⁇ m, more preferably 10 ⁇ m to 60 ⁇ m, and further preferably 20 ⁇ m to 40 ⁇ m.
  • Adhesive layer can be formed using any suitable adhesive.
  • the adhesive layer preferably comprises a UV curable adhesive.
  • the adhesive layer is formed with the following curable resin composition.
  • the adhesive layer is a curable resin composition containing a compound represented by the following general formula (1): (In the formula, X is a functional group containing a reactive group, and R 1 and R 2 are independently hydrogen atoms, unsubstituted or substituted aliphatic hydrocarbon groups, aryl groups, or heterocycles. Represents groups, which may be linked to each other to form a ring.)
  • the above X represents a functional group including a reactive group.
  • the reactive group include a hydroxyl group, an amino group, an aldehyde group, a carboxyl group, a vinyl group, a (meth) acrylic group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group, an oxetane group and the like. ..
  • the reactive group contained in X is preferably a vinyl group, a (meth) acrylic group, a styryl group, a (meth) acrylamide group, a vinyl ether group, or an epoxy.
  • the reactive group contained in X is preferably at least one reactive group selected from the group consisting of (meth) acrylic group, styryl group and (meth) acrylamide group. It is a radical.
  • the (meth) acrylamide group has high reactivity, and when it is used in combination with an active energy ray-curable resin, the copolymerization rate can be improved. It is also preferable because the (meth) acrylamide group has high polarity and excellent adhesiveness.
  • the reactive group contained in X is preferably from a hydroxyl group, an amino group, an aldehyde group, a carboxyl group, a vinyl ether group, an epoxy group, an oxetane group and a mercapto group. It is at least one functional group of choice, more preferably an epoxy group.
  • an epoxy group is contained, the adhesion between the adhesive layer and the adherend can be further improved.
  • a vinyl ether group is provided as the reactive group, the curability of the curable resin composition can be improved.
  • the functional group represented by X is preferably a functional group represented by the following formula.
  • Z is a group consisting of a vinyl group, a (meth) acrylic group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group.
  • R 1 and R 2 independently represent a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group, an aryl group, or a heterocyclic group, respectively.
  • the aliphatic hydrocarbon group include an unsubstituted or substituted linear or branched alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cyclic alkyl group having 3 to 20 carbon atoms, and a carbon number of carbon atoms. Examples include 2 to 20 alkenyl groups.
  • aryl group examples include an unsubstituted or substituted phenyl group having 6 to 20 carbon atoms, an unsubstituted or substituted naphthyl group having 10 to 20 carbon atoms, and the like.
  • Heterocyclic groups include, for example, unsubstituted or substituted 5- or 6-membered ring groups containing at least one heteroatom. These may be connected to each other to form a ring.
  • R 1 and R 2 are preferably a hydrogen atom and a linear or branched alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.
  • the curable resin composition further comprises at least one organometallic compound selected from the group consisting of metal alkoxides and metal chelates.
  • a metal alkoxy is a compound in which at least one alkoxy group, which is an organic group, is bonded to a metal
  • a metal chelate is a compound in which an organic group is bonded or coordinated to a metal via an oxygen atom.
  • any suitable metal can be used, preferably titanium, aluminum, zirconium, and more preferably titanium. By using titanium, the adhesive water resistance of the adhesive layer can be further improved.
  • the number of carbon atoms of the organic group contained in the metal alkoxide is preferably 4 or more, and more preferably 6 or more.
  • the pot life of the curable resin composition may be shortened, and the effect of improving the adhesive water resistance may be reduced.
  • the organic group having 6 or more carbon atoms include an octoxy group, which can be preferably used.
  • suitable metal alkoxides include, for example, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetraoctyl titanate, tertiary aluminum titanate, tetratershaly butyl titanate, tetrastearyl titanate, zirconium tetraisopropoxide, zirconium.
  • the number of carbon atoms of the organic group contained in the metal chelate is preferably 4 or more.
  • the pot life of the curable resin composition may be shortened and the effect of improving the adhesive water resistance may be reduced.
  • the organic group having 4 or more carbon atoms include an acetylacetonate group, an ethylacetacetate group, an isostearate group, and an octylene glycolate group.
  • an acetylacetonate group or an ethylacetacetate group is preferable as the organic group from the viewpoint of improving the adhesive water resistance of the adhesive layer.
  • suitable metal chelates include, for example, titanium acetylacetonate, titanium octylene glycolate, titanium tetraacetylacetonate, titanium ethylacetate acetate, polyhydroxytitanium stearate, dipropoxy-bis (acetylacetonato) titanium, di Butoxytitanium-bis (octylene glycolate), dipropoxytitanium-bis (ethylacetoneacetate), titanium lactate, titanium diethanolaminate, titanium triethanolaminate, dipropoxytitanium-bis (lactate), dipropoxytitanium-bis (lactate) Triethanol aminate), di-n-butoxytitanium-bis (triethanolaminate), tri-n-butoxytitanium monostearate, diisopropoxybis (ethylacetacetate) titanium, diisopropoxybis (acetyl) Acetate) Titanium, Diisopropoxybis (Acetylacetone) Titanium, Titanium Phos
  • the organic metal compounds include organic carboxylic acid metal salts such as zinc octylate, zinc laurate, zinc stearate, and tin octylate, acetylacetone zinc chelate, benzoylacetone zinc chelate, dibenzoylmethane zinc chelate, and ethyl acetoacetate.
  • organic carboxylic acid metal salts such as zinc octylate, zinc laurate, zinc stearate, and tin octylate, acetylacetone zinc chelate, benzoylacetone zinc chelate, dibenzoylmethane zinc chelate, and ethyl acetoacetate.
  • zinc chelate compounds such as zinc chelate.
  • the content ratio of the organic metal compound is preferably 0.05 parts by weight to 9 parts by weight, more preferably 0.1 parts by weight to 8 parts by weight, based on 100 parts by weight of the total amount of the active energy ray-curable component. Yes, more preferably 0.15 parts by weight to 5 parts by weight. If the blending amount exceeds 9 parts by weight, the storage stability of the adhesive composition may deteriorate. In addition, the ratio of the components for adhering to the polarizer, the retardation layer, the protective film, etc. may be relatively insufficient, and the adhesiveness may be lowered. If it is less than 0.05 parts by weight, the effect of adhesive water resistance may not be sufficiently exhibited.
  • the curable resin composition further contains other curable components.
  • the curable component include a thermosetting resin and an active energy ray-curable resin.
  • the thermosetting resin include polyvinyl alcohol resin, epoxy resin, unsaturated polyester, urethane resin, acrylic resin, urea resin, melamine resin, phenol resin and the like, and polyvinyl alcohol resin and epoxy resin are preferably used. ..
  • the thermosetting resin may be used in combination with a curing agent, if necessary.
  • the active energy ray-curable resin include electron beam-curable resin, ultraviolet-curable resin, and visible light-curable resin as the classification of the active energy ray-curable resin.
  • an active energy ray-curable resin is used, and more preferably, an ultraviolet curable resin is used.
  • the compound represented by the above formula (1) and the following curable component are collectively referred to as an active energy ray-curable component.
  • active energy rays having a wavelength range of 10 nm to less than 380 nm are referred to as ultraviolet rays
  • active energy rays having a wavelength range of 380 nm to 800 nm are referred to as visible light.
  • curable components include radically polymerizable compounds.
  • the radically polymerizable compound include compounds having a radically polymerizable functional group of a carbon-carbon double bond such as a (meth) acryloyl group and a vinyl group.
  • These curable components may be monofunctional radical-polymerizable compounds or bifunctional or higher-functional polyfunctional radical-polymerizable compounds.
  • these radically polymerizable compounds may be used alone or in combination of two or more.
  • compounds having a (meth) acryloyl group are suitable.
  • (meth) acryloyl means acryloyl group and / or methacryloyl group, and "(meth)" has the same meaning below.
  • the curable resin composition preferably further contains a photopolymerization initiator.
  • a photopolymerization initiator any suitable photopolymerization initiator can be used.
  • benzophenone compounds such as benzyl, benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone; 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, ⁇ -hydroxy Aromatic ketone compounds such as - ⁇ , ⁇ '-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, ⁇ -hydroxycyclohexylphenylketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2 Acetphenone compounds such as -diethoxyacetophenone, 2-methyl-1- [4- (methylthio) -phenyl] -2-morpholinopropane-1; benzoin methyl ether, benzoin ethy
  • the visible light curable resin composition is used as the curable resin composition.
  • a radically polymerizable resin composition and a cationically polymerizable curable resin composition can be mentioned.
  • the curable component contained in the radical polymerization curable resin composition include radical polymerizable compounds used in the radical polymerization curable resin composition.
  • the radically polymerizable compound include compounds having a radically polymerizable functional group of a carbon-carbon double bond such as a (meth) acryloyl group and a vinyl group.
  • these curable components either a monofunctional radical-polymerizable compound or a bifunctional or higher-functional polyfunctional radical-polymerizable compound can be used.
  • these radically polymerizable compounds may be used alone or in combination of two or more.
  • a compound having a (meth) acryloyl group can be preferably used.
  • Examples of the monofunctional radically polymerizable compound include a compound represented by the following general formula (2).
  • R 3 is a hydrogen atom or a methyl group
  • R 4 and R 5 independently represent a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group or a cyclic ether group
  • R 4 and R are R. 5 may form a cyclic heterocycle
  • the carbon number of the alkyl moiety of the alkyl group, hydroxyalkyl group, and / or alkoxyalkyl group can be set to any suitable value. For example, one having 1 to 4 carbon atoms is used. Examples of the cyclic heterocycle that R 4 and R 5 may form include N-acryloyl morpholine and the like.
  • Specific examples of the compound represented by the general formula (2) include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N-isopropyl ( N-alkyl group-containing (meth) acrylamide derivatives such as meta) acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide; N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N -N-hydroxyalkyl group-containing (meth) acrylamide derivatives such as methylol-N-propane (meth) acrylamide; N-alkoxy group-containing (meth) acrylamide derivatives such as N-methoxymethylacrylamide and N-ethoxymethylacrylamide.
  • N-alkyl group-containing (meth) acrylamide derivatives such as meta) acrylamide, N-butyl (
  • Examples of the cyclic ether group-containing (meth) acrylamide derivative include a heterocyclic (meth) acrylamide derivative in which the nitrogen atom of the (meth) acrylamide group forms a heterocycle.
  • N-acryloyl morpholine, N-acryloyl piperidine, N-methacryloyl piperidine, N-acryloyl pyrrolidine and the like can be mentioned.
  • N-hydroxyethylacrylamide and N-acryloylmorpholine can be preferably used from the viewpoints of excellent reactivity, a cured product having a high elastic modulus, and excellent adhesiveness.
  • This curable resin composition may contain another monofunctional radically polymerizable compound as a curable component in addition to the compound represented by the general formula (2).
  • the monofunctional radically polymerizable compound include various (meth) acrylic acid derivatives having a (meth) acryloyloxy group; (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, and fumaric acid.
  • Carboxyl group-containing monomers such as crotonic acid and isocrotonic acid; lactam-based vinyl monomers such as N-vinylpyrrolidone, N-vinyl- ⁇ -caprolactam, and methylvinylpyrrolidone; Vinyl-based monomers having a nitrogen-containing heterocycle such as vinylpyrrole, vinylimidazole, vinyloxazole, and vinylmorpholin; and radically polymerizable compounds having an active methylene group can be used.
  • esterified products with alcohol 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene.
  • Specific examples include Aronix M-220 (manufactured by Toagosei Co., Ltd.), Light Acrylate 1,9ND-A (manufactured by Kyoeisha Chemical Co., Ltd.), Light Acrylate DGE-4A (manufactured by Kyoeisha Chemical Co., Ltd.), Light Acrylate DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.).
  • SR-531 manufactured by Sartomer
  • CD-536 manufactured by Sartomer
  • the polyfunctional (meth) acrylamide derivative is preferably contained in the curable resin composition because the polymerization rate is high and the productivity is excellent, and the crosslinkability when the resin composition is used as a cured product is excellent.
  • the radical polymerization curable resin composition further contains a photopolymerization initiator.
  • a photopolymerization initiator those exemplified above can be used.
  • the cationically polymerizable compound used in the cationically polymerizable curable resin composition includes a monofunctional cationically polymerizable compound having one cationically polymerizable functional group in the molecule and two or more cationically polymerizable functional groups in the molecule. It is classified as a polyfunctional cationically polymerizable compound having. Since the monofunctional cationically polymerizable compound has a relatively low liquid viscosity, the liquid viscosity of the resin composition can be lowered by containing the monofunctional cationically polymerizable compound in the resin composition.
  • monofunctional cationically polymerizable compounds often have functional groups that express various functions, and by containing them in the resin composition, various functions are exhibited in the resin composition and / or the cured product of the resin composition. Can be made to.
  • the polyfunctional cationically polymerizable compound is preferably contained in the resin composition because the cured product of the resin composition can be three-dimensionally crosslinked.
  • Examples of the cationically polymerizable functional group include an epoxy group, an oxetanyl group, and a vinyl ether group.
  • Examples of the compound having an epoxy group include an aliphatic epoxy compound, an alicyclic epoxy compound, and an aromatic epoxy compound. It is preferable to contain an alicyclic epoxy compound because it is excellent in curability and adhesiveness.
  • Examples of the alicyclic epoxy compound include caprolactone-modified products and trimethylcaprolactone-modified products of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.
  • Valerolactone modified products and the like, specifically, seroxide 2021, seroxide 2021A, seroxide 2021P, seroxide 2081, seroxide 2083, seroxide 2085 (all manufactured by Daicel Chemical Industry Co., Ltd.), silacure UVR-6105, silacure. UVR-6107, Cyracure 30, R-6110 (all manufactured by Dow Chemical Japan Co., Ltd.) and the like can be mentioned.
  • a compound having an oxetanyl group By further containing a compound having an oxetanyl group, the effects of improving curability and lowering the liquid viscosity of the composition can be obtained.
  • Compounds having an oxetane group include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, and the like. Di [(3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, phenol novolac oxetane, etc.
  • Aron oxetane OXT-101 and Aron oxetane OXT-121 are mentioned, and Aron oxetane OXT-101 and Aron oxetane OXT-121 are mentioned. , Aron Oxetane OXT-221, Aron Oxetane OXT-221, Aron Oxetane OXT-212 (all manufactured by Toa Synthetic Co., Ltd.) and the like.
  • a compound having a vinyl ether group By further containing a compound having a vinyl ether group, the effects of improving curability and lowering the liquid viscosity of the composition can be obtained.
  • compounds having a vinyl ether group include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol vinyl ether, triethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanedimethanol monovinyl ether, and tricyclodecane vinyl ether. , Cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, pentaerythritol type tetravinyl ether and the like.
  • the cationic polymerization curable resin composition further contains a photocationic polymerization initiator.
  • the photocationic polymerization initiator generates a cationic species or Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and initiates a polymerization reaction of an epoxy group and an oxetanyl group.
  • active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams
  • a photoacid generator can be preferably used as the photocationic polymerization initiator.
  • a photosensitizer that exhibits maximum absorption in combination with light having a wavelength longer than 380 nm, it is sensitive to light having a wavelength in the vicinity of this and promotes the generation of cation species or acids from the photocation polymerization initiator. be able to.
  • the curable resin composition further contains an acrylic oligomer; a photoacid generator; a compound containing an alkoxyl group or an epoxy group; a silane coupling agent; a compound having a vinyl ether group; a compound that causes keto-enol tvariability and the like. You may be.
  • various additives may be contained as other optional components. Additives include epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, silicone.
  • Polymers or oligomers such as system oligomers and polysulfide oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization initiators; leveling agents; wettability improvers; surfactants ; Plasticizers; UV absorbers; Inorganic fillers; Pigments; Dyes and the like.
  • the method for manufacturing a polarizing plate with a retardation layer is a polarizer and a retardation layer, and / or a first retardation layer and a second retardation.
  • a laminate (a laminate of a polarizer and a retardation layer, or a first retardation layer and a second retarder) laminated through the adhesive layer.
  • the step of heating the laminated body with the retardation layer) is included.
  • the first polarizing plate with a retardation layer includes a protective layer, a polarizer, an adhesive layer, and a retardation layer which is an orientation-solidifying layer of a liquid crystal compound in this order.
  • the first method for manufacturing a polarizing plate with a retardation layer includes a step of laminating a polarizer and a retardation layer via an adhesive layer.
  • the second polarizing plate with a retardation layer includes a protective layer, a polarizer, a first adhesive layer, a first retardation layer, a second adhesive layer, and a second retardation layer. Are prepared in this order.
  • the method for manufacturing a polarizing plate with a second retardation layer includes a step of laminating the first retardation layer and the second retardation layer.
  • the method for producing a polarizing plate with a second retardation layer preferably further includes a step of laminating a polarizer and a first retardation layer via an adhesive layer.
  • the step of laminating the polarizer and the first retardation layer via the adhesive layer is preferably performed before the heating step described later.
  • the laminating step via the adhesive layer can be performed by any suitable method.
  • the adhesive layer forming composition specifically, the curable resin composition
  • the retardation layers are laminated. be able to.
  • the adhesive composition is applied to the first polarizing plate with a retardation layer to form a second adhesive layer, and the second retardation layer is laminated.
  • the second retardation layer is laminated.
  • the first retardation layer and the polarizer are laminated via the first adhesive layer, a laminate of the first retardation layer and the polarizer is produced.
  • the second retardation layer may be adhered to the surface of the laminate on the side of the first retardation layer via the adhesive layer, and the first retardation layer and the second retarder may be bonded to the polarizer.
  • a laminate in which the retardation layer and the retardation layer are laminated via the adhesive layer may be laminated via the adhesive layer.
  • the first adhesive layer and the second adhesive layer may be formed of the same adhesive composition (curable resin composition), or may be formed of different adhesive compositions.
  • the slow axis of the retardation layer and the absorption axis of the polarizer are laminated so as to form an arbitrary appropriate angle.
  • any appropriate method can be used as the method for applying the adhesive layer forming composition.
  • reverse coaters gravure coaters (direct, reverse, and offset), bar reverse coaters, roll coaters, die coaters, bar coaters, rod coaters, and the like can be mentioned.
  • the solvent is substantially not used in the laminating process via the adhesive layer. That is, it is preferable to carry out the laminating step using an adhesive composition that does not substantially contain a solvent.
  • an adhesive composition that is substantially free of solvent the adhesive layer can be cured without the need for drying and heating steps.
  • the occurrence of defects due to the remaining solvent for example, deterioration of heating durability and poor appearance
  • substantially not contained means that the solvent-derived component is not more than the detection limit value when the obtained adhesive layer is analyzed.
  • the adhesive layer is formed of an active energy ray-curable adhesive composition, preferably an ultraviolet curable adhesive composition.
  • the adhesive layer can be formed by irradiating the applied adhesive composition with ultraviolet rays and curing the composition.
  • the irradiation light source any suitable light source can be used, and examples thereof include a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a xenon lamp, an LED, a black light, and a chemical lamp.
  • the irradiation intensity can be set to any appropriate value depending on the adhesive layer forming composition used.
  • Irradiation energy integrated light quantity
  • light irradiation may be carried out under heating conditions in order to promote the curing reaction.
  • the method for manufacturing a polarizing plate with a retardation layer includes a step of heating a laminated body laminated via an adhesive layer. By heating the laminated body laminated through the adhesive layer, a polarizing plate with a retardation layer having excellent heating durability can be obtained with a small change in optical characteristics even when exposed to a high temperature environment for a long time. ..
  • the laminate can be heated by any suitable method.
  • a heating furnace such as an oven, an infrared heater, a roll heater and the like can be mentioned.
  • the heating temperature is preferably 90 ° C. to 120 ° C., more preferably 90 ° C. to 110 ° C.
  • the heating time preferably exceeds 1 hour, more preferably 2 hours to 120 hours, and further preferably 6 hours to 48 hours.
  • the polarizing plate with a retardation layer (for example, a polarizing plate with a second retardation layer) includes a laminate laminated via two or more adhesive layers.
  • the heating step may be performed for each step of producing a laminate via each adhesive layer, and each layer is laminated via an adhesive layer to form a desired polarizing plate with a retardation layer. After that, it may be subjected to a heating step.
  • any suitable other steps may be included.
  • a step of laminating the protective layer and the polarizer can be mentioned.
  • the polarizer and the protective layer can be laminated by any suitable method.
  • a method of applying an arbitrary suitable adhesive or adhesive to one surface of the polarizer and laminating a protective layer can be mentioned.
  • the above-mentioned polarizing plate with a retardation layer can be applied to an image display device.
  • the image display device include a liquid crystal display device and an electroluminescence (EL) display device (for example, an organic EL display device and an inorganic EL display device).
  • the polarizing plate with a retardation layer can be arranged on the visual side of an image display device.
  • the polarizing plate with a retardation layer is laminated so that the retardation layer is on the image display cell side (for example, a liquid crystal cell, an organic EL cell, an inorganic EL cell) (so that the polarizing film is on the visual recognition side).
  • Adhesive Layer Formation Composition 1 1 part by weight of a compound represented by the above general formula (1) (3-acrylamide phenylboronic acid, manufactured by Genuine Chemical Co., Ltd.) and a metal alkoxide (manufactured by Matsumoto Fine Chemical Co., Ltd.).
  • Adhesive Layer Formation Composition 2 10 parts by weight of hydroxyethyl acrylamide (manufactured by Kojin Co., Ltd.) and 30 parts by weight of acryloylmorpholin (manufactured by Kojin Co., Ltd.) with respect to 100% by weight of the total amount of the curable resin composition.
  • 1,9-Nonandiol diacrylate manufactured by Kyoeisha Chemical Co., Ltd. 45 parts by weight
  • ARUFON UP1190 acrylic oligomer obtained by polymerizing (meth) acrylic monomer, manufactured by Toa Synthetic Co., Ltd.
  • IRGACURE 907 polymerization started
  • An adhesive layer forming composition curable resin composition 2 containing 3 parts by weight of an agent (manufactured by BASF) and 2 parts by weight of KAYACURE DETX-S (polymerization initiator, manufactured by Nippon Kayaku Co., Ltd.) was obtained.
  • Example 1 Preparation of Polarizer Laminate
  • a long amorphous polyethylene terephthalate (A-PET) film (manufactured by Mitsubishi Plastics, trade name “Novaclear", thickness 100 ⁇ m) was prepared as a base material.
  • An aqueous solution of polyvinyl alcohol (PVA) resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "Gosenol (registered trademark) NH-26”) is applied and dried at 60 ° C. on one side of the base material, and a PVA system having a thickness of 7 ⁇ m is applied.
  • a resin layer was formed.
  • the laminate thus obtained was immersed in an insolubilizing bath at a liquid temperature of 30 ° C. for 30 seconds (insolubilization step). Then, it was immersed in a dyeing bath having a liquid temperature of 30 ° C. for 60 seconds (dyeing step). Then, it was immersed in a cross-linking bath having a liquid temperature of 30 ° C. for 30 seconds (cross-linking step). Then, the laminate was uniaxially stretched in the longitudinal direction (long direction) between rolls having different peripheral speeds while being immersed in a boric acid aqueous solution having a liquid temperature of 60 ° C. The immersion time in the boric acid aqueous solution was 120 seconds, and the laminate was stretched until just before breaking.
  • Preparation of First Phase Difference Layer A phase difference layer (first retardation layer) was prepared in the same manner as in Example 75 of International Publication No. 2017/090418.
  • the in-plane retardation (Re (550)) of the first retardation layer is 140 nm, Re (450) / Re (550) is 0.85, and Re (650) / Re (550) is 1. It was .03. 4.
  • Preparation of Second Phase Difference Layer 20 parts by weight of side chain type liquid crystal polymer represented by the following chemical formula (I), 80 parts by weight of polymerizable liquid crystal (manufactured by BASF: trade name Palocolor LC242) showing a nematic liquid crystal phase, and a photopolymerization initiator.
  • a liquid crystal coating liquid was prepared by dissolving 5 parts by weight in 400 parts by weight of cyclopentanone. Then, the liquid crystal is formed by applying the coating liquid to a base film (norbornene resin film: manufactured by Nippon Zeon Corporation, trade name "Zeonoa”) with a bar coater, and then heating and drying at 70 ° C. for 4 minutes. Oriented. By irradiating this liquid crystal layer with ultraviolet rays and curing the liquid crystal layer, a liquid crystal solidified layer (thickness: 1 ⁇ m) to be a second retardation layer was formed on the base material.
  • the Re (550) of the second retardation layer was 0 nm, and the Rth (550) was ⁇ 71 nm (nx: 1.5326, ny: 1.5326, nz: 1.6550). 5.
  • Manufacture of a polarizing plate with a retardation layer The retardation film is placed on the polarizer side of the polarizing plate so that the angle between the absorption axis of the polarizer and the slow axis of the first retardation layer is 45 °.
  • the adhesive composition 1 obtained in Production Example 1 was used for bonding.
  • the second retardation layer is transferred to the surface of the first retardation layer opposite to the polarizer via the adhesive composition 2 obtained in Production Example 2, and the protective layer / polarizer is transferred.
  • a laminate having the composition of / adhesive layer / first retardation layer / adhesive layer / second retardation layer was obtained.
  • the obtained laminate was heat-treated in an oven at 90 ° C. for 12 hours to obtain a polarizing plate with a retardation layer
  • Example 2 A polarizing plate 2 with a retardation layer was obtained in the same manner as in Example 1 except that it was heat-treated in an oven at 90 ° C. for 1 hour.
  • Example 3 A polarizing plate 3 with a retardation layer was obtained in the same manner as in Example 1 except that it was heat-treated in an oven at 85 ° C. for 24 hours.
  • the polarizing plate with a retardation layer of the present invention is suitably used as a circular polarizing plate for a liquid crystal display device, an organic EL display device, and an inorganic EL display device.
  • Protective layer 20 Polarizer 30 Adhesive layer 31 First adhesive layer 32 Second adhesive layer 40 Phase difference layer 41 First phase difference layer 42 Second phase difference layer 100 Polarizing plate with retardation layer 101 Polarizing plate with retardation layer

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
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