WO2021205726A1 - 光学積層体 - Google Patents

光学積層体 Download PDF

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Publication number
WO2021205726A1
WO2021205726A1 PCT/JP2021/003880 JP2021003880W WO2021205726A1 WO 2021205726 A1 WO2021205726 A1 WO 2021205726A1 JP 2021003880 W JP2021003880 W JP 2021003880W WO 2021205726 A1 WO2021205726 A1 WO 2021205726A1
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Prior art keywords
layer
liquid crystal
group
gas barrier
retardation
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PCT/JP2021/003880
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English (en)
French (fr)
Japanese (ja)
Inventor
光 出▲崎▼
Original Assignee
住友化学株式会社
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Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to KR1020227038976A priority Critical patent/KR20220156654A/ko
Priority to CN202180040579.2A priority patent/CN115917378A/zh
Publication of WO2021205726A1 publication Critical patent/WO2021205726A1/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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to an optical laminate, particularly an optical laminate including a retardation layer and a gas barrier layer adjacent to the retardation layer.
  • a retardation plate used in a flat panel display As a retardation plate used in a flat panel display (FPD), a retardation plate exhibiting anti-wavelength dispersibility is known.
  • the polymerizable liquid crystal compound forming such a retardation plate generally has maximum absorption in the ultraviolet region, and the retardation value of the retardation plate formed from the polymerizable liquid crystal compound is visible from ultraviolet light. It is known that it is easily changed due to light exposure in the light region. Since a change in the retardation value in the retardation plate can cause a decrease in the optical performance of the retardation plate, development of a retardation plate in which the change in the retardation value is unlikely to occur even when exposed to ultraviolet light or the like. Has been made.
  • Patent Document 1 describes two or more kinds including a polymerizable liquid crystal compound whose retardation value changes in the positive direction and a polymerizable liquid crystal compound whose retardation value changes in the negative direction when exposed to ultraviolet light. Disclosed is a technique for maintaining a balance of changes in the retardation value of the entire retardation plate by producing a retardation plate using the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound of the above.
  • Patent Document 1 In recent years, as disclosed in Patent Document 1, the development of a retardation plate that is unlikely to cause a change in the retardation value with respect to light exposure has progressed, but an optical laminate (phase difference plate) having high durability has been developed. There is still a strong demand for.
  • the present invention meets the above requirements without using a novel solution different from Patent Document 1, that is, two types of polymerizable liquid crystal compounds that cause a phase difference value change relative to light exposure.
  • the purpose is to provide a means capable of satisfying the above requirements, and the optical performance is unlikely to change even when irradiated with high-intensity ultraviolet rays, and the performance is unlikely to change even in a harsh environment.
  • a retardation layer containing a retardation expression layer composed of a cured product of a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound, and a gas barrier layer adjacent to at least one surface of the retardation layer.
  • Including and The gas barrier layer has a 500cm 3 / (m 2 ⁇ 24h ⁇ atm) or less of the oxygen gas permeability, optical laminate.
  • the crosslinked structure is derived from a hydrophobic crosslinking agent.
  • an optical laminate including a retardation layer having high durability which is unlikely to cause a change in optical performance even when irradiated with high-intensity ultraviolet rays and is unlikely to cause a change in performance even in a harsh environment, can be obtained.
  • a retardation layer having high durability which is unlikely to cause a change in optical performance even when irradiated with high-intensity ultraviolet rays and is unlikely to cause a change in performance even in a harsh environment.
  • the optical laminate of the present invention includes a retardation layer and a gas barrier layer adjacent to at least one surface of the retardation layer.
  • a retardation layer and a gas barrier layer adjacent to at least one surface of the retardation layer.
  • the optical laminate 11 shown in FIG. 1 includes a retardation layer 1 and a gas barrier layer 2 adjacent to one surface of the retardation layer 1.
  • the retardation layer 1 is composed of an alignment film 3 and a retardation expression layer 4 formed on the alignment film 3.
  • the retardation layer means a configuration composed of an alignment film and a retardation expression layer formed on the alignment film when the retardation expression layer is formed on the alignment film.
  • the retardation expression layer is formed without an alignment film, it means a configuration composed of the retardation expression layer.
  • the optical laminate of the present invention may be configured to include, in addition to the retardation layer and the gas barrier layer, other layers having various functions that can be incorporated into an image display device or the like.
  • other layers include a (peelable) base material, a polarizing element layer, a cured resin layer such as a protective layer and a hard coat layer, an adhesive layer, and a front plate.
  • the retardation layer 1 is formed on the peelable base material 5.
  • the alignment film 3 side of the retardation layer 1 is formed.
  • an optical laminate 11 having the gas barrier layers 2 on both sides of the retardation layer 1 can be obtained as shown in FIG.
  • the phase difference is obtained by laminating the polarizer layer 7 on the gas barrier layer 2 of the laminated body having the layer structure as shown in FIGS. 1 and 2 via the pressure-sensitive adhesive layer 6.
  • An optical laminate 11 (elliptical polarizing plate) including the layer 1 and the polarizer layer 7 is obtained.
  • These optical laminates can be incorporated into an image display device or the like by, for example, attaching a retardation layer 1 to a display element or the like via an adhesive layer after peeling off the peelable base material 5. can.
  • the liquid crystal cured product due to the light exposure in the environment where oxygen is present. It is thought that this is due to the generation of peroxide radicals.
  • the adhesive layer constituting the optical laminate generally has high gas permeability, when the adhesive layer is included as the layer constituting the optical laminate, oxygen in a gaseous state is adhered to the adhesive layer. It is easy for the agent layer to penetrate into the optical laminate, and oxygen that has penetrated into the optical laminate is likely to diffuse into the retardation layer.
  • the optical laminate of the present invention is a laminate excellent in the effect of suppressing the diffusion of oxygen into the retardation layer.
  • the optical laminate of the present invention includes a gas barrier layer adjacent to at least one surface of the retardation layer, the gas barrier layer has a 500cm 3 / (m 2 ⁇ 24h ⁇ atm) or less of the oxygen gas permeability.
  • an oxygen gas permeability of the gas barrier layer adjacent to the phase difference layer is preferably 300cm 3 / (m 2 ⁇ 24h ⁇ atm) or less, more preferably 200 cm 3 / ( m 2 ⁇ 24h ⁇ atm) or less, more preferably 150cm 3 / (m 2 ⁇ 24h ⁇ atm) or less, particularly preferably 100cm 3 / (m 2 ⁇ 24h ⁇ atm) or less.
  • the oxygen gas permeability excellent low as oxygen gas diffusion suppression effect it can lower the lower limit of the oxygen gas permeability in the present invention is not particularly limited, and may be a 0cm 3 / (m 2 ⁇ 24h ⁇ atm) .
  • the oxygen gas permeability of the gas barrier layer can be measured by a differential pressure type gas permeability measuring method based on JIS K 7126-1. In detail, the measurement can be performed according to the method described in Examples described later.
  • the gas barrier layer may be provided on only one side of the retardation layer, or may be provided adjacent to both sides. Which surface of the retardation layer the gas barrier layer is to be arranged may be appropriately determined according to the types of other layers constituting the optical laminate other than the retardation layer and the gas barrier layer and their arrangement. It is preferable that the gas barrier layer is present on the surface of the retardation layer on the side where the pressure-sensitive adhesive layer is present in a typical optical laminate.
  • the retardation layer is composed of an alignment film and a retardation expression layer, it is preferable that the gas barrier layer is present on the surface of the retardation expression layer opposite to the alignment film.
  • the oxygen gas permeability of at least one of the gas barrier layers must be equal to or less than the above upper limit, and the oxygen gas permeability of both gas barrier layers must be equal to or less than the above upper limit. Is preferable.
  • the gas barrier layer covers at least one side surface of the retardation layer in the thickness direction.
  • a general optical laminate often has a rectangular single-wafer shape in the end, and in such an optical laminate, there are four sides in the thickness direction of the retardation layer.
  • the fact that the gas barrier layer covers at least one side surface of the retardation layer in the thickness direction means that, for example, at least one of the side surfaces of such a retardation layer is a gas barrier layer at least in a part thereof. It means the state covered with.
  • the side surface of the retardation layer in the thickness direction is covered with the gas barrier layer, the region where the retardation layer is in direct contact with the external environment (outside air) can be reduced, and oxygen and moisture in the air of the retardation layer can be reduced. It is possible to prevent invasion into the layer through the side surface in the thickness direction. As a result, it becomes easy to effectively suppress a decrease in the retardation value of the retardation layer due to light exposure.
  • the entire surface of at least one side surface of the retardation layer in the thickness direction is covered with the gas barrier layer, and the entire surface of all the side surfaces of the retardation layer is covered with the gas barrier layer. Is more preferable.
  • the thickness of the gas barrier layer arranged adjacent to the retardation layer can be appropriately determined according to the material constituting the gas barrier layer, the layer structure of the optical laminate, and the like.
  • the thickness of the gas barrier layer is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, still more preferably 0.1 ⁇ m or more, from the viewpoint of ensuring sufficient gas barrier properties. Further, from the viewpoint of thinning the optical laminate, suppressing color unevenness due to interference, and imparting flexibility, the thickness is preferably 50 ⁇ m or less, more preferably 10 ⁇ m or less, and further preferably 5 ⁇ m or less.
  • the thicknesses of the gas barrier layers may be the same or different from each other, but all of the plurality of gas barrier layers have a thickness within the above range. Is preferable.
  • the film thickness of the gas barrier layer can be measured with a film thickness meter.
  • the gas barrier layer arranged adjacent to the retardation layer is preferably a layer containing a polymer.
  • the polymeric material may constitute a gas barrier layer, so long as the oxygen gas permeability is obtained a layer of a 500cm 3 / (m 2 ⁇ 24h ⁇ atm) or less is not particularly limited, the use of known polymer materials However, it is preferable to include a resin as the polymer material.
  • the resin constituting the gas barrier layer may be either a thermoplastic resin or a thermosetting resin, and for example, a polyvinyl alcohol-based resin, a polyester-based resin, a polyolefin-based resin, a polyamide-based resin, and a polyimide-based resin.
  • polycarbonate-based resins examples thereof include polycarbonate-based resins, acrylic-based resins, and epoxy-based resins. These may be used alone or in combination of two or more.
  • polyvinyl alcohol-based resin and epoxy-based resin are preferable as the polymer material, and polyvinyl alcohol-based resin is easy to form a gas barrier layer having low oxygen gas permeability and excellent effect of suppressing invasion of oxygen gas into the retardation layer. Is more preferable.
  • the gas barrier layer arranged adjacent to the retardation layer is formed from a resin composition containing a polyvinyl alcohol-based resin (hereinafter, also referred to as “PVA-based resin composition”).
  • PVA-based resin composition a resin composition containing a polyvinyl alcohol-based resin
  • the polyvinyl alcohol-based resin refers to a resin containing 50% by mass or more of a structural unit derived from vinyl alcohol.
  • the polyvinyl alcohol-based resin refers to a resin containing 50% by mass or more of a structural unit derived from vinyl alcohol.
  • the polyvinyl alcohol-based resin can be obtained by saponifying a polyvinyl ester-based resin having a structural unit derived from vinyl ester. Examples of the vinyl ester constituting the polyvinyl ester resin include vinyl acetate, vinyl butyrate, vinyl propionate and the like, but vinyl acetate is preferable.
  • the polyvinyl ester-based resin may be a homopolymer of a vinyl ester such as vinyl acetate, or may be a copolymer of the vinyl ester and another monomer copolymerizable.
  • examples of other monomers copolymerizable with vinyl esters include unsaturated carboxylic acids, unsaturated sulfonic acids, olefins, vinyl ethers, and acrylamides having an ammonium group.
  • the polyvinyl alcohol-based resin used for the gas barrier layer may be a partially saponified polyvinyl alcohol-based resin or a completely saponified polyvinyl alcohol-based resin.
  • the degree of saponification of the polyvinyl alcohol-based resin is not particularly limited and may be appropriately determined, but is generally 70 mol% or more, preferably 80 mol% or more, more preferably 85 mol% or more, still more preferable. Is 90 mol% or more.
  • the degree of saponification of the polyvinyl alcohol-based resin is at least the above lower limit, the water resistance of the obtained gas barrier layer and the adhesion between the gas barrier layer and the adjacent layer are likely to be improved.
  • the upper limit of the degree of saponification of the polyvinyl alcohol-based resin may be 100 mol% or less, preferably 99.95 mol% or less.
  • the degree of saponification of the polyvinyl alcohol-based resin can be measured according to the method described in JIS K6726.
  • the method for saponifying the polyvinyl ester resin is not particularly limited, and a conventionally known method can be adopted.
  • a method for saponifying in the presence of a catalyst in an organic solvent such as alcohol can be mentioned.
  • the polyvinyl alcohol-based resin used for the gas barrier layer may be a homopolymer or a copolymer.
  • various functions such as suppression of oxygen gas permeation, water resistance and adhesion to an adjacent layer can be imparted to the gas barrier layer.
  • the polyvinyl alcohol copolymer include ethylene-polyvinyl alcohol copolymer, acrylic acid, methyl methacrylate-polyvinyl alcohol and the like.
  • the amount of the vinyl alcohol unit in the polyvinyl alcohol copolymer is preferably 80 to 98 mol%, more preferably 85 to 98 mol%.
  • the average degree of polymerization of polyvinyl alcohol is preferably 1000 to 10000, more preferably 1000 to 5000, and even more preferably 1100 to 3000.
  • the average degree of polymerization is a number average degree of polymerization.
  • the average degree of polymerization of polyvinyl alcohol means the average degree of polymerization measured according to the description of JIS K6726.
  • the polyvinyl alcohol-based resin used for the gas barrier layer is preferably a modified one.
  • the modified polyvinyl alcohol-based resin include an acetacetyl group-modified polyvinyl alcohol-based resin, a carboxylic acid-modified polyvinyl alcohol-based resin, a carbonyl group-modified polyvinyl alcohol-based resin, and a sulfonic acid-modified polyvinyl alcohol-based resin.
  • Hydrazide-modified polyvinyl alcohol-based resin Hydrazide-modified polyvinyl alcohol-based resin, thiol-based modified polyvinyl alcohol-based resin, alkyl group-modified polyvinyl alcohol-based resin, silyl group-modified polyvinyl alcohol-based resin, polyethylene glycol-based modified polyvinyl alcohol-based resin
  • examples thereof include a resin, a polyvinyl alcohol-based resin modified with an ethylene oxide group, a polyvinyl alcohol-based resin modified with a group having a urethane bond, and a polyvinyl alcohol-based resin modified with a phosphoric acid ester group.
  • the options for the cross-linking reaction with the cross-linking agent described later are increased, the cross-linking reactivity can be easily enhanced, the water resistance of the gas barrier layer and the adhesion between the gas barrier layer and the adjacent layer are increased. Is preferable because it improves.
  • the polyvinyl alcohol-based resin may be used alone or in combination of two or more. Moreover, you may use a commercially available product as a polyvinyl alcohol-based resin.
  • the gas barrier layer preferably contains a polymer having a crosslinked structure.
  • the gas barrier layer has a dense structure, and the oxygen gas permeation suppressing effect is easily improved, and the adhesion between the gas barrier layer and the layer adjacent thereto is easily improved.
  • the cross-linking agent that can be used to introduce the cross-linked structure into the polyvinyl alcohol-based polymer a compound known as a cross-linking agent in the polyvinyl alcohol-based resin can be used. ..
  • cross-linking agent examples include water-soluble additives and cross-linking agents such as an ion-binding cross-linking agent such as glyoxalate and an epoxy-based cross-linking agent, an isocyanate-based cross-linking agent, and a polyvalent aldehyde such as glyoxal or a glyoxal derivative.
  • cross-linking agents such as an ion-binding cross-linking agent such as glyoxalate and an epoxy-based cross-linking agent, an isocyanate-based cross-linking agent, and a polyvalent aldehyde such as glyoxal or a glyoxal derivative.
  • hydrophobic cross-linking agent such as a cross-linking agent, a metal compound-based cross-linking agent such as zirconium chloride or titanium lactate.
  • the crosslinked structure of the polymer constituting the gas barrier layer is derived from the hydrophobic crosslinking agent, and isocyanate. More preferably, it is derived from at least one cross-linking agent selected from the group consisting of a system-based cross-linking agent, a polyvalent aldehyde-based cross-linking agent, and a metal compound-based cross-linking agent.
  • the cross-linking agent may be used alone or in combination of two or more.
  • a commercially available product can be used as the cross-linking agent.
  • the water-soluble cross-linking agent include “Safelink SPM-01” (manufactured by Mitsubishi Chemical Corporation) and “Sumirez Resin650” (manufactured by Taoka Chemical Industry Co., Ltd.).
  • the hydrophobic cross-linking agent include “Bernock DNW-5000” (manufactured by DIC Corporation), “Organix ZB-400” (manufactured by Matsumoto Fine Chemical Co., Ltd.), and “Organic TC-310” (manufactured by Matsumoto Fine Chemical Co., Ltd.). (Made by Co., Ltd.), etc.
  • the amount of the cross-linking agent added may be appropriately determined according to the type of the cross-linking agent used and the like.
  • the content of the cross-linking agent in the PVA-based resin composition is usually 0.1 to 100 parts by mass, preferably 1 to 50 parts by mass, and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the polyvinyl alcohol-based resin. It is a department.
  • the content of the cross-linking agent is within the above range, the gas barrier layer becomes dense, the oxygen gas permeation suppressing effect is likely to be improved, and the adhesion between the gas barrier layer and the layer adjacent thereto is likely to be improved. Further, when a hydrophobic cross-linking agent is used, a sufficiently high water resistance can be imparted to the obtained gas barrier layer.
  • the PVA-based resin composition capable of forming the gas barrier layer is usually prepared as a solution in which a polyvinyl alcohol-based resin is dissolved in a solvent.
  • the solvent in the PVA-based resin composition include water, alcohol, a mixture of water and alcohol, and the like, and water is preferable.
  • a gas barrier layer can be obtained by applying a PVA-based resin composition to the surface forming the gas barrier layer, drying the coating film, and curing the coating film.
  • the solid content concentration of the PVA-based resin obtained by adding a solvent to the polyvinyl alcohol-based resin or the cross-linking agent is preferably 2 to 50% by mass, more preferably 5 to 30% by mass, still more preferably 5 to 15% by mass. be.
  • the term "solid content” as used herein refers to a component obtained by removing a solvent such as water from the PVA-based resin composition.
  • the PVA-based resin composition may contain other components such as additives in addition to a solvent such as a polyvinyl alcohol-based resin, a cross-linking agent and water.
  • a solvent such as a polyvinyl alcohol-based resin, a cross-linking agent and water.
  • other components include preservatives, leveling agents and the like.
  • the amount thereof is preferably 10% by mass or less, more preferably 5% by mass or less, based on the solid content of the composition for forming a gas barrier layer. ..
  • the method for forming the coating film of the PVA-based resin composition is not particularly limited, and for example, a coating method such as a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, an applicator method, or a flexographic method.
  • a coating method such as a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, an applicator method, or a flexographic method.
  • a known method such as a printing method such as is mentioned.
  • the drying temperature and time for forming the gas barrier layer from the coating film of the PVA-based resin composition are not particularly limited, and may be appropriately determined according to the composition of the gas barrier layer forming composition to be used.
  • the drying treatment can be performed, for example, by blowing hot air, and the temperature is usually in the range of 40 to 100 ° C, preferably 60 to 100 ° C.
  • the drying time is usually 10 to 600 seconds.
  • the gas barrier layer arranged adjacent to the retardation layer is also referred to as a curable composition containing an active energy ray-curable resin (hereinafter, also referred to as "curable composition for forming a gas barrier layer"). ) Is formed from.
  • curable composition for forming a gas barrier layer include a cationically polymerizable curable composition containing an epoxy compound and a cationic polymerization initiator, and a radically polymerizable curing containing an acrylic curing component and a radical polymerization initiator.
  • a curable composition that is cured by irradiating an electron beam without containing a polymerization initiator.
  • the gas barrier layer is preferably a layer containing an epoxy resin, and a cationically polymerizable epoxy containing an epoxy compound. It is preferably formed from a curable composition containing a system compound.
  • an epoxy compound that can be preferably used, a hydride epoxy compound (aliphatic ring) obtained by reacting epichlorohydrin with an alicyclic polyol obtained by hydrogenating the aromatic ring of an aromatic polyol.
  • Glycidyl ether of a polyol having a formula ring an aliphatic epoxy compound such as an aliphatic polyhydric alcohol or a polyglycidyl ether of an alkylene oxide adduct thereof; having one or more epoxy groups bonded to the alicyclic ring in the molecule.
  • examples thereof include an alicyclic epoxy compound which is an epoxy compound. These may be used alone or in combination of two or more.
  • the curable composition for forming a gas barrier layer may be solvent-free, or the active ingredient may be diluted with a solvent.
  • the solvent when the active ingredient is diluted with a solvent include volatile solvents such as toluene, xylene, methyl ethyl ketone, and methylene chloride.
  • the dilution ratio of the active ingredient when diluted with a solvent is preferably 2 to 40 times, more preferably 10 to 30 times.
  • the above-mentioned "active ingredient” refers to the solid content of the curable composition for forming a gas barrier layer, that is, all the components excluding volatile components such as a solvent from the curable composition for forming a gas barrier layer. means.
  • the content of the epoxy compound in the active ingredient of the curable composition for forming a gas barrier layer is preferably 70 to 99% by mass, more preferably 90 to 95% by mass.
  • the curable composition for forming a gas barrier layer contains a cationic epoxy compound as a curable component, it preferably contains a photocationic polymerization initiator.
  • the photocationic polymerization initiator include aromatic diazonium salts; onium salts such as aromatic iodonium salts and aromatic sulfonium salts; and iron-allene complexes.
  • the content of the photocationic polymerization initiator in the curable composition for forming a gas barrier layer is preferably 0.1 to 30 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the cationic epoxy compound. be.
  • the curable composition for forming a gas barrier layer includes, if necessary, a cationic polymerization accelerator such as oxetane and a polyol, a photosensitizer, an ion trapping agent, an antioxidant, a chain transfer agent, a tackifier, a thermoplastic resin, and the like. It can contain additives such as fillers, flow modifiers, plasticizers, defoamers, antistatic agents, leveling agents, and / or solvents.
  • the gas barrier layer can be formed by applying the curable composition for forming the gas barrier layer to the surface on which the gas barrier layer is formed and then irradiating the surface with active energy rays to cure the composition.
  • a method for applying the curable composition for forming a gas barrier layer the same method as the method for applying the PVA-based resin composition can be adopted.
  • Examples of the light source of the active energy ray include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excima laser, and a wavelength range of 380.
  • Examples thereof include an LED light source that emits light of up to 440 nm, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and a metal halide lamp.
  • the ultraviolet irradiation intensity is usually 10 to 3,000 mW / cm 2 .
  • the ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activating the polymerization initiator.
  • the time for irradiating light is usually 0.1 seconds to 10 minutes, preferably 1 second to 5 minutes, more preferably 5 seconds to 3 minutes, and even more preferably 10 seconds to 1 minute.
  • the integrated light intensity is 10 to 3,000 mJ / cm 2 , preferably 50 to 2,000 mJ / cm 2 , and more preferably 100 to 1,000 mJ / cm. It is 2.
  • the gas barrier layer covers at least one side surface in the thickness direction of the retardation layer, for example, a composition (solution) for forming the gas barrier layer in the retardation layer covered with the gas barrier layer.
  • a composition (solution) for forming the gas barrier layer in the retardation layer covered with the gas barrier layer Immerse in the inside, the side surface of the retardation layer is covered with the side surface of the release film, and the retardation layer and the release film are adhered via a composition (solution) for forming a gas barrier.
  • the side surface of the retardation layer in the thickness direction can be covered with the gas barrier layer.
  • the retardation layer is a retardation expression layer made of a cured product of a polymerizable liquid crystal composition (hereinafter, also referred to as “polymerizable liquid crystal composition”) containing at least one polymerizable liquid crystal compound.
  • polymerizable liquid crystal composition a polymerizable liquid crystal composition
  • the polymerizable liquid crystal compound forming the retardation layer can be appropriately selected from conventionally known polymerizable liquid crystal compounds in the field of retardation films, depending on the desired optical properties.
  • the polymerizable liquid crystal compound is a liquid crystal compound having a polymerizable group.
  • the polymerizable liquid crystal compound generally, the polymer (cured product) obtained by polymerizing the polymerizable liquid crystal compound alone in a state of being oriented in a specific direction is opposite to that of the polymerizable liquid crystal compound exhibiting positive wavelength dispersibility. Examples thereof include polymerizable liquid crystal compounds exhibiting wavelength dispersibility. In the present invention, only one of the polymerizable liquid crystal compounds may be used, or both types of the polymerizable liquid crystal compound may be mixed and used.
  • the optical laminate of the present invention is excellent in the effect of reducing the amount of oxygen gas diffused into the retardation layer by arranging the gas barrier layer having low oxygen gas permeability adjacent to the retardation layer. For this reason, in general, it often has maximum absorption in the ultraviolet region, and includes a retardation expression layer formed from a polymerizable liquid crystal compound that easily generates peroxide radicals when exposed to light in an environment where oxygen is present. In some cases, the effect of the present invention can be obtained more remarkably. Therefore, the retardation expression layer constituting the optical laminate of the present invention is preferably a cured product of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound exhibiting so-called reverse wavelength dispersibility.
  • a polymerizable group is a group that can participate in a polymerization reaction.
  • the polymerizable group contained in the polymerizable liquid crystal compound forming the retardation layer is preferably a photopolymerizable group.
  • the photopolymerizable group is a polymerizable group and refers to a group capable of participating in a polymerization reaction by a reactive active species generated from a photopolymerization initiator, for example, an active radical or an acid.
  • Examples of the photopolymerizable group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, a (meth) acryloyl group, an oxylanyl group and an oxetanyl group.
  • a (meth) acryloyl group, a vinyloxy group, an oxylanyl group and an oxetanyl group are preferable, and an acryloyl group is more preferable.
  • the liquid crystal property exhibited by the polymerizable liquid crystal compound may be a thermotropic liquid crystal or a lyotropic liquid crystal, but a thermotropic liquid crystal is preferable in that precise film thickness control is possible. Further, the phase-ordered structure of the thermotropic liquid crystal may be a nematic liquid crystal, a smectic liquid crystal, or a discotic liquid crystal.
  • the polymerizable liquid crystal compound can be used alone or in combination of two or more.
  • a polymerizable liquid crystal compound having a so-called T-shaped or H-shaped molecular structure tends to exhibit reverse wavelength dispersibility when polymerized and cured, and a polymerizable liquid crystal compound having a T-shaped molecular structure is stronger. It tends to exhibit reverse wavelength dispersibility.
  • the inverse wavelength dispersibility is an optical characteristic in which the in-plane retardation value at a short wavelength becomes larger than the in-plane retardation value at a long wavelength.
  • the polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility is specifically a polymer in an oriented state of the polymerizable liquid crystal compound having the following formula: Re (450) ⁇ Re (550) ⁇ Re (650) [Re ( ⁇ ) represents the front retardation of the retardation plate at wavelength ⁇ ] Means a compound that satisfies.
  • the polymer in the oriented state of the polymerizable liquid crystal compound satisfies the following formulas (I) and (II).
  • Re ( ⁇ ) has the same meaning as above. ]
  • the polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility is preferably a compound having the following characteristics (A) to (D).
  • B) The polymerizable liquid crystal compound has ⁇ electrons in the long axis direction (a).
  • D A polymerizable liquid crystal compound defined by the following formula (i), where the total number of ⁇ electrons existing in the major axis direction (a) is N ( ⁇ a) and the total molecular weight existing in the major axis direction is N (Aa).
  • the major axis direction (a) and the number of ⁇ electrons N are defined as follows.
  • the major axis direction (a) is, for example, the rod-shaped major axis direction of a compound having a rod-shaped structure.
  • the number of ⁇ electrons N ( ⁇ a) existing in the major axis direction (a) does not include ⁇ electrons that disappear due to the polymerization reaction.
  • the number of ⁇ electrons N ( ⁇ a) existing in the long axis direction (a) is the total number of ⁇ electrons on the long axis and ⁇ electrons conjugated thereto, for example, existing in the long axis direction (a).
  • the number of ⁇ electrons present in the ring that satisfies Hückel's law is included.
  • the number of ⁇ electrons N ( ⁇ b) existing in the crossing direction (b) does not include ⁇ electrons that disappear due to the polymerization reaction.
  • the polymerizable liquid crystal compound satisfying the above has a mesogen structure in the major axis direction.
  • the liquid crystal phase (nematic phase, smectic phase) is expressed by this mesogen structure.
  • nematic phase or a smectic phase by heating the polymerizable liquid crystal compound satisfying the above (A) to (D) to a phase transition temperature or higher.
  • the polymerizable liquid crystal compounds are usually oriented so that the major axis directions are parallel to each other, and the major axis direction is the nematic phase or smectic phase. Is the orientation direction of.
  • a polymer film composed of the polymer polymerized in a state oriented in the long axis direction (a) can be formed. ..
  • This polymer film absorbs ultraviolet rays by ⁇ electrons in the long axis direction (a) and ⁇ electrons in the crossing direction (b).
  • the absorption maximum wavelength of ultraviolet rays absorbed by ⁇ electrons in the crossing direction (b) is defined as ⁇ bmax.
  • ⁇ bmax is usually 300 nm to 400 nm.
  • the density of ⁇ electrons satisfies the above equation (iii), and since the ⁇ electron density in the crossing direction (b) is larger than the ⁇ electron density in the major axis direction (a), the oscillating surface in the crossing direction (b).
  • the absorption of linearly polarized ultraviolet rays (wavelength is ⁇ bmax) having a vibration plane in the long axis direction (a) is larger than the absorption of linearly polarized ultraviolet rays (wavelength is ⁇ bmax) having a vibration plane.
  • the ratio (the ratio of the absorbance in the crossing direction (b) of the linearly polarized ultraviolet rays / the absorbance in the major axis direction (a)) is, for example, more than 1.0, preferably 1.2 or more, usually 30 or less, for example, 10 or less. Is.
  • a polymerizable liquid crystal compound having the above characteristics often exhibits a reverse wavelength dispersibility in the birefringence of the polymer when polymerized in a state of being oriented in one direction.
  • a polymerizable liquid crystal compound for example, the following formula (1): Examples thereof include the polymerizable liquid crystal compound (1) represented by (hereinafter, also referred to as “polymerizable liquid crystal compound (1)”).
  • the polymerizable liquid crystal compound is a compound having a structure represented by the above formula (1), it exhibits inverse wavelength dispersibility, can perform uniform polarization conversion in a wide wavelength range, and is used in a display device.
  • a polymerizable liquid crystal composition that can impart good display characteristics can be obtained.
  • Ar a is a divalent aromatic group which may have a substituent.
  • L 1a , L 2a , B 1a and B 2a are independently single-bonded or divalent linking groups, each of which is an alkylene group having 1 to 4 carbon atoms, -COO-, -OCO-, -O-,-.
  • R independently represents a single bond or an alkylene group having 1 to 4 carbon atoms
  • R'independently an alkyl group or a hydrogen atom having 1 to 4 carbon atoms.
  • G 1a and G 2a independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group
  • the hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom and has 1 to 1 to carbon atoms. It may be substituted with an alkyl group of 4 or a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and the divalent aromatic group or the divalent alicyclic group.
  • the carbon atom constituting the formula hydrocarbon group may be substituted with an oxygen atom, a sulfur atom or a nitrogen atom.
  • E 1a and E 2a each independently represent an alkanediyl group having 1 to 17 carbon atoms.
  • the hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, and -CH 2- contained in the alkanediyl group is substituted with -O-, -S-, and -Si-. It may have been.
  • P 1a and P 2a independently represent a hydrogen atom or a polymerizable group, and at least one of P 1a and P 2a is a polymerizable group.
  • k a and l a each independently represent an integer of 0 to 3, satisfying the relation of 1 ⁇ k a + l a.
  • B 1a and B 2a G 1a and G 2a may each be the same as each other or may be different.
  • -N N-
  • -CR' CR'-, or -C ⁇ C-.
  • R independently represents a single bond or an alkylene group having 1 to 4 carbon atoms
  • R'independently represents an alkyl group or a hydrogen atom having 1 to 4 carbon atoms.
  • L 1a and L 2a are independently, more preferably single-bonded, -OR “-, -CH 2- , -CH 2 CH 2- , -COOR”-, or -OCOR "-, respectively.
  • R'' independently represents either single bond, -CH 2- , or -CH 2 CH 2-.
  • L 1a and L 2a are independent, more preferably single bond, -O-, -CH 2 CH 2- , -COO-, -COOCH 2 CH 2- or -OCO-, respectively.
  • L 1a and L 2a may be the same or different from each other, but from the viewpoint of facilitating the production of the polymerizable liquid crystal compound and suppressing the production cost, L 1a and L are L.
  • L 1a and L 2a are the same as each other means that the structures of L 1a and L 2a are the same when viewed with A a as the center.
  • B 1a and B 2a G 1a and G 2a , E 1a and E 2a , and P 1a and P 2a.
  • R independently represents a single bond or an alkylene group having 1 to 4 carbon atoms.
  • B 1a and B 2a are independently, more preferably single-bonded, -OR "-, -CH 2- , -CH 2 CH 2- , -COOR"-, or -OCOR "-, respectively.
  • R'' independently represents either single bond, -CH 2- , or -CH 2 CH 2-.
  • the B 1a and B 2a may each independently, more preferably a single bond, -O -, - CH 2 CH 2 -, - COO -, - COOCH 2 CH 2 -, - OCO- or -OCOCH 2 CH 2 - is ..
  • B 1a and B 2a may be the same or different from each other, but from the viewpoint of facilitating the production of the polymerizable liquid crystal compound and suppressing the production cost, B 1a and B It is preferable that 2a is the same as each other.
  • G 1a and G 2a are each independently substituted with at least one substituent preferably selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, a 1,4-phenylenediyl group.
  • a 1,4-cyclohexanediyl group optionally substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably 1 substituted with a methyl group.
  • G 1a and G 2a may be the same or different from each other, but from the viewpoint of facilitating the production of the polymerizable liquid crystal compound and suppressing the production cost, G 1a and G It is preferable that 2a is the same as each other.
  • G 1a and G 2a When a plurality of G 1a and G 2a are present, it is preferable that at least one of them is a divalent alicyclic hydrocarbon group. Further, it is more preferable that at least one of G 1a and G 2a bonded to L 1a or L 2a is a divalent alicyclic hydrocarbon group, and in particular, L 1a exhibits good liquid crystallinity. Alternatively, it is more preferable that both G 1a and G 2a bonded to L 2a are 1,4-trans-cyclohexanediyl groups.
  • E 1a and E 2a are each independently preferably an alkanediyl group having 1 to 17 carbon atoms, and more preferably an alkanediyl group having 4 to 12 carbon atoms.
  • E 1a and E 2a may be the same or different from each other, but from the viewpoint of facilitating the production of the polymerizable liquid crystal compound and suppressing the production cost, E 1a and E It is preferable that 2a is the same as each other.
  • the polymerizable group represented by P 1a or P 2a includes an epoxy group, a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, and an oxylanyl group. , And an oxetanyl group and the like.
  • an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxylanyl group and an oxetanyl group are preferable, and an acryloyloxy group is more preferable.
  • P 1a and P 2a may be the same or different from each other, but from the viewpoint of facilitating the production of the polymerizable liquid crystal compound and suppressing the production cost, E 1a and E It is preferable that 2a is the same as each other.
  • Ar a is a divalent aromatic group that may have a substituent.
  • the aromatic group is a group having a planar cyclic structure, and the number of ⁇ electrons in the ring structure is [4n + 2] (n represents an integer) according to Hückel's law.
  • n represents an integer
  • the aromatic group which may have a substituent represented by Ar a has an aromatic hydrocarbon ring which may have a substituent or an aromatic hetero ring which may have a substituent. Is preferable.
  • the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring and the like, and examples thereof include a benzene ring and a naphthalene ring.
  • Examples of the aromatic heterocycle include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a triazine ring, a pyrrolin ring, an imidazole ring, and a pyrazole ring.
  • Ar a contains a nitrogen atom, the nitrogen atom preferably has ⁇ electrons.
  • Ar a preferably has an aromatic heterocycle containing at least two heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, and more preferably has a thiazole ring or a benzothiazole ring. , It is more preferable to have a benzothiazole ring.
  • Ar a has an aromatic hetero ring containing at least two hetero atoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom
  • the aromatic hetero ring is L 1a in the formula (1).
  • L 2b may be directly bonded to form a divalent aromatic group, or may be contained as a substituent of a divalent aromatic group directly bonded to L 1a and L 2b.
  • the entire Ar a group containing an aromatic heterocyclic ring is sterically arranged substantially perpendicular direction to the molecular alignment direction is preferred.
  • the total number N ⁇ of ⁇ electrons contained in the divalent aromatic group represented by Ar a is preferably 12 or more, more preferably 13 or more, still more preferably 16 or more. .. Further, it is preferably 32 or less, more preferably 30 or less, still more preferably 28 or less, and particularly preferably 24 or less.
  • Examples of the aromatic group represented by Ar a include groups represented by the following formulas (Ar-1) to (Ar-22).
  • Z 0 , Z 1 and Z 2 are independently hydrogen atoms, halogen atoms, and alkyl having 1 to 12 carbon atoms.
  • Q 1 and Q 2 each independently, -CR 2 'R 3' - , - S -, - NH -, - NR 2 '-, - CO- or -O- and represents, R 2' and R 3 ' Independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • J 1 and J 2 independently represent a carbon atom or a nitrogen atom, respectively.
  • Y 1 , Y 2 and Y 3 each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may be substituted.
  • W 1 and W 2 independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer of 0 to 6.
  • Examples of the aromatic hydrocarbon group in Y 1 , Y 2 and Y 3 include an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and a biphenyl group, and a phenyl group.
  • a naphthyl group is preferable, and a phenyl group is more preferable.
  • the aromatic heterocyclic group has 4 to 20 carbon atoms containing at least one heteroatom such as a nitrogen atom such as a frill group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group or a benzothiazolyl group, an oxygen atom and a sulfur atom.
  • Aromatic heterocyclic groups are mentioned, and a frill group, a thienyl group, a pyridinyl group, a thiazolyl group, and a benzothiazolyl group are preferable.
  • Y 1 , Y 2 and Y 3 may be independently substituted polycyclic aromatic hydrocarbon groups or polycyclic aromatic heterocyclic groups, respectively.
  • the polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aromatic ring assembly.
  • the polycyclic aromatic heterocyclic group refers to a fused polycyclic aromatic heterocyclic group or a group derived from an aromatic ring assembly.
  • Z 0 , Z 1 and Z 2 are preferably hydrogen atoms, halogen atoms, alkyl groups having 1 to 12 carbon atoms, cyano groups, nitro groups, and alkoxy groups having 1 to 12 carbon atoms, respectively.
  • 0 is more preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a cyano group
  • Z 1 and Z 2 are further preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, and a cyano group.
  • Q 1 and Q 2 -NH -, - S -, - NR 2 '-, - O- are preferable, R 2' is preferably a hydrogen atom. Of these, -S-, -O-, and -NH- are particularly preferable.
  • Y 1 may form an aromatic heterocyclic group together with the nitrogen atom to which it is attached and Z 0.
  • the aromatic heterocyclic group include those described above as the aromatic heterocycle that Ar may have.
  • a pyrrole ring, an imidazole ring, a pyrroline ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, and an indole examples thereof include a ring, a quinoline ring, an isoquinoline ring, a purine ring, and a pyrroline ring.
  • This aromatic heterocyclic group may have a substituent.
  • Y 1 may be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group which may be substituted as described above, together with the nitrogen atom to which the Y 1 is bonded and Z 0.
  • a benzofuran ring, a benzothiazole ring, a benzoxazole ring and the like can be mentioned.
  • the formulas (Ar-1) to (Ar-22) are preferable from the viewpoint of molecular stability. Above all, it is more preferable that it is a divalent aromatic group represented by the following formula (1-1-A).
  • Examples of the aromatic group represented by Ar a include a group represented by the following formula (Ar-23).
  • Examples of the substituent R' are a hydrogen atom, a halogen atom, an alkyl group, an alkyl halide group, an alkenyl group, an aryl group, a cyano group, an amino group, a nitro group, a nitroso group, a carboxy group, and an alkyl having 1 to 6 carbon atoms.
  • the two R's may be the same as each other or different from each other.
  • examples of the polymerizable liquid crystal compound (1) include compounds described in JP-A-2019-0031777.
  • the polymerizable liquid crystal compound (1) was irradiated with ultraviolet rays of 500 mJ / cm 2 in a state in which the polymer in the oriented state of the polymerizable liquid crystal compound exhibited reverse wavelength dispersibility and the polymerizable liquid crystal compound was oriented alone.
  • the polymer of the above exhibits reverse wavelength dispersibility, and the phase difference value at a wavelength of 450 nm measured after irradiating ultraviolet rays of 500 mJ / cm 2 in a state where the polymerizable liquid crystal compound is oriented alone [R (A, 500, 450) )],
  • the phase difference value [R (A, 3000, 450)] at a wavelength of 450 nm measured after irradiating the polymerizable liquid crystal compound with ultraviolet rays of 3000 mJ / cm 2 in a state of being oriented alone is in the negative direction.
  • the phase difference value "changing in the positive direction” means a position at a wavelength of 450 nm measured after irradiation with ultraviolet rays of 500 mJ / cm 2 in a state where the target polymerizable liquid crystal compound is oriented alone.
  • the phase difference value at a wavelength of 450 nm measured after irradiation with ultraviolet rays of 3000 mJ / cm 2 in a state where the polymerizable liquid crystal compound is oriented alone [R ( A, 3000, 450)] means that it becomes larger.
  • phase difference value "changes in the negative direction"
  • the phase difference value [R (A, 3000, 450)] becomes smaller than the phase difference value [R (A, 500, 450)].
  • the change of ⁇ Re (450) is 1.5 nm or less in absolute value, preferably 1 nm or less, more preferably 0.5 nm or less
  • the polymerizable liquid crystal compound is the above-mentioned specific ultraviolet rays. It is assumed that the compound has a property that the phase difference value does not change under irradiation conditions.
  • the phase difference value [R (A, 500, 450)] of the polymerizable liquid crystal compound is obtained by applying a solution containing the polymerizable liquid crystal compound to which a predetermined amount of the polymerization initiator and the solvent is added onto the alignment film. After that, it is a value obtained by irradiating ultraviolet rays having a wavelength of 365 nm so that the integrated light amount at the wavelength of 365 nm is 500 mJ / cm 2 , and measuring the in-plane retardation value of the liquid crystal cured layer with respect to the light having a wavelength of 450 nm. ..
  • the retardation value [R (A, 3000, 450)] of the polymerizable liquid crystal compound has a wavelength of 365 nm with respect to the liquid crystal cured layer for which the retardation value [R (A, 500, 450)] has been measured.
  • irradiation to integrated light intensity of the ultraviolet at a wavelength of 365nm is 2,500 mJ / cm 2 (i.e., cumulative ultraviolet irradiated during the production of the liquid crystal cured layer as the accumulated amount of light upon irradiation at a wavelength of 365nm is 3000 mJ / cm 2 It is a value obtained by measuring the inner surface retardation value of the cured liquid crystal layer after irradiation) with respect to light having a wavelength of 450 nm.
  • a polymerizable liquid crystal compound may change its optical characteristics by irradiation with ultraviolet rays. Whether ⁇ Re (450) changes in the positive direction or the negative direction when the polymerizable liquid crystal compound is irradiated with ultraviolet rays under the above specific conditions is usually determined by the molecular structure of the polymerizable liquid crystal compound, and in particular, the above. In the polymerizable liquid crystal compound represented by the formula (1), it is considered that it is determined by the molecular structure of Ar a.
  • the above ultraviolet irradiation conditions are not necessarily limited.
  • the phase difference value below tends to change in the positive direction. Therefore, when the aromatic group represented by Ar a in the formula (1) is a divalent aromatic group composed of a nitrogen atom, a sulfur atom, an oxygen atom, a carbon atom and a hydrogen atom, the polymerizable group is used.
  • the liquid crystal compound is often a compound whose phase difference value changes in the positive direction under the above-mentioned ultraviolet irradiation conditions.
  • Retardation value in the ultraviolet irradiation conditions as a polymerizable liquid crystal compound changes in a positive direction (A), more specifically, for example, the formula (1-1-A) Q 1 in is -S-,
  • Examples thereof include a compound represented by the formula (1) in which Y 1 is an aromatic group having a polycyclic aromatic heterocycle having an alkenyl structure. When it has an alkenyl structure, it undergoes a photooxidation reaction, and the alkenyl moiety is oxidized, and the retardation value tends to increase (change in the positive direction).
  • the aromatic group represented by Ar a in the formula (1) is composed of a nitrogen atom, a sulfur atom, a carbon atom and a hydrogen atom
  • the above-mentioned ultraviolet irradiation conditions The phase difference value in is apt to change in the negative direction. Therefore, when the aromatic group represented by Ar a in the formula (1) is a divalent aromatic group composed of a nitrogen atom, a sulfur atom, a carbon atom and a hydrogen atom, the polymerizable liquid crystal compound is used.
  • the phase difference value under the above-mentioned ultraviolet irradiation conditions is a compound that changes in the negative direction.
  • the polymerizable liquid crystal composition contains a polymerizable liquid crystal compound in which ⁇ Re (450) changes in the positive direction by irradiation with ultraviolet rays and a polymerizable liquid crystal compound in which ⁇ Re (450) changes in the negative direction, or when irradiated with ultraviolet rays.
  • the changes in the optical properties of the individual polymerizable liquid crystal compounds are canceled out, and the changes in the optical properties of the polymerizable liquid crystal composition during irradiation with ultraviolet rays can be suppressed.
  • they are adjacent to the retardation layer.
  • the gas barrier layer arranged in the above can suppress the generation of peroxide radicals caused by light exposure in the presence of oxygen, so that the above ⁇ Re (450) changes in the positive direction of the polymerizable liquid crystal compound. Even when only one of the polymerizable liquid crystal compound (B) in which (A) and ⁇ Re (450) change in the negative direction is contained, the change in the retardation value in the retardation layer is suppressed and the durability is excellent.
  • An optical laminate may be provided.
  • the polymerizable liquid crystal composition forming the retardation expression layer only one type may be used alone or a plurality of types may be used in combination as the polymerizable liquid crystal compound.
  • the polymerizable compound other than the polymerizable liquid crystal compound (1) include a polymerizable liquid crystal compound which does not absorb light in the ultraviolet region and whose phase difference value does not change under the above ultraviolet irradiation conditions.
  • specific examples thereof include polymerizable liquid crystal compounds exhibiting many positive wavelength dispersibility. For example, Liquid Crystal Handbook (edited by Liquid Crystal Handbook Editorial Committee, Maruzen Co., Ltd., October 2000).
  • the polymerizable liquid crystal composition forming the retardation expression layer preferably contains the polymerizable liquid crystal compound (1).
  • the content thereof is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, still more preferably 80 parts by mass or more, based on 100 parts by mass of the total amount of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition.
  • the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition may be all the polymerizable liquid crystal compound (1).
  • the content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, based on 100 parts by mass of the solid content of the polymerizable liquid crystal composition. Yes, more preferably 85 to 98 parts by mass, and even more preferably 90 to 95 parts by mass.
  • the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the obtained retardation expression layer.
  • the solid content of the polymerizable liquid crystal composition means all the components of the polymerizable liquid crystal composition excluding volatile components such as organic solvents.
  • the polymerizable liquid crystal composition forming the retardation expression layer preferably contains a polymerization initiator.
  • the polymerization initiator is a compound capable of producing a reactive species by the contribution of heat or light and initiating a polymerization reaction of a polymerizable liquid crystal display or the like.
  • the reactive active species include active species such as radicals, cations and anions.
  • a photopolymerization initiator that generates radicals by light irradiation is preferable from the viewpoint of easy reaction control.
  • photopolymerization initiator examples include benzoin compounds, benzophenone compounds, benzyl ketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, triazine compounds, iodonium salts and sulfonium salts.
  • Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure 379EG (above, BASF Japan Co., Ltd.) (Made), Sakeol BZ, Sakeol Z, Sakeol BEE (manufactured by Seiko Kagaku Co., Ltd.), Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), ADEKA PUTMER SP- 152, ADEKA OPTMER SP-170, ADEKA OPTMER N-1717, ADEKA PTMER N-1919, ADEKA ARCLUDS NCI-831
  • the maximum absorption wavelength is preferably 300 nm to 400 nm, more preferably 300 nm to 380 nm, and above all, the ⁇ -acetophenone type.
  • a polymerization initiator and an oxime-based photopolymerization initiator are preferable.
  • Examples of the ⁇ -acetophenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1.
  • Examples of commercially available ⁇ -acetophenone compounds include Irgacure 369, 379EG, 907 (above, manufactured by BASF Japan Ltd.) and Sequol BEE (manufactured by Seiko Kagaku Co., Ltd.).
  • the oxime-based photopolymerization initiator generates methyl radicals when irradiated with light. With this methyl radical, the polymerization of the polymerizable liquid crystal compound in the deep part of the formed liquid crystal cured layer (phase difference expression layer) proceeds preferably. Further, from the viewpoint of more efficiently advancing the polymerization reaction in the deep part of the formed liquid crystal cured layer, it is preferable to use a photopolymerization initiator capable of efficiently utilizing ultraviolet rays having a wavelength of 350 nm or more.
  • a triazine compound and an oxime ester type carbazole compound are preferable, and an oxime ester type carbazole compound is more preferable from the viewpoint of sensitivity.
  • the oxime ester-type carbazole compound include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methylbenzoyl)]. ) -9H-carbazole-3-yl] -1- (O-acetyloxime) and the like.
  • oxime ester-type carbazole compound Commercially available products of the oxime ester-type carbazole compound include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (above, manufactured by BASF Japan Ltd.), ADEKA PUTMER N-1919, and ADEKA ARCLUS NCI-831 (above). , Made by ADEKA CORPORATION) and the like.
  • the amount of the photopolymerization initiator added is usually 0.1 part by mass to 30 parts by mass, preferably 1 part by mass to 20 parts by mass, and more preferably 1 part by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. It is a mass part to 15 parts by mass. Within the above range, the reaction of the polymerizable group proceeds sufficiently, and the orientation of the polymerizable liquid crystal compound is not easily disturbed.
  • Polymerization inhibitors include hydroquinones having substituents such as hydroquinone and alkyl ethers; catechols having substituents such as alkyl ethers such as butyl catechol; pyrogallols, 2,2,6,6-tetramethyl-1- Radical trapping agents such as piperidinyloxy radicals; thiophenols; ⁇ -naphthylamines and ⁇ -naphthols.
  • the content of the polymerization inhibitor is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound in order to polymerize the polymerizable liquid crystal compound without disturbing the orientation of the polymerizable liquid crystal compound. Yes, preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass.
  • the photopolymerization initiator can be made highly sensitive.
  • the photosensitizer include xanthones such as xanthones and thioxanthones; anthracenes having substituents such as anthracene and alkyl ethers; phenothiazines; rubrenes.
  • the photosensitizer include xanthones such as xanthones and thioxanthones; anthracenes having substituents such as anthracene and alkyl ethers; phenothiazines; rubrenes.
  • the content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 0.1 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. 3 parts by mass.
  • the polymerizable liquid crystal composition may contain a leveling agent.
  • the leveling agent is an additive having a function of adjusting the fluidity of the polymerizable liquid crystal composition and flattening the film obtained by applying the leveling agent, for example, silicone-based, polyacrylate-based and perfluoroalkyl-based. Leveling agent can be mentioned.
  • DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all manufactured by Toray Dow Corning Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all momentary performance materials Japan GK) , Florinert (registered trademark) FC-72, FC-40, FC-43, FC-3283 (all manufactured by Sumitomo 3M Co., Ltd.), Megafuck (registered trademark) R-08 , R-30, R-90, F-410, F-411, F-443, F-445, F-470, F-477, F
  • F-483 (all manufactured by DIC Co., Ltd.), Ftop (trade name) EF301, EF303, EF351, EF352 (all manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.), Surflon (registered) Trademarks) S-381, S-382, S-383, S-393, SC-101, SC-105, KH-40, SA-100 (all manufactured by AGC Seimi Chemical Co., Ltd.) , Product name E1830, E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100, BYK-352, BYK-353 and BYK-361N (all trade names: manufactured by BM Chemie), etc. Can be mentioned. Of these, polyacrylate-based leveling agents and perfluoroalkyl-based leveling agents are preferable.
  • the content of the leveling agent in the polymerizable liquid crystal composition is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound.
  • the content of the leveling agent is within the above range, it is easy to horizontally orient the polymerizable liquid crystal compound, and the obtained retardation layer tends to be smoother, which is preferable.
  • the polymerizable liquid crystal composition may contain two or more kinds of leveling agents.
  • the phase difference expression layer has optical properties represented by the following formulas (I), (II) and (III).
  • the retardation expression layer is usually a cured product obtained by curing the polymerizable liquid crystal compound in a state of being oriented horizontally with respect to the retardation expression layer plane.
  • Re ( ⁇ ) represents the in-plane retardation value at the wavelength ⁇ nm of the retardation expression layer
  • Re (nx ( ⁇ ) ⁇ ny ( ⁇ )) ⁇ d (d is the retardation expression layer).
  • Re represents the thickness
  • nx represents the main refractive index at a wavelength of ⁇ nm in the direction parallel to the plane of the retardation expression layer in the refractive index ellipse formed by the retardation expression layer
  • ny represents the retardation index formed by the retardation expression layer.
  • the refractive index ellipse it represents the refractive index at a wavelength of ⁇ nm which is parallel to the plane of the retardation expression layer and perpendicular to the nx direction).
  • the phase difference expression layer When the phase difference expression layer satisfies the formulas (I) and (II), the phase difference expression layer has an in-plane retardation value at a short wavelength smaller than an in-plane retardation value at a long wavelength, that is, the so-called inverse. Shows wavelength dispersibility.
  • Re (450) / Re (550) is preferably 0.70 or more, more preferably 0.78 or more, and therefore, because the inverse wavelength dispersibility is improved and the optical characteristics of the retardation layer are further improved. It is preferably 0.92 or less, more preferably 0.90 or less, still more preferably 0.88 or less, particularly preferably 0.87 or less, and even more preferably 0.86 or less.
  • Re (650) / Re (550) is preferably 1.0 or more, more preferably 1.01 or more, and further preferably 1.02 or more.
  • the retardation expression layer satisfies the formula (III)
  • a more preferable range of the in-plane retardation value is 120 nm ⁇ Re (550) ⁇ 170 nm, and a more preferable range is 130 nm ⁇ Re (550) ⁇ 150 nm.
  • the retardation layer is, for example, A step of forming a coating film of a polymerizable liquid crystal composition on a supporting base material or an alignment film, drying the coating film, and orienting the polymerizable liquid crystal compound in the polymerizable liquid crystal composition, and It can be produced by a method including a step of polymerizing a polymerizable liquid crystal compound while maintaining an oriented state to form a retardation expression layer which is a liquid crystal curing layer.
  • the coating film of the polymerizable liquid crystal composition can be formed by applying the polymerizable liquid crystal composition on a supporting base material or an alignment film described later.
  • the viscosity of the polymerizable liquid crystal composition is preferably adjusted to, for example, 10 mPa ⁇ s or less, preferably about 0.1 to 7 mPa ⁇ s so that it can be easily applied.
  • the viscosity of the polymerizable liquid crystal composition can be adjusted by adjusting the content of the solvent.
  • the solvent a solvent capable of dissolving the polymerizable liquid crystal compound is preferable, and a solvent that is inert to the polymerization reaction of the polymerizable liquid crystal compound is preferable.
  • the solvent include water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether and propylene glycol monomethyl ether and other alcohol solvents; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate.
  • Ester solvents such as ⁇ -butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; aliphatic carbonization such as pentane, hexane and heptane.
  • Hydrogen solvent aromatic hydrocarbon solvent such as toluene and xylene; nitrile solvent such as acetonitrile; ether solvent such as tetrahydrofuran and dimethoxyethane; chlorine-containing solvent such as chloroform and chlorobenzene; dimethylacetamide, dimethylformamide, N-methyl- Examples thereof include amide-based solvents such as 2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone. Only one type of these solvents may be used, or two or more types may be used in combination. Of these, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents and aromatic hydrocarbon solvents are preferable.
  • the content of the solvent in 100 parts by mass of the polymerizable liquid crystal composition is preferably 50 to 98 parts by mass, more preferably 70 to 95 parts by mass. Therefore, the solid content concentration in the polymerizable liquid crystal composition is preferably 2 to 50% by mass, more preferably 5 to 30%, still more preferably 5 to 15%.
  • the viscosity of the polymerizable liquid crystal composition is lowered, so that the thickness of the retardation developing layer obtained by applying the polymerizable liquid crystal composition becomes substantially uniform and uneven. Tends to be less likely to occur.
  • the solid content is at least the above lower limit value, the retardation layer does not become too thin, and the birefringence required for optical compensation of the liquid crystal panel tends to be given.
  • the solid content can be appropriately determined in consideration of the thickness of the retardation expression layer to be produced.
  • the supporting base material examples include a glass base material and a film base material, and a film base material is preferable from the viewpoint of processability.
  • the resin constituting the film base material include polyolefins such as polyethylene, polypropylene, and norbornene-based polymers; cyclic olefin-based resins; polyvinyl alcohols; polyethylene terephthalates; polymethacrylic acid esters; polyacrylic acid esters; triacetyl celluloses and diacetyl celluloses.
  • plastics such as cellulose esters such as cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyether ketones; polyphenylene sulfide and polyphenylene oxide;
  • a commercially available product may be used as the supporting base material.
  • Examples of commercially available cellulose ester base materials include “Fujitac Film” (manufactured by Fuji Photo Film Co., Ltd.); “KC8UX2M”, “KC8UY” and “KC4UY” (manufactured by Konica Minolta Opto Co., Ltd.).
  • cyclic olefin resins include “Topas” (registered trademark) (Ticona (Germany)), “Arton” (registered trademark) (JSR Corporation), “ZEONOR” (registered trademark), Examples thereof include “ZEONEX” (registered trademark) (above, manufactured by Nippon Zeon Corporation) and “Apel” (registered trademark) (manufactured by Mitsui Chemicals, Inc.).
  • Such a cyclic olefin resin can be used as a base material by forming a film by a known means such as a solvent casting method and a melt extrusion method.
  • a commercially available cyclic olefin resin base material can also be used.
  • cyclic olefin resin base materials include “Scina” (registered trademark), “SCA40” (registered trademark) (above, manufactured by Sekisui Chemical Co., Ltd.), and “Zeonor Film” (registered trademark) (manufactured by Optis Corporation). ) And “Arton Film” (registered trademark) (manufactured by JSR Corporation).
  • the thickness of the base material is preferably thin in that it has a mass that can be handled practically, but if it is too thin, the strength tends to decrease and the workability tends to be inferior.
  • the thickness of the base material is usually 5 ⁇ m to 300 ⁇ m, preferably 20 ⁇ m to 200 ⁇ m. Further, by peeling off the base material and transferring only the retardation layer, a further thinning effect can be obtained.
  • Examples of the method for applying the polymerizable liquid crystal composition to a substrate or the like include a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, an applicator method and other coating methods, and a flexography method and other printing methods. And the like, a known method can be mentioned.
  • the solvent is removed by drying or the like to form a dry coating film.
  • the drying method include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.
  • the heating temperature of the coating film can be appropriately determined in consideration of the polymerizable liquid crystal compound to be used and the material of the base material or the like forming the coating film. , It is necessary that the temperature is equal to or higher than the liquid crystal phase transition temperature.
  • the liquid crystal phase transition temperature (smetic phase) of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition can be heated to a temperature of about (transition temperature or nematic phase transition temperature) or higher.
  • the liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature control stage, a differential scanning calorimeter (DSC), a thermal weight differential thermal analyzer (TG-DTA), or the like.
  • the phase transition temperature is a polymerization in which all the polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition are mixed at the same ratio as the composition in the polymerizable liquid crystal composition. It means a temperature measured in the same manner as when one kind of polymerizable liquid crystal compound is used by using a mixture of sex liquid crystal compounds. Further, it is generally known that the liquid crystal phase transition temperature of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition may be lower than the liquid crystal phase transition temperature of the polymerizable liquid crystal compound alone.
  • the heating time can be appropriately determined depending on the heating temperature, the type of the polymerizable liquid crystal compound used, the type of the solvent, its boiling point and its amount, etc., but is usually 15 seconds to 10 minutes, preferably 0.5 to 0.5 minutes. 5 minutes.
  • the solvent may be removed from the coating film at the same time as heating the polymerizable liquid crystal compound to the liquid crystal phase transition temperature or higher, or separately, but it is preferable to remove the solvent at the same time from the viewpoint of improving productivity.
  • the solvent in the coating film Before heating the polymerizable liquid crystal compound to a temperature equal to or higher than the liquid crystal phase transition temperature, the solvent in the coating film is appropriately added under the condition that the polymerizable liquid crystal compound contained in the coating film obtained from the polymerizable liquid crystal composition does not polymerize.
  • a pre-drying step may be provided for removal.
  • drying method in the pre-drying step examples include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method, and the drying temperature (heating temperature) in the drying step is the type of polymerizable liquid crystal compound to be used and the solvent. It can be appropriately determined according to the type of the solvent, its boiling point, its amount, and the like.
  • the polymerizable liquid crystal compound is polymerized while maintaining the orientation state of the polymerizable liquid crystal compound, so that the phase difference is a polymer of the polymerizable liquid crystal compound existing in the desired orientation state.
  • An expression layer is formed.
  • a photopolymerization method is usually used.
  • the light irradiating the dry coating film includes the type of photopolymerization initiator contained in the dry coating film and the type of polymerizable liquid crystal compound (particularly, the type of polymerizable group contained in the polymerizable liquid crystal compound). And appropriately selected according to the amount.
  • ultraviolet light is preferable because it is easy to control the progress of the polymerization reaction and it is possible to use a photopolymerization apparatus widely used in the art. It is preferable to select the type of the polymerizable liquid crystal compound or the photopolymerization initiator contained in the polymerizable liquid crystal composition.
  • the polymerization temperature can be controlled by irradiating light while cooling the dry coating film by an appropriate cooling means.
  • a cooling means By adopting such a cooling means, if the polymerizable liquid crystal compound is polymerized at a lower temperature, a phase difference expression layer can be appropriately formed even if a base material having a relatively low heat resistance is used. It is also possible to promote the polymerization reaction by raising the polymerization temperature within a range in which defects due to heat during light irradiation (deformation due to heat of the base material, etc.) do not occur.
  • a patterned cured film can also be obtained by masking or developing during photopolymerization.
  • Examples of the light source of the active energy ray include the same as those exemplified above as the light source of the active energy ray that can be used at the time of curing the curable composition for forming a gas barrier layer.
  • the ultraviolet irradiation intensity is usually 10 to 3,000 mW / cm 2 .
  • the ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activating the photopolymerization initiator.
  • the time for irradiating light is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, still more preferably 0.1 seconds to 1 minute. be.
  • the integrated light intensity is 10 to 3,000 mJ / cm 2 , preferably 50 to 2,000 mJ / cm 2 , and more preferably 100 to 1,000 mJ / cm. It is 2.
  • the thickness of the retardation layer can be appropriately selected depending on the application of the optical laminate, the display device to be applied, and the like, and is preferably 0.1 to 10 ⁇ m, more preferably 0.2 to 5 ⁇ m, and further preferably 0.2. It is ⁇ 3 ⁇ m.
  • the coating film of the polymerizable liquid crystal composition may be formed on the alignment film.
  • the alignment film has an orientation-regulating force that aligns the polymerizable liquid crystal compound in a desired direction.
  • horizontal orientation having an orientation restricting force for orienting the polymerizable liquid crystal compound in the horizontal direction.
  • the orientation regulating force can be arbitrarily adjusted according to the type of alignment film, surface condition, rubbing conditions, etc., and when the alignment film is formed of a photo-alignable polymer, it can be arbitrarily adjusted according to polarization irradiation conditions, etc. It is possible to do.
  • the alignment film preferably has solvent resistance that does not dissolve when the polymerizable liquid crystal composition is applied, and also has heat resistance in heat treatment for removing the solvent and aligning the polymerizable liquid crystal compound.
  • the alignment film include an alignment film containing an orientation polymer, a photoalignment film, a grub alignment film having an uneven pattern or a plurality of grooves on the surface, a stretched film stretched in the orientation direction, and the like, and the accuracy of the orientation angle and From the viewpoint of quality, a photoalignment film is preferable.
  • the oriented polymer examples include polyamides and gelatins having an amide bond in the molecule, polyimide having an imide bond in the molecule and polyamic acid, which is a hydrolyzate thereof, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, and poly. Examples thereof include oxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylic acid esters. Of these, polyvinyl alcohol is preferable.
  • the oriented polymer can be used alone or in combination of two or more.
  • the alignment film containing the orientation polymer is usually obtained by applying a composition in which the orientation polymer is dissolved in a solvent (hereinafter, may be referred to as "orientation polymer composition") to a substrate to remove the solvent or. It is obtained by applying an oriented polymer composition to a substrate, removing the solvent, and rubbing (rubbing method).
  • the solvent include the same solvents as those exemplified above as the solvents that can be used in the polymerizable liquid crystal composition.
  • the concentration of the oriented polymer in the oriented polymer composition may be within the range in which the oriented polymer material can be completely dissolved in the solvent, but is preferably 0.1 to 20% in terms of solid content with respect to the solution, and is 0. .1 to 10% is more preferable.
  • orientation polymer composition a commercially available alignment film material may be used as it is.
  • alignment film materials include Sunever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and Optomer (registered trademark, manufactured by JSR Corporation).
  • Examples of the method of applying the oriented polymer composition to the base material include the same methods as those exemplified as the method of applying the polymerizable liquid crystal composition to the supporting base material.
  • Examples of the method for removing the solvent contained in the oriented polymer composition include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.
  • Rubbing treatment can be performed as needed to impart orientation regulating force to the alignment film (rubbing method).
  • a rubbing cloth is wrapped around a rotating rubbing roll, and an orientation polymer composition is applied to the substrate and annealed to form the surface of the substrate. Examples thereof include a method in which a film of an oriented polymer is brought into contact with each other. If masking is performed during the rubbing treatment, a plurality of regions (patterns) having different orientation directions can be formed on the alignment film.
  • the photo-alignment film is usually formed by applying a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter, also referred to as “composition for forming a photo-alignment film”) to a substrate, removing the solvent, and then polarized light. It is obtained by irradiating (preferably polarized UV).
  • composition for forming a photo-alignment film a composition containing a polymer or monomer having a photoreactive group and a solvent
  • polarized light preferably polarized UV
  • the photoalignment film is also advantageous in that the direction of the orientation regulating force can be arbitrarily controlled by selecting the polarization direction of the polarized light to be irradiated.
  • a photoreactive group is a group that produces a liquid crystal alignment ability when irradiated with light.
  • Specific examples thereof include groups involved in photoreactions that are the origin of liquid crystal orientation ability such as molecular orientation induction or isomerization reaction, dimerization reaction, photocrosslinking reaction or photodecomposition reaction generated by light irradiation. Of these, groups involved in the dimerization reaction or photocrosslinking reaction are preferable because they are excellent in orientation.
  • a photoreactive group involved in a photodimerization reaction is preferable, and a photoalignment film having a relatively small amount of polarized light required for photoalignment and excellent thermal stability and stability over time can be easily obtained.
  • a cinnamoyl group and a chalcone group are preferable.
  • the polymer having a photoreactive group a polymer having a cinnamoyl group having a cinnamic acid structure at the end of the side chain of the polymer is particularly preferable.
  • a photoalignment-inducing layer By applying the composition for forming a photoalignment film on a base material, a photoalignment-inducing layer can be formed on the base material.
  • the solvent contained in the composition include the same solvents as those exemplified above as the solvents that can be used in the polymerizable liquid crystal composition, and are appropriately selected depending on the solubility of the polymer having a photoreactive group or the monomer. can do.
  • the content of the polymer or monomer having a photoreactive group in the composition for forming a photo-alignment film can be appropriately adjusted depending on the type of the polymer or monomer and the thickness of the target photo-alignment film, but the composition for forming a photo-alignment film. It is preferably at least 0.2% by mass, and more preferably in the range of 0.3 to 10% by mass.
  • the composition for forming a photoalignment film may contain a polymer material such as polyvinyl alcohol or polyimide or a photosensitizer as long as the characteristics of the photoalignment film are not significantly impaired.
  • Examples of the method of applying the composition for forming a photoalignment film to the base material include the same method as the method of applying the orientation polymer composition to the base material.
  • Examples of the method for removing the solvent from the applied composition for forming a photoalignment film include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.
  • the polarized light is irradiated from the base material side to obtain polarized light. It may be in the form of transmitting and irradiating. Further, it is particularly preferable that the polarized light is substantially parallel light.
  • the wavelength of the polarized light to be irradiated is preferably in the wavelength range in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet rays) having a wavelength in the range of 250 to 400 nm is particularly preferable.
  • Examples of the light source used for the polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, ultraviolet light lasers such as KrF and ArF, and high-pressure mercury lamps, ultra-high pressure mercury lamps and metal halide lamps. preferable.
  • a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp are preferable because they have a high emission intensity of ultraviolet rays having a wavelength of 313 nm.
  • Polarized UV can be irradiated by irradiating the light from the light source through an appropriate polarizer.
  • a polarizing element a polarizing filter, a polarizing prism such as Gran Thomson or Gran Tailor, or a wire grid type polarizing element can be used.
  • the groove alignment film is a film having an uneven pattern or a plurality of grooves on the film surface.
  • the polymerizable liquid crystal compound is applied to a film having a plurality of linear grubs arranged at equal intervals, the liquid crystal molecules are oriented in the direction along the groove.
  • a method of forming an uneven pattern by developing and rinsing after exposure through an exposure mask having a pattern-shaped slit on the surface of a photosensitive polyimide film, or a plate having a groove on the surface A method of forming a layer of UV-curable resin before curing on a shaped master, transferring the formed resin layer to a substrate and then curing, and a film of UV-curable resin before curing formed on the substrate. Examples thereof include a method in which a roll-shaped master having a plurality of grooves is pressed to form irregularities and then cured.
  • the thickness of the alignment film is usually in the range of 10 to 10000 nm, preferably in the range of 10 to 1000 nm, more preferably 10 to 500 nm or less, and further preferably. Is in the range of 10 to 300 nm, particularly preferably 50 to 250 nm.
  • the optical laminate is configured to include a layer that functions optically (for example, a layer that functions to improve the visibility of an image), and can be incorporated into an image display device such as an organic EL display device. It means a laminated body having various optical characteristics.
  • the optical laminate of the present invention may include a retardation layer and a gas barrier layer adjacent to the retardation layer, and even if the optical laminate is composed of only the retardation layer and the gas barrier layer, the retardation layer In addition to the gas barrier layer, other layers such as a polarizer layer may be included.
  • the optical laminate of the present invention may be configured to include a base material layer or the like that can be peeled off when incorporated into an image display device or the like.
  • the optical laminate of the present invention contains a polarizer layer in addition to the retardation layer and the gas barrier layer, the optical laminate can function as an elliptical polarizing plate.
  • the polarizer layer is a layer having a polarizing function including at least a linear polarizer, and may further include a thermoplastic resin film or the like attached to at least one surface of the linear polarizer.
  • the linear polarized light refers to an optical element having a property of transmitting linearly polarized light having a vibration plane orthogonal to the absorption axis when unpolarized light is incident.
  • the linear polarizer may be, for example, one in which a polyvinyl alcohol-based resin film is oriented and a dichroic dye such as iodine is adsorbed and oriented.
  • the linear polarizer may be a monolayer polyvinyl alcohol-based resin film (polyvinyl alcohol molecules contained in the polyvinyl alcohol resin film oriented) with a bicolor dye adsorbed or oriented on the base film. It may be a laminated film having two or more layers provided with a polyvinyl alcohol-based resin layer in which a bicolor dye is adsorbed and oriented.
  • Such a linear polarizer includes, for example, a step of uniaxially stretching a polyvinyl alcohol-based resin film, a step of dyeing a polyvinyl alcohol-based resin film with a dichroic dye to adsorb the dichroic dye, and a dichroism. It can be produced by a method known in the art, such as a method of treating a polyvinyl alcohol-based resin film on which a dye is adsorbed with an aqueous boric acid solution and a step of washing with water after the treatment with the aqueous boric acid solution.
  • the thickness of the linear polarizer in which the dichroic dye is adsorbed and oriented on the single-layer polyvinyl alcohol resin film is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, and further preferably 10 ⁇ m or less.
  • the polarizer layer has a structure in which a linear polarizer and a thermoplastic resin film or the like are laminated on at least one surface thereof, the linear polarizer and the thermoplastic resin film can be bonded to each other by an adhesive or the like.
  • the thermoplastic resin film a film similar to the resin film exemplified as the supporting base material that can be used for forming the retardation layer can be preferably used.
  • the optical laminate of the present invention contains a polarizer layer, the polarizer layer, the gas barrier layer, and / or the retardation layer are the slow axis (optical axis) of the retardation expression layer and the absorption axis of the polarizer layer. It is preferable to stack them so that the forming angle is 45 ⁇ 5 °.
  • the retardation layer 1 and the polarizer layer 7 are laminated only via the gas barrier layer 2 adjacent to the retardation layer 1. That is, in the embodiment, there is no adhesive layer for adhering the gas barrier layer and the polarizer layer adjacent to the retardation layer. Many of the adhesive layers, especially the adhesive layer, easily allow gaseous oxygen gas and moisture to enter, and when the adhesive layer exists near the retardation layer, the oxygen gas and moisture in the retardation layer Is likely to spread.
  • the retardation layer and the polarizer layer are laminated only through the gas barrier layer, the amount of oxygen gas and water that penetrates into the optical laminate can be reduced, and the oxygen gas and / or water content of the gas barrier layer can be reduced. Since the diffusion suppressing effect of the above can be obtained, it can be expected that higher durability is imparted to the optical laminate.
  • the polarizer layer and the gas barrier layer and / or the retardation layer can be laminated via, for example, an adhesive layer or the like.
  • the adhesive layer for bonding the polarizer layer to the gas barrier layer and / or the retardation layer is preferably formed from an adhesive.
  • any known pressure-sensitive adhesive composition can be used as long as it can function as a layer for laminating each layer such as a gas barrier layer and a polarizer layer.
  • examples of the pressure-sensitive adhesive composition include a pressure-sensitive adhesive composition containing a resin as a main component, such as (meth) acrylic type, rubber type, urethane type, ester type, silicone type, and polyvinyl ether type.
  • a pressure-sensitive adhesive composition using a (meth) acrylic resin having excellent transparency, weather resistance, heat resistance and the like as a base polymer is preferable.
  • Examples of the (meth) acrylic resin (base polymer) used in the pressure-sensitive adhesive composition include butyl (meth) acrylate, ethyl (meth) acrylate, isooctyl (meth) acrylate, and 2- (meth) acrylate.
  • a polymer or copolymer containing one or more (meth) acrylic acid esters such as ethylhexyl as a monomer is preferably used. It is preferable that the base polymer is copolymerized with a polar monomer.
  • Examples of the polar monomer include (meth) acrylic acid, 2-hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, and glycidyl ().
  • Examples thereof include monomers having a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group and the like, such as meta) acrylate.
  • the pressure-sensitive adhesive containing such a copolymer has excellent adhesiveness, and even when it is removed after being bonded to the transferred body, it can be removed relatively easily without causing adhesive residue on the transferred body. Is preferable because it is possible.
  • the pressure-sensitive adhesive composition may contain only the above-mentioned base polymer, but may also contain a cross-linking agent.
  • a cross-linking agent a metal ion having a valence of 2 or more that forms a carboxylic acid metal salt with a carboxyl group; a polyamine compound that forms an amide bond with a carboxyl group; poly.
  • Epoxy compounds and polyols that form an ester bond with a carboxyl group; polyisocyanate compounds that form an amide bond with a carboxyl group are exemplified.
  • the pressure-sensitive adhesive composition may contain a solvent, if necessary, and examples of the solvent include the solvents exemplified as the solvents that can be used for the polymerizable liquid crystal composition and the like.
  • the thickness of the pressure-sensitive adhesive layer can be appropriately determined according to the layer structure of the optical laminate and the like. Since the optical laminate of the present invention has a gas barrier layer adjacent to the retardation layer, it suppresses a change in the retardation value in the retardation layer even when oxygen gas or moisture enters the optical laminate from the pressure-sensitive adhesive layer. Excellent effect. Therefore, it is possible to provide an optical laminate having excellent durability even when the thickness of the pressure-sensitive adhesive layer in which oxygen gas or moisture easily penetrates is relatively large. Therefore, the thickness of the pressure-sensitive adhesive layer in the optical laminate of the present invention may be, for example, 1 ⁇ m or more and 100 ⁇ m or less.
  • the optical laminate of the present invention contains a plurality of pressure-sensitive adhesive layers
  • the thickness of the pressure-sensitive adhesive layer provided at least adjacent to or close to the retardation layer and / or the gas barrier layer is preferably within the above range. It is more preferable that the thickness of all the pressure-sensitive adhesive layers contained in the optical laminate of the present invention is within the above range.
  • the optical laminate of the present invention includes a front plate.
  • the front plate 8 is bonded to the polarizer layer 7 via the adhesive layer 9.
  • the front plate may be, for example, a thermoplastic resin film.
  • the resin constituting the thermoplastic resin film include polyolefin resins such as polyethylene and polypropylene; cyclic polyolefin resins such as norbornene polymers; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; poly (meth) acrylic acid.
  • (Meta) acrylic acid resins such as methyl; cellulose ester resins such as triacetyl cellulose, diacetyl cellulose and cellulose acetate propionate; vinyl alcohol resins such as polyvinyl alcohol and polyvinyl acetate; polycarbonate resins; polystyrene resins From polyarylate resin; polysulfone resin; polyethersulfone resin; polyamide resin; polyimide resin; polyetherketone resin; polyphenylene sulfide resin; polyphenylene oxide resin, and mixtures and copolymers thereof. Examples thereof include a resin film to be formed.
  • thermoplastic resin film may be a single layer obtained by mixing one or more of the above resin materials, or may have a multilayer structure of two or more layers.
  • the resins constituting each layer may be the same or different from each other.
  • additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, color retardants, flame retardants, nucleating agents, antistatic agents, pigments and colorants.
  • the thickness of the thermoplastic resin film used as the front plate is preferably 2 ⁇ m or more and 300 ⁇ m or less, more preferably 5 ⁇ m or more and 200 ⁇ m, from the viewpoint of thinning and flexibility of the optical laminate and the durability of the optical laminate. Below, it is more preferably 5 ⁇ m or more and 100 ⁇ m or less, particularly preferably 5 ⁇ m or more and 50 ⁇ m or less, and particularly preferably 5 ⁇ m or more and 30 ⁇ m or less.
  • the adhesive layer for adhering the front plate to the polarizer layer or the like is preferably formed of an adhesive, particularly a water-based adhesive.
  • a water-based adhesive any known water-based adhesive composition may be used as long as it can function as a layer that adheres and holds the front plate to the polarizer layer or the like.
  • the water-based adhesive composition is an adhesive containing a water-soluble resin or a water-dispersible resin as a main component.
  • the water-soluble resin or water-dispersible resin include (meth) acrylic resin; polyvinyl alcohol resin; polyvinyl acetal resin; ethylene-vinyl alcohol copolymer resin; polyvinyl pyrrolidone resin; polyamide amine resin; epoxy.
  • Examples include melamine-based resins; urea-based resins; polyamide-based resins; polyester-based resins; polyurethane-based resins; cellulose-based resins such as methyl cellulose, hydroethyl cellulose, and carboxymethyl cellulose; polysaccharides such as sodium alginate and starch.
  • (meth) acrylic resins; hydroxyl group-containing resins such as polyvinyl alcohol-based resins and polyvinyl acetal-based resins are preferable, and polyvinyl alcohol-based resins are more preferable.
  • the content of the water-soluble resin or the water-dispersible resin in the water-based adhesive composition may be appropriately determined depending on the type of resin used and the like, but is usually 1 to 10 parts by mass with respect to 100 parts by mass of water. Yes, preferably 1 to 5 parts by mass.
  • the thickness of the adhesive layer formed from the water-based adhesive composition is usually 0.02 to 5 ⁇ m, preferably 0.05 to 2 ⁇ m, and more preferably 0.1 to 1 ⁇ m. If the adhesive layer formed from the dry-solidified adhesive is too thick, the appearance tends to be poor.
  • the present invention can provide a display device including the optical laminate of the present invention as one of the embodiments.
  • the display device is a device having a display mechanism, and includes a light emitting element or a light emitting device as a light emitting source.
  • the display devices include a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a touch panel display device, an electron emission display device (electric field emission display device (FED, etc.)), and a surface electric field emission display device.
  • the liquid crystal display device includes any of a transmissive liquid crystal display device, a semi-transmissive liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, a projection type liquid crystal display device, and the like. These display devices may be display devices that display two-dimensional images, or may be stereoscopic display devices that display three-dimensional images.
  • KC2UA triacetyl cellulose-based resin film
  • ⁇ Base material for mold release> As the release base material A, a 40 ⁇ m-thick triacetyl cellulose-based resin film (manufactured by Konica Minolta Co., Ltd., “KC4UY”) that had not been subjected to a saponification treatment was used. As the release base material B, a 25 ⁇ m-thick triacetyl cellulose-based resin film (manufactured by Konica Minolta Co., Ltd., “KC2UA”) that had not been saponified was used.
  • release base material C a 50 ⁇ m-thick cycloolefin resin film (manufactured by Nippon Zeon Corporation, “ZF-14-50”) that had not been subjected to corona treatment was used.
  • release base material D a 23 ⁇ m-thick cycloolefin resin film (manufactured by Nippon Zeon Corporation, “ZF-14-23”) that had not been subjected to corona treatment was used.
  • composition liquid A An acetoacetyl group-modified polyvinyl alcohol-based resin (manufactured by Mitsubishi Chemical Corporation, "Gosenol Z200") having a saponification degree of 99.2 mol% is dissolved in water (distilled water), and the solid content is 8% by mass. PVA aqueous solution was prepared.
  • the prepared 8 mass% PVA solution and 40% aqueous solution of glioxal are mixed so that the mass ratio is 3.0: 0.7, and further adjusted so that the total solid content is 3 parts with respect to 100 parts of water to compose the composition.
  • Liquid A was prepared.
  • Composition liquid B An acetoacetyl group-modified polyvinyl alcohol-based resin (manufactured by Mitsubishi Chemical Corporation, "Gosenol Z200") having a saponification degree of 99.2 mol% is dissolved in water (distilled water), and the solid content is 8% by mass.
  • PVA aqueous solution was prepared.
  • the prepared 8% by mass PVA solution and zinc chloride are mixed so that the mass ratio is 3.0: 0.09, and further adjusted so that the total solid content is 3 parts with respect to 100 parts of water, and the composition liquid B was produced.
  • polarizer layer As the polarizer layer, a linear polarizer (thickness: 8 ⁇ m), which is a uniaxially stretched film formed by adsorbing and orienting iodine on a polyvinyl alcohol-based resin film, was prepared.
  • Preparation of First Laminated Body A front plate is laminated on one surface of the polarizing element layer via a composition for forming an aqueous adhesive layer, and a release base material A is purely applied to the other surface of the polarizing element layer. It is laminated through water, passed between a pair of bonding rolls, and then dried at 85 ° C. for 3 minutes to have a layer structure of a front plate / water-based adhesive layer / polarizer layer / release base material A. The laminate 1 was obtained. No adhesive is interposed between the polarizer layer and the release base material A, and the release base material A is releasably laminated on the polarizer layer. By peeling off the release base material A of the laminate 1, a first laminate having a layer structure of a front plate / water-based adhesive layer / polarizer layer can be obtained.
  • the retardation layer comprises the following photoalignment film and a retardation expression layer releasably formed on the following retardation layer base material.
  • composition for forming a photo-alignment film 5 parts (weight average molecular weight: 30,000) of a photo-alignment material having the following structure and 95 parts of cyclopentanone (solvent) were mixed. The obtained mixture was stirred at 80 ° C. for 1 hour to obtain a composition for forming a photoalignment film.
  • phase difference expression layer (Ii) Preparation of Composition for Forming Phase Difference Expression Layer
  • the following polymerizable liquid crystal compound ⁇ and polymerizable liquid crystal compound ⁇ were used to form the phase difference expression layer.
  • the polymerizable liquid crystal compound ⁇ was produced by the method described in JP-A-2010-31223. Further, the polymerizable liquid crystal compound ⁇ was produced according to the method described in JP-A-2009-173893. The molecular structure of each is shown below.
  • the polymerizable liquid crystal compound ⁇ was oriented alone with respect to the phase difference value [R (A, 500, 450)] at a wavelength of 450 nm measured after irradiation with ultraviolet rays of 500 mJ / cm 2 in a state of being oriented alone.
  • phase difference value [R (A, 3000, 450)] at a wavelength of 450 nm measured after irradiation with ultraviolet rays of 3000 mJ / cm 2 in the state changes in the positive direction.
  • the phase difference value at a wavelength of 550 nm is also relative to the phase difference value [R (A, 500, 550)] measured after irradiation with ultraviolet rays of 500 mJ / cm 2 in a state of being oriented alone at a wavelength of 550 nm.
  • the phase difference value [R (A, 3000, 550)] measured after irradiation with ultraviolet rays of 3000 mJ / cm 2 in the state of being oriented alone also changes in the positive direction.
  • the polymerizable liquid crystal compound ⁇ is a polymerizable liquid crystal compound having a property that the phase difference value does not change under the above-mentioned specific ultraviolet irradiation conditions.
  • the polymerizable liquid crystal compound ⁇ and the polymerizable liquid crystal compound ⁇ were mixed at a mass ratio of 87:13.
  • a leveling agent manufactured by DIC Corporation, "Megafuck F-556”
  • 2-dimethylamino-2-benzyl-1- (4) as a polymerization initiator -Molholinophenyl
  • Butane-1-one (“Omnirad 369" manufactured by IGM Resins VV) was added in 6 parts.
  • N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 13%, and the mixture was stirred at 80 ° C. for 1 hour to obtain a composition for forming a phase difference expression layer.
  • a composition for forming a photo-alignment film is applied to a retardation layer substrate fixed on a glass substrate with a wire bar coater (“G-7 type coating device” manufactured by Orihara Seisakusho Co., Ltd.). It was applied and dried at 80 ° C. for 1 minute.
  • a polarized UV irradiation device (“SPOT CURE SP-9” manufactured by Ushio, Inc.) was used for the coating film at an axial angle of 45 ° so that the integrated light intensity at a wavelength of 313 nm was 100 mJ / cm 2. Polarized UV exposure was performed.
  • the film thickness of the obtained photoalignment film was measured with an optical film thickness meter (“F20” manufactured by Filmometrics Co., Ltd.) and found to be 100 nm.
  • (V) Formation of Phase Difference Expression Layer The composition for forming a retardation expression layer is applied onto the photoalignment film with a wire bar coater (“G-7 type coating device” manufactured by Orihara Industrial Co., Ltd.), and 120 It was dried at ° C. for 1 minute.
  • the coating film is irradiated with ultraviolet rays (in a nitrogen atmosphere, integrated light intensity at a wavelength of 365 nm: 500 mJ / cm 2 ) using a high-pressure mercury lamp (“UNICURE VB-15201BY-A” manufactured by Ushio, Inc.). , A retardation expression layer was formed.
  • a pressure-sensitive adhesive layer is laminated on the retardation-developing layer, and a laminate having a layer structure of a phase-difference expression layer / photoalignment film / retardation layer base material is bonded to glass via the pressure-sensitive adhesive layer.
  • a lightly peelable non-carrier film hereinafter, also simply referred to as “lightly peeling NCF” laminated on one surface of a (meth) acrylic pressure-sensitive adhesive layer (thickness: 15 ⁇ m), and others.
  • An adhesive laminate having a heavy peeling non-carrier film hereinafter, also simply referred to as “heavy peeling NCF” to be laminated on the side surface was prepared.
  • the optical laminate containing the pressure-sensitive adhesive layer is obtained by closely transferring the exposed surface of the lightly peeled NCF to the adherend layer (phase difference developing layer). Then, the retardation layer substrate was peeled off to obtain a sample for measuring retardation.
  • the retardation at a wavelength of 550 nm was 142 nm as a result of measuring with a phase difference measuring device (“KOBRA-WPR” manufactured by Oji Measuring Instruments Co., Ltd.).
  • Gas barrier layers 1 to 3 were prepared according to the following.
  • the prepared 8% by mass PVA solution and 10% by mass of sodium glyoxylate (manufactured by Mitsubishi Chemical Corporation, "Safelink SPM-01") as a cross-linking agent were mixed so as to have a mass ratio of 3.0: 0.3, and further.
  • a composition for forming a gas barrier 1 was prepared by adjusting the total solid content to 3 parts with respect to 100 parts of water.
  • composition for forming gas barrier 2 hydrophobic crosslinked PVA-based resin composition
  • An acetoacetyl group-modified polyvinyl alcohol-based resin manufactured by Mitsubishi Chemical Corporation, "Gosenol Z200" having a saponification degree of 99.2 mol% is dissolved in water (distilled water) to prepare a PVA aqueous solution having a solid content of 8% by mass.
  • the prepared 8% by mass PVA solution and a 40% aqueous solution of glioxal as a cross-linking agent are mixed so that the mass ratio is 3.0: 0.7, and further adjusted so that the total solid content is 3 parts with respect to 100 parts of water. Then, PVA-based resin composition A was obtained.
  • an acetoacetyl group-modified polyvinyl alcohol-based resin (manufactured by Mitsubishi Chemical Co., Ltd., "Gosenol Z200") having a saponification degree of 99.2 mol% was dissolved in water (distilled water) to have a solid content of 8 mass.
  • % PVA aqueous solution was prepared.
  • the prepared 8% by mass PVA solution and zinc chloride are mixed so that the mass ratio is 3.0: 0.09, and further adjusted so that the total solid content is 3 parts with respect to 100 parts of water, and the PVA system is used.
  • a resin composition B was obtained.
  • the PVA-based resin compositions A and B prepared above were mixed at room temperature at a mass ratio of 1: 1 and stirred for 30 minutes to prepare a composition for forming a gas barrier 2.
  • composition for forming gas barrier 3 As the composition for forming the gas barrier 3, a composition for forming the gas barrier 3 containing an epoxy-based polymerizable compound, a polymerization initiator, a photosensitizer and a leveling agent and containing no solvent was prepared.
  • Oxygen gas permeability measuring method ⁇ Oxygen gas permeability measuring method>
  • the gas permeability of oxygen gas was measured using a differential pressure type gas permeability measuring device (“GTR-30AS” manufactured by GTR Tech Co., Ltd.) conforming to JIS K 7126-1 (differential pressure method).
  • GTR-30AS differential pressure type gas permeability measuring device
  • JIS K 7126-1 differential pressure method
  • ⁇ Gas barrier layer 1> A 25 ⁇ m-thick triacetyl cellulose-based resin film (manufactured by Konica Minolta Co., Ltd., “KC2UA”) that has been saponified and a release base material A are dropped with a composition for forming a gas barrier 1 to form a pair. After passing between the bonding rolls, the film was dried at 80 ° C. for 3 minutes to obtain a laminate having a layer structure of a 25 ⁇ m-thick triacetyl cellulose-based resin film base material / gas barrier layer 1 / release base material A. rice field.
  • KC2UA triacetyl cellulose-based resin film
  • the oxygen permeability of the laminate of the release for triacetyl cellulose of 25 ⁇ m thickness was obtained by peeling off the base material
  • a resin film substrate / consists gas barrier layer 1 stack, 100cm 3 / (m 2 ⁇ 24h ⁇ It was less than atm) and was the lower limit of detection. From the calculated value by the measured value and the formula (X), the oxygen permeability of the gas barrier layer 1 was less than 100cm 3 / (m 2 ⁇ 24h ⁇ atm). Further, when the thickness of the gas barrier layer 1 was measured by measuring the length of the cut surface using a scanning electron microscope (“JSM-7500F” manufactured by JEOL Ltd.), the thinnest part was 0.1 ⁇ m and the thickest part was 0.2 ⁇ m. Met.
  • JSM-7500F scanning electron microscope
  • a laminate having a layer structure of the base material A was formed, and the oxygen permeability was measured. Oxygen permeability of the gas barrier layer 2 was less than 100cm 3 / (m 2 ⁇ 24h ⁇ atm). Further, when the thickness of the gas barrier layer 2 was measured by measuring the length of the cut surface using a scanning electron microscope (“JSM-7500F” manufactured by JEOL Ltd.), the thinnest part was 0.1 ⁇ m and the thickest part was 0.2 ⁇ m. Met.
  • JSM-7500F scanning electron microscope
  • ⁇ Gas barrier 3> A composition for forming a gas barrier 3 is dropped between a corona-treated 25 ⁇ m-thick triacetyl cellulose-based resin film (“KC2UA” manufactured by Konica Minolta Co., Ltd.) base material and a mold release base material C, and a pair of bonding is performed. After passing between the rolls, ultraviolet rays were irradiated using an ultraviolet irradiation device (using a deuterium lamp manufactured by Heleus Co., Ltd.) so that the integrated light amount was 400 mJ / cm 2 (UVB).
  • KC2UA triacetyl cellulose-based resin film
  • a laminate having a layer structure of a 25 ⁇ m-thick triacetyl cellulose-based resin film base material / gas barrier layer 3 / release base material C was obtained.
  • the thickness of the gas barrier layer 3 was measured using a scanning electron microscope (“F20” manufactured by Filmometrics Co., Ltd.) and found to be 2.5 ⁇ m.
  • a 25 ⁇ m thick acrylic pressure-sensitive adhesive layer is laminated on a base material to create a 25 ⁇ m-thick triacetyl cellulose-based resin film / pressure-sensitive adhesive layer.
  • Example 1 Preparation of the second laminate> Release group via a gas barrier 2 forming composition on the retardation layer surface of the retardation layer (configuration of retardation layer substrate / photoalignment film / retardation expression layer) formed on the retardation layer substrate.
  • Material A is laminated, passed between a pair of bonding rolls, and then dried at 80 ° C. for 3 minutes to form a laminate composed of a release base material A / a gas barrier layer 2 / a retardation layer / a retardation layer base material.
  • the sample width of the retardation layer is the same as the sample width of the release base material A, and the release base material A is releasably laminated on the gas barrier layer 2.
  • the release base material A is releasably laminated on the gas barrier layer 2.
  • the second laminated body (without the gas barrier layer on the light emitting portion (glass plate) side) composed of the pressure-sensitive adhesive layer / gas barrier layer 2 / retardation layer and the retardation layer base material A laminated body made of the above can be obtained.
  • ⁇ Preparation of sample for environmental test> The polarizer layer side of the first laminate and the adhesive layer side of the second laminate and the laminate of the retardation layer base material are adhered and laminated to form a front plate / water-based adhesive layer / polarizer layer / adhesive.
  • the retardation layer base material of the laminated body was peeled off and the exposed surface and a glass plate having a thickness of 0.7 mm were adhered and laminated via an adhesive layer to obtain a sample for an environmental test.
  • the sample for environmental test was composed of a third laminate / adhesive layer / glass plate, and was prepared so that each side of the third laminate was located 10 mm inside each side of the glass plate.
  • the size of the glass plate was 50 mm ⁇ 50 mm.
  • the pressure-sensitive adhesive layer for bonding the laminated body and the glass plate is the same as the pressure-sensitive adhesive layer for bonding the first laminated body and the second laminated body.
  • Example 2 Preparation of the second laminate> Release group via a gas barrier 2 forming composition on the retardation layer surface of the retardation layer (configuration of retardation layer substrate / photoalignment film / retardation expression layer) formed on the retardation layer substrate.
  • Material A is laminated, passed between a pair of bonding rolls, and then dried at 80 ° C. for 3 minutes to form a laminate composed of a release base material A / a gas barrier layer 2 / a retardation layer / a retardation layer base material.
  • the release base material B is laminated on the exposed surface by peeling the retardation layer base material from the laminated body via the gas barrier 2 forming composition, and then passed between the pair of bonding rolls.
  • the mixture was dried at 80 ° C. for 3 minutes to obtain a laminate composed of a mold release base material A / a gas barrier layer 2 / a retardation layer / a gas barrier layer 2 / a mold release base material B.
  • the two release base materials are respectively laminated on the gas barrier layer 2 so that they can be peeled off, and the release base material A can be peeled off before the release base material B.
  • the heavy-release NCF / adhesive A laminate having a layer structure consisting of an agent layer / a gas barrier layer 2 / a retardation layer / a gas barrier layer 2 / a release base material B was obtained.
  • the second laminated body double-sided gas barrier layer
  • the adhesive layer / gas barrier layer 2 / retardation layer / gas barrier layer 2 and the release base material B are laminated. You can get a body.
  • ⁇ Preparation of sample for environmental test> The polarizer layer side of the first laminated body and the adhesive layer side of the laminated body of the second laminated body and the release base material B are adhered and laminated to form a front plate / water-based adhesive layer / polarizer layer /.
  • a laminate composed of a third laminate composed of the pressure-sensitive adhesive layer / gas barrier layer 2 / retardation layer / gas barrier layer 2 and a release base material B was obtained.
  • the exposed surface of the laminate B for mold release and a glass plate having a thickness of 0.7 mm were adhered and laminated via an adhesive layer similar to that used in Example 1.
  • a sample for environmental test was obtained.
  • the sample for environmental test was composed of a third laminate / adhesive layer / glass plate, and was prepared so that each side of the third laminate was located 10 mm inside each side of the glass plate.
  • the size of the glass plate was 50 mm ⁇ 50 mm.
  • Example 3 Preparation of the second laminate>
  • the sample width of the retardation layer is 10 mm as compared with the sample width of the release base material A.
  • a second laminated body was obtained in the same manner as in Example 2 except that the gas barrier layer 2 was formed at all ends of the retardation layer in the thickness direction.
  • Example 4 The retardation layer surface of the retardation layer and the polarizer layer surface of the first laminated body are laminated via a composition for forming a gas barrier 2, passed between a pair of bonding rolls, and then dried at 80 ° C. for 3 minutes. , Front plate / Water-based adhesive layer / Polarizer layer / Gas barrier layer 2 / Phase difference layer (no adhesive layer and no light emitting part (glass plate) side gas barrier layer) and retardation layer group A laminate made of wood was obtained. A surface exposed by peeling the retardation layer base material from the laminate and a glass plate having a thickness of 0.7 mm are adhered and laminated via an adhesive layer similar to that used in Example 1 for environmental testing. A sample was obtained. The sample for environmental test was composed of a third laminate / adhesive layer / glass plate, and was prepared so that each side of the third laminate was located 10 mm inside each side of the glass plate. The size of the glass plate was 50 mm ⁇ 50 mm.
  • Example 5 Preparation of the second laminate> A second laminate (without a gas barrier layer on the light emitting portion (glass plate) side) was obtained in the same manner as in Example 1 except that the composition for forming the gas barrier 1 was used as the composition for forming the gas barrier.
  • (Vi) Comparative Example 1 The polarizer layer surface of the first laminate and the retardation expression layer surface of the retardation layer are laminated via the pressure-sensitive adhesive layer, and the first laminated body is composed of a front plate / water-based adhesive layer / polarizer layer / pressure-sensitive adhesive layer / retardation layer.
  • a laminated body having a layer structure consisting of a three-layered body and a retardation layer base material was obtained.
  • a surface exposed by peeling the retardation layer base material from the laminate and a glass plate having a thickness of 0.7 mm are adhered and laminated via an adhesive layer similar to that used in Example 1 for environmental testing. A sample was obtained.
  • (Vii) Comparative Example 2 Preparation of the second laminate>
  • a release base material C is laminated on the retardation layer surface of the retardation layer via a composition for forming a gas barrier 3, passed between a pair of bonding rolls, and then an ultraviolet irradiation device (manufactured by Heleus Co., Ltd.). Using a deuterium lamp), irradiate ultraviolet rays so that the integrated light amount is 400 mJ / cm 2 (UVB), from the mold release base material C / gas barrier layer 3 / retardation layer / retardation layer base material. A laminate was obtained.
  • the release base material C is releasably laminated on the gas barrier layer 3.
  • the heavy-release NCF / adhesive layer / A laminate having a layer structure composed of a gas barrier layer 3 / a retardation layer / a retardation layer base material was obtained.
  • the release base material D is laminated on the exposed surface by peeling the retardation layer base material from the laminated body via the gas barrier 3 forming composition, and then passed between the pair of bonding rolls.
  • the integrated light intensity is 400 mJ / cm 2 (UVB)
  • a laminate composed of the release base material C / gas barrier layer 3 / retardation layer / gas barrier layer 3 / release base material D is formed. Obtained.
  • Each of the two release base materials is releasably laminated on the gas barrier layer 3, and the release base material C can be peeled off before the release base material D.
  • the heavy peeling NCF / adhesive is formed by closely laminating the adhesive layer surface of the laminated body composed of the heavy peeling NCF / adhesive layer on the three surfaces of the gas barrier layer exposed by peeling off the mold release base material C of the laminated body.
  • a laminate having a layer structure consisting of a layer / a gas barrier layer 3 / a retardation layer / a gas barrier layer 3 / a release base material D was obtained.
  • ⁇ Preparation of sample for environmental test> The polarizer layer side of the first laminate and the adhesive layer side of the second laminate and the laminate of the release base material D are adhered and laminated to form a front plate / water-based adhesive layer / polarizer layer / adhesive.
  • the exposed surface of the laminate D for mold release and a glass plate having a thickness of 0.7 mm were adhered and laminated via an adhesive layer similar to that used in Example 1. An environmental test sample was obtained.
  • Measuring device ATLAS Suntest XLS + (manufactured by AMETEK, Inc.) Conditions: 267 W / m 2 x 300 hours with irradiation energy in the wavelength band of 300 nm to 800 nm
  • Phase difference layer 2 Phase difference layer 2: Gas barrier layer 3: Alignment film 4: Phase difference expression layer 5: Detachable base material 6: Adhesive layer 7: Polarizer layer 8: Front plate 9: Adhesive layer 11: Optical laminate

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  • Physics & Mathematics (AREA)
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  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Laminated Bodies (AREA)
  • Liquid Crystal (AREA)
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003195271A (ja) * 2001-12-25 2003-07-09 Fuji Photo Film Co Ltd 表示装置用基板及びその製造方法
JP2005162892A (ja) * 2003-12-03 2005-06-23 Dainippon Ink & Chem Inc 水性硬化性樹脂組成物及びその硬化皮膜よりなる積層体
JP2010117537A (ja) * 2008-11-13 2010-05-27 Sumitomo Chemical Co Ltd 偏光板及びそれを用いた投射型液晶表示装置
JP2010150513A (ja) * 2008-09-30 2010-07-08 Fujifilm Corp 二色性色素組成物、光吸収異方性膜及び偏光素子
JP2013173357A (ja) * 2012-01-25 2013-09-05 Mitsubishi Paper Mills Ltd 可逆性感熱記録材料
WO2017217282A1 (ja) * 2016-06-14 2017-12-21 株式会社Adeka 水溶性組成物およびこれからなる硬化物
WO2018047497A1 (ja) * 2016-09-12 2018-03-15 ソニー株式会社 光学補償素子、液晶ライトバルブ組立体及び液晶プロジェクタ装置
WO2018186500A1 (ja) * 2017-04-07 2018-10-11 富士フイルム株式会社 偏光素子、円偏光板および画像表示装置
WO2019054441A1 (ja) * 2017-09-15 2019-03-21 住友化学株式会社 積層体及びデバイス
JP2019120949A (ja) * 2017-12-28 2019-07-22 富士フイルム株式会社 光学積層体および画像表示装置

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7255975B2 (ja) 2017-06-09 2023-04-11 住友化学株式会社 重合性液晶組成物および位相差板

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003195271A (ja) * 2001-12-25 2003-07-09 Fuji Photo Film Co Ltd 表示装置用基板及びその製造方法
JP2005162892A (ja) * 2003-12-03 2005-06-23 Dainippon Ink & Chem Inc 水性硬化性樹脂組成物及びその硬化皮膜よりなる積層体
JP2010150513A (ja) * 2008-09-30 2010-07-08 Fujifilm Corp 二色性色素組成物、光吸収異方性膜及び偏光素子
JP2010117537A (ja) * 2008-11-13 2010-05-27 Sumitomo Chemical Co Ltd 偏光板及びそれを用いた投射型液晶表示装置
JP2013173357A (ja) * 2012-01-25 2013-09-05 Mitsubishi Paper Mills Ltd 可逆性感熱記録材料
WO2017217282A1 (ja) * 2016-06-14 2017-12-21 株式会社Adeka 水溶性組成物およびこれからなる硬化物
WO2018047497A1 (ja) * 2016-09-12 2018-03-15 ソニー株式会社 光学補償素子、液晶ライトバルブ組立体及び液晶プロジェクタ装置
WO2018186500A1 (ja) * 2017-04-07 2018-10-11 富士フイルム株式会社 偏光素子、円偏光板および画像表示装置
WO2019054441A1 (ja) * 2017-09-15 2019-03-21 住友化学株式会社 積層体及びデバイス
JP2019120949A (ja) * 2017-12-28 2019-07-22 富士フイルム株式会社 光学積層体および画像表示装置

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