Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
• • 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
  • B32B7/022—Mechanical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/023—Optical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/06—Interconnection of layers permitting easy separation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/22—Absorbing filters
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2255/00—Coating on the layer surface
  • B32B2255/26—Polymeric coating
• • 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
  • B32B2305/00—Condition, form or state of the layers or laminate
  • B32B2305/55—Liquid crystals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
  • B32B2307/416—Reflective
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/546—Flexural strength; Flexion stiffness
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/732—Dimensional properties
  • B32B2307/737—Dimensions, e.g. volume or area
  • B32B2307/7375—Linear, e.g. length, distance or width
  • B32B2307/7376—Thickness
• • 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
  • B32B2451/00—Decorative or ornamental articles
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/38—Polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
  • C09K19/54—Additives having no specific mesophase characterised by their chemical composition

Definitions

• the present disclosure relates to laminates and manufacturing methods thereof, decorative films, articles, decorative panels, and display devices.
• International Publication No. 2020/262474 has a plastic substrate and a reflective layer provided on the plastic substrate and having a central wavelength of a selective reflection wavelength in the range of 380 nm or more and 780 nm or less, and the plastic substrate Disclosed is a decorative film for molding, wherein the elastic modulus of the reflective layer at a temperature of +10°C of the glass transition point of the material is 0.00001 GPa or more and 0.5 GPa or less.
• WO 2020/175527 has a protective layer, a substrate, a reflective layer having a maximum reflection wavelength in the wavelength range of 380 nm to 2,000 nm, and an adhesive layer in this order, and the elastic modulus of the protective layer is It discloses a laminate that satisfies the relationship of E1 ⁇ E2>E3, where E1 is the elastic modulus of the base material, E2 is the elastic modulus of the base material, and E3 is the elastic modulus of the pressure-sensitive adhesive layer.
• WO 2017/018468 discloses a cholesteric resin laminate comprising a substrate, an intermediate layer, and a cholesteric resin layer in this order, and the center of the reflection band of the cholesteric resin layer before and after heating the laminate at 130°C for 8 hours.
• a cholesteric resin laminate having a wavelength difference of 50 nm or less is disclosed.
• the problem to be solved by the embodiments of the present disclosure is to provide a laminate having excellent bending resistance and a method for manufacturing the same.
• a problem to be solved by another embodiment of the present disclosure is to provide a decorative film, an article, a decorative panel, and a display device using the laminate.
• Means for solving the above problems include the following aspects. ⁇ 1> Having a substrate, an adhesive layer, and a first cured liquid crystal layer obtained by curing a liquid crystal layer containing a cholesteric liquid crystal compound in this order, the storage elastic modulus E1 of the substrate at 25 ° C.
• the storage elastic modulus E2 of the adhesive layer at 25° C. and the storage elastic modulus E3 of the first cured liquid crystal layer at 25° C. satisfy E1 ⁇ E3>E2, and E2 is 1.0 ⁇ 10 5 Pa ⁇ 1. .0 ⁇ 10 9 Pa laminate.
• ⁇ 2> The laminate according to ⁇ 1>, wherein the first cured liquid crystal layer has a storage modulus of 1.0 ⁇ 10 8 Pa or more over the entire temperature range of 25° C.
• ⁇ 3> The laminate according to ⁇ 1> or ⁇ 2>, wherein the adhesive layer has a thickness of 3 ⁇ m or more and 30 ⁇ m or less.
• ⁇ 4> The laminate according to any one of ⁇ 1> to ⁇ 3>, further comprising a second cured liquid crystal layer.
• ⁇ 5> The laminate according to any one of ⁇ 1> to ⁇ 4>, which has at least one reflection band having a maximum value of reflectance in a wavelength range of 300 nm or more and 900 nm or less.
• ⁇ 6> The laminate according to ⁇ 5>, wherein the maximum value of reflectance in the reflection band is 40% or more.
• ⁇ 7> The laminate according to any one of ⁇ 1> to ⁇ 6>, wherein the first cured liquid crystal layer has a crosslink density of 0.8 mol/L or more due to the polymerizable groups.
• ⁇ 8> Preparing a composition containing a liquid crystal compound having a polymerizable group, an optically active compound, and a photopolymerization initiator, applying the composition onto a peelable substrate, Curing the composition with light to form a first cured liquid crystal layer, and laminating the first cured liquid crystal layer on another substrate via an adhesive layer in this order, The storage elastic modulus E1 at 25° C. of the substrate, the storage elastic modulus E2 at 25° C. of the adhesive layer, and the storage elastic modulus E3 at 25° C.
• a method for producing a laminate wherein the E2 is 1.0 ⁇ 10 5 Pa to 1.0 ⁇ 10 9 Pa.
• a decorative film comprising the laminate according to any one of ⁇ 1> to ⁇ 7>.
• An article comprising the laminate according to any one of ⁇ 1> to ⁇ 7>.
• a decorative panel comprising the decorative film according to ⁇ 9>.
• a display device comprising the decorative panel according to ⁇ 11>.
• the laminate having excellent bending resistance and a method for manufacturing the same.
• notations that do not describe substitution and unsubstituted include not only those not having substituents but also those having substituents.
• an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• Light in the present disclosure means actinic rays or radiation.
• actinic rays or “radiation” in the present disclosure refers to, for example, the emission line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam) and the like.
• exposure in the present disclosure means, unless otherwise specified, not only exposure by the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV light, but also electron beams and ion beams. It also includes exposure by particle beams such as.
• the term “ ⁇ ” is used to include the numerical values before and after it as lower and upper limits.
• (meth)acrylate refers to acrylate and methacrylate
• (meth)acryl refers to acrylic and methacrylic
• the weight-average molecular weight (Mw) of the resin component, the number-average molecular weight (Mn) of the resin component, and the degree of dispersion (also referred to as molecular weight distribution) (Mw/Mn) of the resin component are measured using GPC (Gel Permeation Chromatography) equipment.
• the amount of each component in the composition means the total amount of the corresponding multiple substances present in the composition when there are multiple substances corresponding to each component in the composition, unless otherwise specified. do.
• the term “step” includes not only independent steps, but also if the intended purpose of the step is achieved even if it cannot be clearly distinguished from other steps.
• total solid content refers to the total mass of components excluding the solvent from the total composition of the composition.
• solid content is a component excluding the solvent from the total composition of the composition, and may be solid or liquid at 25° C., for example.
• “% by mass” and “% by weight” are synonymous, and “parts by mass” and “parts by weight” are synonymous.
• a combination of two or more preferred aspects is a more preferred aspect.
• a laminate according to the present disclosure has a substrate, an adhesive layer, and a first cured liquid crystal layer obtained by curing a liquid crystal layer containing a cholesteric liquid crystal compound in this order, and the storage elasticity of the substrate at 25 ° C.
• the modulus E1, the storage modulus E2 of the adhesive layer at 25° C., and the storage modulus E3 of the first cured liquid crystal layer at 25° C. satisfy E1 ⁇ E3>E2, and E2 is 1.0 ⁇ 10. 5 Pa to 1.0 ⁇ 10 9 Pa.
• a laminate having a conventional cured liquid crystal layer has a problem that the resistance to bending is not sufficient and the cured liquid crystal layer is easily cracked.
• the present inventors have found that a laminate having excellent bending resistance can be obtained by adopting the above aspect.
• the storage elastic modulus E1 at 25° C. of the substrate, the storage elastic modulus E2 at 25° C. of the adhesive layer, and the storage elastic modulus E3 at 25° C. of the first cured liquid crystal layer satisfy E1 ⁇ E3>E2.
• E2 of 1.0 ⁇ 10 5 Pa to 1.0 ⁇ 10 9 Pa the strain difference between the first cured liquid crystal layer and the adhesive layer when stress such as bending is applied is small. It is presumed that this is suppressed, the conformability of the first cured liquid crystal layer to the base material is improved, and a laminate having excellent bending resistance is obtained.
• the storage elastic modulus E1 of the substrate at 25°C, the storage elastic modulus E2 of the adhesive layer at 25°C, and the storage elastic modulus E3 of the first cured liquid crystal layer at 25°C are It is preferable that E1 ⁇ E3>E2 is satisfied, and E1>E3>E2 from the viewpoint of bending resistance.
• the storage elastic modulus E1 of the substrate at 25° C. is preferably 1.0 ⁇ 10 8 Pa to 1.0 ⁇ 10 11 Pa, more preferably 1.0 ⁇ 10 9 Pa to 5 from the viewpoint of bending resistance. 0 ⁇ 10 10 Pa, more preferably 2.0 ⁇ 10 9 Pa to 2.0 ⁇ 10 10 Pa, and 3.0 ⁇ 10 9 Pa to 1.0 ⁇ 10 10 Pa is particularly preferred.
• the storage elastic modulus E2 of the adhesive layer at 25° C. is 1.0 ⁇ 10 5 Pa to 1.0 ⁇ 10 9 Pa, and from the viewpoint of bending resistance and durability, it is 2.0 ⁇ 10 8 Pa. It is preferably from 8.0 ⁇ 10 8 Pa, more preferably from 4.0 ⁇ 10 8 Pa to 6.0 ⁇ 10 8 Pa.
• the storage elastic modulus E3 of the first cured liquid crystal layer at 25° C. is preferably 1.0 ⁇ 10 7 Pa to 1.0 ⁇ 10 11 Pa from the viewpoint of bending resistance and durability. It is more preferably 1.0 ⁇ 10 8 Pa to 5.0 ⁇ 10 10 Pa, even more preferably 5.0 ⁇ 10 8 Pa to 1.0 ⁇ 10 10 Pa, and 1.0 ⁇ 10 9 Pa to 5.0 ⁇ 10 9 Pa is particularly preferred.
• the storage elastic modulus of the first cured liquid crystal layer is preferably 1.0 ⁇ 10 7 Pa or more in the entire range of 25° C. to 80° C. from the viewpoint of bending resistance. It is more preferably 10 8 Pa or more, further preferably 1.0 ⁇ 10 8 Pa to 1.0 ⁇ 10 10 Pa, and 2.0 ⁇ 10 9 Pa to 5.0 ⁇ 10 9 Pa. is particularly preferred. Furthermore, the storage elastic modulus of the first cured liquid crystal layer at 80° C. is preferably 1.0 ⁇ 10 6 Pa to 1.0 ⁇ 10 11 Pa from the viewpoint of bending resistance. 10 7 Pa to 5.0 ⁇ 10 10 Pa is more preferred, and 1.0 ⁇ 10 8 Pa to 1.0 ⁇ 10 10 Pa is even more preferred.
• the storage elastic modulus of the first cured liquid crystal layer at 80° C. is preferably greater than E2 from the viewpoint of bending resistance.
• E1-E3 is preferably 0 Pa or more and 5.0 ⁇ 10 10 Pa or less, and more than 0 Pa and 1.0 ⁇ 10 10 Pa or less, from the viewpoint of bending resistance and durability. more preferably 1.0 ⁇ 10 7 Pa or more and 8.0 ⁇ 10 9 Pa or less, and particularly preferably 1.0 ⁇ 10 8 Pa or more and 5.0 ⁇ 10 9 Pa or less .
• the value of E3/E2 is preferably 1.5 to 10 5 , more preferably 2 to 10 3 , and 2 to 10 2 from the viewpoint of bending resistance and durability. is more preferred, and 2 to 10 is particularly preferred.
• the measurement of the storage elastic modulus of each layer in the present disclosure is performed by conditioning each sample 5 mm ⁇ 25 mm at 25 ° C. and a relative humidity of 60% for 2 hours or more. (manufactured by Control Co., Ltd.)), the storage modulus of each layer is measured at a grip distance of 10 mm, a heating rate of 5° C./min, a measurement temperature range of ⁇ 100° C. to 200° C., and a frequency of 10 Hz.
• Each layer may be measured in a cut section of the laminate, or may be measured by exposing the layer to be measured by cutting or the like, or may be measured on the surface of the laminate.
• the laminate preferably has selective reflectivity, and more preferably has a reflection band in a partial wavelength range.
• the laminate preferably has at least one reflection band having a maximum value of reflectance in the wavelength range of 300 nm or more and 900 nm or less from the viewpoint of brilliance and design. It is more preferable to have at least one reflection band with a maximum reflectance value in the range, and it is particularly preferable to have at least one reflection band with a maximum value of reflectance in the wavelength range of 500 nm or more and 600 nm or less.
• the maximum value of the reflectance in the reflection band is preferably 20% or more, more preferably 30% or more, and 40% or more from the viewpoint of brilliance and design. More preferably, it is particularly preferably 45% or more.
• the reflectance (reflection band, maximum value of reflectance) of the laminate is measured as follows. Using a spectrophotometer (eg, V-670 manufactured by JASCO Corporation) equipped with a large integrating sphere device (eg, ILV-471 manufactured by JASCO Corporation), light with a wavelength of 300 nm to 900 nm is emitted vertically. The light is incident from the direction (angle of 90° with respect to the surface of the first cured liquid crystal layer), and the reflectance is obtained from the obtained spectral spectrum.
• a spectrophotometer eg, V-670 manufactured by JASCO Corporation
• a large integrating sphere device eg, ILV-471 manufactured by JASCO Corporation
• a laminate according to the present disclosure has a substrate.
• the base material include base materials used for molding such as three-dimensional molding and insert molding.
• the substrate is preferably a resin substrate, and preferably a resin film.
• resins examples include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), acrylic resin, urethane resin, urethane-acrylic resin, polycarbonate (PC), acrylic-polycarbonate, polyolefin, triacetylcellulose (TAC), cycloolefin.
• PET polyethylene terephthalate
• PEN polyethylene naphthalate
• acrylic resin acrylic resin
• PC polycarbonate
• acrylic-polycarbonate polyolefin
• TAC triacetylcellulose
• COP acrylonitrile/butadiene/styrene copolymers
• ABS resin acrylonitrile/butadiene/styrene copolymers
• the substrate is a resin film containing at least one resin selected from the group consisting of polyethylene terephthalate, acrylic resin, urethane resin, urethane-acrylic resin, polycarbonate, acrylic-polycarbonate and polypropylene. More preferably a resin film containing at least one resin selected from the group consisting of polyethylene terephthalate, acrylic resin, polycarbonate and acrylic-polycarbonate resin, most preferably polyethylene terephthalate.
• the base material may have a single layer structure or a multilayer structure.
• a preferred laminated film is, for example, a laminated film of acrylic resin/polycarbonate resin.
• the base material may contain additives as necessary.
• Additives include, for example, mineral oils, hydrocarbons, fatty acids, alcohols, fatty acid esters, fatty acid amides, metallic soaps, natural waxes, lubricants such as silicone, inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, halogen-based Organic flame retardants such as phosphorus, organic or inorganic fillers such as metal powder, talc, calcium carbonate, potassium titanate, glass fiber, carbon fiber, wood powder, antioxidants, UV inhibitors, lubricants, dispersants, Coupling agents, foaming agents, additives such as colorants, polyolefins, polyesters, polyacetals, polyamides, polyphenylene ether resins and the like, engineering plastics other than the resins mentioned above, and the like.
• the base material may be a commercially available product.
• Commercially available products include, for example, Technolloy (registered trademark) series (acrylic resin film or acrylic resin/polycarbonate resin laminated film, Sumitomo Chemical Co., Ltd.) ABS film (Okamoto Co., Ltd.), ABS sheet (Sekisui Seisei Co., Ltd.), Te Flex (registered trademark) series (PET film, Teijin Film Solutions Co., Ltd.), Lumirror (registered trademark) Easy-to-form type (PET film, Toray Industries, Inc.) and Pure Thermo (polypropylene film, Idemitsu Unitech Co., Ltd.), Cosmo Shine (registered trademark) series (PET film, Toyobo Co., Ltd.).
• the thickness of the substrate is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, still more preferably 20 ⁇ m or more, and particularly preferably 50 ⁇ m or more.
• the thickness of the substrate is preferably 500 ⁇ m or less, more preferably 450 ⁇ m or less, and particularly preferably 200 ⁇ m or less.
• each layer in the present disclosure are measured, for example, by using a spectrophotometer to measure the transmission spectrum of a single film of the layer to be measured formed on the alkali-free glass OA-10G, and the transmission spectrum and the transmittance calculated by the optical interferometry.
• the refractive index may be measured using a Carnew precision refractometer (KPR-3000, Shimadzu Corporation).
• a laminate according to the present disclosure has an adhesive layer.
• the adhesive layer can improve adhesion between the substrate and each layer, for example.
• the adhesive layer preferably contains an adhesive, and may further contain components other than the adhesive. From the viewpoint of bending resistance, the adhesive layer is preferably adjacent to the first cured liquid crystal layer. From the viewpoint of bending resistance, the adhesive layer preferably has a breaking elongation greater than or equal to that of the first cured liquid crystal layer.
• the ratio of the breaking elongation of the adhesive layer to the breaking elongation of the first cured liquid crystal layer is preferably 1.0 to 50, more preferably 1.5 to 30, and more preferably 1.75 to 20. It is even more preferable to have
• the type of adhesive is not limited, and the adhesive may be any known adhesive used for permanent adhesion.
• the adhesive may be any known adhesive used for temporary bonding.
• the adhesive is preferably a component that stretches along with the first cured liquid crystal layer during molding.
• adhesives examples include urethane resin adhesives, polyester adhesives, acrylic resin adhesives, ethylene vinyl acetate resin adhesives, polyvinyl alcohol adhesives, polyamide adhesives, and silicone adhesives.
• a urethane resin adhesive or a silicone adhesive is preferable from the viewpoint of high adhesive strength.
• the adhesive may be a thermosetting adhesive.
• the adhesive may be a UV curable adhesive.
• Adhesives include, for example, adhesives. That is, the adhesive layer may contain a pressure-sensitive adhesive as an adhesive.
• adhesives include acrylic adhesives, rubber adhesives, and silicone adhesives.
• adhesives include acrylic adhesives and ultraviolet (UV) curable adhesives described in "Release Paper/Release Film and Adhesive Tape Characteristic Evaluation and Control Technology, Information Organization, 2004, Chapter 2". agents and silicone adhesives.
• An acrylic pressure-sensitive adhesive refers to a pressure-sensitive adhesive containing a polymer of (meth)acrylic monomers.
• the adhesive-containing layer may contain a tackifier in addition to the adhesive.
• Examples of adhesives include UVX-6282 (manufactured by Toagosei Co., Ltd.), NCF-D692 (manufactured by Lintec Corporation), and UF-3007 (manufactured by Kyoeisha Chemical Co., Ltd.).
• the thickness of the adhesive layer is preferably 2 ⁇ m or more and 50 ⁇ m or less, more preferably 3 ⁇ m or more and 30 ⁇ m or less, and 3 ⁇ m or more and 15 ⁇ m or less, from the viewpoint of bending resistance, adhesion, and handling properties. is more preferable, and 3 ⁇ m or more and 10 ⁇ m or less is particularly preferable.
• the method of forming the adhesive layer is not limited.
• Examples of the method for forming the adhesive layer include a method of bonding a film having an adhesive layer and the first cured liquid crystal layer together, a method of bonding a single adhesive layer and the first cured liquid crystal layer together, and a composition containing an adhesive.
• a method of coating a substance on the liquid crystal layer can be mentioned.
• a laminate according to the present disclosure has a first cured liquid crystal layer obtained by curing a liquid crystal layer containing a cholesteric liquid crystal compound.
• the first cured liquid crystal layer is preferably a layer obtained by polymerizing at least a polymerizable compound, more preferably a layer obtained by polymerizing at least an ethylenically unsaturated compound.
• the first cured liquid crystal layer is preferably a cholesteric liquid crystal layer.
• a “cholesteric liquid crystal layer” is a layer having a molecular alignment state unique to cholesteric liquid crystals.
• the "orientation state of molecules peculiar to cholesteric liquid crystal” may be referred to as "cholesteric orientation state" or simply “orientation state”.
• the alignment state may include an alignment state that reflects right-handed circularly polarized light, an alignment state that reflects left-handed circularly polarized light, or both.
• the orientation state may be fixed by methods such as polymerization and cross-linking.
• the crosslink density of the polymerizable groups in the first cured liquid crystal layer is preferably 0.2 mol/L or more, more preferably 0.5 mol/L or more, from the viewpoint of bending resistance and durability. It is preferably 0.8 mol/L or more, and particularly preferably 0.9 mol/L to 1.5 mol/L.
• the polymerizable group is not particularly limited, and a known polymerizable group can be used, but an ethylenically unsaturated group is preferred.
• the crosslink density of the polymerizable groups in the first cured liquid crystal layer is measured by the following method when the polymerizable groups are ethylenically unsaturated groups.
• FT/IR-4000 manufactured by JASCO Corporation and a measuring device based on this are used.
• (1) Calculate the reaction consumption rate of C C double bond (that is, ethylenically unsaturated bond) using the following formula.
• the first cured liquid crystal layer preferably has selective reflectivity.
• selective reflectivity means that a selective reflection wavelength exists in a specific wavelength range.
• Selective reflection wavelength is the average of two wavelengths showing the half-value transmittance (T1/2, unit: %) represented by the following formula, where Tmin (%) is the minimum transmittance of the object. means value.
• the selective reflection wavelength of the first cured liquid crystal layer may be set, for example, within the range of visible light (380 nm to 780 nm) and near-infrared light (over 780 nm and 2,000 nm or less).
• the first cured liquid crystal layer preferably has selective reflectivity in at least part of the wavelength range from 300 nm to 1,200 nm, and more preferably has selective reflectivity in at least part of the wavelength range from 300 nm to 900 nm.
• Formula: half-value transmittance T1/2 100-(100-Tmin)/2
• Components of the liquid crystal layer before curing forming the first cured liquid crystal layer include, for example, a cholesteric liquid crystal compound, an optically active compound, a polymerization initiator, a polymerizable monomer, a polyfunctional polymerizable compound, a photoisomerization compound, and a cross-linking agent. , solvents and other additives. Aspects of each component are described in the component descriptions of the compositions below.
• Preferred components of the first cured liquid crystal layer include, for example, a polymer having a structural unit derived from a cholesteric liquid crystal compound having a polymerizable group, a polymer having a structural unit derived from an optically active compound having a polymerizable group, and Examples thereof include polymers having structural units derived from a cholesteric liquid crystal compound having a polymerizable group and structural units derived from an optically active compound having a polymerizable group.
• the first cured liquid crystal layer is preferably a cured composition containing a cholesteric liquid crystal compound and an optically active compound.
• the composition is cured, for example, by light or heat. A preferred method of curing the composition is described in the description of the laminate production method below.
• the cured product may not contain a compound having liquid crystallinity.
• the cured product may contain a compound having no liquid crystallinity formed by polymerization or crosslinking of a cholesteric liquid crystal compound having a reactive group.
• Components of the composition include, for example, cholesteric liquid crystal compounds, optically active compounds, polymerization initiators, polymerizable monomers, polyfunctional polymerizable compounds, photoisomerizable compounds, cross-linking agents, solvents and other additives.
• the composition preferably contains a cholesteric liquid crystal compound and an optically active compound. More preferably, the composition contains a cholesteric liquid crystal compound, an optically active compound, and a polymerization initiator. Specific aspects of each component are described below.
• the first cured liquid crystal layer in the laminate according to the present disclosure is a layer obtained by curing a liquid crystal layer containing a cholesteric liquid crystal compound.
• the composition preferably contains a cholesteric liquid crystal compound.
• the type of cholesteric liquid crystal compound is not limited.
• the cholesteric liquid crystal compound may be a known cholesteric liquid crystal compound.
• the cholesteric liquid crystal compound preferably has a reactive group.
• the reactive group is preferably a polymerizable group.
• Polymerizable groups include, for example, radically polymerizable groups and cationic polymerizable groups.
• the cholesteric liquid crystal compound preferably has a radically polymerizable group.
• the radical polymerizable group is preferably at least one polymerizable group selected from the group consisting of a vinyl group, an acryloyl group and a methacryloyl group, and at least one polymerizable group selected from the group consisting of an acryloyl group and a methacryloyl group. More preferably, it is a polymerizable group.
• the cholesteric liquid crystal compound may have two or more reactive groups.
• the cholesteric liquid crystal compound may have two or more reactive groups.
• the cholesteric liquid crystal compound may be a cholesteric liquid crystal compound having two or more reactive groups with different crosslinking mechanisms.
• the cross-linking mechanism may be a condensation reaction, hydrogen bonding or polymerization. At least one of the cross-linking mechanisms of the two or more reactive groups is preferably polymerization.
• the cross-linking mechanism preferably involves two or more types of polymerization. Examples of reactive groups utilized in the above-described crosslinking mechanism include vinyl groups, (meth)acryl groups, epoxy groups, oxetanyl groups, vinyl ether groups, hydroxy groups, carboxy groups and amino groups.
• the cholesteric liquid crystal compound having two or more reactive groups with different cross-linking mechanisms may be a compound that can be cross-linked step by step.
• the reactive groups react according to the cross-linking mechanism of each stage.
• Methods for stepwise crosslinking of two or more reactive groups include, for example, a method of changing the reaction conditions in each step. Changes in reaction conditions include, for example, temperature, wavelength of light (irradiation), and polymerization mechanism. Utilization of a difference in polymerization mechanism is preferable because the reaction can be easily separated.
• the polymerization mechanism is controlled, for example, by the type of polymerization initiator.
• the combination of polymerizable groups includes a radical polymerizable group of vinyl group or (meth)acrylic group, and a cationically polymerizable group of epoxy group, oxetanyl group or vinyl ether group.
• a polymerizable group an ethylenically unsaturated group is preferable.
• the cholesteric liquid crystal compound preferably contains a cholesteric liquid crystal compound having one reactive group (preferably a polymerizable group).
• the ratio of the content of the cholesteric liquid crystal compound having one reactive group to the content of the cholesteric liquid crystal compound is preferably from 96% by mass to 100% by mass, and from 97% by mass to It is more preferably 100% by mass, preferably 98% by mass to 100% by mass.
• the cholesteric liquid crystal compound preferably contains a cholesteric liquid crystal compound having one reactive group and a cholesteric liquid crystal compound having two or more reactive groups. More preferably, the cholesteric liquid crystal compound includes a cholesteric liquid crystal compound having one reactive group and a cholesteric liquid crystal compound having two reactive groups. From the viewpoint of stretchability and heat resistance, the ratio of the content of the cholesteric liquid crystal compound having two or more reactive groups to the content of the cholesteric liquid crystal compound having one reactive group is 0 to 0 on a mass basis. 0.05 is preferred, 0 to 0.04 is more preferred, and 0 to 0.02 is preferred.
• reactive groups are shown below. However, the reactive group is not limited to the specific examples below.
• Et represents an ethyl group and n-Pr represents an n-propyl group.
• Cholesteric liquid crystal compounds include, for example, rod-shaped cholesteric liquid crystal compounds and disk-shaped cholesteric liquid crystal compounds.
• the rod-shaped cholesteric liquid crystal compound may be a low-molecular-weight or high-molecular-weight compound.
• the discotic cholesteric liquid crystal compounds may be low-molecular-weight or high-molecular-weight compounds.
• the term "polymer" used with respect to cholesteric liquid crystal compounds means compounds having a degree of polymerization of 100 or more (Polymer Physics, Phase Transition Dynamics, Masao Doi, p.2, Iwanami Shoten, 1992 ).
• Two or more types of rod-shaped cholesteric liquid crystal compounds, two or more types of discotic liquid crystal compounds, or mixtures of rod-shaped cholesteric liquid crystal compounds and discotic liquid crystal compounds may be used. At least one of the two or more cholesteric liquid crystal compounds preferably has a reactive group.
• the cholesteric liquid crystal compound is preferably a rod-shaped cholesteric liquid crystal compound.
• Rod-shaped cholesteric liquid crystal compounds include, for example, azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenyl Included are pyrimidines, phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles.
• Rod-shaped cholesteric liquid crystal compounds also include, for example, polymers of rod-shaped cholesteric liquid crystal compounds having reactive groups.
• Examples of rod-shaped cholesteric liquid crystal compounds include compounds described in JP-A-2008-281989, JP-A-11-513019 and JP-A-2006-526165.
• rod-shaped cholesteric liquid crystal compounds are shown below.
• the rod-shaped cholesteric liquid crystal compound is not limited to the following specific examples.
• the compounds shown below are synthesized, for example, by the method described in Japanese Patent Publication No. 11-513019.
• rod-shaped cholesteric liquid crystal compounds having one polymerizable group examples include the following compounds. "Me” shown in the following chemical formula means a methyl group.
• discotic cholesteric liquid crystal compounds include the following compounds. (1) C.I. Destrade et al., see, for example, Mol. Cryst. 71, 111 (1981) benzene derivatives (2) C.I. Destrade et al., see, for example, Mol. Cryst. 122, 141 (1985) and Physicslett, A, 78, 82 (1990) truxene derivatives (3)B. Kohne et al., see, for example, Angew. Chem. 96, 70 (1984) (4) J. Am. M. Lehn et al.'s research report (J. Chem. Commun., 1794 (1985) and J. Zhang et al.'s research report (J. Am. Chem. Soc. 116, 2655 (1994)) Azacrown-based or phenylacetylene-based macrocycles
• the discotic cholesteric liquid crystal compound has a structure in which the various structures described above are used as a discotic mother nucleus at the center of the molecule, and groups such as linear alkyl groups, alkoxy groups and substituted benzoyloxy groups are arranged radially, Liquid crystal compounds that exhibit liquid crystallinity and are generally called discotic liquid crystals are included. Negative uniaxiality appears when aggregates of such compounds are uniformly oriented.
• discotic cholesteric liquid crystal compounds include compounds described in paragraphs 0061 to 0075 of JP-A-2008-281989.
• the discotic cholesteric liquid crystal compound having a reactive group may be fixed in an alignment state such as horizontal alignment, vertical alignment, tilt alignment and twist alignment.
• the composition may contain one or more cholesteric liquid crystal compounds.
• the ratio of the content of the cholesteric liquid crystal compound to the total mass of the solid content of the composition is preferably 30% by mass to 99% by mass, more preferably 40% by mass to 99% by mass, and 60% by mass to More preferably 99% by mass, particularly preferably 70% to 98% by mass.
• the composition preferably contains an optically active compound (also referred to as a "chiral agent").
• An optically active compound can induce a helical structure of cholesteric liquid crystals.
• an optically active compound can modulate helical pitch.
• optically active compound is not limited.
• the optically active compound may be a known optically active compound.
• the optically active compound may be selected according to the desired helical structure. Examples of optically active compounds include Liquid Crystal Device Handbook (Chapter 3, Section 4-3, Chiral Agents for TN and STN, p. 199, Japan Society for the Promotion of Science, 142nd Committee, 1989), and JP-A-2003-287623. , JP-A-2002-302487, JP-A-2002-80478, JP-A-2002-80851, JP-A-2010-181852 and JP-A-2014-034581.
• the optically active compound preferably has a cinnamoyl group.
• the optically active compound preferably contains an asymmetric carbon atom.
• the optically active compound may be an axially asymmetric compound or planar asymmetric compound containing no asymmetric carbon atoms.
• Examples of axially chiral compounds and planar chiral compounds include binaphthyl, helicene, paracyclophane, and derivatives thereof.
• the optically active compound may have a reactive group.
• the reactive group is preferably a polymerizable group.
• the polymerizable group is preferably at least one polymerizable group selected from the group consisting of an ethylenically unsaturated group, an epoxy group and an aziridinyl group, more preferably an ethylenically unsaturated group, an acryloyl group and at least one polymerizable group selected from the group consisting of methacryloyl groups.
• the optically active compound may have two or more reactive groups.
• the optically active compound may have two or more reactive groups.
• the optically active compound preferably contains an optically active compound having one polymerizable group.
• the ratio of the content of the optically active compound having one polymerizable group to the content of the optically active compound is , preferably more than 0% by mass, more preferably 50% by mass or more, and even more preferably 70% by mass or more.
• the upper limit may be 100% by mass.
• the ratio of the content of the optically active compound having one polymerizable group to the content of the optically active compound may be 0% by mass to 100% by mass.
• the composition preferably contains a cholesteric liquid crystal compound having a polymerizable group and an optically active compound having a polymerizable group.
• the reaction between an optically active compound having a polymerizable group and a cholesteric liquid crystal compound having a polymerizable group is derived from a structural unit derived from a cholesteric liquid crystal compound having a polymerizable group and an optically active compound having a polymerizable group.
• the type of polymerizable group in the optically active compound is preferably the same as the type of polymerizable group in the cholesteric liquid crystal compound.
• the optically active compound may be a cholestech liquid crystal compound.
• the optically active compound may be a photoisomerizable compound that also acts as an optically active compound, from the viewpoints of ease of forming a liquid crystal layer, ease of adjusting the helical pitch, and bending resistance.
• photoisomerizable compounds that also act as optically active compounds include compounds represented by formula (CH1) described below.
• Preferred optically active compounds include, for example, isosorbide derivatives, isomannide derivatives and binaphthyl derivatives.
• optically active compounds are shown below. However, the optically active compound is not limited to the specific examples below.
• n represents an integer of 2 to 12. From the viewpoint of synthesis cost, n is preferably 2 or 4.
• the composition may contain one or more optically active compounds.
• the content of the optically active compound should be 1% by mass to 20% by mass with respect to the total mass of the solid content of the composition. is preferred, more preferably 2% by mass to 10% by mass, even more preferably 3% by mass to 9% by mass, and particularly preferably 4% by mass to 8% by mass.
• the ratio of the content of the optically active compound having a polymerizable group to the total mass of the solid content of the composition is preferably 0.2% by mass to 15% by mass, and preferably 0.5% by mass. % to 10% by mass, more preferably 1% to 8% by mass, and particularly preferably 1.5% to 5% by mass.
• the ratio of the content of the optically active compound having no polymerizable group to the total mass of the solid content of the composition is preferably 0.2% by mass to 20% by mass, and preferably 0.5% by mass. It is more preferably from 2% to 10% by mass, and particularly preferably from 2% to 8% by mass.
• the helical pitch and the selective reflection wavelength and its range are adjusted, for example, not only according to the type of cholesteric liquid crystal compound but also according to the content of the optically active compound. For example, when the content of the optically active compound in the liquid crystal layer is doubled, the helical pitch is halved and the central value of the selective reflection wavelength is also halved.
• the composition preferably contains a polymerization initiator.
• the type of polymerization initiator is not limited.
• the polymerization initiator may be a known polymerization initiator.
• the polymerization initiator is preferably a photopolymerization initiator.
• Examples of photopolymerization initiators include ⁇ -carbonyl compounds (see, for example, US Pat. Nos. 2,367,661 and 2,367,670) and acyloin ether compounds (see, for example, US Pat. No. 2,448,828). , ⁇ -hydrocarbon-substituted aromatic acyloin compounds (see, for example, US Pat. No.
• photopolymerization initiators examples include photoradical polymerization initiators and photocationic polymerization initiators.
• Preferred radical photopolymerization initiators include, for example, ⁇ -hydroxyalkylphenone compounds, ⁇ -aminoalkylphenone compounds, acylphosphine oxide compounds, thioxanthone compounds and oxime ester compounds.
• Preferred photocationic polymerization initiators include iodonium salt compounds and sulfonium salt compounds.
• the composition may contain one or more polymerization initiators.
• the content of the polymerization initiator relative to the total mass of the solid content of the composition is 0.05% by mass to 10% by mass. It is preferably 0.05% by mass to 5% by mass, more preferably 0.1% by mass to 4% by mass, and 0.2% by mass to 3% by mass. Especially preferred.
• the composition may contain a polymerizable monomer.
• Polymerizable monomers can promote cross-linking of cholesteric liquid crystal compounds.
• Polymerizable monomers include, for example, monomers or oligomers that have two or more ethylenically unsaturated groups and undergo addition polymerization upon irradiation with light. Examples of polymerizable monomers include compounds having an ethylenically unsaturated group.
• Polymerizable monomers include monofunctional acrylates, monofunctional methacrylates, multifunctional acrylates and multifunctional methacrylates.
• Polymerizable monomers include, for example, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate and phenoxyethyl (meth)acrylate.
• polymerizable monomers include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolethane triacrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane diacrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, hexanediol di(meth)acrylate, tri Methylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, tri(acryloyloxyethyl)cyanurate and glycerin tri(meth)acrylate.
• polymerizable monomers examples include compounds formed by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as trimethylolpropane and glycerin, followed by (meth)acrylate.
• polymerizable monomers examples include urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193.
• polymerizable monomers examples include polyester acrylates described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490.
• examples of polymerizable monomers include epoxy acrylates, which are reaction products of epoxy resins and (meth)acrylic acid.
• Preferred polymerizable monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate and dipentaerythritol penta(meth)acrylate. Further, preferred polymerizable monomers include, for example, "polymerizable compound B" described in JP-A-11-133600.
• the polymerizable monomer may be a cationically polymerizable monomer.
• cationic polymerizable monomers include, for example, JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, JP-A-2001-55507, JP-A-2001-310938, Examples include epoxy compounds, vinyl ether compounds and oxetane compounds described in JP-A-2001-310937 and JP-A-2001-220526.
• Epoxy compounds include, for example, aromatic epoxides, alicyclic epoxides and aliphatic epoxides.
• Aromatic epoxides include diglycidyl ether or polyglycidyl ether of bisphenol A, diglycidyl ether or polyglycidyl ether of alkylene oxide adduct of bisphenol A, diglycidyl ether or polyglycidyl ether of hydrogenated bisphenol A, hydrogenated bisphenol A and diglycidyl ethers or polyglycidyl ethers of alkylene oxide adducts of and novolac type epoxy resins.
• Alkylene oxides include, for example, ethylene oxide and propylene oxide.
• Alicyclic epoxides include, for example, cyclohexene oxide-containing compounds obtained by epoxidizing compounds having a cycloalkane ring (e.g., cyclohexene and cyclopentene rings) with an oxidizing agent (e.g., hydrogen peroxide and peracid). or a cyclopentene oxide-containing compound.
• a cycloalkane ring e.g., cyclohexene and cyclopentene rings
• an oxidizing agent e.g., hydrogen peroxide and peracid
• Aliphatic epoxides include, for example, diglycidyl ethers or polyglycidyl ethers of aliphatic polyhydric alcohols and diglycidyl ethers or polyglycidyl ethers of alkylene oxide adducts of aliphatic polyhydric alcohols.
• Aliphatic epoxides include, for example, diglycidyl ethers of alkylene glycols (eg, diglycidyl ethers of ethylene glycol, diglycidyl ethers of propylene glycol, and diglycidyl ethers of 1,6-hexanediol).
• Aliphatic epoxides include, for example, polyglycidyl ethers of polyhydric alcohols (eg, diglycidyl ethers or polyglycidyl ethers of glycerin and diglycidyl ethers or polyglycidyl ethers of alkylene oxide adducts of glycerin).
• Aliphatic epoxides include, for example, diglycidyl ethers of polyalkylene glycols (eg, diglycidyl ethers of polyethylene glycol or its alkylene oxide adducts and diglycidyl ethers of polypropylene glycol or its alkylene oxide adducts).
• Alkylene oxides include, for example, ethylene oxide and propylene oxide.
• Examples of cationic polymerizable monomers include monofunctional or bifunctional oxetane monomers.
• 3-ethyl-3-hydroxymethyloxetane eg, OXT101 manufactured by Toagosei Co., Ltd.
• 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene eg, OXT121 manufactured by Toagosei Co., Ltd.
• 3-ethyl-3-(phenoxymethyl) oxetane eg, OXT211 manufactured by Toagosei Co., Ltd.
• di(1-ethyl-3-oxetanyl) methyl ether eg, OXT221 manufactured by Toagosei Co., Ltd.
• 3-ethyl -3-(2-ethylhexyloxymethyl)oxetane eg, OXT212 manufactured by Toagosei Co., Ltd.
• 3-ethyl-3-hydroxymethyloxetane 3-ethyl-3-(phenoxymethyl)oxetane and di(1-ethyl-3-oxetanyl)methyl ether.
• Monofunctional or polyfunctional oxetane compounds described in JP-A-2001-220526 and JP-A-2001-310937 may also be used.
• the composition may contain a polyfunctional polymerizable compound.
• the polyfunctional polymerizable compound can contribute to suppression of change in reflectance after molding.
• a cholesteric liquid crystal compound having two or more ethylenically unsaturated groups and no cyclic ether group for example, a cholesteric liquid crystal compound having two or more cyclic ether groups and an ethylenic A cholesteric liquid crystal compound having no unsaturated groups, a cholesteric liquid crystal compound having two or more ethylenically unsaturated groups and two or more cyclic ether groups, an optically active compound having two or more polymerizable groups, and a cross-linking agent. mentioned.
• Preferred ethylenically unsaturated groups include, for example, (meth)acrylic groups. More preferred ethylenically unsaturated groups include, for example, (meth)acryloxy groups.
• Preferred cyclic ether groups include, for example, epoxy groups and oxetanyl groups. More preferred cyclic ether groups include, for example, oxetanyl groups.
• the polyfunctional polymerizable compound is a cholesteric liquid crystal compound having two or more ethylenically unsaturated groups and no cyclic ether groups, and two or more cyclic ether groups and an ethylenically unsaturated group. It preferably contains at least one compound selected from the group consisting of a cholesteric liquid crystal compound having no and an optically active compound having two or more polymerizable groups, and an optically active compound having two or more polymerizable groups It is more preferable to include
• the composition may contain one or more polyfunctional polymerizable compounds.
• the ratio of the content of the polyfunctional polymerizable compound to the total solid content of the composition is preferably 0.5% by mass to 70% by mass, and 1% by mass to 50% by mass. more preferably, 1.5% by mass to 20% by mass, and particularly preferably 2% by mass to 10% by mass.
• the composition may contain a photoisomerizable compound.
• the type of photoisomerizable compound is not limited.
• the photoisomerizable compound may be a known photoisomerizable compound. From the viewpoint of suppression of change in reflectance after molding and maintenance of the isomerized structure, a compound whose steric structure changes upon exposure is preferred.
• a photoisomerizable compound has a photoisomerizable structure.
• the photoisomerizable compound preferably has a structure whose steric structure changes upon exposure, and the EZ configuration is isomerized upon exposure. It is more preferable to have a disubstituted or more ethylenically unsaturated bond that isomerizes, and it is particularly preferable to have a disubstituted ethylenically unsaturated bond whose EZ configuration is isomerized by exposure.
• Isomerization of the EZ configuration includes cis-trans isomerization.
• the disubstituted ethylenically unsaturated bond is preferably an ethylenically unsaturated bond substituted with an aromatic group and an ester bond.
• the photoisomerization compound preferably has two or more photoisomerization structures.
• the number of photoisomerizable structures in the photoisomerizable compound is preferably two to four, more preferably two.
• the photoisomerizable compound is preferably a photoisomerizable compound that also acts as the optically active compound described above.
• the photoisomerizable compound that also acts as an optically active compound is preferably an optically active compound having a molar extinction coefficient of 30,000 or more at a wavelength of 313 nm.
• Examples of photoisomerizable compounds that also act as optically active compounds include compounds represented by the following formula (CH1).
• the compound represented by the formula (CH1) can change its orientation structure such as helical pitch (twisting force, helical twist angle) depending on the amount of light irradiated.
• the compound represented by the formula (CH1) is a compound in which the EZ configuration of two ethylenically unsaturated bonds can be isomerized by exposure.
• Ar CH1 and Ar CH2 each independently represent an aryl group or a heteroaromatic ring group
• R CH1 and R CH2 each independently represent a hydrogen atom or a cyano group
• Ar 4 CH1 and Ar 4 CH2 in formula (CH1) are each independently preferably an aryl group.
• the aryl group may have a substituent.
• substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, hydroxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, A carboxy group, a cyano group or a heterocyclic group is preferable, and a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an acyloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group is more preferable.
• the total carbon number of the aryl group is preferably 6-40, more preferably 6-30.
• Ar CH1 and Ar CH2 are each independently preferably an aryl group represented by the following formula (CH2) or the following formula (CH3).
• R CH3 and R CH4 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, a hydroxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carboxy group, or a cyano group
• L CH1 and L CH2 each independently represent a halogen atom, an alkyl group, an alkoxy group, or a hydroxy group
• nCH1 represents an integer of 0 to 4
• nCH2 represents an integer of 0 to 6
• * represents a bonding position with an ethylenically unsaturated bond in formula (CH1).
• R CH3 and R CH4 in formula (CH2) and formula (CH3) are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, Alternatively, it is preferably an acyloxy group, more preferably an alkoxy group, a hydroxy group, or an acyloxy group, and particularly preferably an alkoxy group.
• L CH1 and L CH2 in formula (CH2) and formula (CH3) are preferably each independently an alkoxy group having 1 to 10 carbon atoms or a hydroxy group.
• nCH1 in formula (CH2) is preferably 0 or 1.
• nCH2 in formula (CH3) is preferably 0 or 1.
• the heteroaromatic ring groups in Ar 2 CH1 and Ar 2 CH2 of formula (CH1) may have a substituent.
• Preferred substituents include, for example, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, a hydroxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, or a cyano group.
• Halogen atoms, alkyl groups, alkenyl groups, aryl groups, alkoxy groups, or acyloxy groups are more preferred.
• the total carbon number of the heteroaromatic ring group is preferably 4-40, more preferably 4-30.
• the heteroaromatic ring group is preferably a pyridyl group, a pyrimidinyl group, a furyl group or a benzofuranyl group, more preferably a pyridyl group or a pyrimidinyl group.
• R CH1 and R CH2 in formula (CH1) are preferably each independently a hydrogen atom.
• Bu represents an n-butyl group.
• the steric configuration of each ethylenically unsaturated bond in the following compounds is E-form (trans-form), and changes to Z-form (cis-form) upon exposure.
• the composition may contain one or more photoisomerizable compounds.
• the ratio of the content of the photoisomerizable compound to the total mass of the solid content of the composition is preferably 1% by mass to 20% by mass, and is 2% by mass to 10% by mass. is more preferable, more preferably 3% by mass to 9% by mass, and particularly preferably 4% by mass to 8% by mass.
• the composition may contain a cross-linking agent.
• the cross-linking agent can improve the strength and durability of the liquid crystal layer after curing.
• the type of cross-linking agent is not limited.
• the cross-linking agent may be a known cross-linking agent.
• the cross-linking agent is preferably a compound that cures with ultraviolet light, heat or moisture.
• cross-linking agents include polyfunctional acrylate compounds such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate; glycidyl (meth)acrylate, ethylene glycol diglycidyl ether, 3′,4′-epoxycyclohexyl Epoxy compounds such as methyl 3,4-epoxycyclohexanecarboxylate; oxetane compounds such as 2-ethylhexyloxetane and xylylene bisoxetane; 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate], 4 , 4-bis(ethyleneiminocarbonylamino)diphenylmethane and other aziridine compounds; hexamethylene diisocyanate, biuret isocyanate and other isocyanate compounds; polyoxazoline compounds having an oxazoline group in the side chain; vinyltri
• the composition may contain one or more crosslinkers.
• the content ratio of the cross-linking agent to the total solid content of the composition is preferably 1% by mass to 20% by mass, and 3% by mass to 15% by mass. It is more preferable to have
• the composition may contain a solvent.
• solvents include organic solvents.
• organic solvents include ketone compounds (e.g., methyl ethyl ketone and methyl isobutyl ketone), alkyl halide compounds, amide compounds, sulfoxide compounds, heterocyclic compounds, hydrocarbon compounds, ester compounds, ether compounds and alcohol compounds.
• a ketone compound is preferred in consideration of the load on the environment.
• solvents include high-boiling solvents.
• the boiling point of the high boiling point solvent is preferably 150° C. or higher, more preferably 160° C. or higher.
• high-boiling solvents include furfuryl alcohol, 2-thiophene methanol, benzyl alcohol, tetrahydrofurfuryl alcohol, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, ethyl acetoacetate, methyl benzoate, ethyl benzoate and o - methyl toluate.
• the composition may contain one or more solvents.
• the ratio of the solvent content to the total mass of the composition is preferably 50% by mass to 85% by mass, more preferably 60% by mass to 80% by mass, and 65% by mass to 75% by mass. is more preferred.
• the ratio of the content of the high-boiling solvent to the content of the solvent is preferably 2% by mass to 30% by mass, more preferably 4% by mass to 25% by mass. More preferably, it is 6% by mass to 20% by mass.
• composition may contain other additives.
• additives include, for example, surfactants, polymerization inhibitors, antioxidants, horizontal alignment agents, UV absorbers, light stabilizers, colorants and metal oxide particles.
• the laminate may have one or more cured liquid crystal layers, and from the viewpoint of brilliance, it preferably further has a second cured liquid crystal layer other than the first cured liquid crystal layer.
• the cured liquid crystal layer other than the first cured liquid crystal layer there are two or more cured liquid crystal layers, such as the case of having the second cured liquid crystal layer, and the case of having the second cured liquid crystal layer and the third cured liquid crystal layer.
• the first cured liquid crystal layer, the second cured liquid crystal layer, etc. are also collectively referred to simply as the "cured liquid crystal layer".
• one cured liquid crystal layer may be in direct contact with another cured liquid crystal layer (e.g. the second cured liquid crystal layer). Often, direct contact is preferred.
• one cured liquid crystal layer e.g., first cured liquid crystal layer
• another cured liquid crystal layer e.g., second cured liquid crystal layer
• another layer e.g., adhesive layer
• the color of one cured liquid crystal layer is different from the color of another cured liquid crystal layer (for example, the second cured liquid crystal layer). They may be the same or different. If the tint of one cured liquid crystal layer is different from the tint of another cured liquid crystal layer, the design is improved by additive color mixture.
• the composition of the two or more cured liquid crystal layers may be the same or different from each other.
• the combination of alignment states of the cured liquid crystal layers is not limited. Cured liquid crystal layers with the same orientation may be stacked. Cured liquid crystal layers with different alignment states may be stacked. Among them, from the viewpoint of improving brightness and reflectance, the laminate includes a first cured liquid crystal layer having a helical structure and a second cured liquid crystal layer having a helical structure having a reverse rotation to the helical structure. It is preferred to have A "helical structure" means a helical structure of a cholesteric liquid crystal.
• the thickness of the cured liquid crystal layer is preferably less than 10 ⁇ m, more preferably 5 ⁇ m or less, even more preferably 0.05 ⁇ m to 5 ⁇ m, and even more preferably 0.1 ⁇ m to 5 ⁇ m. It is particularly preferred to have When the laminate includes two or more cured liquid crystal layers, the two or more cured liquid crystal layers are preferably independently adjusted to the above ranges.
• the color of the cured liquid crystal layer and the change in color depending on the viewing angle are adjusted, for example, by at least one selected from the group consisting of helical pitch, refractive index and thickness.
• the helical pitch is adjusted, for example, by adding an optically active compound (chiral agent). Details are described, for example, in "Fuji Film Research Report No. 50 (2005) pp. 60-63".
• the helical pitch may be adjusted by the conditions such as temperature, illuminance and irradiation time when fixing the cholesteric alignment state.
• the laminate may have an alignment layer adjacent to the cured liquid crystal layer.
• the alignment layer can orient the molecules of the cholesteric liquid crystal compound during the manufacturing process of the cured liquid crystal layer.
• the alignment layer is provided, for example, by rubbing an organic compound (preferably polymer), oblique vapor deposition of an inorganic compound such as SiO, or formation of a layer having microgrooves.
• an orientation layer is also known in which an orientation function is produced by application of an electric field, application of a magnetic field, or light irradiation.
• the alignment layer includes, for example, a rubbing alignment layer and a photo-alignment layer.
• the rubbing treatment alignment layer is formed by, for example, rubbing treatment.
• a photo-alignment layer is formed by light irradiation, for example.
• Examples of the polymer used for the rubbing alignment layer include methacrylate copolymers, styrene copolymers, polyolefins, polyvinyl alcohols, modified polyvinyl alcohols, poly(N -methylolacrylamide), polyesters, polyimides, vinyl acetate copolymers, carboxymethylcellulose and polycarbonates.
• Examples of polymers used in the rubbing alignment layer include silane coupling agents.
• the polymer used for the rubbing treatment alignment layer is preferably, for example, a water-soluble polymer (eg, poly(N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol and modified polyvinyl alcohol), gelatin, polyvinyl alcohol or modified polyvinyl alcohol. is more preferred, and polyvinyl alcohol or modified polyvinyl alcohol is particularly preferred.
• the rubbing treatment is performed, for example, by rubbing the surface of the film containing a polymer as a main component with paper or cloth in a certain direction.
• a general rubbing method is described, for example, in "Liquid Crystal Handbook” (published by Maruzen Co., Ltd., Oct. 30, 2000).
• the rubbing density (L) is quantified by the following formula (A).
• Formula (A): L Nl(1+2 ⁇ rn/60v)
• N represents the number of times of rubbing
• l represents the contact length of the rubbing roller
• r represents the radius of the roller
• n represents the rotation speed of the roller (rpm: revolutions per minute)
• v represents the stage Represents movement speed (seconds).
• Methods for increasing the rubbing density include, for example, increasing the number of times of rubbing, increasing the contact length of the rubbing roller, increasing the radius of the roller, increasing the number of rotations of the roller, and slowing down the stage movement speed. method.
• the opposite condition of the above method can lower the rubbing density.
• Japanese Patent No. 4052558 may be referred to as conditions for the rubbing treatment.
• photo-alignment material used in the photo-alignment layer for example, JP-A-2006-285197, JP-A-2007-76839, JP-A-2007-138138, JP-A-2007-94071, JP-A-2007- 121721, JP-A-2007-140465, JP-A-2007-156439, JP-A-2007-133184, JP-A-2009-109831, JP-A-3883848 and JP-A-4151746.
• the photo-alignment layer is formed, for example, by applying linearly polarized light or non-polarized light to a layer formed of the above materials.
• Linearly polarized light irradiation is an operation for causing a photoreaction in the photoalignment material.
• the light used for light irradiation is preferably light with a peak wavelength of 200 nm to 700 nm, more preferably ultraviolet light with a peak wavelength of 400 nm or less.
• Examples of light sources used for light irradiation include lamps (e.g., tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury xenon lamps and carbon arc lamps), lasers (e.g., semiconductor lasers, helium neon lasers). , argon ion lasers, helium cadmium lasers and YAG lasers), light emitting diodes and cathode ray tubes.
• lamps e.g., tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury xenon lamps and carbon arc lamps
• lasers e.g., semiconductor lasers, helium neon lasers.
• argon ion lasers, helium cadmium lasers and YAG lasers argon ion lasers, helium cadmium lasers and YAG lasers
• light emitting diodes and cathode ray tubes.
• Methods for obtaining linearly polarized light include, for example, a method using a polarizing plate (e.g., an iodine polarizing plate, a dichroic dye polarizing plate, and a wire grid polarizing plate), a prism-based element (e.g., a Glan-Thompson prism), or a Brewster angle.
• a method using a reflective polarizer and a method using light emitted from a laser light source having polarized light may be selectively irradiated using a filter or a wavelength conversion element.
• light may be irradiated perpendicularly or obliquely to the upper or lower surface of the alignment layer.
• the angle of incidence of light on the alignment layer is preferably 0° to 90°, more preferably 40° to 90°.
• the upper or lower surface of the alignment layer is obliquely irradiated with non-polarized light.
• the incident angle is preferably 10° to 80°, more preferably 20° to 60°, particularly preferably 30° to 50°.
• the irradiation time is preferably 1 minute to 60 minutes, more preferably 1 minute to 10 minutes.
• the thickness of the orientation layer is preferably 0.01 ⁇ m to 10 ⁇ m.
• the lower layer can be made to function as an orientation layer by directly subjecting the lower layer to orientation treatment (for example, rubbing treatment) even if the orientation layer is not provided.
• orientation treatment for example, rubbing treatment
• the lower layer as described above include polyethylene terephthalate (PET).
• the lower cured liquid crystal layer acts as an alignment layer, and the cholesteric liquid crystal compound may be oriented during the manufacturing process of the upper cured liquid crystal layer in contact with the lower cured liquid crystal layer. .
• the cholesteric liquid crystal compound is oriented in the manufacturing process of the upper cured liquid crystal layer without providing an orientation layer or performing an orientation treatment (for example, rubbing treatment).
• the laminate may have a colored layer. By having a colored layer, designability is improved.
• the position of the colored layer in the laminate is not restricted.
• the laminate preferably includes a colored layer, a substrate, an adhesive layer, and a first cured liquid crystal layer in this order.
• the laminate preferably includes a substrate, an adhesive layer, a first cured liquid crystal layer, and a colored layer.
• the laminate may contain two or more colored layers. At least one colored layer in the laminate is preferably a layer visible through the first cured liquid crystal layer. When at least one colored layer is a layer visible through the first cured liquid crystal layer, based on the anisotropy according to the angle of light incident on the first cured liquid crystal layer, the viewing angle of the colored layer changes. It is thought that a change in color occurs accordingly and a special design property is exhibited. When the laminate includes two or more colored layers, at least one colored layer is a layer that is visible through the first cured liquid crystal layer, and at least one of the other colored layers is higher than the liquid crystal layer. A layer close to an observer (also referred to as a "color filter layer”) is preferred.
• the color filter layer may be a layer that is highly transmissive to light of specific wavelengths.
• the color filter layer may be a monochromatic color filter layer.
• the color filter layer may be a color filter layer having a color filter structure of two or more colors and, if necessary, a black matrix or the like. According to the color filter layer, for example, a layered product having excellent design properties and being visible in a specific wavelength range can be obtained.
• the total light transmittance of at least one colored layer is preferably 10% or less.
• the colors of the colored layer include, for example, black, gray, white, red, orange, yellow, green, blue and purple.
• the color of the colored layer may be a metallic color.
• the components of the colored layer include, for example, colorants, resins (eg binder polymers), dispersants and other additives.
• the colored layer may contain a polymerizable compound and a polymerization initiator.
• the colored layer preferably contains a coloring agent.
• Colorants include, for example, pigments and dyes. From the viewpoint of durability, pigments are preferred.
• the metallic colored layer may contain components such as metallic particles and pearl pigments. Methods such as vapor deposition and plating may be applied to form the metallic colored layer.
• pigments include inorganic pigments and organic pigments.
• inorganic pigments include white pigments (e.g., titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide and barium sulfate), black pigments (e.g., carbon black, titanium black, titanium carbon, iron oxide and graphite), iron oxide, barium yellow, cadmium red and chrome yellow.
• white pigments e.g., titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide and barium sulfate
• black pigments e.g., carbon black, titanium black, titanium carbon, iron oxide and graphite
• iron oxide barium yellow
• cadmium red and chrome yellow e.g., iron oxide, barium yellow, cadmium red and chrome yellow.
• organic pigments for example, phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; Azo pigments such as azo yellow and azo orange, quinacridone pigments such as quinacridone red, syncash red and syncash magenta, perylene pigments such as perylene red and perylene maroon, carbazole violet, anthrapyridine, flavanthrone yellow, isoindoline Yellow, indathron blue, dibromoanzathrone red, anthraquinone red and diketopyrrolopyrroles.
• organic pigments include C.I. I.
• the organic pigment an organic pigment described in paragraph 0093 of JP-A-2009-256572 may be applied.
• the pigment may be a pigment having light transmittance and light reflectivity (so-called luster pigment).
• Luster pigments include, for example, metallic luster pigments such as aluminum, copper, zinc, iron, nickel, tin, aluminum oxide and alloys thereof, interference mica pigments, white mica pigments, graphite pigments and glass flake pigments. be done.
• the bright pigment may be a colorless bright pigment.
• the glitter pigment may be a colored glitter pigment. When exposure is performed in molding the laminate, the bright pigment is preferably used within a range that does not interfere with curing by exposure.
• the colored layer may contain one or more colorants.
• a combination of inorganic and organic pigments may be applied.
• the content of the coloring agent in the total weight of the colored layer is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 50% by mass. more preferably 10% by mass to 40% by mass.
• the colored layer preferably further contains a binder polymer.
• the binder polymer is preferably a transparent resin.
• a resin having a total light transmittance of 80% or more is preferable. The total light transmittance is measured with a spectrophotometer (eg, spectrophotometer UV-2100 manufactured by Shimadzu Corporation).
• binder polymers examples include acrylic resins, silicone resins, polyesters, polyurethanes and polyolefins.
• the binder polymer may be a homopolymer or a copolymer.
• the colored layer may contain one or more binder polymers.
• the content of the binder polymer relative to the total mass of the colored layer is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and 20% by mass. % to 60% by weight is particularly preferred.
• the colored layer may further contain a dispersant.
• the dispersant can improve the dispersibility of the colorant (especially pigment) in the colored layer and improve the uniformity of color.
• the dispersant is preferably a polymer dispersant.
• Polymeric dispersants include, for example, silicone polymers, acrylic polymers and polyester polymers. From the viewpoint of heat resistance, the dispersant is preferably a silicone polymer such as a grafted silicone polymer.
• the weight average molecular weight of the dispersant is preferably 1,000 to 5,000,000, more preferably 2,000 to 3,000,000, and 2,500 to 3,000,000. is particularly preferred. When the weight average molecular weight is 1,000 or more, the dispersibility of the colorant is further improved.
• the dispersant may be a commercially available product.
• Commercially available products include EFKA 4300 (acrylic polymer dispersant) available from BASF Japan Co., Ltd., Homogenol L-18, Homogenol L-95 and Homogenol L-100 available from Kao Corporation, Lubrizol Japan Co., Ltd. Solsperse 20000 and Solsperse 24000 available from the company, DISPERBYK-110, DISPERBYK-164, DISPERBYK-180 and DISPERBYK-182 available from BYK-Chemie Japan. "Homogenol”, “Solsperse” and “DISPERBYK” are all registered trademarks.
• the colored layer may contain one or more dispersants.
• the content of the dispersant for 100 parts by weight of the colorant is preferably 1 to 30 parts by weight.
• the colored layer may further contain other additives.
• additives include, for example, paragraph 0017 of Japanese Patent No. 4502784, surfactants described in Japanese Patent Application Laid-Open No. 2009-237362, paragraphs 0060 to 0071, and thermal polymerization inhibitors described in Japanese Patent No. 4502784, paragraph 0018. (Also referred to as a polymerization inhibitor. Preferred is phenothiazine.) and additives described in paragraphs 0058 to 0071 of JP-A-2000-310706.
• the thickness of the colored layer is preferably 0.5 ⁇ m or more, more preferably 3 ⁇ m or more, even more preferably 3 ⁇ m to 50 ⁇ m, even more preferably 3 ⁇ m to 20 ⁇ m. It is particularly preferred to have When the laminate includes two or more colored layers, it is preferable that the two or more colored layers are independently adjusted within the above ranges.
• Examples of methods for forming the colored layer include a method using a colored layer-forming composition and a method of bonding colored films.
• a method for forming the colored layer a method using a composition for forming a colored layer is preferable.
• the colored layer may be formed using commercially available paints such as nax Real series, nax Admira series, nax Multi series (Nippon Paint Co., Ltd.), and Retan PG series (Kansai Paint Co., Ltd.).
• Examples of the method using the colored layer-forming composition include a method of forming a colored layer by applying the colored layer-forming composition and a method of printing the colored layer-forming composition to form a colored layer.
• Printing methods include, for example, screen printing, inkjet printing, flexographic printing, gravure printing and offset printing.
• the components of the composition for forming the colored layer include, for example, the components of the colored layer described above.
• the content of each component of the composition for forming a colored layer is, for example, the “total mass of the colored layer” described in the description of the content of each component of the colored layer described above, and the “solid content of the composition for forming a colored layer”. It is adjusted within the range read as "total mass of minutes”.
• the colored layer-forming composition preferably further contains an organic solvent.
• organic solvents include alcohol compounds, ester compounds, ether compounds, ketone compounds and aromatic hydrocarbon compounds.
• the colored layer-forming composition may contain one or more organic solvents.
• the content of the organic solvent is preferably 5% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, relative to the total mass of the composition for forming a colored layer.
• Examples of the method for preparing the colored layer-forming composition include a method of mixing an organic solvent and a component to be introduced into the colored layer, such as a colorant.
• a component to be introduced into the colored layer such as a colorant.
• the composition for forming a colored layer contains a pigment as a coloring agent, from the viewpoint of further enhancing the uniform dispersibility and dispersion stability of the pigment, the composition for forming a colored layer is prepared using a pigment dispersion containing a pigment and a dispersant. is preferred.
• the laminate may have an ultraviolet absorbing layer.
• the ultraviolet absorption layer can improve light resistance.
• the position of the UV absorbing layer is not restricted.
• the ultraviolet absorbing layer is preferably located closer to the viewer than the first cured liquid crystal layer. That is, it is preferable to have the ultraviolet absorption layer on the viewing side of the first cured liquid crystal layer. In other words, it is preferable that the ultraviolet absorbing layer be arranged so that the first cured liquid crystal layer can be seen through the ultraviolet absorbing layer.
• the ultraviolet absorption layer is preferably a layer containing an ultraviolet absorber, more preferably a layer containing an ultraviolet absorber and a binder polymer.
• the ultraviolet absorber may be an organic compound or an inorganic compound.
• UV absorbers include triazine compounds, benzotriazole compounds, benzophenone compounds, salicylic acid compounds, and metal oxide particles.
• the UV absorber may be a polymer containing UV absorbing structures. Examples of the polymer containing an ultraviolet absorbing structure include acrylic resins containing monomer units derived from acrylic acid ester compounds containing at least part of compounds such as triazine compounds, benzotriazole compounds, benzophenone compounds and salicylic acid compounds.
• Metal oxide particles include, for example, titanium oxide particles, zinc oxide particles and cerium oxide particles.
• binder polymers examples include polyolefins, acrylic resins, polyesters, fluororesins, siloxane resins, and polyurethanes.
• the ultraviolet absorbing layer is formed, for example, using a composition for forming an ultraviolet absorbing layer.
• the ultraviolet absorbing layer may be formed by applying a composition for forming an ultraviolet absorbing layer and, if necessary, drying the composition.
• the composition for forming an ultraviolet absorbing layer contains the components of the ultraviolet absorbing layer described above and, if necessary, a solvent.
• the thickness of the ultraviolet absorbing layer is preferably 0.01 ⁇ m to 100 ⁇ m, more preferably 0.1 ⁇ m to 50 ⁇ m, and more preferably 0.5 ⁇ m to 20 ⁇ m, from the viewpoint of light resistance and three-dimensional moldability. Especially preferred.
• the laminate may have a protective layer.
• the protective layer preferably has sufficient strength to protect a layer, such as the first cured liquid crystal layer, and has excellent weatherability.
• Weather resistance includes, for example, durability against environmental factors such as ultraviolet rays and moist heat. From the viewpoint of visibility and suppression of reflection of light (for example, reflection of fluorescent light), the protective layer may have antireflection ability.
• the protective layer preferably contains a resin, at least one selected from the group consisting of siloxane resin, fluororesin, acrylic resin, melamine resin, polyolefin, polyester, polycarbonate and urethane resin. It more preferably contains a resin, and more preferably contains at least one resin selected from the group consisting of siloxane resins, fluororesins, acrylic resins, and urethane resins having voids.
• the protective layer contains a siloxane resin or a fluororesin, the refractive index of the protective layer tends to be 1.5 or less (preferably 1.4 or less), and a protective layer having excellent antireflection performance can be easily obtained.
• the protective layer contains low refractive index particles, the same antireflection effect can be obtained even if the refractive index of the protective layer is lowered to 1.5 or less.
• a siloxane resin is obtained, for example, by hydrolytic condensation of a siloxane compound.
• the siloxane compound is at least one compound selected from the group consisting of a siloxane compound represented by the following formula 1 and a hydrolysis condensate of the siloxane compound represented by the following formula 1 (hereinafter also referred to as a specific siloxane compound). is preferably
• R 1 , R 2 and R 3 each independently represent an alkyl group having 1 to 6 carbon atoms or an alkenyl group
• R 4 is each independently an alkyl group, vinyl group, Alternatively, vinyl group, epoxy group, vinylphenyl group, (meth)acryloxy group, (meth)acrylamide group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyoxyalkyl group, carboxy group and quaternary represents an alkyl group having a group selected from the group consisting of an ammonium group, m represents an integer of 0-2, and n represents an integer of 1-20.
• the hydrolytic condensate of the siloxane compound represented by Formula 1 is obtained by hydrolyzing at least a part of the siloxane compound represented by Formula 1 and the substituents on the silicon atoms in the siloxane compound represented by Formula 1. , and a compound having a silanol group are condensed.
• the alkyl group or alkenyl group having 1 to 6 carbon atoms in R 1 , R 2 and R 3 in Formula 1 may be linear, branched, or have a ring structure. good too.
• the alkyl group or alkenyl group having 1 to 6 carbon atoms is preferably an alkyl group from the viewpoint of strength, light transmittance and haze of the protective layer.
• Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, n-hexyl group and cyclohexyl group. is preferably a methyl group or an ethyl group, more preferably a methyl group.
• each of the plurality of R 4 is preferably an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms. is more preferable.
• the number of carbon atoms in R 4 in Formula 1 is preferably 1-40, more preferably 1-20, and particularly preferably 1-8.
• n in Formula 1 is preferably 1 or 2, more preferably 2, from the viewpoint of the strength, light transmittance and haze of the protective layer.
• n in Formula 1 is preferably an integer of 2 to 20 from the viewpoint of the strength, light transmittance and haze of the protective layer.
• siloxane compounds include, for example, Shin-Etsu Chemical Co., Ltd. KBE-04, KBE-13, KBE-22, KBE-1003, KBM-303, KBE-403, KBM-1403, KBE-503, KBM-5103 , KBE-903, KBE-9103P, KBE-585, KBE-803, KBE-846, KR-500, KR-515, KR-516, KR-517, KR-518, X-12-1135, X-12 -1126, X-12-1131; Dynasylan 4150 manufactured by Evonik Japan Co., Ltd.; MKC silicate MS51, MS56, MS57, MS56S manufactured by Mitsubishi Chemical Corporation; Ethyl silicate 28, N-propyl silicate, N-butyl manufactured by Colcoat Co., Ltd. Silicate, SS-101.
• the protective layer-forming composition may contain a condensation catalyst that promotes condensation of the siloxane compound.
• a condensation catalyst may be any known condensation catalyst.
• fluororesins examples include resins described in paragraphs 0076 to 0106 of JP-A-2009-217258 and paragraphs 0083-0127 of JP-A-2007-229999.
• fluororesins include fluorinated alkyl resins.
• fluororesins include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxyalkane, perfluoroethylenepropene, and ethylenetetrafluoroethylene.
• Examples of the source of the fluororesin include a fluororesin dispersion obtained by copolymerization with an emulsifier or a component that increases affinity with water and dispersing it in water.
• Raw materials for the fluororesin include, for example, compounds having at least one of a polymerizable functional group and a crosslinkable functional group and containing a fluorine atom.
• Raw materials for the fluororesin include, for example, radically polymerizable monomers such as perfluoroalkyl (meth)acrylates, vinyl fluoride monomers, and vinylidene fluoride monomers.
• Raw materials for the fluororesin include, for example, cationic polymerizable monomers such as perfluorooxetane.
• fluororesins or raw materials for fluororesins examples include Lumiflon and Obbligato manufactured by AGC Corporation, ZEFFLE and NEOFLON manufactured by Daikin Industries, Ltd., Teflon (registered trademark) manufactured by DuPont, Kynar manufactured by Arkema, and Kyoeisha Chemical Co., Ltd. LINC3A manufactured by Daikin Industries, Ltd., Optool manufactured by Daikin Industries, Ltd., Opstar manufactured by Arakawa Chemical Industries, Ltd., and Tetrafluorooxetane manufactured by Daikin Industries, Ltd. can be mentioned.
• low refractive index particles examples include particles described in paragraphs 0075 to 0103 of JP-A-2009-217258.
• the low refractive index particles include hollow particles using inorganic oxide particles such as silica, hollow particles using resin particles such as acrylic resin particles, porous particles having a porous structure on the particle surface, and materials themselves having a low refractive index. Fluoride particles may be mentioned.
• Commercially available hollow particles include Sururia manufactured by Nikki Shokubai Kasei Co., Ltd., Silinax manufactured by Nittetsu Mining Co., Ltd., and Techpolymer MBX, SBX and NH manufactured by Sekisui Plastics Co., Ltd.
• Commercial products of the porous particles include, for example, Light Star manufactured by Nissan Chemical Industries, Ltd.
• fluoride particles include, for example, magnesium fluoride nanoparticles manufactured by Rare Metals Laboratory Co., Ltd.
• Core-shell particles may be used to form closed voids in a resin-containing matrix.
• Examples of the method of forming a protective layer by applying a composition containing hollow particles include, for example, the method described in paragraphs 0028 to 0029 of JP-A-2009-103808, and paragraphs 0030 to 0030 of JP-A-2008-262187. The method described in paragraph 0031 or paragraph 0018 of JP-A-2017-500384 may be applied.
• a urethane resin can be obtained, for example, by a reaction between a diisocyanate compound and a polyol or a polymerization reaction of a urethane (meth)acrylate compound.
• Diisocyanate compounds include, for example, aromatic diisocyanates (e.g., 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, p- or m-phenylene diisocyanate, xylylene diisocyanate and m-tetramethylxylylene diisocyanate Diisocyanate compounds include, for example, alicyclic diisocyanates (e.g., isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate and hydrogenated tolylene diisocyanate).
• diisocyanate compounds include aliphatic diisocyanates (eg, hexamethylene diisocyanate).From the viewpoint of resistance to fading, alicyclic diisocyanates (
• polyols examples include polyester polyols, polyether polyols, polycarbonate polyols and polyacrylic polyols. From the viewpoint of impact resistance, polyester polyols or polyacrylic polyols are preferred.
• a polyester polyol can be obtained, for example, by a known method using an esterification reaction using a polybasic acid and a polyhydric alcohol.
• Polybasic acids include, for example, polycarboxylic acids.
• a monobasic fatty acid may also be used in combination, if desired.
• polycarboxylic acids include aromatic polycarboxylic acids (e.g., phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydroisophthalic acid, hexahydrophthalic acid, hexahydroterephthalic acid, trimellitic acid and pyromellitic acid). ).
• Polycarboxylic acids include, for example, aliphatic polycarboxylic acids such as adipic acid, sebacic acid, succinic acid, azelaic acid, fumaric acid, maleic acid and itaconic acid. Polycarboxylic acids may also be anhydrides of the previously mentioned compounds. One or more polybasic acids may be used.
• Polyhydric alcohols include, for example, glycols and trihydric or higher polyhydric alcohols.
• Glycols include, for example, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, hexylene glycol, 1,3-butanediol, 1,4 -butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, methylpropanediol, cyclohexanedimethanol and 3,3-diethyl-1,5 - Pentanediol.
• trihydric or higher polyhydric alcohols examples include glycerol, trimethylolethane, trimethylolpropane, pentaerythritol and dipentaerythritol.
• One or more polyhydric alcohols may be used.
• polyacrylic polyols examples include known polyacrylic polyols having hydroxyl groups capable of reacting with isocyanate groups.
• Monomers for polyacrylic polyol include, for example, (meth)acrylic acid, (meth)acrylic acid to which a hydroxyl group is added, (meth)acrylic acid alkyl esters, (meth)acrylamide and derivatives thereof, and carboxylic acid esters of vinyl alcohol. , unsaturated carboxylic acids and hydrocarbons with linear unsaturated alkyl moieties.
• a urethane (meth)acrylate compound is obtained, for example, by urethanizing a compound having a hydroxy group and a (meth)acryloyl group and a polyisocyanate compound.
• Examples of compounds having a hydroxy group and a (meth)acryloyl group include monofunctional (meth)acrylates having a hydroxy group and polyfunctional (meth)acrylates having a hydroxy group.
• Monofunctional (meth)acrylates having a hydroxy group include, for example, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxy-n-butyl (meth)acrylate, 2-hydroxypropyl ( meth) acrylate, 2-hydroxy-n-butyl (meth) acrylate, 3-hydroxy-n-butyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N-(2-hydroxyethyl) ( meth)acrylamide, glycerin mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, 2-(me
• Polyfunctional (meth)acrylates having a hydroxy group include, for example, trimethylolpropane di(meth)acrylate, isocyanurate ethylene oxide (EO)-modified diacrylate, pentaerythritol tri(meth)acrylate and dipentaerythritol penta(meth) Acrylates are mentioned. From the viewpoint of scratch resistance of the protective layer, pentaerythritol triacrylate or dipentaerythritol pentaacrylate is preferred.
• One or more compounds having a hydroxy group and a (meth)acryloyl group may be used.
• polyisocyanate compounds include aromatic diisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, m-xylylene diisocyanate, and m-phenylenebis(dimethylmethylene) diisocyanate.
• polyisocyanate compounds include hexamethylene diisocyanate, lysine diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanate.
• Aliphatic or alicyclic diisocyanate compounds such as natocyclohexane, 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate can be mentioned.
• Urethane (meth)acrylate is cured, for example, by irradiation with actinic rays.
• Actinic rays refer to ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
• the protective layer preferably contains a photopolymerization initiator from the viewpoint of curability. From the viewpoint of curability, the protective layer may further contain a photosensitizer as needed.
• the protective layer preferably has a refractive index of 1.05 to 1.6, more preferably 1.2 to 1.5, and 1.2 to 1.5. 4 is more preferred.
• the refractive index is the refractive index for light with a wavelength of 550 nm at 25°C.
• the refractive index of the protective layer is in a range close to the refractive index of wax and gasoline (for example, 1.4 to 1.5) in order to prevent stains caused by wax and gasoline from becoming conspicuous.
• a rate is preferably set.
• the thickness of the protective layer is preferably 2 ⁇ m or more, more preferably 4 ⁇ m or more, still more preferably 4 ⁇ m to 50 ⁇ m, and even more preferably 4 ⁇ m to 20 ⁇ m. Especially preferred.
• the protective layer is formed, for example, by applying a protective layer-forming composition and, if necessary, drying.
• the protective layer is formed, for example, by laminating film-formed protective layers.
• Application methods include spray coating, brush coating, roller coating, bar coating and dip coating.
• the object to which the composition for forming a protective layer is applied may be subjected to a surface treatment.
• Surface treatments include, for example, corona discharge treatment, glow treatment, atmospheric pressure plasma treatment, flame treatment and ultraviolet irradiation treatment.
• the drying of the protective layer-forming composition may be performed at room temperature (25°C).
• the protective layer-forming composition may be dried by heating.
• the drying of the protective layer-forming composition should be carried out at 40° C. or higher. It is preferably carried out by heating at 200°C.
• the heating time is preferably 1 minute to 30 minutes.
• the manufacturing method of the protective layer-forming composition is not limited.
• the composition for forming a protective layer can be prepared, for example, by mixing an organic solvent, a surfactant and water to disperse the organic solvent in water, then adding a specific siloxane compound to the dispersion and applying it to the surface of the dispersed organic solvent. It is manufactured by forming a shell layer to form a core-shell particle.
• a composition for forming a protective layer is produced by, for example, mixing an organic solvent, a surfactant, a resin and a monomer.
• the protective layer-forming composition preferably contains a surfactant.
• Surfactants include, for example, nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants.
• the protective layer-forming composition may contain other components in addition to the components described above, depending on the purpose.
• Other ingredients include, for example, antistatic agents and preservatives.
• the protective layer-forming composition may contain an antistatic agent.
• the antistatic agent imparts antistatic properties to the protective layer and can suppress adhesion of contaminants.
• the antistatic agent is preferably at least one antistatic agent selected from the group consisting of metal oxide particles, metal nanoparticles, conductive polymers and ionic liquids.
• Metal oxide particles include, for example, tin oxide particles, antimony-doped tin oxide particles, tin-doped indium oxide particles, zinc oxide particles, and silica particles.
• the average primary particle size of the metal oxide particles is preferably 100 nm or less, more preferably 50 nm or less, and particularly preferably 30 nm or less.
• the average primary particle size of the metal oxide particles is preferably 2 nm or more.
• the average primary particle size of metal oxide particles is calculated from images of 300 or more particles observed using a transmission electron microscope.
• the average particle size (average primary particle size) is calculated by determining the projected area of the particles from the image and determining the equivalent circle diameter based on the projected area.
• the average primary particle size may be calculated by another method (for example, dynamic light scattering method).
• the shape of the metal oxide particles may be spherical, plate-like or needle-like.
• the protective layer-forming composition may contain one or more antistatic agents. Two or more antistatic agents having different compositions from each other may be used. Two or more antistatic agents having different average primary particle sizes may be used. Two or more antistatic agents having different shapes may be used.
• the content of the antistatic agent relative to the total mass of the solid content of the protective layer-forming composition is 40% by mass or less. is preferably 30% by mass or less, and particularly preferably 20% by mass or less.
• the ratio of the content of the metal oxide particles to the total mass of the solid content of the protective layer-forming composition is preferably 30% by mass or less, and 20% by mass. % or less, and particularly preferably 10 mass % or less.
• the laminate may have, for example, a resin layer between the first cured liquid crystal layer and the colored layer. By having the resin layer, the planarity of the first cured liquid crystal layer can be ensured.
• the resin layer preferably contains a different type of resin from the resin contained in the protective layer.
• the resin layer is preferably a transparent resin layer, more preferably a layer made of a transparent film.
• transparent as used in reference to transparent films means having a total light transmission of 85% or greater. The total light transmittance of the transparent film is measured by the method described above.
• the transparent film is preferably a film obtained by forming a transparent resin.
• a transparent resin at least one selected from the group consisting of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), acrylic resin, polycarbonate (PC), triacetyl cellulose (TAC) and cycloolefin polymer (COP).
• PET polyethylene terephthalate
• PEN polyethylene naphthalate
• acrylic resin polycarbonate
• TAC triacetyl cellulose
• COP cycloolefin polymer
• a resin film containing a terephthalate resin is preferred.
• a resin film containing acrylic resin in an amount of 60% by mass or more (more preferably 80% by mass or more, still more preferably 100% by mass) relative to the total mass of resins contained in the transparent film is more preferable.
• Examples of commercially available transparent films include Acryprene (registered trademark) HBS010 (acrylic resin film, manufactured by Mitsubishi Chemical Corporation), Technoloy (registered trademark) S001G (acrylic resin film, manufactured by Sumitomo Chemical Co., Ltd.), C000 (polycarbonate resin film, manufactured by Sumitomo Chemical Co., Ltd.) and C001 (acrylic resin/polycarbonate resin laminated film, manufactured by Sumitomo Chemical Co., Ltd.).
• the thickness of the resin layer is preferably 50 ⁇ m to 150 ⁇ m.
• Examples of methods for forming the resin layer include a method of bonding a transparent film and a liquid crystal layer or a colored layer together.
• Apparatus for the bonding process includes, for example, a laminator, a vacuum laminator and an autocut laminator.
• the laminator preferably has a heatable roller, such as a rubber roller, and has pressure and heat capability. Heating using a laminator partially melts at least one of the transparent film and the liquid crystal layer, and can enhance adhesion between the liquid crystal layer and the transparent film.
• the heating temperature is determined, for example, according to the material of the transparent film and the melting temperature of the liquid crystal layer. A heating temperature that makes the temperature of the transparent film 60° C. to 150° C. is preferred.
• a heating temperature that makes the temperature of the transparent film 65° C. to 130° C. is more preferable.
• a heating temperature that makes the temperature of the transparent film 70° C. to 100° C. is more preferable.
• the linear pressure in the bonding step is preferably 60 N/cm to 200 N/cm, more preferably 70 N/cm to 160 N/cm, even more preferably 80 N/cm to 120 N/cm.
• the laminate may contain a cover film as the outermost layer.
• the cover film includes, for example, a film having flexibility and peelability.
• cover films include resin films such as polyethylene films. The cover film is introduced into the laminate, for example, by laminating the cover film and the protective layer.
• the laminate may contain other layers.
• Other layers include, for example, a self-healing layer, an antistatic layer, an antifouling layer, an anti-electromagnetic layer and a conductive layer.
• Other layers include, for example, layers included in known laminates.
• the other layer is formed, for example, through application of a composition containing components of the other layer and, if necessary, drying.
• each layer may have one layer alone or may have two or more layers independently, depending on the use of the laminate.
• the laminate according to the present disclosure can be used for decoration of display devices such as Among them, the laminate according to the present disclosure can be suitably used for decorating electronic devices (for example, wearable devices and smartphones).
• the laminate according to the present disclosure is also excellent in three-dimensional moldability, it is suitable as a decorative film for molding, which is used for molding such as three-dimensional molding and insert molding. is more suitable as
• the method for producing the laminate according to the present disclosure is not particularly limited, and a known method may be used, or a known method may be applied to produce the laminate.
• the method for producing a laminate according to the present disclosure includes, for example, preparing a composition containing a liquid crystal compound having a polymerizable group, an optically active compound, and a photopolymerization initiator (hereinafter referred to as a “preparation step”.
• coating step applying the composition on a peelable substrate (hereinafter referred to as “coating step”), and curing the composition with light to form a cholesteric liquid crystal layer (hereinafter referred to as “curing and laminating the cholesteric liquid crystal layer on another base material via an adhesive layer (hereinafter referred to as an “adhesive layer forming step”) in this order.
• a composition containing a liquid crystal compound having a polymerizable group, an optically active compound, and a photopolymerization initiator is prepared.
• the optically active compound preferably contains an optically active compound having a polymerizable group, and more preferably contains an optically active compound having one polymerizable group.
• An optically active compound having one polymerizable group (hereinafter also referred to as "monofunctional optically active compound”) is introduced into a polymer chain by reaction with a cholesteric liquid crystal compound having a polymerizable group or a polymer thereof. Conceivable.
• monofunctional optically active compounds are considered to be incapable of cross-linking macromolecules. As a result, the content of the low-molecular compound in the liquid crystal layer formed through the curing process is reduced, and the liquid crystal layer having excellent stretchability is formed through the curing process.
• the cholesteric liquid crystal compound having a polymerizable group preferably contains a cholesteric liquid crystal compound having a polymerizable group.
• the cholesteric liquid crystal compound having a polymerizable group preferably includes a cholesteric liquid crystal compound having one polymerizable group and a cholesteric liquid crystal compound having two or more polymerizable groups.
• the composition is applied onto the release substrate.
• the composition may be applied to the surface of the peelable substrate.
• the composition may be coated on the peelable substrate via another layer.
• the composition is preferably applied to the surface of the peelable substrate.
• peelable substrates include substrates that can be peeled off from the laminate after forming the laminate.
• the peelable substrate include a laminate including a substrate and an easy-adhesion layer.
• the substrate includes, for example, the substrates described in the "Substrate" section above.
• commercially available release substrates include COSMOSHINE A4160 (manufactured by Toyobo Co., Ltd.). Orientation treatment may be applied to the release substrate (preferably the substrate included in the release substrate).
• the state of the composition may be a solution containing a solvent.
• the state of the composition may be a melted liquid.
• the composition may be applied by a roll coating method, a gravure printing method, or a spin coating method. Application of the composition may be done by wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating or die coating. Application of the composition may be performed using an inkjet device. In the coating method using an inkjet device, the composition may be discharged from a nozzle.
• the composition applied on the release substrate may be dried by a known method.
• the composition may be dried by standing.
• the composition may be dried by air drying.
• the composition may be dried by heating. It is preferable that the cholesteric liquid crystal compound is oriented in the composition after application and drying.
• the composition is cured by light to form a first cured liquid crystal layer.
• the curing step can maintain and fix the alignment state of the molecules of the liquid crystal compound in the composition prepared in the preparation step.
• the exposure step not only the composition but also the constituent elements other than the composition may be cured.
• the light source may be selected according to the type and properties of the photopolymerization initiator.
• a light source capable of emitting light having at least one wavelength selected from the group consisting of 285 nm, 365 nm and 405 nm is preferred.
• Light sources include, for example, light-emitting diodes (UV-LEDs) that emit ultraviolet rays, ultrahigh-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps.
• the exposure dose is preferably 5 mJ/cm 2 to 2,000 mJ/cm 2 and more preferably 10 mJ/cm 2 to 1,000 mJ/cm 2 .
• the exposure step may include curing the composition with light under heating conditions. Heating in the exposure process can facilitate alignment of liquid crystal compounds.
• the heating temperature may be determined according to the composition of the composition. The heating temperature may be 30°C to 120°C.
• the oxygen concentration in the curing process is not limited.
• the curing step may be performed under an oxygen atmosphere.
• the curing step may be performed under air.
• the curing step may be performed in a low-oxygen atmosphere (preferably with an oxygen concentration of 1,000 ppm or less).
• the oxygen concentration may be 0 ppm.
• the oxygen concentration may be greater than 0 ppm and less than or equal to 1,000 ppm.
• the curing step is preferably performed in a low-oxygen atmosphere, more preferably under heating and in a low-oxygen atmosphere.
• the exposure method for example, the method described in paragraphs 0035 to 0051 of JP-A-2006-23696 may be applied.
• Step of forming adhesive layer In the step of forming the adhesive layer, the first cured liquid crystal layer is laminated on another substrate via the adhesive layer.
• the adhesive layer forming step may form an adhesive layer adjacent to the first cured liquid crystal layer.
• the adhesive layer In the adhesive layer forming step, the adhesive layer may be formed on the first cured liquid crystal layer via another layer. It is preferable that the adhesive layer forming step forms an adhesive layer adjacent to the first cured liquid crystal layer.
• the method of forming the adhesive layer is as described above.
• the laminate manufacturing method may include other steps. Depending on the desired layer configuration, the laminate manufacturing method may include forming layers other than the first cured liquid crystal layer and the adhesive layer.
• the method for producing a laminate may include photoisomerization of an uncured liquid crystal layer (also referred to simply as a "liquid crystal layer”) (hereinafter referred to as a "photoisomerization step").
• the photoisomerization step preferably includes photoisomerization of the photoisomerizable compound contained in the liquid crystal layer. From the viewpoint of designability and brilliance, it is preferable to isomerize the liquid crystal layer so that the photoisomerization ratio differs from region to region. It is more preferable to isomerize so that there is a difference in In the photoisomerization step, part of the liquid crystal layer may be isomerized, or part of the liquid crystal layer may be isomerized depending on the shape to be molded. In the photoisomerization step, the isomerization ratio of the photoisomerization compound may be changed according to the shape to be molded.
• the photoisomerization step may form a portion with an isomerization rate of 0% and a portion with an isomerization rate of 100% in the liquid crystal layer.
• the photoisomerization step may form a portion with an isomerization rate of 10% and a portion with an isomerization rate of 80% in the liquid crystal layer.
• the photoisomerization step may form a portion in the liquid crystal layer where the isomerization rate varies from 0% to 100%.
• the photoisomerization step may form a portion where the isomerization ratio is 0% and a portion where the isomerization ratio changes from 50% to 100% in the liquid crystal layer.
• the isomerization ratio is higher in the portion where the stretch ratio of the laminate is increased during molding.
• the progress of photoisomerization is confirmed by measuring the maximum wavelength of the reflectance of the isomerization part.
• the photoisomerization ratio represents the ratio of the number of photoisomerized photoisomerized compound molecules to the total number of molecules of the target photoisomerizable compound, and is similarly determined by measuring the maximum wavelength of reflectance.
• the photoisomerization step it is preferable to isomerize the liquid crystal layer by changing the intensity of exposure to the liquid crystal layer depending on the region.
• the isomerization may be performed by exposing the liquid crystal layer to light with a plurality of steps of difference in exposure intensity or a stepless continuous difference. Isomerization is preferably achieved by exposing only a portion of the liquid crystal layer.
• the isomerization rate may be controlled according to the exposure intensity.
• the wavelength of light with which the liquid crystal layer is irradiated may be determined according to the photoisomerizable compound.
• light with a wavelength range of 400 nm or less is preferably used, more preferably light with a wavelength range of 380 nm or less is used, and light with a wavelength range of 300 nm or more and 380 nm or less is used. is more preferred.
• the adjustment of the wavelength of light may be performed by known means and methods.
• Methods for adjusting the wavelength of light include, for example, a method using an optical filter, a method using two or more types of optical filters, and a method using a light source with a specific wavelength.
• the liquid crystal layer is preferably irradiated with light in a wavelength range that does not generate polymerization initiation species from the photopolymerization initiator.
• a mask is preferably used that transmits light in the wavelength range that causes photoisomerization of the photoisomeric compound and blocks light in the wavelength range that causes polymerization initiation species to be generated from the photopolymerization initiator.
• the mask may be a known mask.
• the mask may be a mask made by gravure printing, screen printing, or a method of patterning a sputtered chromium film with a photoresist.
• the mask may be a mask made using a laser printer or an inkjet printer. One or more masks may be used.
• different masks may be used for the portions of the liquid crystal layer that are photoisomerizable and the portions that are not photoisomerizable.
• a mask may be used in which the amount of transmitted light is not constant but varies.
• Light sources include ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.
• Light sources include light-emitting diodes capable of emitting light with a narrow wavelength range.
• a mask may or may not be used when using a light source capable of emitting light with a narrow wavelength band.
• the exposure dose in the photoisomerization step is preferably 5 mJ/cm 2 to 2,000 mJ/cm 2 , more preferably 10 mJ/cm 2 to 1,000 mJ/cm 2 .
• the amount of exposure may be changed in each part of the liquid crystal layer.
• Isomerization by exposure is preferably carried out under heating conditions.
• the heating temperature is, for example, 30.degree. C. to 100.degree.
• the exposure method in the photoisomerization step for example, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 may be applied.
• a step of peeling off the substrate from the laminate produced in the aspect containing the substrate can be mentioned, and the decorative film in the aspect not including the substrate can be produced.
• other steps include a colored layer forming step, an orientation layer forming step, and a forming step of other layers.
• the details and formation method of the colored layer and the alignment layer are as described above. Further, the details of the other layers are as described above, and known methods may be used as the method of forming the other layers.
• the laminate according to the present disclosure can be used for various applications.
• the laminate can be molded and used as a molded body.
• the decorative film according to the present disclosure includes the laminate according to the present disclosure, and may be formed by molding the laminate according to the present disclosure.
• An article according to the present disclosure is an article comprising a laminate according to the present disclosure.
• Such laminates can be provided in a variety of articles. Examples of such articles include electronic devices such as smartphones, mobile phones, and tablets, automobiles, electrical appliances, packaging containers, and the like, and can be particularly preferably used for electronic devices. Electronic devices more preferably include display devices such as displays, smartphones, mobile phones, and tablets.
• a retardation film may be provided between the laminate according to the present disclosure and a display member such as a display.
• a known retardation film can be used.
• the means for molding the laminate according to the present disclosure to obtain a molded body is not particularly limited, and may be, for example, known methods such as three-dimensional molding and insert molding.
• the means for applying the laminate according to the present disclosure to an article is not particularly limited, and a known method may be appropriately used according to the type of article.
• a decorative panel according to the present disclosure includes a decorative film according to the present disclosure.
• the shape of the decorative panel is not restricted.
• the shape of the decorative panel may be determined, for example, according to the application.
• the decorative panel may be flat, for example.
• the decorative panel may have a curved surface.
• the decorative panel can be used, for example, for the interior and exterior of various articles. Articles include those mentioned above (eg, electronic devices, automobiles, and electrical appliances).
• the decorative panel can be produced, for example, by bonding the surface of the decorative film on the side of the layer that expresses the structural color and the surface of the member that will be the surface layer of the decorative panel.
• the member that becomes the surface layer of the decorative panel include a glass panel.
• the adhesive layer described above can be used for adhesion between the decorative film and the member that forms the surface layer of the decorative panel.
• a molded decorative film may be used alone as a decorative panel without combining the decorative film with other members.
• a display device according to the present disclosure is a display device including the decorative panel according to the present disclosure. Examples of display devices include displays, smartphones, mobile phones, tablets, and the like.
• ⁇ Peelable substrate> A polyethylene terephthalate film (Cosmo Shine A4160, manufactured by Toyobo Co., Ltd., film thickness: 100 ⁇ m; PET) having an easy-adhesion layer on one side was prepared as a peelable substrate. Rubbing treatment (rayon cloth, pressure: 0.1 kgf, number of revolutions: 1,000 rpm (revolutions per minute), transport speed: 10 m / min, Number of times: 1 time) was performed.
• Liquid crystal compound 1 31.39 parts by mass Chiral agent 1: 1.77 parts by mass Photopolymerization initiator (diethylthioxanthone, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.): 0.31 parts by mass Surfactant 1: 0.016 Parts by mass Surfactant 2: 0.017 parts by mass Methyl ethyl ketone (solvent): 55.86 parts by mass Furfuryl alcohol (solvent): 10.64 parts by mass
• Liquid crystal compound 1 the following compound
• Surfactant 1 the following compound
• Surfactant 2 the following compound
• Liquid crystal compound 1 29.69 parts by mass Chiral agent 2: 2.59 parts by mass Photopolymerization initiator (diethylthioxanthone, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.): 1.19 parts by mass Surfactant 1: 0.015 Parts by mass Surfactant 2: 0.016 parts by mass Methyl ethyl ketone (solvent): 60.52 parts by mass Furfuryl alcohol (solvent): 5.99 parts by mass
• Chiral agent 2 the following compound
• Liquid crystal compound 1 22.91 parts by mass
• Liquid crystal compound 2 8.47 parts by mass
• Chiral agent 1 1.77 parts by mass
• Photopolymerization initiator diethylthioxanthone, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.
• Surfactant 1 0.016 parts by mass
• Surfactant 2 0.017 parts by mass Methyl ethyl ketone (solvent): 55.86 parts by mass Furfuryl alcohol (solvent): 10.64 parts by mass
• Liquid crystal compound 2 the following compound, Me represents a methyl group.
• Liquid crystal compound 1 21.97 parts by mass
• Liquid crystal compound 2 7.72 parts by mass
• Chiral agent 2 2.59 parts by mass
• Photopolymerization initiator diethylthioxanthone, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.
• Surfactant 1 0.015 parts by mass
• Surfactant 2 0.016 parts by mass Methyl ethyl ketone (solvent): 60.52 parts by mass Furfuryl alcohol (solvent): 5.99 parts by mass
• Liquid crystal compound 1 6.28 parts by mass
• Liquid crystal compound 2 25.11 parts by mass
• Chiral agent 1 1.77 parts by mass
• Photopolymerization initiator diethylthioxanthone, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.
• Surfactant 1 0.016 parts by mass
• Surfactant 2 0.017 parts by mass Methyl ethyl ketone (solvent): 55.86 parts by mass Furfuryl alcohol (solvent): 10.64 parts by mass
• Liquid crystal compound 1 6.83 parts by mass
• Liquid crystal compound 2 22.87 parts by mass
• Chiral agent 2 2.59 parts by mass
• Photopolymerization initiator diethylthioxanthone, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.
• Surfactant 1 0.015 parts by mass
• Surfactant 2 0.016 parts by mass Methyl ethyl ketone (solvent): 60.52 parts by mass Furfuryl alcohol (solvent): 5.99 parts by mass
• Liquid crystal layer-forming coating liquid 7 having the following composition was prepared.
• Liquid crystal compound 1 31.00 parts by mass
• Chiral agent 1 2.16 parts by mass
• Photopolymerization initiator 0.31 parts by mass Diethylthioxanthone (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
• Surfactant 1 0.016 parts by mass
• Surfactant 2 0.017 parts by mass Methyl ethyl ketone (solvent): 55.86 parts by mass Furfuryl alcohol (solvent): 10.64 parts by mass
• Liquid crystal layer forming coating liquid 8 having the following composition was prepared.
• Liquid crystal compound 1 30.12 parts by mass
• Chiral agent 2 2.15 parts by mass
• Photopolymerization initiator 1.21 parts by mass Diethylthioxanthone (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
• Surfactant 1 0.015 parts by mass
• Surfactant 2 0.017 parts by mass Methyl ethyl ketone (solvent): 60.52 parts by mass Furfuryl alcohol (solvent): 5.99 parts by mass
• Photopolymerization initiator 0.32 parts by mass diethylthioxanthone (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
• Surfactant 1 0.016 parts by mass
• Surfactant 2 0.017 parts by mass Methyl ethyl ketone (solvent): 56.53 parts by mass
• Liquid crystal layer-forming coating liquid 10 having the composition described below was prepared.
• Liquid crystal compound 1 31.75 parts by mass
• Chiral agent 4 1.40 parts by mass
• Photopolymerization initiator 0.32 parts by mass diethylthioxanthone (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
• Surfactant 1 0.016 parts by mass
• Surfactant 2 0.017 parts by mass Methyl ethyl ketone (solvent): 56.53 parts by mass
• Liquid crystal layer forming coating liquid 11 having the following composition was prepared. Liquid crystal compound 3: 20.84 parts by mass
• Liquid crystal compound 4 5.21 parts by mass
• Liquid crystal compound 5 5.21 parts by mass
• Chiral agent 5 0.65 parts by mass LC-756 (manufactured by BASF)
• Chiral agent 6 1.30 parts by mass
• Photopolymerization initiator 0.26 parts by mass Diethylthioxanthone (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
• Surfactant 1 0.013 parts by mass
• Surfactant 2 0.014 parts by mass Methyl ethyl ketone (solvent): 60.52 parts by mass
• Example 1 As described above, a rubbing-treated peelable substrate was prepared. Then, the liquid crystal layer forming coating solution 1 was applied with a wire bar #8 to form the liquid crystal layer 1 . Next, the liquid crystal layer 1 was subjected to a curing treatment to cure the liquid crystal layer 1 . Specifically, the liquid crystal layer 1 is irradiated with light from a metal halide lamp (MAL625NAL manufactured by GS Yuasa Co., Ltd.) on a hot plate at 85° C. in a low-oxygen atmosphere (oxygen concentration of 1,000 ppm or less). Layer 1 was cured to form cured liquid crystal layer 1 . At this time, light of 340 nm or less was cut.
• a metal halide lamp MAL625NAL manufactured by GS Yuasa Co., Ltd.
• the irradiation amount of light was 1,000 mJ/cm 2 .
• the liquid crystal layer forming coating solution 2 was applied onto the cured liquid crystal layer 1 with a wire bar #8 to form a liquid crystal layer 2 .
• a curing treatment was performed in the same manner as for the liquid crystal layer 1 except that light of 340 nm or less was not cut, thereby curing the liquid crystal layer 2 and obtaining a cured liquid crystal layer 2 .
• the reflected wavelength tint of the cured liquid crystal layers 1 and 2 was green.
• an adhesive (UVX-6282 manufactured by Toagosei Co., Ltd.) is applied, and further a base material (Cosmoshine A4360 (thickness 50 ⁇ m, manufactured by Toyobo Co., Ltd.), polyethylene terephthalate (PET ) film) and passed through a laminator.
• the adhesive layer was cured by irradiating light (1,000 mJ/cm 2 ) from a metal halide lamp at 25°C.
• the rubbing-treated peelable substrate was peeled off to obtain a laminate 1A.
• the thickness of the adhesive layer was 5 ⁇ m.
• the laminate 1A obtained by the above procedure has a substrate, an adhesive layer, a cured liquid crystal layer 2 (cholesteric liquid crystal layer), and a cured liquid crystal layer 1 (cholesteric liquid crystal layer) in this order.
• Example 2 The steps up to the cured liquid crystal layer 2 were formed in the same manner as in Example 1 except for the following. Next, an adhesive layer was formed on the cured liquid crystal layer 2 using an adhesive (NCF-D692 manufactured by Lintec Corporation). Next, a base material (Cosmoshine A4360 (thickness: 50 ⁇ m), PET film manufactured by Toyobo Co., Ltd.) was laminated on the adhesive. Finally, the rubbing-treated peelable substrate was peeled off to obtain a laminate 2A. The thickness of the adhesive layer was 5 ⁇ m.
• Example 3> A laminate 3A was obtained by the same procedure as in Example 1, except that the adhesive was changed to UF-3007 manufactured by Kyoeisha Chemical Co., Ltd. The thickness of the adhesive layer was 5 ⁇ m.
• Example 4> A laminate 4A was obtained in the same manner as in Example 1, except that the base material was changed to Technoloy C000 (polycarbonate (PC) resin single layer sheet) manufactured by Sumika Acrylic Co., Ltd. The thickness of the adhesive layer was 5 ⁇ m.
• Technoloy C000 polycarbonate (PC) resin single layer sheet
• Example 5> A laminate 5A was obtained by the same procedure as in Example 3, except that the thickness of the adhesive layer was changed. The thickness of the adhesive layer was 31 ⁇ m.
• Example 6 A liquid crystal layer 1 was formed on a peelable substrate by the same procedure as in Example 1. Next, the liquid crystal layer 1 was subjected to curing treatment to cure the liquid crystal layer. Specifically, in a low oxygen atmosphere (oxygen concentration of 1,000 ppm or less), on a hot plate at 85 ° C., by irradiating the liquid crystal layer with light from a metal halide lamp (manufactured by GS Yuasa Co., Ltd., MAL625NAL), the liquid crystal is cured. got a layer. The irradiation amount of light was 1,000 mJ/cm 2 . The reflected wavelength tint of the cured liquid crystal layer visually was green.
• a low oxygen atmosphere oxygen concentration of 1,000 ppm or less
• MAL625NAL metal halide lamp
• an adhesive (UF-3007 manufactured by Kyoeisha Chemical Co., Ltd.) was applied onto the cured liquid crystal layer, and a base material (Cosmoshine A4360 (50 ⁇ m) manufactured by Toyobo Co., Ltd.) was placed thereon and passed through a laminator. Subsequently, the adhesive layer was cured by irradiating light (1,000 mJ/cm 2 ) from a metal halide lamp at 25°C. Finally, the rubbing-treated peelable substrate was peeled off to obtain a laminate 6A. The thickness of the adhesive layer was 5 ⁇ m.
• Example 7 A laminate 7A was obtained in the same procedure as in Example 3, except that the liquid crystal layer forming coating liquid 1 was changed to the liquid crystal layer forming coating liquid 3, and the liquid crystal layer forming coating liquid 2 was changed to the liquid crystal layer forming coating liquid 4. Ta. The thickness of the adhesive layer was 5 ⁇ m.
• Example 8> A laminate 8A was obtained in the same manner as in Example 3, except that the liquid crystal layer forming coating liquid 1 was changed to the liquid crystal layer forming coating liquid 5 and the liquid crystal layer forming coating liquid 2 was changed to the liquid crystal layer forming coating liquid 6. Ta. The thickness of the adhesive layer was 5 ⁇ m.
• Example 9> A laminate 9A was obtained in the same manner as in Example 3, except that the liquid crystal layer forming coating liquid 1 was changed to the liquid crystal layer forming coating liquid 7 and the liquid crystal layer forming coating liquid 2 was changed to the liquid crystal layer forming coating liquid 8. Ta.
• the reflection wavelength tint of the laminate was magenta.
• the thickness of the adhesive layer was 5 ⁇ m.
• Example 10> A laminate 10A was obtained by the same procedure as in Example 3, except that the liquid crystal layer forming coating liquid 9 was used as the liquid crystal layer forming coating liquid 9 and the liquid crystal layer forming coating liquid 2 was changed to the liquid crystal layer forming coating liquid 10. Ta. The reflected wavelength color of the laminate was bluish green. The thickness of the adhesive layer was 5 ⁇ m.
• Example 11> A laminate 11A was obtained by the same procedure as in Example 3, except that the wire bar used in coating was changed to #4. The thickness of the adhesive layer was 5 ⁇ m.
• Example 12> A laminate 12A was obtained by the same procedure as in Example 3, except that the thickness of the substrate was changed to 100 ⁇ m. The thickness of the adhesive layer was 5 ⁇ m.
• Example 13> A laminate 3A was obtained by the procedure of Example 3. After that, the nax real super black paint manufactured by Nippon Paint Co., Ltd. is applied to the base material surface using a wire bar #20 and dried at 100 ° C. for 2 minutes to obtain a laminate 13A with a colored layer having a thickness of 10 ⁇ m. got
• a liquid crystal layer 1 was formed on a peelable substrate by the same procedure as in Example 1. Next, the liquid crystal layer 1 was subjected to curing treatment to cure the liquid crystal layer. Specifically, in a low oxygen atmosphere (oxygen concentration of 1,000 ppm or less), on a hot plate at 85 ° C., by irradiating the liquid crystal layer with light from a metal halide lamp (manufactured by GS Yuasa Co., Ltd., MAL625NAL), the liquid crystal is cured. got a layer. The irradiation amount of light was 1,000 mJ/cm 2 . The reflected wavelength tint of the cured liquid crystal layer visually was green.
• a low oxygen atmosphere oxygen concentration of 1,000 ppm or less
• MAL625NAL metal halide lamp
• an adhesive layer was formed on the cured liquid crystal layer using an adhesive (NNE75 manufactured by Gunze Co., Ltd.).
• a substrate Cosmoshine A4360 (50 ⁇ m), manufactured by Toyobo Co., Ltd.
• the thickness of the adhesive layer was 75 ⁇ m.
• ⁇ Comparative Example 2> A cured liquid crystal layer was formed by the same procedure as in Comparative Example 1. Next, the adhesive was changed to EP171 manufactured by Cemedine Co., Ltd. and passed through the laminator in the same manner as in Example 1. Next, heat curing was performed in an oven at 80° C. for 30 minutes, followed by heat curing at 120° C. for 10 minutes, and the rubbed release base material was peeled off to obtain a laminate 2B. The thickness of the adhesive layer was 1 ⁇ m.
• Example 4 A laminate 4B was obtained in the same manner as in Example 6, except that the liquid crystal layer forming coating liquid 1 was changed to the liquid crystal layer forming coating liquid 11 and the light irradiation amount was changed to 60 mJ/cm 2 .
• Example 5 A laminate 5B was obtained in the same manner as in Example 6, except that the substrate was changed to Torayfan NO ZK500 (50 ⁇ m; CPP) manufactured by Toray Industries, Inc.
• the storage elastic modulus was obtained by conditioning each sample 5 mm ⁇ 25 mm at 25 ° C. and a relative humidity of 60% for 2 hours or more, and then using a dynamic viscoelasticity measuring device (Vibron: DVA-225 (manufactured by IT Instrument Control Co., Ltd.)).
• the storage modulus of each layer was measured at a grip distance of 10 mm, a heating rate of 5° C./min, a measurement temperature range of ⁇ 100° C. to 200° C., and a frequency of 10 Hz.
• the in-plane average reflectance of the laminates produced in Examples and Comparative Examples was measured, and the brightness was evaluated based on the following evaluation criteria.
• the in-plane average reflectance was measured as follows. For each laminate, using a spectrophotometer (manufactured by JASCO Corporation, V-670) equipped with a large integrating sphere device (manufactured by JASCO Corporation, ILV-471), light with a wavelength of 300 nm to 900 nm was incident in the vertical direction (at an angle of 90° with respect to the surface of the cured liquid crystal layer), the peak wavelength was read from the obtained spectral spectrum, and the reflectance at the peak wavelength was obtained.
• the reflectance at the peak wavelength was measured over the entire surface of the hardened liquid crystal layer on the outermost surface, and the average was taken as the in-plane average reflectance. (Evaluation criteria) A: The in-plane average reflectance was 50% or more. B: The in-plane average reflectance was 30% or more and less than 50%. C: The in-plane average reflectance was less than 30%.
• ⁇ Durability evaluation> Using a spectrophotometer (manufactured by JASCO Corporation, spectrophotometer V670; hereinafter the same in this paragraph), the transmittance of the target laminate was measured. Next, the laminate was allowed to stand in an oven at 80° C. for 240 hours, and the transmittance of the laminate after 240 hours was measured using a spectrophotometer. The difference ⁇ s between the center wavelength of the visible light reflection band calculated based on the transmittance measured before heating and the center wavelength of the visible light reflection band calculated based on the transmittance measured after heating was obtained. .
• Reflection band center wavelengths are obtained by inverting the transmittance graph obtained using a spectrophotometer, giving a reflectance of 30% of the reflectance R for a single layer and a reflectance of 60% of the reflectance R for a multilayer.
• ⁇ s ( ⁇ 1+ ⁇ 2)/2 based on the wavelength ⁇ 1 on the short wavelength side and the wavelength ⁇ 2 on the long wavelength side of the two wavelengths indicating the ratio.
• Durability was evaluated according to the following criteria. The smaller the ⁇ s, the smaller the change in color under the heat environment. (Evaluation criteria) A: ⁇ s ⁇ 10 nm B: 10 nm ⁇ s ⁇ 20 nm C: 20 nm ⁇ ⁇ s
• the reflection color in Table 1 represents the maximum value of reflectance in the wavelength range of 300 nm or more and 900 nm or less.
• the laminates of Examples were laminates having excellent bending resistance as compared with the laminates of Comparative Examples. Further, as shown in Table 1, the laminates of Examples 1 to 13 were excellent in glitter, and the laminates of Examples 1 to 7 and 9 to 13 were excellent in durability.

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