WO2021132666A1 - Stratifié et son procédé de fabrication, article moulé et son procédé de fabrication, panneau de logement pour dispositif électronique, et dispositif électronique - Google Patents

Stratifié et son procédé de fabrication, article moulé et son procédé de fabrication, panneau de logement pour dispositif électronique, et dispositif électronique Download PDF

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Publication number
WO2021132666A1
WO2021132666A1 PCT/JP2020/048992 JP2020048992W WO2021132666A1 WO 2021132666 A1 WO2021132666 A1 WO 2021132666A1 JP 2020048992 W JP2020048992 W JP 2020048992W WO 2021132666 A1 WO2021132666 A1 WO 2021132666A1
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Prior art keywords
liquid crystal
layer
compound
group
crystal layer
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PCT/JP2020/048992
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English (en)
Japanese (ja)
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佑一 早田
千裕 増田
諭史 長野
渉 馬島
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富士フイルム株式会社
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Priority to JP2021567726A priority Critical patent/JP7309919B2/ja
Priority to CN202080077483.9A priority patent/CN114667214A/zh
Publication of WO2021132666A1 publication Critical patent/WO2021132666A1/fr

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    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class

Definitions

  • the present disclosure relates to a laminate and its manufacturing method, a molded product and its manufacturing method, a housing panel of an electronic device, and an electronic device.
  • the laminate in which the liquid crystal layer is provided on the base material can be used as, for example, a decorative molding film.
  • the decorative molded film includes a base material and a liquid crystal layer which is a decorative film, and by performing a molding process, a decorative molded product (hereinafter, may be referred to as a "molded product") can be obtained. ..
  • a decorative molded product in which a decorative film is arranged on the surface of a resin molded body to color the surface to a desired hue or to provide a desired pattern on the surface.
  • the decorative molded product is obtained, for example, by arranging a decorative molding film in a mold in advance and injecting a base resin into the mold, and the decorative film is integrated on the surface of the resin molded body.
  • performing injection molding of the base resin after arranging the decorative molding film in the mold in advance may be generally referred to as film insert molding or simply insert molding.
  • the decorative molded body may be manufactured by attaching a decorative film to the molded body after molding.
  • Japanese Patent Application Laid-Open No. 2001-105795 describes a hot stamping foil in which a cholesteric liquid crystal polymer layer having a selective reflection wavelength range in visible light is laminated as a transfer layer. Has been done.
  • An object to be solved by one embodiment of the present disclosure is to provide a laminate having a pattern formed by light selective reflection of different wavelengths, having a high design property, and having excellent sharpness of boundaries between patterns. It is in.
  • An object to be solved by other embodiments of the present disclosure is to provide a method for producing the above-mentioned laminate.
  • An object to be solved by another embodiment of the present disclosure is to provide a molded product obtained by molding the above-mentioned laminate.
  • An object to be solved by other embodiments of the present disclosure is to provide a method for producing the above-mentioned molded product.
  • An object to be solved by another embodiment of the present disclosure is to provide a housing panel of an electronic device provided with the above-mentioned laminate.
  • An object to be solved by other embodiments of the present disclosure is to provide an electronic device comprising the above-mentioned molded product.
  • Means for solving the above problems include the following aspects.
  • a laminate having a base material and a liquid crystal layer containing a liquid crystal compound and a photoisomerized compound provided on the base material.
  • a plurality of patterns having different selective reflection wavelengths are formed in the in-plane direction.
  • a laminate in which the width of bleeding at the boundary of a plurality of patterns is 1 ⁇ m or more and less than 100 ⁇ m.
  • the laminate according to ⁇ 1> which is a decorative molded film.
  • a method for producing a laminate which comprises a step of irradiating a liquid crystal layer with light through an optical mask layer to photoisomerize a photoisomerizing compound.
  • ⁇ 5> The method for producing a laminate according to ⁇ 3> or ⁇ 4>, wherein at least a part of the plurality of patterns has different light transmittances in a wavelength range of 250 nm to 400 nm.
  • ⁇ 6> The method for producing a laminate according to any one of ⁇ 3> to ⁇ 5>, wherein the plurality of patterns differ in the maximum value of light transmittance by 30% or more.
  • ⁇ 7> The method for producing a laminate according to any one of ⁇ 3> to ⁇ 6>, wherein the plurality of patterns have an in-plane average transmittance of 50% or more in a wavelength range of 400 nm to 780 nm.
  • ⁇ 8> The method for producing a laminate according to any one of ⁇ 3> to ⁇ 7>, wherein the optical mask layer is formed by a printing method.
  • ⁇ 9> The method for manufacturing a laminate according to any one of ⁇ 3> to ⁇ 8>, wherein the laminate is a decorative molded film used for decorating a housing panel of an electronic device.
  • ⁇ 10> A molded product obtained by molding the laminate according to ⁇ 1> or ⁇ 2>.
  • ⁇ 11> A method for producing a molded product, which comprises a step of molding the laminate obtained by the method for producing a laminate according to any one of ⁇ 3> to ⁇ 9>.
  • ⁇ 12> A housing panel of an electronic device provided with the laminate according to ⁇ 1> or ⁇ 2>.
  • ⁇ 13> An electronic device comprising the molded product according to ⁇ 10>.
  • a laminated body in which patterns are formed by light selective reflection of different wavelengths has high designability, and is excellent in sharpness of boundaries between patterns.
  • it is possible to provide a method for producing the above-mentioned laminate it is possible to provide a molded product obtained by molding the above-mentioned laminate.
  • it is possible to provide a method for producing the above-mentioned molded product it is possible to provide a housing panel of an electronic device provided with the above-mentioned laminate.
  • an electronic device including the above-mentioned molded product it is possible to provide.
  • FIG. 1 is a schematic plan view schematically showing a pattern of an optical mask layer.
  • FIG. 2A is a schematic plan view schematically showing an example of the shape of the glass member.
  • FIG. 2B is a schematic cross-sectional view schematically showing a cross section cut in a direction parallel to the longitudinal direction of the glass member of FIG. 2A.
  • the amount of each component in the composition is the total amount of the plurality of applicable substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition.
  • the term "process” is included in this term as long as the intended purpose of the process is achieved, not only in an independent process but also in cases where it cannot be clearly distinguished from other processes.
  • the "total solid content” refers to the total mass of the components excluding the solvent from the total composition of the composition.
  • the “solid content” is a component excluding the solvent as described above, and may be, for example, a solid or a liquid at 25 ° C.
  • the notation that does not describe substitution or non-substituent includes those having no substituent as well as those having a substituent.
  • the "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).
  • (meth) acrylic is a term used in a concept that includes both acrylic and methacryl
  • “(meth) acrylate” is a term that is used as a concept that includes both acrylate and methacrylate. is there.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure are gels using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Toso Co., Ltd.). It is a molecular weight converted by detecting with a solvent THF (tetrahydrofuran) and a differential refractometer by a permeation chromatography (GPC) analyzer and using polystyrene as a standard substance.
  • THF tetrahydrofuran
  • GPC permeation chromatography
  • light is a concept including active energy rays such as ⁇ -rays, ⁇ -rays, electron beams, ultraviolet rays, and visible rays.
  • active energy rays such as ⁇ -rays, ⁇ -rays, electron beams, ultraviolet rays, and visible rays.
  • the laminate according to the present disclosure has a base material and a liquid crystal layer containing a liquid crystal compound and a photoisomerized compound provided on the base material.
  • a plurality of patterns having different selective reflection wavelengths are formed in the in-plane direction, and the width of bleeding at the boundary portion of the plurality of patterns is 1 ⁇ m or more and less than 100 ⁇ m.
  • the "liquid crystal layer” means a cured product of a liquid crystal composition in a laminated body, and may be referred to as a "cured liquid crystal layer” or a "cured liquid crystal layer", and production of the laminated body.
  • the liquid crystal material described later used in the above it means an uncured product of the liquid crystal composition.
  • the "liquid crystal composition” is a composition containing components contained in the liquid crystal layer, and the "cured product of the liquid crystal composition” includes a dried product and a polymerization cured product of the liquid crystal composition.
  • the maximum wavelength of the reflected light of the liquid crystal layer can be changed, and a pattern by selective reflection of different wavelengths can be formed on the liquid crystal layer.
  • the optical mask layer is adjacent to the liquid crystal layer or the base material, for example, if it is directly laminated on the base material, the distance between the liquid crystal layer and the optical mask layer is close, and the reflection wavelength of the pattern boundary portion changes. It is presumed that a laminated body having excellent sharpness can be provided.
  • the liquid crystal layer may be on the base material and may not be in direct contact with the base material.
  • the liquid crystal layer may be placed on the base material via another layer such as a colored layer described later.
  • ⁇ Liquid crystal layer> In the liquid crystal layer, a plurality of patterns having different selective reflection wavelengths are formed in the in-plane direction. As a result, the color of the liquid crystal layer can be changed in the in-plane direction, and a laminated body having high designability can be obtained.
  • the selective reflection wavelength is the half-value transmittance expressed by the following formula, where T min (%) is the minimum and minimum value of the transmittance of the target object (member) : T 1 /. It refers to the average value of two wavelengths showing 2 (%), and having selective reflectivity means having a specific wavelength range satisfying the selective reflection wavelength.
  • the transmittance is measured using a spectrophotometer (for example, a spectrophotometer "UV-2100" manufactured by Shimadzu Corporation, a spectrophotometer "V-670” manufactured by JASCO Corporation).
  • the selective reflection wavelength in the liquid crystal layer is not particularly limited, and can be set to any range of visible light (380 nm to 780 nm) and near infrared light (more than 780 nm and 2,000 nm or less), for example. .. Above all, the liquid crystal layer preferably has selective reflectivity in at least a part of the wavelength range of 380 nm to 1,200 nm.
  • the maximum wavelength of the reflectance of the laminate according to the present disclosure is preferably in the range of 380 nm to 780 nm. Further, it is preferable that the pattern is formed by selective reflection of different wavelengths in the range of 380 nm to 780 nm. More preferably, the difference in the maximum wavelength of the reflectance includes a region of 100 nm or more in the plane.
  • the reflectance of the laminate according to the present disclosure is such that a black polyethylene terephthalate (PET) film (manufactured by Tomagawa Paper Manufacturing Co., Ltd., trade name "Clear Mierre”) is attached to the outermost layer of the laminate on the side opposite to the visible side. It is obtained from a reflection spectrum measured using a spectrophotometer (for example, a spectrophotometer "V-670” manufactured by JASCO Corporation) with the surface on which the liquid crystal layer is formed as an incident surface.
  • PET polyethylene terephthalate
  • V-670 spectrophotometer
  • the width of the bleeding at the boundary portion of the plurality of patterns is 1 ⁇ m or more and less than 100 ⁇ m, whereby a laminated body having excellent sharpness of the boundary between the patterns can be obtained.
  • the color of the reflected light changes because the spiral pitch of the cholesteric liquid crystal changes, and the region where the spiral pitch changes by 10% or more in the in-plane direction of the liquid crystal layer is recognized as blurring.
  • the in-plane width of the liquid crystal layer recognized as such bleeding at the boundary portion of the pattern is referred to as "the width of bleeding at the boundary portion of the pattern”. The width of the bleeding at the boundary of the pattern is measured as follows.
  • a section of the laminate was prepared using a microtome (for example, RX-860 manufactured by Daiwa Kouki Kogyo Co., Ltd.), and a scanning electron microscope (for example, Co., Ltd.) was used to scan the boundary of the pattern for the cross section of the liquid crystal layer of the section. ) Observe using Hitachi High-Tech, SU3800). At the pattern boundary portion, the width of the region where the spiral pitch changes by 10% or more in the in-plane direction of the liquid crystal layer is measured and used as the “width of bleeding at the boundary portion of the pattern”.
  • a microtome for example, RX-860 manufactured by Daiwa Kouki Kogyo Co., Ltd.
  • a scanning electron microscope for example, Co., Ltd.
  • the width of the bleeding at the boundary of the plurality of patterns is preferably 1 ⁇ m or more and less than 20 ⁇ m, and more preferably 2 ⁇ m or more and less than 8 ⁇ m.
  • the liquid crystal layer may be formed of only one layer or two or more layers. Further, each of the two or more liquid crystal layers may be a layer having the same composition or a different layer, and at least one layer may be a liquid crystal layer containing a liquid crystal compound and a photoisomerizing compound. It may have a liquid crystal layer containing no isomerized compound.
  • the thickness of the liquid crystal layer is preferably less than 10 ⁇ m, more preferably 5 ⁇ m or less, still more preferably 0.05 ⁇ m to 5 ⁇ m, from the viewpoint of suppressing the change in reflectance after molding of the laminate. It is particularly preferably 0.1 ⁇ m to 4 ⁇ m.
  • each liquid crystal layer is independently in the above thickness range.
  • Base material As the base material used in the present disclosure, conventionally known base materials for molding such as three-dimensional molding and insert molding can be used without particular limitation, and the use of the laminate (in some embodiments, the decorative molding film) and the insert It may be appropriately selected according to the suitability for molding and the like.
  • the shape and material of the base material are not particularly limited and may be appropriately selected as desired. From the viewpoint of ease of molding (particularly ease of insert molding) and chipping resistance, the base material is preferably a resin base material, and preferably a resin film base material.
  • the base material for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), acrylic resin, urethane resin, urethane-acrylic resin, polycarbonate (PC), acrylic-polycarbonate resin, triacetyl cellulose (TAC).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • acrylic resin acrylic resin
  • urethane resin urethane-acrylic resin
  • PC polycarbonate
  • acrylic-polycarbonate resin acrylic-polycarbonate resin
  • TAC triacetyl cellulose
  • a resin film containing a resin such as a polyolefin, a cycloolefin polymer (COP), and an acrylonitrile / butadiene / styrene copolymer resin (ABS resin).
  • the base material may be a laminated resin base material having two or more layers. For example, an acrylic resin / polycarbonate laminated film is preferable.
  • the base material may contain additives, if necessary.
  • additives include mineral oils, hydrocarbons, fatty acids, alcohols, fatty acid esters, fatty acid amides, metal soaps, natural waxes, lubricants such as silicones, inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, halogen-based additives, and the like.
  • Organic flame retardants such as phosphorus, metal powder, talc, calcium carbonate, potassium titanate, glass fiber, carbon fiber, wood powder and other organic or inorganic fillers, antioxidants, UV inhibitors, lubricants, dispersants, Additives such as coupling agents, foaming agents and colorants, polyester resins, polyacetal resins, polyamide resins, polyphenylene ether resins and the like, and engineering plastics other than the above-mentioned resins can be mentioned.
  • a commercially available product may be used as the base material.
  • Commercially available products include, for example, Technoroy (registered trademark) series (acrylic resin film or acrylic resin / polycarbonate resin laminated film, manufactured by Sumitomo Chemical Co., Ltd.) ABS film (manufactured by Okamoto Co., Ltd.), ABS sheet (Sekisui Molding Industry (Sekisui Molding Industry)).
  • the thickness of the base material may be determined according to the intended use of the molded product to be produced, the handleability of the base material, and the like.
  • the thickness is not particularly limited, but from the viewpoint of handleability, 1 ⁇ m or more is preferable, 10 ⁇ m or more is more preferable, 15 ⁇ m or more is further preferable, and 30 ⁇ m or more is particularly preferable.
  • the upper limit is preferably 200 ⁇ m or less, more preferably 125 ⁇ m or less, further preferably 75 ⁇ m or less, and particularly preferably 50 ⁇ m or less, from the viewpoint of obtaining high sharpness at the pattern boundary portion.
  • the laminate (in a certain aspect, the decorative molded film) according to the present disclosure further has a colored layer.
  • the colored layer is a layer containing a colorant.
  • the position of the colored layer is not particularly limited and can be provided at a desired position, but the following two aspects are preferably mentioned.
  • the laminate further has a colored layer between the base material and the liquid crystal layer.
  • the laminated body may have only one colored layer or two or more colored layers.
  • at least one of the colored layers is a layer for visual recognition through the liquid crystal layer.
  • the color changes according to the angle viewed by the colored layer based on the anisotropy according to the angle of the incident light in the liquid crystal layer, which is a special case. It is presumed that the design is shown.
  • at least one of the colored layers is a layer for viewing through the liquid crystal layer, and at least the other one layer of the colored layer is in the viewing direction as compared with the liquid crystal layer.
  • a mode in which the layer is close to (hereinafter, also referred to as “color filter layer”) is preferable.
  • the colored layer that is, the color filter layer
  • the layer structure is not particularly limited, and is a monochromatic color filter layer. It 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.
  • the total light transmittance of the colored layer for visual recognition through at least one layer of the colored layer, preferably the liquid crystal layer, is preferably 10% or less from the viewpoint of visibility.
  • the total light transmittance can be measured by a spectrophotometer (for example, a spectrophotometer "UV-2100" manufactured by Shimadzu Corporation).
  • the color of the colored layer is not limited and can be appropriately selected depending on the use of the laminated body and the like.
  • Examples of the color of the coloring layer include black, gray, white, red, orange, yellow, green, blue, and purple. Further, the color of the colored layer may be a metallic color.
  • the colored layer preferably contains a resin from the viewpoint of strength and scratch resistance.
  • the resin include a binder resin described later.
  • the colored layer may be a layer obtained by curing the polymerizable compound, or may be a layer containing the polymerizable compound and the polymerization initiator.
  • the polymerizable compound and the polymerization initiator are not particularly limited, and known ones can be used.
  • the colorant include pigments and dyes, and pigments are preferable from the viewpoint of durability.
  • the colored layer metallic metal particles, pearl pigments and the like can be applied, and methods such as thin film deposition and plating can also be applied.
  • the pigment is not limited, and known inorganic pigments, organic pigments and the like can be applied.
  • the inorganic pigment include white pigments such as titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide and barium sulfate, carbon black, titanium black, titanium carbon, iron oxide and graphite. Black pigments, iron oxide, barium yellow, cadmium red, chrome yellow and the like.
  • the inorganic pigments described in paragraphs 0015 and 0114 of JP-A-2005-7765 can also be applied.
  • organic pigments examples include phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, azo pigments such as azo red, azo yellow and azo orange, quinacridone pigments such as quinacridone red, cinacridone red and cincasha magenta, and perylene red.
  • Perylene pigments such as perylene maroon, carbazole violet, anthrapyridine, flavanthron yellow, isoindrin yellow, induslon blue, dibrom anzasron red, anthraquinone red, diketopyrrolopyrrole and the like can be mentioned.
  • Specific examples of organic pigments include C.I. I.
  • the organic pigment described in paragraph 093 of JP2009-256572 can also be applied.
  • the pigment may include a pigment having light transmission and light reflection (so-called brilliant pigment).
  • the glitter pigment include metal glitter pigments such as aluminum, copper, zinc, iron, nickel, tin, aluminum oxide, and alloys thereof, interfering mica pigments, white mica pigments, graphite pigments, and glass flake pigments. Can be mentioned.
  • the bright pigment may be uncolored or colored. When the bright pigment is exposed in the molding of the laminate, it is preferably used within a range that does not interfere with the curing due to the exposure.
  • the colorant may be used alone or in combination of two or more. Further, when two or more kinds of colorants are used, an inorganic pigment and an organic pigment may be combined.
  • the content of the colorant in the colored layer is preferably 1% by mass to 50% by mass and 5% by mass to 50% by mass with respect to the total mass of the colored layer from the viewpoint of the development of the desired color and the suitability for molding. % Is more preferable, and 10% by mass to 40% by mass is particularly preferable.
  • the colored layer may contain a dispersant.
  • the dispersant By including the dispersant, the dispersibility of the colorant in the formed colored layer is improved, and the color can be made uniform in the obtained laminate.
  • the dispersant can be appropriately selected depending on the type, shape and the like of the colorant, and a polymer dispersant is preferable.
  • the polymer dispersant include silicone polymers, acrylic polymers, polyester polymers and the like.
  • a silicone polymer such as a graft type silicone polymer as a dispersant.
  • 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.
  • dispersant a commercially available product may be used.
  • Commercially available products include BASF Japan's EFKA 4300 (acrylic polymer dispersant), Kao Corporation's Homogenol L-18, Homogenol L-95 and Homogenol L-100, and Nippon Lubrizol Co., Ltd.
  • Examples thereof include Solspers 20000 and Solspers 24000, DISPERBYK-110, DISPERBYK-164, DISPERBYK-180 and DISPERBYK-182 manufactured by Big Chemie Japan Ltd.
  • "Homogenol”, “Solsperse”, and "DISPERBYK” are all registered trademarks.
  • the dispersant may be used alone or in combination of two or more.
  • the content of the dispersant in the colored layer is preferably 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the colorant.
  • the colored layer preferably contains a binder resin from the viewpoint of proper molding process.
  • the binder resin is not limited, and a known resin can be applied.
  • the binder resin is preferably a transparent resin from the viewpoint of obtaining a desired color, and specifically, a resin having a total light transmittance of 80% or more is preferable.
  • the total light transmittance can be measured with a spectrophotometer (for example, a spectrophotometer "UV-2100" manufactured by Shimadzu Corporation).
  • the binder resin is not limited, and a known resin can be applied.
  • the binder resin include acrylic resin, silicone resin, polyester, polyurethane, and polyolefin.
  • the binder resin may be a homopolymer of a specific monomer or a copolymer of a specific monomer and another monomer.
  • the binder resin may be used alone or in combination of two or more.
  • the content of the binder resin in the colored layer is preferably 5% by mass to 70% by mass, and 10% by mass to 60% by mass, based on the total mass of the colored layer, from the viewpoint of moldability. Is more preferable, and 20% by mass to 60% by mass is particularly preferable.
  • the colored layer may contain additives in addition to the above components, if necessary.
  • the additive is not limited, and a known additive can be applied.
  • the additive include the surfactant described in paragraphs 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Application Laid-Open No. 2009-237362, and the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784.
  • agents also referred to as polymerization inhibitors, preferably phenothiazine
  • a method for forming the colored layer examples include a method using a composition for forming a colored layer, a method of laminating colored films, and the like.
  • a method for forming the colored layer a method using a composition for forming a colored layer is preferable.
  • a colored layer may be formed by using a commercially available paint such as nax real series, nax admira series, nax multi series (manufactured by Nippon Paint Co., Ltd.), and Retan PG series (manufactured by Kansai Paint Co., Ltd.).
  • Examples of the method of using the composition for forming a colored layer include a method of applying a composition for forming a colored layer to form a colored layer, a method of printing a composition for forming a colored layer to form a colored layer, and the like.
  • Examples of the printing method include screen printing, inkjet printing, flexographic printing, gravure printing, offset printing and the like.
  • the composition for forming a colored layer contains a colorant. Further, the composition for forming a colored layer preferably contains an organic solvent, and may contain each of the above components that can be contained in the colored layer.
  • the content of each of the above components that can be contained in the composition for forming a colored layer is the amount obtained by replacing "colored layer” with "composition for forming a colored layer” in the description regarding the content of each of the above components in the colored layer. It is preferable to adjust within the range of.
  • the organic solvent is not limited, and a known organic solvent can be applied.
  • examples of the organic solvent include alcohol compounds, ester compounds, ether compounds, ketone compounds, aromatic hydrocarbon compounds and the like.
  • the organic solvent may be used alone or in combination of two or more.
  • the content of the organic solvent in the composition for forming a colored layer is preferably 5% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, based on the total mass of the composition for forming a colored layer.
  • Examples of the method for preparing the composition for forming a colored layer include a method of mixing an organic solvent and a component contained in the colored layer such as a colorant.
  • a pigment dispersion liquid containing the pigment and the dispersant is used from the viewpoint of further enhancing the uniform dispersibility and dispersion stability of the pigment to form a colored layer. It is preferable to prepare a composition for formation.
  • the thickness of the colored layer is not particularly limited, but from the viewpoint of visibility and three-dimensional moldability, it is preferably 0.5 ⁇ m or more, more preferably 3 ⁇ m or more, and further preferably 3 ⁇ m to 50 ⁇ m. It is preferably 3 ⁇ m to 20 ⁇ m, and particularly preferably 3 ⁇ m to 20 ⁇ m.
  • each colored layer is independently in the above thickness range.
  • the laminate according to the present disclosure may have an orientation layer in contact with the liquid crystal layer.
  • the alignment layer is used to orient the molecules of the liquid crystal compound in the liquid crystal layer when the liquid crystal layer is formed.
  • the alignment layer is used when forming a layer such as a liquid crystal layer, and the alignment layer may or may not be included in the laminated body.
  • the alignment layer can be provided by means such as rubbing treatment of an organic compound (preferably a polymer), oblique vapor deposition of an inorganic compound such as SiO, and formation of a layer having microgrooves.
  • an orientation layer in which an orientation function is generated by applying an electric field, applying a magnetic field, or irradiating light is also known.
  • the material of the lower layer such as the base material and the liquid crystal layer, it is possible to function as the alignment layer by directly aligning the lower layer (for example, rubbing treatment) without providing the alignment layer.
  • PET polyethylene terephthalate
  • the lower liquid crystal layer behaves as an alignment layer, and the liquid crystal compound for producing the upper layer may be oriented.
  • the liquid crystal compound in the upper layer can be oriented without providing the alignment layer and without performing a special orientation treatment (for example, rubbing treatment).
  • -Rubbing treatment alignment layer examples include methacrylate-based copolymers, styrene-based copolymers, polyolefins, polyvinyl alcohols, and modified polyvinyl alcohols described in paragraph 0022 of JP-A-8-338913.
  • Poly (N-methylolacrylamide), polyester, polyimide, vinyl acetate copolymer, carboxymethyl cellulose, polycarbonate and the like are included.
  • a silane coupling agent can be used as a polymer.
  • Water-soluble polymers eg, poly (N-methylolacrylamide), carboxymethyl cellulose, gelatin, polyvinyl alcohol, modified polyvinyl alcohol
  • gelatin, polyvinyl alcohol or modified polyvinyl alcohol are more preferred, and polyvinyl alcohol or modified polyvinyl alcohol is particularly preferred. ..
  • the liquid crystal composition is applied to the rubbing-treated surface of the alignment layer to orient the molecules of the liquid crystal compound. Then, if necessary, the liquid crystal layer can be formed by reacting the alignment layer polymer with the polyfunctional monomer contained in the liquid crystal layer, or by cross-linking the alignment layer polymer with a cross-linking agent.
  • the thickness of the alignment layer is preferably in the range of 0.01 ⁇ m to 10 ⁇ m.
  • the surface of the alignment layer, the base material, or the other layer to which the liquid crystal composition is applied may be subjected to a rubbing treatment, if necessary.
  • the rubbing treatment can be generally carried out by rubbing the surface of the film containing the polymer as a main component with paper or cloth in a certain direction.
  • a general method of rubbing processing is described in, for example, "LCD Handbook" (published by Maruzen-sha, October 30, 2000).
  • N represents the number 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 movement speed. Represents (speed per second).
  • the photo-alignment material used for the photo-alignment layer formed by light irradiation is described in many documents and the like.
  • the photocrosslinkable silane derivative described above, the photocrosslinkable polyimide, polyamide, or ester described in Japanese Patent Application Laid-Open No. 2003-520878, Japanese Patent Application Laid-Open No. 2004-522220, and Japanese Patent No. 4162850 are preferable examples. Particularly preferred are azo compounds, photocrosslinkable polyimides, polyamides, or esters.
  • the photo-aligned layer formed from the above material is irradiated with linearly polarized light or non-polarized light to produce a photo-aligned layer.
  • linearly polarized light irradiation is an operation for causing a photoreaction in a photoaligned material.
  • the wavelength of light used varies depending on the photoalignment material used, and is not particularly limited as long as it is a wavelength required for the photoreaction.
  • the peak wavelength of the light used for light irradiation is 200 nm to 700 nm, and more preferably, ultraviolet light having a peak wavelength of light of 400 nm or less.
  • Light sources used for light irradiation are known light sources such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury xenon lamps, carbon arc lamps and other lamps, and various lasers (eg, semiconductor lasers, helium neon). Laser, argon ion laser, helium cadmium laser, YAG laser), light emitting diode, cathode wire tube and the like can be mentioned.
  • a method using a polarizing plate eg, iodine polarizing plate, two-color dye polarizing plate, wire grid polarizing plate
  • reflection using a prism element eg, Gran Thomson prism
  • a Brewster angle e.g., a Brewster angle
  • a method using a type polarizing element or a method using light emitted from a polarized laser light source can be adopted. Further, only light having a required wavelength may be selectively irradiated by using a filter, a wavelength conversion element, or the like.
  • the incident angle of light varies depending on the photoalignment material, but is preferably 0 ° to 90 ° (vertical), more preferably 40 ° to 90 °, with respect to the alignment layer.
  • the incident angle is preferably 10 ° to 80 °, more preferably 20 ° to 60 °, and particularly preferably 30 ° to 50 °.
  • the irradiation time is preferably 1 minute to 60 minutes, more preferably 1 minute to 10 minutes.
  • the laminate according to the present disclosure may also have a protective layer.
  • the protective layer may be a layer having sufficient strength to protect the liquid crystal layer or the like and having excellent weather resistance such as ultraviolet light (UV (Ultra Violet) light) and moist heat. Further, from the viewpoint of visibility and blackening (suppression of reflection by reflected light from the outside, for example, suppression of reflection of fluorescent lamp), the protective layer may have an antireflection ability.
  • the protective layer may be formed by applying a coating liquid for forming a protective layer containing the components described below.
  • the protective layer preferably contains a resin from the viewpoint of strength and weather resistance, and is a group consisting of a siloxane resin, a fluororesin, an acrylic resin, a melamine resin, a polyolefin resin, a polyester resin, a polycarbonate resin, and a urethane resin. It is more preferable to contain at least one resin selected from the above, and it is further preferable to contain at least one resin selected from the group consisting of a siloxane resin having voids, a fluororesin, an acrylic resin, and a urethane resin. ..
  • the refractive index of the protective layer is preferably 1.05 to 1.6, more preferably 1.2 to 1.5, and even more preferably 1.2 to 1.4, from the viewpoint of visibility and antireflection. ..
  • the refractive index is the refractive index for light having a wavelength of 550 nm at 25 ° C.
  • the refractive index should be set in a range close to those refractive indexes, that is, in the range of 1.4 to 1.5 in order to make the contamination of wax, gasoline, etc. inconspicuous. , Dirt becomes less noticeable, which is preferable.
  • the refractive index of each layer in the present disclosure is the same as the transmittance obtained by measuring the transmittance spectrum with a spectrophotometer for a single protective layer formed on the non-alkali glass OA-10G.
  • the thickness and refractive index of each layer shall be obtained by performing a fitting analysis using the transmittance calculated by the optical interferometry. It can also be measured using a Carnew precision refractometer (for example, "KPR-3000" manufactured by Shimadzu Corporation).
  • the refractive index of the protective layer can be 1.5 or less, preferably 1.4 or less, and the antireflection ability is also increased. An excellent protective layer can be easily obtained. Further, by including the 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.
  • the thickness of the protective layer is not particularly limited, but from the viewpoint of scratch resistance and three-dimensional moldability, it is preferably 2 ⁇ m or more, more preferably 4 ⁇ m or more, and further preferably 4 ⁇ m to 50 ⁇ m. It is particularly preferably 4 ⁇ m to 20 ⁇ m.
  • the fluororesin is not particularly limited, and examples thereof include those described in paragraphs 0076 to 0106 of JP2009-217258A and paragraphs 0083 to 0127 of JP2007-2299999.
  • Examples of the fluororesin include a fluoroalkyl resin in which hydrogen in an olefin is replaced with fluorine, and examples thereof include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxyalkane, and perfluoro.
  • copolymers such as ethylene propene and ethylene tetrafluoroethylene, or fluororesin dispersions that are water-dispersed by copolymerizing with emulsifiers or components that enhance affinity with water.
  • fluororesins include Lumiflon manufactured by Asahi Glass Co., Ltd., Obbligato, Zeffle manufactured by Daikin Industries, Ltd., Neophron, Teflon manufactured by DuPont (registered trademark), and Arkema Co., Ltd.
  • a compound having at least one of a polymerizable functional group and a crosslinkable functional group and containing a fluorine atom may be used, and a perfluoroalkyl (meth) acrylate, a vinyl fluoride monomer, and a fluorine atom may be used.
  • a radically polymerizable monomer such as a vinylidene compound monomer and a cationically polymerizable monomer such as perfluorooxetane.
  • fluorine compounds include LINK3A manufactured by Kyoeisha Chemical Co., Ltd., Optool manufactured by Daikin Industries, Ltd., Opstar manufactured by Arakawa Chemical Industry Co., Ltd., and tetrafluorooxetane manufactured by Daikin Industries, Ltd. ..
  • the low refractive index particles preferably particles having a refractive index of 1.45 or less, are not particularly limited, and examples thereof include those described in paragraphs 0075 to 0103 of JP2009-217258A.
  • Examples of low refractive index particles include 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 the refractive index of the material itself. Examples include low fluoride particles. Specific examples of such hollow particles include JGC Catalysts and Chemicals Co., Ltd. Sururia, Nittetsu Mining Co., Ltd. Sirinax, Sekisui Kasei Kogyo Co., Ltd.
  • porous particles include Light Star manufactured by Nissan Chemical Industry Co., Ltd.
  • fluoride particles include magnesium fluoride nanoparticles manufactured by Rare Metal Materials Research Institute Co., Ltd. ..
  • core-shell particles may be used to form closed voids in a matrix composed of the above resin.
  • the method for forming the protective layer by applying the coating liquid for forming a protective layer containing hollow particles include the methods described in paragraphs 0028 to 0029 of JP2009-103808, or JP2008-262187. The method described in paragraphs 0030 to 0031 of the above, or paragraph 0018 of Japanese Patent Application Laid-Open No. 2017-520384 can be applied.
  • the coating liquid for forming the protective layer preferably contains a siloxane compound.
  • a suitable siloxane resin can be obtained by hydrolyzing and condensing the siloxane compound.
  • the siloxane compound at least one compound selected from the group consisting of a siloxane compound represented by the following formula 1 and a hydrolyzed condensate of a siloxane compound represented by the following formula 1 (hereinafter, specific siloxane). Also referred to as a compound) is preferable.
  • R 1 , R 2 and R 3 each independently represent an alkyl group or an alkenyl group having 1 to 6 carbon atoms
  • R 4 independently represents an alkyl group, a vinyl group, respectively in the case of a plurality of carbon groups.
  • a vinyl group an epoxy group, a vinylphenyl group, a (meth) acryloxy group, a (meth) acrylamide group, an amino group, an isocyanurate group, a ureido group, a mercapto group, a sulfide group, a polyoxyalkyl group, a carboxy group and a fourth group.
  • It represents an alkyl group having a group selected from the group consisting of primary ammonium groups, where m represents an integer of 0 to 2 and n represents an integer of 1 to 20.
  • the hydrolyzed condensate of the siloxane compound represented by the formula 1 is obtained by hydrolyzing at least a part of the substituents on the silicon atom of the siloxane compound represented by the formula 1 and the siloxane compound represented by the formula 1. , A compound in which a compound that is a silanol group is condensed.
  • the alkyl group or alkenyl group having 1 to 6 carbon atoms in R 1 , R 2 and R 3 in the formula 1 has a ring structure regardless of whether it is linear or has a branch. May be good.
  • the alkyl group or alkenyl group having 1 to 6 carbon atoms is preferably an alkyl group from the viewpoint of the strength of the protective layer, light transmission and haze.
  • alkyl group having 1 to 6 carbon atoms examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group and a cyclohexyl group. It is preferably a methyl group or an ethyl group, and more preferably a methyl group. From the viewpoint of the strength of the protective layer, light transmission, and haze, it is preferable that R 4 in the formula 1 is an alkyl group independently in each case, and more preferably an alkyl group having 1 to 8 carbon atoms. preferable.
  • the number of carbon atoms of R 4 in Formula 1 is preferably 1 to 40, more preferably 1 to 20, and particularly preferably 1-8.
  • m in the formula 1 is preferably 1 or 2, and more preferably 2.
  • N in Formula 1 is preferably an integer of 2 to 20 from the viewpoint of the strength of the protective layer, light transmission, and haze.
  • Examples of specific siloxane compounds include KBE-04, KBE-13, KBE-22, KBE-1003, KBM-303, KBE-403, KBM-1403, KBE-503, KBM-, manufactured by Shinetsu Chemical Industry Co., Ltd. 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 Ebonic Japan Co., Ltd .; MKC silicate MS51, MKC silicate MS56, MKC silicate MS57, MKC silicate MS56S manufactured by Corcote Co., Ltd.
  • the condensation catalyst is not particularly limited, and a known condensation catalyst can be used.
  • the urethane resin that can be suitably used for the protective layer can be obtained by a reaction of a polyisocyanate compound (for example, a diisocyanate compound) with a polyol, a polymerization reaction of a urethane (meth) acrylate compound, or the like.
  • a polyisocyanate compound for example, a diisocyanate compound
  • a polyol for example, a polymerization reaction of a urethane (meth) acrylate compound
  • polyols used for synthesizing polyurethane resins include polyester polyols, polyether polyols, polycarbonate polyols, and polyacrylic polyols. Of these, polyester polyols or polyacrylic polyols are preferable from the viewpoint of impact resistance.
  • the polyester polyol can be obtained by a known method using an esterification reaction using a polybasic acid and a polyhydric alcohol.
  • Polycarboxylic acid is used as the polybasic acid component of the polyester polyol, but monobasic fatty acids and the like may also be used if necessary.
  • Examples of polycarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydroisophthalic acid, hexahydrophthalic acid, hexahydroterephthalic acid, trimellitic acid, pyromellitic acid, and other such aromatics.
  • polycarboxylic acids includes polycarboxylic acids, adipic acids, sebacic acids, succinic acids, azelaic acids, phthalic acids, maleic acids, itaconic acids, and other such aliphatic polycarboxylic acids, as well as their anhydrides. These polybasic acids may be used alone, or a combination of two or more thereof may be used.
  • Examples of the polyhydric alcohol component of the polyester polyol and similarly, the polyhydric alcohol used in the synthesis of the polyurethane resin include glycol and a trihydric or higher polyhydric alcohol.
  • Examples of glycols are 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-.
  • trihydric or higher polyhydric alcohols include glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and the like. These polyhydric alcohols can be used alone or in combination of two or more of them.
  • dimethylol alkanoate examples include dimethylol propionate, dimethylol butanoate, dimethylol pentanate, dimethylol heptanate, dimethylol octanate, and dimethylol nonanoate. These dimethylol alkanoates can be used alone or in combination of two or more of them.
  • polyacrylic polyol various known polyacrylic polyols having a hydroxy group capable of reacting with an isocyanate group can be used.
  • (meth) acrylic acid various (meth) acrylic acids with added hydroxy groups
  • (meth) acrylic acid alkyl esters various (meth) acrylamide and derivatives thereof
  • vinyl alcohol carboxylic acid esters vinyl alcohol carboxylic acid esters
  • unsaturated carboxylic acids examples thereof include polyacrylic polyols having at least one or more monomers such as hydrocarbons having a chain unsaturated alkyl moiety.
  • polyisocyanate compounds are 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 1,5-naphthalenediocyanate, p- or m-phenylenediocyanate, xylylene diisocyanate, and m.
  • Aromatic diisocyanates such as tetramethylxylylene diisocyanate, isophorone diisocyanates, 4,4'-dicyclohexylmethane diisocyanates, 1,4-cycloheximethylene diisocyanates, and alicyclic di-isocyanates such as hydrogenated tolylene diisocyanates, and Includes aliphatic diisocyanates such as hexamethylene diisocyanate. Of these, alicyclic diisocyanates are preferable in terms of resistance to fading and the like. These diisocyanate compounds may be used alone, or a combination of two or more thereof may be used.
  • Urethane (meth) acrylate will be explained.
  • Examples of the method for producing a urethane (meth) acrylate include a method in which a compound having a hydroxy group and a (meth) acryloyl group and a polyisocyanate compound are subjected to a urethanization reaction.
  • Examples of the compound having a hydroxy group and a (meth) acryloyl group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy-n-butyl (meth) acrylate, and 2-hydroxypropyl.
  • EO ethylene oxide
  • Pentaerythritol tri (meth) acrylate polyfunctional (meth) acrylate having a hydroxy group such as dipentaerythritol penta (meth) acrylate, etc.
  • the scratch resistance of the protective layer is improved.
  • Pentaerythritol triacrylate, or dipentaerythritol pentaacrylate is preferred.
  • the compounds having these hydroxy groups and (meth) acryloyl groups can be used alone or in combination of two or more.
  • polyisocyanate examples include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, m-xylylene diisocyanate, and m-phenylene bis (dimethylmethylene) diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, and 1,3-bis (isocyanato).
  • aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, m-xylylene diisocyanate, and m-phenylene bis (dimethylmethylene) diisocyanate
  • hexamethylene diisocyanate hexamethylene diisocyanate
  • lysine diisocyanate lysine diisocyanate
  • 1,3-bis isocyanato
  • Alips or alicyclic diisocyanates such as methyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, etc. And so on.
  • Urethane (meth) acrylate can be cured by irradiating it with active light.
  • This active ray refers to ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
  • a photopolymerization initiator it is preferable to add to the protective layer to improve the curability. Further, if necessary, a photosensitizer can be further added to improve the curability.
  • the coating liquid for forming the protective layer preferably contains a surfactant.
  • the surfactant include a nonionic surfactant, an anionic surfactant which is an ionic surfactant, a cationic surfactant, an amphoteric surfactant and the like, and all of them can be suitably used in the present disclosure.
  • the coating liquid for forming a protective layer may contain other components depending on the purpose, in addition to the above-mentioned components.
  • known additives can be used, and examples thereof include antistatic agents and preservatives.
  • the coating liquid for forming the protective layer may contain an antistatic agent.
  • the antistatic agent is used for the purpose of suppressing the adhesion of contaminants by imparting antistatic properties to the protective layer.
  • the antistatic agent for imparting antistatic properties is not particularly limited.
  • As the antistatic agent used for the protective layer at least one selected from the group consisting of metal oxide particles, metal nanoparticles, conductive polymers, and ionic liquids can be preferably used. Two or more antistatic agents may be used in combination.
  • the metal oxide particles need to be added in a relatively large amount in order to provide antistatic properties, but since they are inorganic particles, the inclusion of the metal oxide particles further enhances the antifouling property of the protective layer. Can be done.
  • the metal oxide particles are not particularly limited, and examples thereof include tin oxide particles, antimony-doped tin oxide particles, tin-doped indium oxide particles, zinc oxide particles, and silica particles.
  • the metal oxide particles have a large refractive index, and if the particle size is large, there is a concern that the light transmittance may decrease due to scattering of transmitted light. Therefore, the average primary particle size of the metal oxide particles is preferably 100 nm or less, preferably 50 nm. It is more preferably less than or equal to, and particularly preferably 30 nm or less. The lower limit is preferably 2 nm or more.
  • the shape of the particles is not particularly limited, and may be spherical, plate-shaped, or needle-shaped.
  • the average primary particle size of the metal oxide particles can be determined from the photograph obtained by observing the dispersed particles with a transmission electron microscope. From the image of the photograph, the projected area of the particles is obtained, and the equivalent circle diameter is obtained from the projected area, which is used as the average particle size (average primary particle size).
  • the average primary particle diameter in the present disclosure, a value calculated by measuring the projected area of 300 or more particles and obtaining the equivalent circle diameter is used.
  • the shape of the metal oxide particles is not spherical, it may be obtained by using another method, for example, a dynamic light scattering method.
  • the content of the antistatic agent is preferably 40% by mass or less, more preferably 30% by mass or less, based on the total solid content of the coating liquid for forming a protective layer. It is particularly preferably 20% by mass or less.
  • the content is preferably 30% by mass or less, more preferably 20% by mass or less, based on the total mass of the coating liquid for forming the protective layer. It is particularly preferably 10% by mass or less.
  • the method for preparing the coating liquid for forming the protective layer is not particularly limited.
  • an organic solvent, a surfactant, and water are mixed, the organic solvent is dispersed in water, and a specific siloxane compound is added to partially add the organic solvent.
  • a method of forming a shell layer on the surface of an organic solvent dispersed by hydrolysis and condensing to prepare core-shell particles to produce a coating liquid for forming a protective layer, an organic solvent, a surfactant, the above-mentioned resin, and a monomer are mixed. And the like.
  • the protective layer forming coating liquid described above is applied onto the lower layer of the protective layer and dried to form the protective layer.
  • the method of applying the coating liquid for forming the protective layer is not particularly limited, and for example, any known coating method such as spray coating, brush coating, roller coating, bar coating, and dip coating can be applied.
  • the lower layer to which the protective layer forming coating liquid is applied is subjected to surface treatment such as corona discharge treatment, glow treatment, atmospheric pressure plasma treatment, flame treatment, and ultraviolet irradiation treatment. May be applied.
  • the coating liquid for forming the protective layer may be dried at room temperature (25 ° C.) or heated.
  • the organic solvent contained in the coating liquid for forming the protective layer is sufficiently volatilized, and from the viewpoint of light transmission and color suppression of the protective layer, and further, the decomposition temperature of the resin base material when the resin base material is used as the base material. From the viewpoint of heating at the following temperature, it is preferable to heat at 40 ° C. to 200 ° C. Further, from the viewpoint of suppressing thermal deformation of the resin base material, it is more preferable to heat the resin base material to 40 ° C. to 120 ° C.
  • the heating time is not particularly limited, but is preferably 1 minute to 30 minutes.
  • the method for forming the protective layer is not particularly limited, and in addition to the above method for forming the protective layer by applying the protective layer forming coating liquid on the lower layer of the protective layer and drying it, a film is formed in advance. Examples thereof include a method of laminating the protective layer on the lower layer and a method of adhering the protective layer to the lower layer via an adhesive.
  • the laminate according to the present disclosure may further have a resin layer between the liquid crystal layer and the colored layer in order to ensure the flatness of the liquid crystal layer.
  • the resin layer is preferably a layer containing a resin of a different type from the protective layer. From the viewpoint of visibility, the resin layer is preferably a transparent resin layer, and more preferably a layer made of a transparent film.
  • the transparent film is not particularly limited as long as it has the required strength and scratch resistance.
  • "transparent" in a transparent film means that the total light transmittance is 85% or more. The total light transmittance of the transparent film can be measured by the same method as the total light transmittance of the colored layer described above.
  • the transparent film is preferably a film obtained by forming a transparent resin film, and specifically, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), acrylic resin, polycarbonate (PC), triacetyl cellulose (TAC). ), A resin film containing a resin such as a cycloolefin polymer (COP).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • acrylic resin polycarbonate
  • PC triacetyl cellulose
  • a resin film containing a resin such as a cycloolefin polymer (COP).
  • 60% by mass or more more (more preferably 80% by mass or more, still more preferably 100) of acrylic resin, polycarbonate, or polyethylene terephthalate is added to the total resin component contained in the transparent film.
  • a resin film containing (% by mass) is preferable.
  • a resin film containing an acrylic resin in an amount of 60% by mass or more (more preferably 80% by mass or more, still more preferably 100% by mass) with respect to all the resin components contained in the transparent film is more preferable.
  • the thickness of the resin layer is not particularly limited, but is preferably 50 ⁇ m to 150 ⁇ m.
  • a commercially available product may be used, and examples of the commercially available product include Acryprene (registered trademark) HBS010 (acrylic resin film, manufactured by Mitsubishi Chemical Co., Ltd.), Technoroy (registered trademark) S001G (acrylic resin film, etc.). Examples thereof include Sumitomo Chemical Co., Ltd.), C000 (polycarbonate resin film, manufactured by Sumitomo Chemical Co., Ltd.), C001 (acrylic resin / polycarbonate resin laminated film, manufactured by Sumitomo Chemical Co., Ltd.) and the like.
  • the method for forming the resin layer is not particularly limited, but a method of laminating a transparent film on the colored layer is preferable.
  • a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further increasing productivity can be used.
  • the laminator is provided with an arbitrary heatable roller such as a rubber roller and can be pressurized and heated. By heating from the laminator, at least one of the transparent film and the liquid crystal layer is partially melted, and the adhesion between the liquid crystal layer and the transparent film can be further improved.
  • the temperature at which the transparent film is laminated may be determined according to the material of the transparent film, the melting temperature of the liquid crystal layer, and the like, but the temperature of the transparent film is preferably a temperature that can be 60 ° C. to 150 ° C. , 65 ° C. to 130 ° C. is more preferable, and 70 ° C. to 100 ° C. is particularly preferable.
  • a linear pressure of 60 N / cm to 200 N / cm between the transparent film and the liquid crystal layer it is preferable to apply a linear pressure of 70 N / cm to 160 N / cm. It is particularly preferable to apply a linear pressure of 80 N / cm to 120 N / cm.
  • the laminate according to the present disclosure may have an adhesive layer from the viewpoint of easy attachment to other members (preferably other molding members) and enhancement of adhesion between layers.
  • the material of the pressure-sensitive adhesive layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a known pressure-sensitive adhesive or a pressure-sensitive adhesive layer containing an adhesive. From the viewpoint of light resistance, it is preferable that the adhesive layer contains an ultraviolet absorber. Examples of the ultraviolet absorber include those described later in the ultraviolet absorbing layer.
  • the pressure-sensitive adhesive examples include an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, and a silicone-based pressure-sensitive adhesive.
  • the adhesive "Characteristic evaluation of release paper / release film and adhesive tape and its control technology", Information Mechanism, 2004, Acrylic adhesive described in Chapter 2, UV (UV) curable adhesive Agents, silicone adhesives and the like.
  • the acrylic pressure-sensitive adhesive refers to a pressure-sensitive adhesive containing a polymer ((meth) acrylic polymer) of a (meth) acrylic monomer. When a pressure-sensitive adhesive is contained, a pressure-sensitive adhesive may be further contained.
  • the adhesive examples include urethane resin adhesives, polyester adhesives, acrylic resin adhesives, ethylene vinyl acetate resin adhesives, polyvinyl alcohol adhesives, polyamide adhesives, silicone adhesives and the like.
  • a urethane resin adhesive or a silicone adhesive is preferable from the viewpoint of higher adhesive strength.
  • the method for forming the adhesive layer is not particularly limited, and a method of laminating a protective film on which the adhesive layer is formed so that the adhesive layer and an adherend (for example, a liquid crystal layer, a base material, a colored layer, etc.) are in contact with each other.
  • a method of laminating the adhesive layer alone so as to be in contact with the adherend a method of applying an adhesive or a composition containing an adhesive onto the adherend, and the like.
  • the laminating method or coating method a method similar to the above-mentioned method of laminating a transparent film or a method of coating a composition for forming a colored layer is preferably mentioned.
  • the thickness of the adhesive layer in the laminated body is preferably 5 ⁇ m to 100 ⁇ m in terms of both adhesive strength and handleability.
  • the laminate according to the present disclosure preferably has an ultraviolet (UV) absorbing layer, and has an ultraviolet absorbing layer at a position where a liquid crystal layer cured via the ultraviolet absorbing layer can be visually recognized.
  • the ultraviolet absorbing layer is preferably a layer containing an ultraviolet absorber, and more preferably a layer containing an ultraviolet absorber and a binder polymer.
  • the ultraviolet absorber a known ultraviolet absorber can be used without particular limitation, and may be an organic compound or an inorganic compound. Examples of the ultraviolet absorber include triazine compounds, benzotriazole compounds, benzophenone compounds, salicylic acid compounds, metal oxide particles and the like.
  • the ultraviolet absorber may be a polymer having an ultraviolet absorbing structure
  • the polymer containing an ultraviolet absorbing structure includes at least a part of the structure such as a triazine compound, a benzotriazole compound, a benzophenone compound and a salicylate compound.
  • examples thereof include an acrylic resin containing a monomer unit derived from an acrylic acid ester compound.
  • the metal oxide particles include titanium oxide particles, zinc oxide particles, and cerium oxide particles.
  • the binder polymer include polyolefin, acrylic resin, polyester, fluororesin, siloxane resin, polyurethane and the like.
  • the ultraviolet absorbing layer is formed by applying each component contained in the ultraviolet absorbing layer and, if necessary, a coating liquid for forming an ultraviolet absorbing layer containing a solvent onto a surface substrate and drying it if necessary. ..
  • the thickness of the ultraviolet absorbing layer is not particularly limited, but is preferably 0.01 ⁇ m to 100 ⁇ m, more preferably 0.1 ⁇ m to 50 ⁇ m, and 0.5 ⁇ m from the viewpoint of light resistance and three-dimensional moldability. It is particularly preferably about 20 ⁇ m.
  • the laminate according to the present disclosure may include an optical mask layer described later for patterning the liquid crystal layer in the manufacturing process thereof.
  • the laminate according to the present disclosure is formed between the base material and the liquid crystal layer on a surface of the liquid crystal layer opposite to the side having the base material, a surface of the base material opposite to the side having the liquid crystal layer, and the like.
  • An optical mask layer may be provided.
  • the laminate according to the present disclosure may have layers other than those described above.
  • other layers include a reflective layer, a self-healing layer, an antistatic layer, an antifouling layer, an electromagnetic wave-proof layer, and a conductive layer, which are known layers in the laminated body.
  • the other layers in the laminate can be formed by known methods. For example, a method of applying a composition containing the components contained in these layers (composition for layer formation) in layers and drying the composition can be mentioned.
  • the laminate according to the present disclosure may have a cover film as the outermost layer for the purpose of preventing stains and the like.
  • a cover film any material having flexibility and good peelability can be used without particular limitation, and examples thereof include a resin film such as a polyethylene film.
  • the method of attaching the cover film is not particularly limited, and examples thereof include known attachment methods, such as a method of laminating a cover film on a protective layer.
  • the layer structure of the laminate according to the present disclosure is not particularly limited except that it has a base material and a cured liquid crystal layer.
  • the layer structure shown below may be used in a mode in which the laminate includes an optical mask layer. Preferred.
  • the outermost layer is visually recognized from the side of the layer described on the right side.
  • Layer structure 1 Base material / optical mask layer / cured liquid crystal layer
  • Layer structure 2 Optical mask layer / base material / cured liquid crystal layer
  • Layer structure 3 Colored layer / optical mask layer / cured liquid crystal layer / base material
  • layer structure 4 Colored Layer / Optical mask layer / Base material / Cured liquid crystal layer
  • the layer configuration 4 is most preferable from the viewpoint of patterning property and suppressing the visibility of the optical mask layer in the above exemplary embodiment.
  • the laminated body has the layers described on the right side as the outermost layer in each layer structure (that is, layer structure 1, layer structure 2, and layer structure) from the viewpoint of stickability to other members.
  • the laminate according to the present disclosure preferably contains an ultraviolet absorber in the adhesive layer or further has an ultraviolet absorbing layer.
  • the position of the ultraviolet absorbing layer is preferably a position where the cured liquid crystal layer can be visually recognized through the ultraviolet absorbing layer.
  • the laminate (in a certain embodiment, a decorative molded film) according to the present disclosure is not particularly limited in use and can be used for various purposes.
  • the interior / exterior of a housing panel of an electronic device, an electronic device, and an automobile examples include interior and exterior (for example, automobile exterior panels), interior and exterior of electric appliances, packaging containers, housings of electric appliances, covers of smartphones and tablets, and the like.
  • it may be preferably used for the housing panel of an electronic device, particularly the exterior of the housing panel of an electronic device, and the interior / exterior of an electric product.
  • the molded product according to the present disclosure is a molded product obtained by molding a laminate (in a certain embodiment, a decorative molding film) according to the present disclosure. Further, the molded product according to the present disclosure is preferably a molded product obtained by molding a laminate manufactured by the method for producing a laminate according to the present disclosure. Further, the molded product according to the present disclosure is not particularly limited in its manufacturing method, but is preferably a molded product manufactured by the molding method according to the present disclosure described later. The molded product according to the present disclosure is not particularly limited in its use, and can be used, for example, for the same purposes as those described above for the laminate according to the present disclosure.
  • the shape of the molded product according to the present disclosure is not particularly limited and may be any desired shape. Further, even if the molded product according to the present disclosure is obtained by molding only the shape of the laminated body according to the present disclosure, the laminated body is insert-molded as described later, and the laminated body is integrated on the surface of the resin molded product. It may be a modified molded product.
  • the housing panel of the electronic device according to the present disclosure may have a known member used for the housing panel of the electronic device, in addition to the molded product according to the present disclosure.
  • the production method of the laminate according to the present disclosure is not particularly limited, but it can be preferably produced by the method for producing the laminate according to the present disclosure described below.
  • the method for manufacturing a laminate according to the present disclosure is as follows. A base material, a liquid crystal layer containing a liquid crystal compound and a photoisomerized compound provided on the base material, and a plurality of patterns adjacent to at least one of the liquid crystal layer and the base material and having different light transmittances are surfaced.
  • a step of preparing a liquid crystal material having an optical mask layer formed in the inward direction (hereinafter, may be referred to as a "liquid crystal material preparation step"), and It includes a step of irradiating a liquid crystal layer with light via an optical mask layer to photoisomerize a photoisomerizing compound (hereinafter, may be referred to as a “photoisomerization step”).
  • the base material, the liquid crystal layer containing the liquid crystal compound and the photoisomerized compound provided on the base material, the liquid crystal layer and at least one of the base materials are adjacent to each other, and the light transmittances of the liquid crystal materials are different from each other.
  • This is a step of preparing a liquid crystal material having an optical mask layer in which a plurality of different patterns are formed in the in-plane direction.
  • the optical mask layer is adjacent to at least one of the liquid crystal layer and the base material, and a plurality of patterns having different light transmittances are formed in the in-plane direction.
  • the liquid crystal is irradiated with light through the optical mask layer to photoisomerize the photoisomerized compounds in the liquid crystal layer, thereby producing a plurality of patterns having different selective reflection wavelengths. It can be formed in the in-plane direction of the liquid crystal layer.
  • the optical mask layer By providing a region having a material for adjusting the light transmittance and a region having no material for adjusting the light transmittance in the optical mask layer, a plurality of patterns having different light transmittances are formed in the in-plane direction. It may be the one.
  • the optical mask layer may be provided with a region in which ink containing a component having light absorption or reflection is printed and a region in which ink is not printed.
  • the optical mask layer may be adjacent to the substrate.
  • a liquid crystal layer may be provided on a surface opposite to the side adjacent to the optical mask layer of the base material.
  • the optical mask layer may be adjacent to the liquid crystal layer.
  • the optical mask layer may be provided on the surface of the liquid crystal layer opposite to the side having the base material.
  • the optical mask layer may be adjacent to both the base material and the liquid crystal layer.
  • an optical mask layer may be provided between the base material and the liquid crystal layer.
  • the optical mask layer is preferably patterned with a difference in light transmittance in the wavelength range of 250 nm to 400 nm. That is, it is preferable that at least a part of the plurality of patterns of the optical mask layer has different light transmittances in the wavelength range of 250 nm to 400 nm.
  • the optical mask layer formed with a plurality of patterns having different light transmittances in the wavelength range of 250 to 400 nm causes 250 to 250 to The transmittance in the wavelength range of 400 nm changes in the in-plane direction.
  • the photoisomerization rate of the photoisomerizing compound in the liquid crystal layer can be controlled in the in-plane direction according to the change in the transmittance in the in-plane direction, and a plurality of patterns having a desired selective reflectance can be formed on the liquid crystal.
  • the plurality of patterns of the optical mask layer preferably have different light transmittances in the wavelength range of 280 nm to 380 nm, more preferably 300 nm to 350 nm.
  • the difference in maximum transmittance is preferably 30% or more, more preferably 50% or more, still more preferably 75% or more.
  • the plurality of patterns of the optical mask preferably differ in the maximum value of the light transmittance by 30% or more, more preferably 50% or more, and further preferably 75% or more.
  • the light transmittances in the wavelength range of 250 nm to 400 nm are different from each other in at least a part of the plurality of patterns of the optical mask layer, the light transmittances in other wavelength regions are not particularly limited.
  • the laminate according to the present disclosure preferably has a form in which the base color layer is visually recognized via a liquid crystal layer, and in order to improve the visibility of the base color layer, a plurality of patterns of the optical mask layer are surfaces in a wavelength range of 400 nm to 780 nm.
  • the average transmittance of the inside is preferably 50% or more.
  • the average transmittance is more preferably 65% or more, still more preferably 80% or more.
  • the light transmittance of the pattern of the optical mask layer can be measured with a spectrophotometer (for example, a spectrophotometer "UV-2100" manufactured by Shimadzu Corporation).
  • a spectrophotometer for example, a spectrophotometer "UV-2100" manufactured by Shimadzu Corporation.
  • the pattern of the optical mask layer preferably contains at least a component having light absorption or reflection in the wavelength range of 250 nm to 400 nm and a binder.
  • a component having light absorption in the wavelength range of 250 nm to 400 nm it is preferable to use a colorant such as a pigment or a dye, an ultraviolet absorber or the like. From the viewpoint of durability, it is preferable to use a pigment or an ultraviolet absorber.
  • the pigment that can be contained in the pattern of the optical mask layer is not limited, and known inorganic pigments, organic pigments and the like can be applied.
  • the inorganic pigment include white pigments such as titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide and barium sulfate, carbon black, titanium black, titanium carbon, iron oxide and graphite. Black pigments, iron oxide, barium yellow, cadmium red, chrome yellow and the like.
  • the inorganic pigments described in paragraphs 0015 and 0114 of JP-A-2005-7765 can also be applied.
  • organic pigments examples include phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, azo pigments such as azo red, azo yellow and azo orange, quinacridone pigments such as quinacridone red, cinacridone red and cincasha magenta, and perylene red.
  • Perylene pigments such as perylene maroon, carbazole violet, anthrapyridine, flavanthron yellow, isoindrin yellow, induslon blue, dibrom anzasron red, anthraquinone red, diketopyrrolopyrrole and the like can be mentioned.
  • Specific examples of organic pigments include C.I. I.
  • the organic pigment described in paragraph 093 of JP2009-256572 can also be applied.
  • the pigment may include a pigment having light transmission and light reflection (so-called brilliant pigment).
  • the glitter pigment include metal glitter pigments such as aluminum, copper, zinc, iron, nickel, tin, aluminum oxide, and alloys thereof, interfering mica pigments, white mica pigments, graphite pigments, and glass flake pigments. Can be mentioned.
  • the bright pigment may be uncolored or colored. When the bright pigment is exposed in the molding of the laminate, it is preferably used within a range that does not interfere with the curing due to the exposure.
  • the colorant that can be contained in the pattern of the optical mask layer may be used alone or in combination of two or more. Further, when two or more kinds of colorants are used, an inorganic pigment and an organic pigment may be combined.
  • the content of the colorant in the pattern of the optical mask layer is preferably 1% by mass to 50% by mass with respect to the total mass of the pattern of the optical mask layer from the viewpoint of the development of the desired color and the suitability for molding. 5% by mass to 50% by mass is more preferable, and 10% by mass to 40% by mass is particularly preferable.
  • the ultraviolet absorber that can be contained in the pattern of the optical mask layer a known ultraviolet absorber can be used without particular limitation, and may be an organic compound or an inorganic compound.
  • the ultraviolet absorber include triazine compounds, benzotriazole compounds, benzophenone compounds, salicylic acid compounds, metal oxide particles and the like.
  • the ultraviolet absorber may be a polymer having an ultraviolet absorbing structure, and the polymer containing an ultraviolet absorbing structure includes at least a part of the structure such as a triazine compound, a benzotriazole compound, a benzophenone compound and a salicylate compound.
  • examples thereof include an acrylic resin containing a monomer unit derived from an acrylic acid ester compound. Particularly preferred is a triazine compound.
  • the metal oxide particles include titanium oxide particles, zinc oxide particles, and cerium oxide particles.
  • binder polymer examples include polyolefin, acrylic resin, polyester, fluororesin, siloxane resin, polyurethane and the like.
  • the optical mask layer may contain other additives other than those described above, if necessary.
  • additives known additives can be used, and examples thereof include surfactants, polymerization inhibitors, antioxidants, horizontal alignment agents, and light stabilizers.
  • the distance between the optical mask layer and the liquid crystal layer is short.
  • the distance is preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably 75 ⁇ m or less, and particularly preferably 50 ⁇ m or less.
  • the optical mask layer forming step is not particularly limited, and may be a step of applying (for example, coating) a composition containing the above-mentioned components to the base material or the liquid crystal layer.
  • the pattern of the optical mask layer is preferably formed by a printing method. Examples of the printing method include a direct gravure printing method, a reverse gravure coating printing method, a screen printing method, a flexographic printing method, an offset printing method, and an inkjet printing method.
  • a direct gravure printing method, a reverse gravure coating printing method, and a screen printing method are preferable, and a direct gravure printing method is more preferable.
  • the optical mask layer is formed, for example, by printing a printing ink containing a component having light absorption in the wavelength range of 250 nm to 400 nm, a binder, and a solvent by the above printing method and drying it if necessary. It's okay.
  • the solvent is not particularly limited, and examples thereof include those described later in the liquid crystal composition.
  • the optical mask layer is a portion formed with an ink containing a component 1 having reflection or light absorption in the wavelength range of 250 nm to 400 nm, and light absorption in the wavelength range of 250 nm to 400 nm from this component, or light absorption in the wavelength range of 250 nm to 400 nm. It is also preferable to include both portions patterned with ink containing components having low reflectance.
  • light absorption or reflectance in the wavelength range of 250 nm to 400 nm is higher than that of this component in a portion where the pattern is not formed by ink containing a component having light absorption or reflection or the printing film thickness is small.
  • the pattern is formed with an ink containing a low-wavelength component, the film thickness of the pattern of the optical mask layer becomes uniform, and the take-up property and handleability of the base material are improved.
  • a liquid crystal layer containing a liquid crystal compound and a photoisomerized compound is provided on the base material.
  • the liquid crystal layer changes the color depending on the viewing angle, and the visible color itself. Can be adjusted.
  • the pitch of the spiral structure can be easily adjusted by changing the amount of the chiral agent added. Specifically, Fujifilm Research Report No. 50 (2005) p. There is a detailed description in 60-63. Further, the pitch of the spiral structure can be adjusted by conditions such as temperature, illuminance, and irradiation time when fixing the cholesteric orientation state.
  • the cured liquid crystal layer after the curing step described later is preferably a cholesteric liquid crystal compound fixed in a cholesteric orientation state.
  • the cholesteric orientation state may include both an orientation state that reflects right circularly polarized light and an orientation state that reflects left circularly polarized light.
  • the cholesteric liquid crystal compound is not particularly limited, and various known compounds can be used.
  • the liquid crystal layer preferably contains a cholesteric liquid crystal compound.
  • the cholesteric liquid crystal compound include a rod-shaped type and a disk-shaped type depending on its shape. Further, low molecular weight type and high molecular weight type are mentioned respectively.
  • the term "polymer" in a cholesteric liquid crystal compound refers to a compound having a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, Masao Doi, p. 2, Iwanami Shoten, 1992). In the present disclosure, any cholesteric liquid crystal compound can be used, but it is preferable to use a rod-shaped cholesteric liquid crystal compound.
  • the low-molecular-weight cholesteric liquid crystal compound has a group that reacts with heat, light, etc., and as a result, it is polymerized or crosslinked by the reaction with heat, light, etc. It may be a layer.
  • the cholesteric liquid crystal compound two or more kinds of rod-shaped cholesteric liquid crystal compounds, two or more kinds of disk-shaped liquid crystal compounds, or a mixture of a rod-shaped cholesteric liquid crystal compound and a disk-shaped cholesteric liquid crystal compound may be used. Since changes in temperature and humidity can be reduced, it is more preferable to use a rod-shaped cholesteric liquid crystal compound or a disk-shaped cholesteric liquid crystal compound having a reactive group, and at least one of them has two or more reactive groups in one liquid crystal molecule. It is more preferable to have. In the case of a mixture of two or more cholesteric liquid crystal compounds, it is preferable that at least one has two or more reactive groups.
  • a cholesteric liquid crystal compound having two or more kinds of reactive groups having different cross-linking mechanisms When the above compound is used, an optically anisotropic layer containing a polymer having an unreacted reactive group is produced by selecting conditions and polymerizing only a part of two or more kinds of reactive groups. Is preferable.
  • the cross-linking mechanism is not particularly limited such as condensation reaction, hydrogen bond, and polymerization, but at least one of the above two or more reactive groups is preferably cross-linked, and it is more preferable to use two or more different polymerizations. preferable.
  • the compounds having two or more types of reactive groups having different cross-linking mechanisms in the present disclosure are compounds that can be cross-linked using stepwise different cross-linking reaction steps, and in each step of the cross-linking reaction step, each cross-linking mechanism is used.
  • the corresponding reactive group reacts as a functional group.
  • a polymer such as polyvinyl alcohol having a hydroxy group in the side chain
  • two or more types are different.
  • the polymer has different reactive groups, and then the reactive groups can be crosslinked stepwise.
  • the reactive group is preferably a polymerizable group.
  • the polymerizable group include a radically polymerizable group and a cationically polymerizable group. Above all, it is particularly preferable to use a cholesteric liquid crystal compound having two or more kinds of polymerizable groups.
  • the reaction conditions for stepwise cross-linking may be any of different temperatures, different wavelengths of light (irradiation rays), and different polymerization mechanisms, but it is preferable to use different polymerization mechanisms from the viewpoint of easy separation of reactions. It is more preferable to control depending on the type of polymerization initiator used.
  • As the combination of the polymerizable group a combination of a radically polymerizable group and a cationically polymerizable group is preferable.
  • the radically polymerizable group is a vinyl group or a (meth) acrylic group and the cationically polymerizable group is an epoxy group, an oxetanyl group or a vinyl ether group is particularly preferable because the reactivity can be easily controlled.
  • the cholesteric liquid crystal compound preferably has a radically polymerizable group from the viewpoint of reactivity and ease of fixing the pitch of the spiral structure. Examples of reactive groups are shown below.
  • Et represents an ethyl group
  • n-Pr represents an n-propyl group.
  • rod-shaped cholesteric liquid crystal compound examples include azomethine compounds, azoxy compounds, cyanobiphenyl compounds, cyanophenyl ester compounds, benzoic acid ester compounds, cyclohexanecarboxylic acid phenyl ester compounds, cyanophenylcyclohexane compounds, cyano-substituted phenylpyrimidine compounds, and alkoxy-substituted phenylpyrimidine compounds.
  • Phenyldioxane compounds, trans compounds and alkenylcyclohexylbenzonitrile compounds are preferred.
  • the polymer cholesteric liquid crystal compound is a polymer compound obtained by polymerizing a rod-shaped cholesteric liquid crystal compound having a low molecular weight reactive group.
  • Examples of the rod-shaped cholesteric liquid crystal compound include those described in JP-A-2008-281989, JP-A-11-513019 (International Publication No. 97/00600) or JP-A-2006-526165.
  • rod-shaped cholesteric liquid crystal compounds are shown below, but the present invention is not limited to these.
  • the compounds shown below can be synthesized by the method described in JP-A No. 11-513019 (International Publication No. 97/00600).
  • disk-shaped cholesteric liquid crystal compound examples include a low molecular weight disk-shaped cholesteric liquid crystal compound such as a monomer, and a polymerizable disk-shaped cholesteric liquid crystal compound.
  • disk-shaped cholesteric liquid crystal compounds include C.I. Research report by Destrade et al., Mol. Cryst. Benzene Derivatives, C.I., p. 71, p. 111 (1981). Research report by Destrade et al., Mol. Cryst. Volume 122, p. 141 (1985), Physicslett, A, 78, p. 82 (1990), Turxene Derivatives, B. et al.
  • the disk-shaped cholesteric liquid crystal compound has a structure in which the above-mentioned various structures are used as a disk-shaped mother nucleus at the center of the molecule, and groups (L) such as a linear alkyl group, an alkoxy group, and a substituted benzoyloxy group are radially substituted. Yes, it exhibits liquid crystallinity, and includes what is generally called a disk-shaped liquid crystal. However, when such an aggregate of molecules is uniformly oriented, it exhibits negative uniaxiality, but is not limited to this description. Examples of the disk-shaped cholesteric liquid crystal compound include those described in paragraphs 0061 to 0075 of JP-A-2008-281989. When a disk-shaped cholesteric liquid crystal compound having a reactive group is used as the cholesteric liquid crystal compound, it is fixed in any of horizontal orientation, vertical orientation, inclined orientation, and torsional orientation in the cured liquid crystal layer described later. You may.
  • a polymerizable monomer may be added in order to promote cross-linking of the cholesteric liquid crystal compound.
  • a monomer or oligomer having two or more ethylenically unsaturated bonds and addition-polymerizing by irradiation with light can be used.
  • Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule.
  • Examples are monofunctional acrylates or monofunctional methacrylates such as polyethylene glycol mono (meth) acrylates, polypropylene glycol mono (meth) acrylates and phenoxyethyl (meth) acrylates; polyethylene glycol di (meth) acrylates, polypropylene glycol di (meth) acrylates.
  • polyester acrylate compound described in Japanese Patent Publication No. 52-30490; a polyfunctional acrylic or methacrylate such as an epoxy acrylate compound which is a reaction product of an epoxy resin and (meth) acrylic acid can be mentioned.
  • trimethylolpropane tri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
  • polymerizable compound B described in JP-A-11-133600 can also be mentioned as a suitable compound. These monomers or oligomers may be used alone or in admixture of two or more.
  • a cationically polymerizable monomer can also be used.
  • Japanese Patent Application Laid-Open No. 6-9714 Japanese Patent Application Laid-Open No. 2001-31892, Japanese Patent Application Laid-Open No. 2001-40068, Japanese Patent Application Laid-Open No. 2001-55507, Japanese Patent Application Laid-Open No. 2001-310938, Japanese Patent Application Laid-Open No. 2001-310937, Japanese Patent Application Laid-Open No. 2001-220526
  • examples thereof include epoxy compounds, vinyl ether compounds, and oxetane compounds exemplified in each of the publications of the above.
  • Examples of the epoxy compound include the following aromatic epoxides, alicyclic epoxides, aliphatic epoxides and the like.
  • Examples of the aromatic epoxide include di or polyglycidyl ether of bisphenol A or its alkylene oxide adduct, di or polyglycidyl ether of hydrogenated bisphenol A or its alkylene oxide adduct, novolak type epoxy resin and the like. ..
  • examples of the alkylene oxide include ethylene oxide and propylene oxide.
  • the alicyclic epoxide is a cyclohexene oxide obtained by epoxidizing a compound having a cycloalkane ring such as at least one cyclohexene or cyclopentene ring with an appropriate oxidizing agent such as hydrogen peroxide or peracid.
  • an appropriate oxidizing agent such as hydrogen peroxide or peracid.
  • a cyclopentene oxide-containing compound can be mentioned.
  • Preferred aliphatic epoxides include di- or polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and typical examples thereof include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, or diglycidyl ether of propylene glycol.
  • Diglycidyl ether of alkylene glycol such as diglycidyl ether of 1,6-hexanediol, polyglycidyl ether of polyhydric alcohol such as diglycidyl ether of glycerin or its alkylene oxide adduct, polyethylene glycol or its alkylene oxide adduct Diglycidyl ether, polypropylene glycol or diglycidyl ether of polyalkylene glycol such as diglycidyl ether of alkylene oxide adduct thereof.
  • alkylene oxide include ethylene oxide and propylene oxide.
  • a monofunctional or bifunctional oxetane monomer can also be used.
  • 3-ethyl-3-hydroxymethyloxetane (trade name OXT101 manufactured by Toa Synthetic Co., Ltd.), 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene (OXT121, etc.), 3 -Ethyl-3- (phenoxymethyl) oxetane (such as OXT211), di (1-ethyl-3-oxetanyl) methyl ether (such as OXT221), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane ( The same OXT212 etc.) can be preferably used, and in particular, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, di (1
  • the combination of the liquid crystal compounds is not particularly limited, and all of the cholesteric liquid crystal compounds are laminated as rod-shaped cholesteric liquid crystal compounds.
  • the body or cholesteric liquid crystal compound either a laminate of a layer containing a disk-shaped cholesteric liquid crystal compound and a layer containing a rod-shaped cholesteric liquid crystal compound, or a laminate of layers in which all of the cholesteric liquid crystal compounds are disk-shaped cholesteric liquid crystal compounds. It may be.
  • the combination of the orientation states of each layer is not particularly limited, and the cured liquid crystal layers having the same orientation state may be laminated, or the cured liquid crystal layers having different orientation states may be laminated.
  • the liquid crystal layer may contain one kind of cholesteric liquid crystal compound alone or two or more kinds.
  • the content of the cholesteric liquid crystal compound is preferably 30% by mass or more and 99% by mass or less, and more preferably 40% by mass or more and 99% by mass or less, based on the total mass of the liquid crystal layer from the viewpoint of design. , 60% by mass or more and 99% by mass or less, and particularly preferably 70% by mass or more and 98% by mass or less.
  • the crosslink density due to the radically polymerizable group in the cured liquid crystal layer in the laminate according to the present disclosure is determined by fixing the liquid crystal orientation, three-dimensional moldability, and molding. From the viewpoint of suppressing the change in reflectance later, it is preferably 0.05 mol / L or more and 1 mol / L or less, more preferably 0.1 mol / L or more and 0.5 mol / L or less, and 0.15 mol / L or less.
  • the liquid crystal layer contains a photoisomerizing compound.
  • the photoisomerized compound may be a compound capable of photoisomerization, but from the viewpoint of suppressing the change in reflectance after molding and maintaining the isomerized structure, the photoisomerized compound may be a compound whose three-dimensional structure changes by exposure. preferable.
  • the photoisomerization structure of the photoisomerizable compound to be photoisomerized is not particularly limited, but it is possible to suppress the change in reflectance after molding, facilitate photoisomerization, and maintain the isomerized structure.
  • the structure changes the three-dimensional structure by exposure, it is more preferable to have an ethylenically unsaturated bond having two or more substitutions in which the EZ configuration is isomerized by exposure, and the EZ configuration is isomerized by exposure. It is particularly preferred to have a substituted ethylenically unsaturated bond.
  • the isomerization of the EZ configuration in the present disclosure also includes cis-trans isomerization.
  • the disubstituted ethylenically unsaturated bond is preferably an ethylenically unsaturated bond in which an aromatic group and an ester bond are substituted.
  • the photoisomerization compound may have only one photoisomerization structure or two or more photoisomerization structures, but suppresses the change in reflectance after molding, ease of photoisomerization, and isomerization. From the viewpoint of maintainability of the chemical structure, it is preferable to have two or more, more preferably two to four, and particularly preferably two.
  • the portion of the liquid crystal layer in which the photoisomerized compound is photoisomerized and the photoisomerized compound are used.
  • the portion where is not photoisomerized can be confirmed by the presence or absence of the non-polymerized photoisomerized compound.
  • the photoisomerizing compound is preferably a photoisomerizing compound that also acts as a chiral agent described later.
  • the photoisomerization compound that also acts as a chiral agent is preferably a chiral agent having a molar extinction coefficient of 30,000 or more at a wavelength of 313 nm.
  • a compound represented by the following formula (CH1) is preferably mentioned as the photoisomerization compound that also acts as a chiral agent.
  • the compound represented by the following formula (CH1) can change the orientation structure such as the spiral pitch (twisting force, spiral twist angle) of the cholesteric liquid crystal phase according to the amount of light at the time of light irradiation.
  • the compound represented by the following formula (CH1) is a compound in which the EZ arrangement in the two ethylenically unsaturated bonds can be isomerized by exposure.
  • Ar CH1 and Ar CH2 independently represent an aryl group or a heteroaromatic ring group, and R CH1 and R CH2 independently represent a hydrogen atom or a cyano group, respectively.
  • Ar CH1 and Ar CH2 in the formula (CH1) are independently aryl groups.
  • the aryl group in Ar CH1 and Ar CH2 of the formula (CH1) may have a substituent, preferably having a total carbon number of 6 to 40, and more preferably a total carbon number of 6 to 30.
  • the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a hydroxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carboxy group, a cyano group, or a heterocycle.
  • the 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. It is preferable that R CH1 and R CH2 in the formula (CH1) are independently hydrogen atoms.
  • Ar CH1 and Ar CH2 an aryl group represented by the following formula (CH2) or formula (CH3) is preferable.
  • R CH3 and R CH 4 are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, alkoxy group, hydroxy group, and acyl.
  • a group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carboxy group, or a cyano group, and L CH1 and L CH2 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 the formula (CH1).
  • R CH3 and R CH4 in the formula (CH2) and the formula (CH3) are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, alkoxy group, hydroxy group, alkoxycarbonyl group, aryloxycarbonyl group, respectively.
  • an acyloxy group is preferable, an alkoxy group, a hydroxy group, or an acyloxy group is more preferable, and an alkoxy group is particularly preferable.
  • L CH1 and L CH2 in the formula (CH2) and the formula (CH3) are each independently preferably an alkoxy group having 1 to 10 carbon atoms or a hydroxy group.
  • the nCH1 in the formula (CH2) is preferably 0 or 1.
  • the nCH2 in the formula (CH3) is preferably 0 or 1.
  • the heteroaromatic ring group in Ar CH1 and Ar CH2 of the formula (CH1) may have a substituent, and has a total carbon number of 4 to 40, more preferably a total carbon number of 4 to 30.
  • a substituent 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 is preferable.
  • a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an acyloxy group is more preferable.
  • a heteroaromatic ring group a pyridyl group, a pyrimidinyl group, a frill group, or a benzofuranyl group is preferable, and a pyridyl group or a pyrimidinyl group is more preferable.
  • the compounds described below are preferably mentioned.
  • Bu represents an n-butyl group.
  • the following compounds are compounds in which the conformation of each ethylenically unsaturated bond is E-form (trans-form), but changes to Z-form (cis-form) by exposure.
  • the liquid crystal layer may contain one kind of photoisomerizing compound alone or two or more kinds.
  • the content of the photoisomerized compound is not particularly limited, but is preferably 1% by mass or more and 20% by mass or less with respect to the total mass of the liquid crystal layer from the viewpoint of suppressing the change in reflectance after molding, and is preferably 2% by mass. It is more preferably% or more and 10% by mass or less, further preferably 3% by mass or more and 9% by mass or less, and particularly preferably 4% by mass or more and 8% by mass or less.
  • the liquid crystal layer preferably contains a chiral agent (optically active compound) from the viewpoint of easy formation of the liquid crystal layer and easy adjustment of the pitch of the spiral structure.
  • the chiral agent has a function of inducing a helical structure in the liquid crystal layer.
  • the chiral agent has a function of inducing a helical structure of a cholesteric liquid crystal phase. Since the chiral compound has a different sense or spiral pitch of the induced spiral depending on the compound, it may be selected according to the purpose.
  • the chiral agent a known compound can be used, but it is preferable to have a cinnamoyl group.
  • Examples of chiral agents include liquid crystal device handbooks (Chapter 3, 4-3, TN, STN chiral agents, 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-2010-1 Examples of the compounds described in Japanese Patent Application Laid-Open No. 81852 and Japanese Patent Application Laid-Open No. 2014-034581 are made.
  • the chiral agent preferably contains an asymmetric carbon atom, but an axial asymmetric compound or a surface asymmetric compound that does not contain an asymmetric carbon atom can also be used as the chiral agent.
  • axial asymmetric compounds or surface asymmetric compounds include binaphthyl, helicene, paracyclophane and derivatives thereof.
  • the chiral agent may have a polymerizable group.
  • the chiral agent having a polymerizable group polymerizable chiral agent
  • the cholesteric liquid crystal compound having a polymerizable group polymerizable cholesteric liquid crystal compound
  • the polymerizable group of the polymerizable chiral agent is preferably a group of the same type as the polymerizable group of the polymerizable cholesteric liquid crystal compound.
  • the polymerizable group of the chiral agent is preferably an ethylenically unsaturated group, an epoxy group or an aziridinyl group, more preferably an ethylenically unsaturated group, and particularly preferably an ethylenically unsaturated polymerizable group. ..
  • the chiral agent may be a cholestec liquid crystal compound.
  • the liquid crystal layer is a photoisomerized compound that acts as a chiral agent and also as the above-mentioned chiral agent from the viewpoints of ease of forming a liquid crystal layer, easy adjustment of the pitch of a spiral structure, and suppression of a change in reflectance after molding. It is preferable to contain at least one kind, and it is more preferable to contain at least one kind of the compound represented by the above formula (CH1).
  • an isosorbide derivative As the chiral agent, an isosorbide derivative, an isomannide derivative, a binaphthyl derivative and the like can be preferably used.
  • an isosorbide derivative a commercially available product such as LC-756 manufactured by BASF may be used.
  • the liquid crystal layer may contain one kind of chiral agent alone or two or more kinds.
  • the content of the chiral agent can be appropriately selected according to the structure of the cholesteric liquid crystal compound to be used and the desired pitch of the spiral structure, but the ease of forming the liquid crystal layer, the ease of adjusting the pitch of the spiral structure, and the molding From the viewpoint of suppressing the change in reflectance later, it is preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 10% by mass or less, and 3% by mass with respect to the total mass of the liquid crystal layer. It is more preferably 9% by mass or less, and particularly preferably 4% by mass or more and 8% by mass or less.
  • the content of the chiral agent having a polymerizable group is preferably 0.2% by mass or more and 15% by mass or less with respect to the total mass of the liquid crystal layer from the viewpoint of suppressing the change in reflectance after molding, and is 0. It is more preferably 5.5% by mass or more and 10% by mass or less, further preferably 1% by mass or more and 8% by mass or less, and particularly preferably 1.5% by mass or more and 5% by mass or less. Further, when a chiral agent having no polymerizable group is contained, the content of the chiral agent having no polymerizable group is 0.2 with respect to the total mass of the liquid crystal layer from the viewpoint of suppressing the change in reflectance after molding.
  • the pitch of the spiral structure of the cholesteric liquid crystal in the liquid crystal layer, and the selective reflection wavelength and its range described later can be easily determined by adjusting not only the type of the cholesteric liquid crystal compound to be used but also the content of the chiral agent. Can be changed. Although it cannot be said unconditionally, when the content of the chiral agent in the liquid crystal layer is doubled, the pitch may be halved and the center value of the selective reflection wavelength may be halved.
  • the liquid crystal layer preferably contains a polymerization initiator, and more preferably contains a photopolymerization initiator.
  • a polymerization initiator a known polymerization initiator can be used.
  • the polymerization initiator is preferably a photopolymerization initiator capable of initiating a polymerization reaction by irradiation with ultraviolet rays. Examples of photopolymerization initiators include ⁇ -carbonyl compounds (described in US Pat. No. 2,376,661 and US Pat. No. 2,376,670), acyloin ether compounds (described in US Pat. No. 2,448,828), and ⁇ -hydrogen substitution. Aromatic acidoine compounds (described in US Pat. No.
  • the photoradical polymerization initiator a known one can be used.
  • the photoradical polymerization initiator include ⁇ -hydroxyalkylphenone compounds, ⁇ -aminoalkylphenone compounds, acylphosphine oxide compounds, and thioxanthone compounds (for example, “Kayacure DETX” (2,4-diethyl) manufactured by Nippon Kayaku Co., Ltd. Thioxanthone)), oxime ester compounds and the like are preferably mentioned.
  • the photocationic polymerization initiator a known one can be used.
  • Preferred examples of the photocationic polymerization initiator include iodonium salt compounds and sulfonium salt compounds.
  • the liquid crystal layer may contain one kind of polymerization initiator alone or two or more kinds.
  • the content of the polymerization initiator can be appropriately selected according to the structure of the cholesteric liquid crystal compound to be used and the desired pitch of the spiral structure, but the pitch of the spiral structure can be easily adjusted, the polymerization rate, and the liquid crystal after curing. From the viewpoint of layer strength, it is preferably 0.05% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less, based on the total mass of the liquid crystal layer. It is more preferably 1% by mass or more and 4% by mass or less, and particularly preferably 0.2% by mass or more and 3% by mass or less.
  • the liquid crystal layer may contain a cross-linking agent in order to improve the strength and durability of the liquid crystal layer after curing.
  • a cross-linking agent one that cures with ultraviolet rays, heat, humidity or the like can be preferably used.
  • the cross-linking agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polyfunctional acrylate compound such as trimethylolpropane tri (meth) acrylate or pentaerythritol tri (meth) acrylate; glycidyl (meth) acrylate.
  • the liquid crystal layer may contain one type of cross-linking agent alone or two or more types.
  • the content of the cross-linking agent is preferably 1% by mass or more and 20% by mass or less, and 3% by mass or more and 15% by mass or less, based on the total mass of the liquid crystal layer. Is more preferable.
  • the liquid crystal layer preferably contains a polyfunctional polymerizable compound from the viewpoint of suppressing a change in reflectance after molding.
  • the polyfunctional polymerizable compound include cholesteric liquid crystal compounds having two or more ethylenically unsaturated groups and no cyclic ether groups in the above-mentioned compounds, and ethylene having two or more cyclic ether groups. Cholesteric liquid crystal compound having no sex unsaturated group, cholesteric liquid crystal compound having two or more ethylenic unsaturated groups and two or more cyclic ether groups, chiral agent having two or more polymerizable groups, the above-mentioned cross-linking. Agents can be mentioned.
  • a (meth) acrylic group is preferably mentioned, and a (meth) acryloyl group is more preferably mentioned.
  • a (meth) acryloyl group is more preferably mentioned.
  • the cyclic ether group an epoxy group and an oxetanyl group are preferably mentioned, and an oxetanyl group is more preferably mentioned.
  • the polyfunctional polymerizable compound a cholesteric liquid crystal compound having two or more ethylenically unsaturated groups and not having a cyclic ether group, and having two or more cyclic ether groups and having an ethylenically unsaturated group.
  • the content of the polyfunctional polymerizable compound is preferably 0.5% by mass or more and 70% by mass or less with respect to the total mass of the liquid crystal layer from the viewpoint of suppressing the change in reflectance after molding, and is preferably 1% by mass or more and 50% by mass. It is more preferably 5% by mass or less, further preferably 1.5% by mass or more and 20% by mass or less, and particularly preferably 2% by mass or more and 10% by mass or less.
  • the liquid crystal layer may contain other additives other than those described above, if necessary.
  • additives known additives can be used, such as surfactants, polymerization inhibitors, antioxidants, horizontal alignment agents, ultraviolet absorbers, light stabilizers, colorants, metal oxide particles, etc. Can be mentioned.
  • the liquid crystal layer forming step is not particularly limited, and is, for example, a step of forming a film (liquid crystal layer) formed by applying (for example, coating) a liquid crystal composition containing a liquid crystal compound and a photoisomerizing compound to a substrate. Is preferable.
  • the liquid crystal composition may contain a solvent.
  • the solvent is not particularly limited and may be appropriately selected depending on the intended purpose, but an organic solvent is preferably used.
  • the organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a ketone compound such as methyl ethyl ketone or methyl isobutyl ketone, an alkyl halide compound, an amide compound, a sulfoxide compound, a heterocyclic compound or a hydrocarbon compound can be selected.
  • Estel compounds, ether compounds, alcohol compounds and the like These may be used alone or in combination of two or more.
  • a ketone compound is particularly preferable in consideration of the burden on the environment.
  • the above-mentioned component may function as a solvent.
  • the content of the solvent is preferably 40% by mass to 90% by mass, more preferably 50% by mass to 80% by mass, based on the total amount of the liquid crystal composition. preferable.
  • the above-mentioned solvent derived from the liquid crystal composition may remain in the cured liquid crystal layer, and the cured liquid crystal layer contains a solvent. You may be.
  • the content of the solvent in the liquid crystal layer after curing is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 2% by mass or less, based on the total mass of the liquid crystal layer. It is preferably 1% by mass or less, and particularly preferably 1% by mass or less.
  • the method for preparing the liquid crystal composition is not particularly limited, and for example, the liquid crystal composition may be prepared by a method of mixing each component such as a liquid crystal compound.
  • the liquid crystal layer is formed by making a liquid crystal composition containing each of the above components into a solution state with a solvent, or making the liquid crystal composition into a liquid material such as a melt by heating, using a roll coating method, a gravure printing method, or a spin coating method. It can be performed by a method of developing by an appropriate method such as a method. Further, it can be carried out by various methods such as a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method. It is also possible to form a coating film by ejecting the liquid crystal composition from a nozzle using an inkjet device.
  • the liquid crystal composition is applied and then dried by a known method.
  • it may be dried by leaving it to stand, or it may be dried by heating.
  • the amount of the liquid crystal composition to be applied may be appropriately set in consideration of the liquid crystal layer after drying.
  • the liquid crystal compound in the liquid crystal layer is oriented.
  • the photoisomerization step is a step of irradiating the liquid crystal layer with light via the optical mask layer to photoisomerize the photoisomerization compound contained in the liquid crystal layer. Thereby, a plurality of patterns having different selective reflection wavelengths can be formed in the in-plane direction of the liquid crystal layer.
  • the isomerization ratio of the photoisomerization compound may be changed according to the shape to be molded.
  • a portion having an isomerization ratio of 0% and a portion having an isomerization ratio of 100% may be formed on the liquid crystal layer, or a portion having an isomerization ratio changing from 0% to 100% may be formed on the liquid crystal layer.
  • a portion where the isomerization ratio is 0% and a portion where the isomerization ratio changes from 50% to 100% may be formed on the liquid crystal layer.
  • the photoisomerization step it is preferable to isomerize the photoisomerization compound by exposing only a part of the liquid crystal layer. It is also possible to control the isomerization ratio according to the exposure intensity.
  • the wavelength of the light to be photoisomerized in the photoisomerization step is not particularly limited and may be appropriately selected depending on the photoisomerization compound.
  • the light to be exposed in the photoisomerization step may be light containing a wavelength capable of photoisomerization, but it is preferable to photoisomerize using at least light in a wavelength range of 400 nm or less, and a wavelength range of 360 nm or less.
  • a known means and a known method can be used for adjusting the exposure wavelength in the photoisomerization step.
  • a method using an optical filter, a method using two or more types of optical filters, a method using a light source having a specific wavelength, and the like can be mentioned.
  • the photoisomerization step it is preferable to perform the above exposure with light in a wavelength range in which the polymerization initiator does not generate a polymerization initiator in the liquid crystal layer.
  • an optical mask layer that transmits light in a wavelength range in which photoisomerization of a photoisomeric compound occurs and shields light in a wavelength range in which a polymerization initiator is generated from a photopolymerization initiator can be preferably used.
  • the light source in the photoisomerization step examples include an ultra-high pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp.
  • a light emitting diode or the like capable of irradiating light having a narrow wavelength range can also be used.
  • a mask other than the optical mask layer may or may not be used, if necessary.
  • Photoisomerization as the exposure amount in the step is not particularly limited, may be appropriately set, is preferably 5mJ / cm 2 ⁇ 2,000mJ / cm 2, at 10mJ / cm 2 ⁇ 1,000mJ / cm 2 More preferably. Further, the exposure amount may be changed in each part of the liquid crystal layer according to the desired isomerization ratio.
  • the heating temperature is not particularly limited and may be selected depending on the photoisomerization compound to be used and the like, and examples thereof include 60 ° C. to 120 ° C.
  • the exposure method is not particularly limited as long as photoisomerization is possible, but for example, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 are preferably used in the present disclosure. Can be done.
  • the distance is preferably 2 mm or less, more preferably 1 mm or less, still more preferably 0.5 mm or less, and particularly preferably 0.1 mm or less.
  • the method for producing a laminate according to the present disclosure preferably includes a step of curing the liquid crystal layer after the photoisomerization step (hereinafter, also referred to as “curing step”).
  • curing step By the above curing, it becomes easy to maintain and fix the molecular orientation state of the liquid crystal compound.
  • the above curing is preferably carried out by a polymerization reaction of a polymerizable group such as an ethylenically unsaturated group or a cyclic ether group contained in the compound contained in the liquid crystal layer. Further, the above-mentioned curing may be performed by exposure or by heat.
  • the curing is preferably performed by exposure.
  • the liquid crystal layer preferably contains a photopolymerization initiator.
  • the light source for exposure it can be appropriately selected and used according to the photopolymerization initiator.
  • a light source capable of irradiating light in a wavelength range for example, 365 nm, 405 nm
  • specific examples thereof include an ultra-high pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp.
  • the exposure amount is not particularly limited and may be appropriately set, is preferably 5mJ / cm 2 ⁇ 2,000mJ / cm 2, more preferably 10mJ / cm 2 ⁇ 1,000mJ / cm 2 ..
  • the heating temperature is not particularly limited and may be selected according to the composition of the liquid crystal layer to be cured, and examples thereof include 60 ° C. to 120 ° C. Further, not only the liquid crystal layer may be formed by the above exposure, but also other layers such as a colored layer may be cured by the exposure as needed. Further, as an exposure method, for example, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be preferably used in the present disclosure.
  • the time between the photoisomerization step and the curing step is preferably 0.01 seconds or more and 10 minutes or less. More preferably, it is 0.1 seconds or more and 5 minutes or less, more preferably 0.2 seconds or more and 1 minute or less, and particularly preferably 0.5 seconds or more and 30 seconds or less.
  • the time between the photoisomerization step and the curing step is within the above range, the liquid crystal compound is reoriented according to the photoisomerization in 0.01 seconds or more, and a pattern in which the reflected light is patterned is produced. It can be easily formed, and in 10 minutes or less, the thermal diffusion in the film of the photoisomerized compound is easily suppressed, and the sharpness of the pattern boundary can be easily maintained.
  • the heating temperature and heating time are not particularly limited and may be appropriately selected according to the thermal polymerization initiator and the like to be used.
  • the heating temperature is preferably 60 ° C. or higher and 200 ° C. or lower, and the heating time is preferably 1 minute to 2 hours.
  • the heating means is not particularly limited, and known heating means can be used, and examples thereof include a heater, an oven, a hot plate, an infrared lamp, and an infrared laser.
  • the oxygen concentration in the curing step is not limited, and may be performed in an oxygen atmosphere, an atmosphere, or a low oxygen atmosphere (preferably, an oxygen concentration of 1,000 ppm or less). Further, in order to further accelerate the curing, the curing step is preferably performed in a low oxygen atmosphere, more preferably under heating and in a low oxygen atmosphere.
  • the method for producing a laminate according to the present disclosure may include other steps other than the above-mentioned steps, if desired.
  • steps include a step of forming each of the above-mentioned layers, specifically, a step of forming a colored layer, a step of forming a protective layer, a step of forming an adhesive layer, and the like.
  • the formation of each of the above layers such as a colored layer can be performed by using the above-mentioned method or a known method.
  • the method for producing a molded product according to the present disclosure includes a step of molding a laminate according to the present disclosure or a laminate produced by the method for producing a laminate according to the present disclosure.
  • the laminate (in a certain embodiment, a film for decorative molding) according to the present disclosure is excellent in molding processability, it can be suitably used for manufacturing a molded product, and is, for example, a group consisting of three-dimensional molding and insert molding. It is particularly suitable for producing a molded product by molding at least one selected from the above.
  • the method for producing the molded product will be described in detail by taking insert molding as an example.
  • a molded product in insert molding, can be obtained, for example, by arranging a laminate in a mold in advance and injection molding a base resin in the mold. By this insert molding, a molded product in which the laminate is integrated on the surface of the resin molded product can be obtained.
  • the method for producing the molded product is a step of arranging the laminate in a mold for injection molding and closing the mold, then a step of injecting the molten resin into the mold, and further taking out when the injection resin is solidified. Including the process.
  • the injection molding mold (that is, the molding mold) used for manufacturing the decorative molded product is a mold having a convex shape (that is, a male mold) and a mold having a concave shape corresponding to the convex shape (that is, a mold).
  • a female mold is provided, and the mold is closed after the laminate is placed on the molding surface which is the inner peripheral surface of the female mold.
  • the laminate is preformed by using the molding die to give the laminate a three-dimensional shape in advance. It is also possible to supply it to the molding mold. Further, when arranging the laminated body in the molding die, it is necessary to align the laminated body and the molding die with the laminated body inserted in the molding die.
  • the alignment hole As a method of aligning the laminate and the molding mold with the laminate inserted into the molding mold, a method of inserting and holding the fixing pin of the male mold into the alignment hole of the female mold. There is.
  • the alignment hole the end portion of the laminated body (the position where the three-dimensional shape is not imparted after molding) is formed in advance in the female mold.
  • the fixing pin is formed in advance at a position where it fits with the alignment hole in the male mold.
  • the following method is used as a method of aligning the laminate and the molding die with the laminate inserted in the molding die. Is possible.
  • the alignment mark is recognized at two or more diagonal points when viewed from the product portion of the injection molded product (decorative molded product).
  • the molten resin is injected into the molding mold into which the laminate is inserted. At the time of injection, the molten resin is injected onto the resin base material side of the laminate.
  • the temperature of the molten resin injected into the molding die is set according to the physical characteristics of the resin used.
  • the temperature of the molten resin is preferably in the range of 240 ° C. or higher and 260 ° C. or lower.
  • the position of the injection port (injection port) of the male mold is molded for the purpose of suppressing abnormal deformation of the laminated body due to heat and gas generated when the molten resin is injected into the molding mold. It may be set according to the shape of the mold or the type of molten resin. After the molten resin injected into the molding die into which the laminate was inserted solidified, the molding die was opened, and the laminate was immobilized from the molding die to the molded base material which was the solidified molten resin. Take out the intermediate decorative molding.
  • the burr and the dummy portion of the molded product are integrated around the decorative portion that finally becomes the product (molded product).
  • the dummy portion there is an insertion hole formed by inserting the fixing pin in the above-mentioned alignment. Therefore, a molded product can be obtained by performing a finishing process for removing the above-mentioned burrs and dummy portions from the intermediate molded product before the finishing process.
  • three-dimensional molding is also preferably mentioned.
  • thermoforming, vacuum molding, compressed air molding, vacuum pressure air molding and the like are preferably mentioned.
  • the method of vacuum forming is not particularly limited, but a method of performing three-dimensional molding in a heated state under vacuum is preferable.
  • the vacuum refers to a state in which the room is evacuated to a degree of vacuum of 100 Pa or less.
  • the temperature at the time of three-dimensional molding may be appropriately set according to the base material for molding to be used, but a temperature range of 60 ° C. or higher is preferable, a temperature range of 80 ° C. or higher is more preferable, and a temperature range of 100 ° C. or higher is further preferable. ..
  • the upper limit of the temperature at the time of three-dimensional molding is preferably 200 ° C.
  • the temperature at the time of three-dimensional molding refers to the temperature of the molding base material used for three-dimensional molding, and is measured by attaching a thermocouple to the surface of the molding base material.
  • the above vacuum forming can be performed by using a vacuum forming technique widely known in the molding field.
  • vacuum forming may be performed using Formech 508FS manufactured by Nippon Drafting Machinery Co., Ltd.
  • the method for producing a molded product according to the present disclosure includes steps other than the above-mentioned steps, for example, a step of attaching a laminate to a molding member, a step of removing burrs from the molded product, and a dummy from the molded product. Any other step may be included, if desired, such as a step of removing the portion.
  • the other steps are not particularly limited and can be performed by using known means and known methods.
  • Example 1 ⁇ Preparation of base material> As a base material, PET with an easy-adhesion layer (thickness 38 ⁇ m, Cosmo Shine (registered trademark) A4300, manufactured by Toyobo Co., Ltd.) was prepared.
  • a mask printing ink 1 having the composition described below was prepared.
  • the pattern shown in FIG. 1 was printed on A4300 using a mask printing ink 1 with a gravure printing machine (K Printing Profer, manufactured by RK Print Coat Instruments).
  • K Printing Profer manufactured by RK Print Coat Instruments
  • the region shown in black is the ink printed portion, and the ink printed portion and the other portion have different light transmittances.
  • the film was dried at 80 ° C. for 2 minutes to prepare a mask.
  • the thickest part of the print film thickness was 3.0 ⁇ m.
  • the average in-plane transmittance of the printed portion of the produced mask at 400 nm to 780 nm exceeded 90%.
  • the difference between the portion having the highest transmittance at a wavelength of 330 nm and the portion having the lowest transmittance exceeded 90%.
  • a coating liquid 1 for a liquid crystal alignment layer having the composition described below was prepared.
  • Compound 1 The following compound. The number at the bottom right of each structural unit represents the molar ratio.
  • a liquid crystal alignment layer forming coating liquid 1 is applied with a wire bar (count # 10) on the surface opposite to the surface on which the optical mask layer of A4300 is formed, and dried at 100 ° C. for 2 minutes to form a liquid crystal alignment layer.
  • a laminate was obtained.
  • the prepared liquid crystal alignment layer was subjected to a rubbing treatment (rayon cloth, pressure 0.1 kgf, rotation speed 1,000 rpm, transfer speed 10 m / min, number of times) in a direction rotated 3 ° counterclockwise with respect to the short side direction. Once) was given.
  • a coating liquid 1 for forming a liquid crystal layer having the composition described below was prepared.
  • -Composition of coating liquid 1 for forming a liquid crystal layer- ⁇ Liquid crystal compound 1 (Compound 2): 2.42 parts by mass ⁇ Liquid crystal compound 2 (Compound 5): 0.30 parts by mass ⁇ Liquid crystal compound 3 (Compound 6): 0.30 parts by mass ⁇ Chiral agent 1 (LC756, 2) Chiral agent having one acryloxy group and liquid crystal structure, manufactured by BASF): 0.204 parts by mass ⁇ Chiral agent 2 (Compound 3): 0.023 parts by mass ⁇
  • Photopolymerization initiator Kerayacure DETX, 2,4-diethylthioxanthone
  • Nippon Kayaku Co., Ltd. 0.091 parts by mass ⁇
  • Surface active agent (Compound 4, 1% diluted solution of methyl ethyl ketone (MEK)): 0.97 parts by mass ⁇ Methyl e
  • Liquid crystal compound 1 (compound 2): The following compound
  • Chiral agent 2 (Compound 3): The following compound.
  • Bu represents an n-butyl group.
  • Liquid crystal compound 2 (compound 5): The following compound
  • Liquid crystal compound 3 (compound 6): The following compound
  • the liquid crystal alignment layer prepared above was coated with the liquid crystal layer forming coating liquid 1 using a wire bar (count # 10) and then dried at 85 ° C. for 2 minutes to form a liquid crystal layer having a thickness of 3 ⁇ m. ..
  • the isomerized portion of the liquid crystal layer is irradiated with light from a metal halide lamp (MAL625NAL manufactured by GS Yuasa Co., Ltd.) having an exposure amount of 50 mJ / cm 2 from the surface side on which the optical mask layer is formed to perform isomerization treatment. went.
  • a metal halide lamp MAL625NAL manufactured by GS Yuasa Co., Ltd.
  • a metal halide lamp (MAL625NAL manufactured by GS Yuasa Co., Ltd.) with an exposure amount of 30 mJ / cm 2 is irradiated with a low oxygen atmosphere (oxygen concentration of 1,000 ppm or less).
  • a low oxygen atmosphere oxygen concentration of 1,000 ppm or less.
  • the reflection characteristics were evaluated using a spectrophotometer V-670 manufactured by JASCO Corporation. Black PET (manufactured by Tomagawa Paper Manufacturing Co., Ltd., trade name "Clear Mierre") is attached to the surface of the laminated body with a liquid crystal layer produced on Technoroy C003 in the above procedure, and the liquid crystal layer is formed. The reflection spectrum was measured with the formed surface as the incident surface, and the reflection wavelengths of the portions having the most different colors were measured.
  • a film for decorative molding was obtained by laminating an adhesive sheet (temperature: 30 ° C., linear pressure 100 N / cm, transport speed 0.1 m / min) on the peeled surface. The protective film on one side was not peeled off.
  • a decorative molding film having a protective film, an adhesive layer, a liquid crystal layer, a liquid crystal alignment layer, a base material, an optical mask layer, and a colored layer in this order was obtained.
  • FIGS. 2A and 2B Three-dimensional moldability was created for the glass member 10 shown in FIGS. 2A and 2B.
  • the member 10 has a main surface 12 shown in FIG. 2A, and a cross section 22 parallel to the longitudinal direction of the member 10 is as shown in FIG. 2B.
  • vacuum forming was performed at a heating temperature of 170 ° C. using a TOM molding machine NGF0406 manufactured by Fuse Vacuum Co., Ltd. to form a molded product.
  • the width of the bleeding at the boundary of the pattern was measured as follows.
  • a section of the laminate was prepared using a microtome (RX-860, manufactured by Daiwa Kouki Kogyo Co., Ltd.), and a scanning electron microscope (for example, Hitachi, Ltd.) was used to scan the boundary of the pattern for the cross section of the liquid crystal layer of the section. It was observed using a high-tech SU3800).
  • the width of the region where the spiral pitch changes by 10% or more in the in-plane direction of the liquid crystal layer was measured and used as the “width of bleeding at the boundary of the pattern”.
  • a and B were judged to be acceptable. A is particularly preferable.
  • Example 2 A decorative panel was produced in the same manner as in Example 1 except that a nax real 320 white paint manufactured by Nippon Paint Co., Ltd. was used as the coloring layer.
  • Example 3 A decorative panel was produced in the same manner as in Example 1 except that nax Real 537 Slen Red Paint manufactured by Nippon Paint Co., Ltd. was used as the coloring layer.
  • Example 4 The light of a metal halide lamp (“MAL625NAL” manufactured by GS Yuasa Co., Ltd.) having an exposure amount of 100 mJ / cm 2 is applied to the isomerized portion of the liquid crystal layer from the surface side on which the optical mask layer is formed.
  • a decorative panel was produced in the same manner as in Example 1 except that it was irradiated and isomerized.
  • Example 5 The light of a metal halide lamp (“MAL625NAL” manufactured by GS Yuasa Co., Ltd.) having an exposure amount of 200 mJ / cm 2 is applied to the isomerized portion of the liquid crystal layer from the surface side on which the optical mask layer is formed.
  • a decorative panel was produced in the same manner as in Example 1 except that it was irradiated and isomerized.
  • Example 6 A decorative panel was produced in the same manner as in Example 1 except that a nax real 320 white paint (mask printing ink 2) manufactured by Nippon Paint Co., Ltd. was used as the ink for forming the optical mask layer.
  • the portion having the highest transmittance at a wavelength of 330 nm had a transmittance of 91% or more, and the portion having the lowest transmittance had an absorption rate of 1% or less.
  • Example 7 A decorative panel was produced in the same manner as in Example 1 except that the mask printing ink 3 having the composition described below was used as the optical mask layer forming ink.
  • the thickest part of the print film thickness was 0.5 ⁇ m.
  • the average in-plane transmittance of the printed portion of the produced mask at 400 nm to 780 nm exceeded 90%. Further, in the optical mask layer, the difference between the portion having the highest transmittance at a wavelength of 330 nm and the portion having the lowest transmittance was 40%.
  • Example 8 A decorative panel was produced in the same manner as in Example 1 except that Technoloy C000 (polycarbonate, 250 ⁇ m) was used as the base material.
  • Technoloy C000 polycarbonate, 250 ⁇ m
  • Example 2 An optical mask layer was printed on A4300 in the same manner as in Example 1. Further, a liquid crystal alignment layer and a liquid crystal layer were formed on another A4300 on which the optical mask layer was not printed by the same method as in Example 1. After that, the surface on the side opposite to the side having the optical mask layer of A4300 on which the optical mask layer is formed is overlapped with the surface opposite to the side having the liquid crystal alignment layer and the liquid crystal layer of A4300 on which the liquid crystal layer is formed. The isomerization treatment was performed via the mask layer. A decorative panel was produced in the same manner as in Example 1 except for the above.
  • Table 1 shows the results of evaluating the design of Examples 1 to 8 and Comparative Examples 1 and 2.

Landscapes

  • Laminated Bodies (AREA)

Abstract

L'invention concerne : un stratifié ayant un matériau de base et une couche de cristaux liquides comprenant un composé de cristaux liquides et un composé de photoisomérisation disposé sur le matériau de base, la couche de cristaux liquides ayant une pluralité de motifs qui ont des longueurs d'onde de réflexion sélective différentes les unes des autres et sont formés dans la direction du plan, et la largeur de flou des limites de la pluralité de motifs étant supérieure ou égale à 1 µm mais inférieure à 100 µm ; un procédé de fabrication du stratifié ; un article moulé et un procédé de fabrication de l'article moulé ; un panneau de logement pour un dispositif électronique ; et un dispositif électronique.
PCT/JP2020/048992 2019-12-25 2020-12-25 Stratifié et son procédé de fabrication, article moulé et son procédé de fabrication, panneau de logement pour dispositif électronique, et dispositif électronique WO2021132666A1 (fr)

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JP2021567726A JP7309919B2 (ja) 2019-12-25 2020-12-25 積層体及びその製造方法、成型物及びその製造方法、電子デバイスの筐体パネル、並びに電子デバイス
CN202080077483.9A CN114667214A (zh) 2019-12-25 2020-12-25 层叠体及其制造方法、成型物及其制造方法、电子器件的壳体面板以及电子器件

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WO2018079625A1 (fr) * 2016-10-25 2018-05-03 富士フイルム株式会社 Stratifié décoratif transmissif et son procédé de production, et substrat de verre équipé d'un stratifié décoratif transmissif
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JP5451235B2 (ja) * 2009-07-31 2014-03-26 富士フイルム株式会社 複屈折パターンを有する物品の製造方法及び複屈折パターン作製材料
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JP2003532565A (ja) * 2000-04-25 2003-11-05 コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ 物品の表面に装飾又はテキストを設ける方法
JP4446444B2 (ja) * 2004-11-22 2010-04-07 日東電工株式会社 偽造防止機能付シートの製造方法、物品、認証カード、バーコードラベル、及び認証システム
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WO2018186184A1 (fr) * 2017-04-06 2018-10-11 富士フイルム株式会社 Corps stratifié, feuille décorative et corps moulé
WO2019142707A1 (fr) * 2018-01-16 2019-07-25 富士フイルム株式会社 Film, stratifié, dispositif d'imagerie, capteur et dispositif d'affichage tête haute
WO2020203815A1 (fr) * 2019-03-29 2020-10-08 日本ゼオン株式会社 Moyen d'identification et article le comprenant

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