WO2023032644A1 - Film décoratif, corps moulé et article - Google Patents

Film décoratif, corps moulé et article Download PDF

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Publication number
WO2023032644A1
WO2023032644A1 PCT/JP2022/030787 JP2022030787W WO2023032644A1 WO 2023032644 A1 WO2023032644 A1 WO 2023032644A1 JP 2022030787 W JP2022030787 W JP 2022030787W WO 2023032644 A1 WO2023032644 A1 WO 2023032644A1
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Prior art keywords
liquid crystal
layer
circularly polarized
light
decorative film
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PCT/JP2022/030787
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English (en)
Japanese (ja)
Inventor
優香 松本
淳 渡部
佑一 早田
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富士フイルム株式会社
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Priority to JP2023545415A priority Critical patent/JPWO2023032644A1/ja
Publication of WO2023032644A1 publication Critical patent/WO2023032644A1/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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • the present disclosure relates to decorative films, moldings, and articles.
  • Patent Document 1 discloses a first antireflection layer disposed on the outermost surface, a first reflective layer, a second reflective layer, and an outermost surface opposite to the first antireflection layer. and a second antireflection layer that is coated in this order, the first reflective layer and the second reflective layer each have wavelength selective reflectivity, and the first reflective layer has a selective reflection wavelength
  • a decorative film is described in which right-handed circularly polarized light is reflected, and the second reflective layer reflects left-handed circularly polarized light having the same selective reflection wavelength as the first reflective layer.
  • Patent Document 2 discloses a retardation plate for a circularly polarizing plate comprising a first optically anisotropic layer and a second optically anisotropic layer, wherein the first optically anisotropic layer has a thickness direction as a helical axis.
  • twist angle of the liquid crystal compound in the first optically anisotropic layer is 81 ⁇ 10°
  • the second optically anisotropic layer of the first optically anisotropic layer The in-plane slow axis on the side surface and the in-plane slow axis of the second optically anisotropic layer are parallel, and the refractive index anisotropy of the first optically anisotropic layer measured at a wavelength of 550 nm
  • the value of the product ⁇ nd of the property ⁇ n and the thickness d of the first optically anisotropic layer, and ReB (550), which is the retardation value of the second optically anisotropic layer measured at a wavelength of 550 nm, are expressed by the following equations.
  • a retardation plate for a circularly polarizing plate is described which satisfies (1) and (2).
  • Formula (1) 142 nm ⁇ nd ⁇ 202 nm
  • Patent Document 3 discloses a printed material having an anti-counterfeiting function, which includes a base material that is a printable support, a printed layer having an information code pattern, and an anti-counterfeiting layer in this order.
  • a printed matter is described in which the prevention layer has a property of reflecting either left-handed circularly polarized light or right-handed circularly polarized light, or both of them, only at specific wavelengths.
  • An object to be solved by an embodiment of the present disclosure is to provide a decorative film that is resistant to intralayer peeling and that can easily change color by combining with a circularly polarized light transmitting member.
  • a problem to be solved by another embodiment of the present disclosure is to provide a molded article obtained by molding the decorative film, and an article including the decorative film or the molded article thereof.
  • the reflective layer includes, in at least a portion of the in-plane direction, a region that reflects the right-handed circularly polarized visible light and a region that reflects the left-handed circularly polarized visible light in the thickness direction.
  • decorative film ⁇ 3> ⁇ 1> or ⁇ 2>, wherein the difference between the selective reflection wavelength of the region that reflects right-handed circularly polarized visible light and the selective reflection wavelength of the region that reflects left-handed circularly polarized visible light is within 100 nm; Decorative film described.
  • FIG. 1 is a schematic cross-sectional view showing an example of a reflective layer in the present disclosure
  • FIG. FIG. 4 is a schematic cross-sectional view showing another example of a reflective layer in the present disclosure
  • FIG. 4 is a schematic cross-sectional view showing still another example of a reflective layer in the present disclosure
  • FIG. 2 is a schematic plan view showing an example of a patterning mask used in Examples
  • 1 is a schematic cross-sectional view showing an example of a liquid crystal material having a substrate and a liquid crystal layer
  • FIG. FIG. 4 is a schematic cross-sectional view showing an example of how a first patterning mask is used to expose a liquid crystal layer with a first light
  • FIG. 10 is a schematic cross-sectional view showing an example of how an uncured portion of the liquid crystal layer is exposed to the second light;
  • FIG. 4 is a schematic plan view showing a glass member used in Examples.
  • FIG. 4 is a schematic cross-sectional view showing members used in Examples.
  • notations that do not describe substitution and unsubstituted include not only those not having substituents but also those having substituents.
  • an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • Light in the present disclosure means actinic rays or radiation.
  • actinic rays or “radiation” in the present disclosure refers to, for example, the emission line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam) and the like.
  • exposure in the present disclosure means, unless otherwise specified, not only exposure by the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV light, but also electron beams and ion beams. It also includes exposure by particle beams such as.
  • the term “ ⁇ ” is used to include the numerical values before and after it as lower and upper limits.
  • (meth)acrylate refers to acrylate and methacrylate
  • (meth)acryl refers to acrylic and methacrylic
  • the weight-average molecular weight (Mw) of the resin component, the number-average molecular weight (Mn) of the resin component, and the degree of dispersion (also referred to as molecular weight distribution) (Mw/Mn) of the resin component are measured using GPC (Gel Permeation Chromatography) equipment.
  • the amount of each component in the composition means the total amount of the corresponding multiple substances present in the composition when there are multiple substances corresponding to each component in the composition, unless otherwise specified. do.
  • the term “step” includes not only independent steps, but also if the intended purpose of the step is achieved even if it cannot be clearly distinguished from other steps.
  • total solid content refers to the total mass of components excluding the solvent from the total composition of the composition.
  • solid content is a component excluding the solvent from the total composition of the composition, and may be solid or liquid at 25° C., for example.
  • “% by mass” and “% by weight” are synonymous, and “parts by mass” and “parts by weight” are synonymous.
  • a combination of two or more preferred aspects is a more preferred aspect.
  • the decorative film according to the present disclosure has a reflective layer having a single-layer structure, and at least a portion of the reflective layer includes a region that reflects right-handed circularly polarized visible light and a region that reflects left-handed circularly polarized visible light.
  • the reflective layer comprises a cholesterically helically aligned liquid crystal compound, a photosensitive chiral agent A that induces the formation of a helical alignment in a first twist direction, and a helical spiral in a twist direction opposite to the first twist direction It is a layer containing a chiral agent B that induces orientation formation, or a cured layer obtained by curing this layer.
  • the decorative film according to the present disclosure can be used for decoration of cards, optical parts, doors, window glass, and building materials.
  • the decorative film according to the present disclosure can be suitably used for decorating electronic devices (for example, wearable devices and smartphones).
  • the decorative film according to the present disclosure is also excellent in three-dimensional moldability, it is suitable as a decorative film for molding, which is used for molding such as three-dimensional molding and insert molding. It is more suitable as a film.
  • the decorative film according to the present disclosure can be suitably used for decorating accessories (for example, accessories).
  • the decorative film according to the present disclosure can be suitably used for decorating cards (for example, anti-counterfeit cards, trading cards, etc.).
  • a left-handed circularly polarized light transmitting member or a right-handed circularly polarized light transmitting member is provided.
  • the reflected light from one side is absorbed, and a different color tone from the original color can be seen.
  • Visually recognizable colors can be easily changed by stacking transmissive films.
  • peeling may occur within the reflective layer.
  • the present inventors have developed a reflective layer having a single-layer structure that includes a region that reflects right-handed circularly polarized visible light and a region that reflects left-handed circularly polarized visible light. can be suppressed.
  • a reflective layer having a single-layer structure that includes a region that reflects right-handed circularly polarized visible light and a region that reflects left-handed circularly polarized visible light.
  • colors means reflected color and chroma.
  • the reflective layer in the decorative film according to the present disclosure has a single-layer structure, and at least a portion of the reflective layer includes a region that reflects right-handed circularly polarized visible light (hereinafter referred to as a “right-handed circularly polarized visible light reflecting portion ”) and a region that reflects left-handed circularly polarized visible light (hereinafter also referred to as a “left-handed circularly polarized visible light reflecting portion”).
  • the reflective layer includes a liquid crystal compound oriented in a cholesteric spiral, a photosensitive chiral agent A that induces formation of helical orientation in the first twist direction, and a helical orientation in the twist direction opposite to the first twist direction. It is a layer containing a chiral agent B that induces formation or a cured layer obtained by curing this layer.
  • the reflective layer having a single-layer structure means that the photosensitive chiral agent A or a cured product thereof and the chiral agent B or a cured product thereof contained in the reflective layer are combined as follows. It shall be demonstrated by fulfilling the requirements.
  • the reflective layer may have a portion having only a region that reflects the right-handed circularly polarized visible light, or have a portion that has only a region that reflects the left-handed circularly polarized visible light. Alternatively, it may have a region that reflects the right-handed circularly polarized visible light and a region that reflects the left-handed circularly polarized visible light in the thickness direction, or it may have a region that does not reflect visible light.
  • the area that reflects the right-handed circularly polarized visible light and the area that reflects the left-handed circularly polarized visible light in at least a part of the in-plane direction have a thickness preferably included in the direction.
  • the thickness of the region that reflects the right-handed circularly polarized visible light or the region that reflects the left-handed circularly polarized visible light may be constant or different.
  • the thickness of the region that reflects right-handed circularly polarized visible light or the region that reflects left-handed circularly polarized visible light is any thickness of 0 or more and less than or equal to the thickness of the reflection layer in the thickness direction of the reflection layer. I wish I had.
  • the shape of the region that reflects right-handed circularly polarized visible light or the region that reflects left-handed circularly polarized visible light is not particularly limited, and may be any shape, and the desired reflection color, desired design, and formation It can be appropriately selected according to the method or the like.
  • the shape of the interface is not particularly limited, and can be any shape. Any shape is acceptable. For example, even if it is a surface parallel to the in-plane direction, a surface perpendicular to the in-plane direction, or a surface with an angle in the in-plane direction, the surface has an irregular shape. may be
  • the selective reflection wavelengths of the region that reflects the right-handed circularly polarized visible light or the region that reflects the left-handed circularly polarized visible light may be different or the same, and may reflect the right-handed circularly polarized visible light.
  • the region or only the region that reflects the left circularly polarized visible light may have regions with different selective reflection wavelengths.
  • the selective reflection wavelength of the region that reflects the right circularly polarized visible light and preferably within 100 nm, more preferably within 80 nm, and particularly preferably within 50 nm. Note that the lower limit is 0 nm.
  • the reflective layer may include, in at least a part of the in-plane direction, a region that reflects the right-handed circularly polarized visible light and a region that reflects the left-handed circularly polarized visible light. More preferably, at least a portion of the in-plane direction includes a portion having only a region that reflects right-handed circularly polarized visible light and a portion having only a region that reflects left-handed circularly polarized visible light.
  • At least a part of the reflective layer has only a region that reflects the right-handed circularly polarized visible light in the entire thickness direction of the reflective layer, and a portion that has only the region that reflects the left-handed circularly polarized visible light in the entire thickness direction of the reflective layer. and is particularly preferred.
  • the “central wavelength of the selective reflection wavelength” means the maximum value of the reflectance in the target object (member) and the maximum value (hereinafter also simply referred to as “maximum reflectance”) R max (% ), it means the average value of two wavelengths showing the half-value reflectance R 1/2 (%) represented by the following formula.
  • one of the two wavelengths is the maximum wavelength in a wavelength range including a wavelength shorter than the wavelength that indicates R max
  • the other wavelength of the two wavelengths is shorter than the wavelength that indicates R max .
  • reflectance is the integrated reflectance measured with a spectrophotometer equipped with an integrating sphere device.
  • a spectrophotometer equipped with an integrating sphere device.
  • commercially available products can be used.
  • the selective reflection wavelength and reflectance characterize the reflection spectrum and contribute to the color. Therefore, the color can be changed by changing at least one of the selective reflection wavelength and the reflectance.
  • colors obtained from reflection spectra with the same selective reflection wavelength may be referred to as "same color”
  • colors obtained from reflection spectra with different selective reflection wavelengths may be referred to as “different colors”. be.
  • by fixing the selective reflection wavelength and changing the reflectance it is possible to adjust the brightness and darkness with the same color.
  • by setting the selective reflection wavelength to 460 nm (blue) and controlling the maximum reflectance between 23% (dark blue) and 48% (bright blue), it is possible to adjust the brightness and darkness with the same type of blue.
  • the reflective layer is preferably a cured layer obtained by curing a layer containing a cholesterically helically aligned liquid crystal compound.
  • the "cured layer obtained by curing a layer” includes a dried product and a polymerized cured product of a composition containing components contained in the layer.
  • the liquid crystal compound is oriented in the region that reflects right-handed circularly polarized visible light or the region that reflects left-handed circularly polarized visible light, and each has a selective reflection wavelength. .
  • the presence or absence of orientation of the liquid crystal compound in the reflective layer can be observed using SEM as follows.
  • the liquid crystal compound is preferably a cholesteric liquid crystal compound.
  • Each component forming the reflective layer will be described in detail in the manufacturing method of the decorative film according to the present disclosure, which will be described later.
  • the method for forming the reflective layer having a region that reflects the right-handed circularly polarized visible light and a region that reflects the left-handed circularly polarized visible light is not particularly limited, but the right-handed circularly polarized light is formed by changing the twist direction in the cholesteric helical structure.
  • a method of forming a region that reflects visible light or a region that reflects left circularly polarized visible light is preferred.
  • HTP helical twisting power
  • the decorative film preferably further has a circularly polarized light transmitting layer.
  • the circularly polarized light transmitting layer is not particularly limited as long as it transmits only circularly polarized light.
  • a known circularly polarized light transmitting film can be used.
  • the direction of rotation of circularly polarized light is not particularly limited, and the layer may be a right-handed circularly polarized light-transmitting layer or a left-handed circularly polarized light transmitting layer.
  • a suitable example of the circularly polarized light transmitting film is a film composed of a linearly polarized film and a quarter retardation film.
  • the decorative film may contain a substrate. This makes it possible to increase the strength of the decorative film, making it easier to handle. Moreover, when the decorative film contains a base material, the base material can be used as a member constituting a molded body obtained by molding the decorative film.
  • the reflective layer may be provided directly on the base material, or may be provided via another layer.
  • Materials for the resin base include, for example, polyethylene (PE), polyethylene naphthalate (PEN), polyamide (PA), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), polyacrylonitrile (PAN).
  • PE polyethylene
  • PEN polyethylene naphthalate
  • PA polyamide
  • PET polyethylene terephthalate
  • PVC polyvinyl chloride
  • PVA polyvinyl alcohol
  • PAN polyacrylonitrile
  • the material of the substrate is polyethylene terephthalate, acrylic resin, urethane resin, urethane-acrylic resin, polycarbonate, acrylic-polycarbonate. It is preferably at least one resin selected from the group consisting of resins and polypropylene.
  • the substrate may be a laminate of a plurality of resin layers made of different materials.
  • the resin base material may contain additives as necessary.
  • Additives include, for example, mineral oils, hydrocarbons, fatty acids, alcohols, fatty acid esters, fatty acid amides, metallic soaps, natural waxes, lubricants such as silicone; inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide; Organic flame retardants such as flame retardants and phosphorus-based flame retardants; organic or inorganic fillers such as metal powder, talc, calcium carbonate, potassium titanate, glass fiber, carbon fiber, and wood flour; antioxidants, UV inhibitors, lubricants , dispersants, coupling agents, foaming agents, colorants, and resins other than the main component resin.
  • the resin base material may be a commercially available product.
  • Commercially available products include, for example, Technolloy (registered trademark) series (acrylic resin film, polycarbonate 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 Co., Ltd.) Kogyo Co., Ltd.), Teflex (registered trademark) series (PET film, Teijin Film Solution Co., Ltd.), Lumirror (registered trademark) easy molding type (PET film, Toray Industries), and Pure Thermo (polypropylene film, Idemitsu Unitech Co., Ltd. made).
  • Technolloy (registered trademark) series acrylic resin film, polycarbonate resin film, or acrylic resin/polycarbonate resin laminated film, manufactured by Sumitomo Chemical Co., Ltd.
  • ABS film manufactured by Okamoto Co
  • the thickness of the base material is not particularly limited, it is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, and 20 ⁇ m or more from the viewpoint of strength of the decorative film and molding processability when molding the decorative film. is more preferred. From the same viewpoint, the thickness of the substrate is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, and even more preferably 150 ⁇ m or less.
  • the decorative film when the decorative film contains a base material, the decorative film may be obtained by peeling off the base material from the decorative film containing the base material.
  • the total light transmittance of the colored layer is preferably 10% or less from the viewpoint of visibility.
  • the total light transmittance can be measured with a spectrophotometer (eg, spectrophotometer “UV-2100” manufactured by Shimadzu Corporation).
  • the color of the colored layer is not particularly limited, and can be appropriately selected according to the application of the decorative film. Colors of the colored layer include, for example, black, gray, white, red, orange, yellow, green, blue, and purple. Also, the color of the colored layer may be a metallic color.
  • the pigment may be an inorganic pigment or an organic pigment.
  • inorganic pigments examples include inorganic pigments described in paragraphs 0015 and 0114 of JP-A-2005-7765.
  • 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, syncash red and syncash magenta; perylene-based pigments such as perylene maroon; carbazole violet, anthrapyridine, flavanthrone yellow, isoindoline yellow, indathrone blue, dibromoanzathrone red, anthraquinone red, and diketopyrrolopyrrole.
  • 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, syncash red and syncash magenta
  • perylene-based pigments such as perylene maroon
  • organic pigments include C.I. I. Pigment Red 177, 179, 224, 242, 254, 255, 264 and other red pigments, C.I. I. Pigment Yellow 138, 139, 150, 180, 185 and other yellow pigments; C.I. I. Pigment Orange 36, 38, 71 and other orange pigments; C.I. I. Pigment Green 7, 36, 58 and other green pigments; C.I. I. Pigment Blue 15:6 and other blue pigments; and C.I. I. Purple pigments such as Pigment Violet 23 can be mentioned.
  • organic pigments examples include organic pigments described in paragraph 0093 of JP-A-2009-256572.
  • the pigment may be a pigment having light transmittance and light reflectivity (so-called luster pigment).
  • Luster pigments include, for example, metallic luster pigments of aluminum, copper, zinc, iron, nickel, tin, aluminum oxide, and alloys thereof, interference mica pigments, white mica pigments, graphite pigments, and glass flake pigments. is mentioned.
  • the bright pigment may be colorless or colored.
  • the content of the colorant is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 50% by mass, relative to the total amount of the colored layer, from the viewpoint of the desired color expression. , 10% by weight to 40% by weight.
  • the colored layer preferably contains a binder resin from the viewpoint of strength, scratch resistance, and suitability for molding.
  • the type of binder resin is not particularly limited.
  • the binder resin is preferably a transparent resin, and more specifically, a resin having a total light transmittance of 80% or more.
  • the total light transmittance can be measured with a spectrophotometer (eg, spectrophotometer “UV-2100” manufactured by Shimadzu Corporation).
  • binder resins examples include acrylic resins, silicone resins, polyesters, polyurethanes, and polyolefins.
  • the binder resin may be a homopolymer or a copolymer.
  • the binder resin may be used singly or in combination of two or more.
  • the content of the binder resin is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, based on the total amount of the colored layer. % to 60% by weight is particularly preferred.
  • the colored layer may contain a dispersant from the viewpoint of improving the dispersibility of the colorant contained in the colored layer, particularly the pigment.
  • a dispersant is contained, the dispersibility of the colorant in the colored layer is improved. Therefore, the color of the obtained decorative film can be made uniform more easily.
  • the dispersant can be appropriately selected according to the type, shape, etc. of the colorant, and is preferably a polymer dispersant.
  • polymeric dispersants examples include silicone polymers, acrylic polymers, and polyester polymers.
  • the dispersant when it is desired to impart heat resistance to the decorative film, is preferably a silicone polymer such as a graft-type silicone polymer.
  • the weight average molecular weight of the dispersant is preferably 1,000 to 5,000,000, more preferably 2,000 to 3,000,000, and 2,500 to 3,000,000. is particularly preferred. When the weight average molecular weight is 1,000 or more, the dispersibility of the colorant is further improved.
  • Dispersants may be used singly or in combination of two or more.
  • the colored layer may contain additives, if necessary, in addition to the above components.
  • the additive is not particularly limited, for example, paragraph 0017 of Japanese Patent No. 4502784, and surfactants described in paragraphs 0060 to 0071 of JP-A-2009-237362; described in paragraph 0018 of Japanese Patent No. 4502784 a thermal polymerization inhibitor (also referred to as a polymerization inhibitor, preferably phenothiazine); and additives described in paragraphs 0058 to 0071 of JP-A-2000-310706.
  • the method of forming a colored layer using the colored layer-forming composition includes a method of forming a colored layer by applying the colored layer-forming composition, for example, a method of printing a colored layer-forming composition to form a colored layer.
  • Method of forming Printing methods include, for example, screen printing, inkjet printing, flexographic printing, gravure printing, and offset printing.
  • the composition for forming a colored layer may contain a colorant and, if necessary, at least one of a binder resin, a dispersant and an additive.
  • the types of each component may be those described above for the colored layer.
  • the content of the coloring agent is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 50% by mass, and 10% by mass with respect to the total solid content of the composition for forming a colored layer. % to 40% by mass is particularly preferred.
  • the content of the binder resin is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, relative to the total solid content of the composition for forming a colored layer, and 20% by mass. % to 60% by mass is particularly preferred.
  • the content of the dispersant is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the colorant.
  • the composition for forming a colored layer may contain an organic solvent from the viewpoint of facilitating application.
  • the organic solvent is not particularly limited, and known organic solvents can be applied.
  • Organic solvents include, for example, alcohols, esters, ethers, ketones, and aromatic hydrocarbons.
  • An organic solvent may be used individually by 1 type, and may use 2 or more types together.
  • the content of the organic solvent is preferably 5% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, relative to the total amount of the composition for forming a colored layer.
  • composition for forming the colored layer for example, commercially available paints such as nax Real series, nax Admira series, and nax Multi series (manufactured by Nippon Paint Co., Ltd.); Retan PG series (manufactured by Kansai Paint Co., Ltd.) may be used.
  • the method for preparing the colored layer-forming composition is not particularly limited, and for example, the colored layer-forming composition may be prepared by mixing each component such as a colorant. Further, when the composition for forming a colored layer contains a pigment as a coloring agent, from the viewpoint of further enhancing the uniform dispersibility and dispersion stability of the pigment, a pigment dispersion containing the pigment and a dispersant is prepared in advance, and the pigment dispersion is prepared. It is preferable to prepare a composition for forming a colored layer by mixing other components into the above.
  • the alignment layer is provided, for example, by rubbing an organic compound (preferably polymer), oblique vapor deposition of an inorganic compound, formation of a layer having microgrooves, or the like.
  • an alignment layer an alignment layer is also known in which an alignment function is produced by application of an electric field, application of a magnetic field, or light irradiation.
  • the rubbing treatment alignment layer and the photo-alignment layer will be described below as preferred examples.
  • the rubbing treatment alignment layer is formed, for example, by performing a rubbing treatment on the surface of the base on which the liquid crystal composition is applied.
  • the rubbing treatment can be performed, for example, by rubbing the surface of the film containing a polymer as a main component with paper or cloth in a certain direction.
  • a general rubbing method is described, for example, in "Liquid Crystal Handbook" (published by Maruzen Co., Ltd., Oct. 30, 2000).
  • the alignment layer polymer for forming a film containing the polymer as a main component examples include methacrylate copolymers, styrene copolymers, polyolefins, and polyolefins described in paragraph 0022 of JP-A-8-338913 Polyvinyl alcohol, modified polyvinyl alcohol, poly(N-methylolacrylamide), polyesters, polyimides, vinyl acetate copolymers, carboxymethylcellulose, and polycarbonates. Also, the alignment layer polymer may be a silane coupling agent.
  • the alignment layer polymer is preferably a water-soluble polymer (eg, poly(N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol, or modified polyvinyl alcohol), more preferably gelatin, polyvinyl alcohol, or modified polyvinyl alcohol, and polyvinyl alcohol. Or modified polyvinyl alcohol is particularly preferred.
  • a water-soluble polymer eg, poly(N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol, or modified polyvinyl alcohol
  • modified polyvinyl alcohol is particularly preferred.
  • Photo-alignment layer As the photo-alignment material used in the photo-alignment layer formed by light irradiation, for example, JP-A-2006-285197, JP-A-2007-76839, JP-A-2007-138138, JP-A-2007-94071 Publications, JP-A-2007-121721, JP-A-2007-140465, JP-A-2007-156439, JP-A-2007-133184, JP-A-2009-109831, JP-A-3883848, and patents Azo compounds described in JP-A-4151746; aromatic ester compounds described in JP-A-2002-229039; Maleimide and/or alkenyl-substituted nadimide compounds; photocrosslinkable silane derivatives described in Japanese Patent No.
  • Photocrosslinkable polyimides, polyamides, or esters described in JP-A-2003-203164 may be mentioned.
  • the photo-alignment material is preferably an azo compound, photocrosslinkable polyimide, polyamide, or ester.
  • a layer formed from a photo-alignment material is irradiated with linearly polarized light or non-polarized light to produce a photo-alignment layer.
  • the light source used for light irradiation includes known light sources such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury xenon lamps, carbon arc lamps, various lasers (e.g., semiconductor lasers, helium neon lasers, argon ion lasers, helium cadmium lasers, or YAG lasers), light emitting diodes, and cathode ray tubes.
  • known light sources such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury xenon lamps, carbon arc lamps, various lasers (e.g., semiconductor lasers, helium neon lasers, argon ion lasers, helium cadmium lasers, or YAG lasers), light emitting diodes, and cathode ray tubes.
  • lasers e.g., semiconductor lasers, helium neon lasers, argon ion lasers,
  • Methods for obtaining linearly polarized light include a method using a polarizing plate (e.g., an iodine polarizing plate, a dichroic dye polarizing plate, or a wire grid polarizing plate), a method using a prism-based element (e.g., a Glan-Thompson prism), or a Brewster angle.
  • a polarizing plate e.g., an iodine polarizing plate, a dichroic dye polarizing plate, or a wire grid polarizing plate
  • a prism-based element e.g., a Glan-Thompson prism
  • Brewster angle e.g., a Brewster angle
  • Examples include a method using a reflective polarizer and a method using light emitted from a polarized laser light source.
  • only light of a required wavelength may be selectively irradiated using a filter, a wavelength conversion element, or the like.
  • the light to be irradiated is linearly polarized light
  • a method of irradiating light in a direction perpendicular to or oblique to the surface of the alignment layer from the upper surface or the back surface of the alignment layer can be used.
  • the incident angle of light varies depending on the photo-alignment material, it is preferably 0° to 90° (perpendicular), more preferably 40° to 90°, with respect to the alignment layer.
  • non-polarized light When using non-polarized light, non-polarized light is irradiated obliquely from the upper surface or the back surface of the alignment layer.
  • the incident angle is preferably 10° to 80°, more preferably 20° to 60°, even more preferably 30° to 50°.
  • the irradiation time is preferably 1 minute to 60 minutes, more preferably 1 minute to 10 minutes.
  • Other layers include a protective layer, an adhesive layer, an ultraviolet absorbing layer, a self-healing layer, an antistatic layer, an antifouling layer, an anti-electromagnetic layer, a conductive layer, etc., which are known layers in decorative films.
  • layers can be formed by known methods. For example, a method of applying a composition (layer-forming composition) containing components contained in these layers in layers and drying the layers can be used.
  • a composition layer-forming composition
  • the method for producing the decorative film according to the present disclosure is not particularly limited, but includes a substrate, a liquid crystal compound oriented in a cholesteric spiral, and a photosensitive chiral agent A that induces the formation of a helical orientation in the first twist direction.
  • a step of preparing a liquid crystal material having a liquid crystal layer containing a chiral agent B that induces formation of a helical alignment in a twist direction opposite to the first twist direction (hereinafter also referred to as a “liquid crystal material preparation step”);
  • a step of irradiating the liquid crystal layer with the first light through a first patterning mask having a plurality of regions with different transmittances for the first light to cure a part of the liquid crystal layer hereinafter referred to as "second a step of changing the twist direction in the cholesteric spiral alignment of the uncured portion of the liquid crystal layer (hereinafter also referred to as a “twist changing step”); It is preferable to include a step of curing the uncured portion (hereinafter also referred to as a “second exposure step”).
  • the method for manufacturing a decorative film according to the present disclosure preferably includes a step of heating the liquid crystal layer to form a cholesteric liquid crystal phase (hereinafter also referred to as "first heating step").
  • the liquid crystal material preparation process is a step of preparing a liquid crystal material having a substrate and a liquid crystal layer containing the liquid crystal compound, the photosensitive chiral agent A, and the chiral agent B.
  • the cholesteric liquid crystal compound is not particularly limited, and may be either a cholesteric liquid crystal compound having a reactive group or a cholesteric liquid crystal compound having no reactive group. From the viewpoint of fixing the helical structure of the cholesteric liquid crystal compound more easily, the cholesteric liquid crystal compound preferably contains a cholesteric liquid crystal compound having a reactive group.
  • Reactive groups include, for example, vinyl groups, (meth)acryloyl groups, epoxy groups, oxetanyl groups, vinyl ether groups, hydroxy groups, carboxy groups, and amino groups.
  • Cross-linking mechanisms of reactive groups include, for example, condensation reactions, hydrogen bonding, and polymerization.
  • the radically polymerizable group is a vinyl group or a (meth)acryloyl group
  • the cationically polymerizable group is an epoxy group, an oxetanyl group, or a vinyl ether group. Combinations are particularly preferred.
  • Et represents an ethyl group
  • n-Pr represents an n-propyl group
  • the shape of the cholesteric liquid crystal compound is not particularly limited, and the cholesteric liquid crystal compound may be a rod-like cholesteric liquid crystal compound or a disk-like cholesteric liquid crystal compound.
  • the cholesteric liquid crystal compound is preferably a rod-shaped cholesteric liquid crystal compound, from the viewpoints of more easily adjusting the helical pitch of the cholesteric alignment portion and more easily suppressing changes in reflectance and color over time.
  • Discotic cholesteric liquid crystal compounds include low molecular weight discotic cholesteric liquid crystal compounds such as monomers, and polymerizable discotic cholesteric liquid crystal compounds.
  • cholesteric liquid crystal compound having a reactive group When a discotic cholesteric liquid crystal compound having a reactive group is used as the cholesteric liquid crystal compound, it may be fixed in any alignment state of horizontal alignment, vertical alignment, tilt alignment, and twist alignment in the cured liquid crystal film. .
  • the liquid crystal layer or reflective layer includes a photosensitive chiral agent A that induces helical alignment formation in a first twist direction and a chiral agent B that induces helical alignment formation in a twist direction opposite to the first twist direction.
  • Each of the photosensitive chiral agent A and the chiral agent B has a function of inducing a helical structure in the cholesteric liquid crystal compound.
  • the chiral agent B may or may not be photosensitive, but is preferably photosensitive.
  • the chiral agent may be selected depending on the intended purpose, since the induced helical twist direction or helical pitch differs depending on the liquid crystal compound.
  • the total content of chiral agents (total content of all chiral agents) in the liquid crystal layer or reflective layer is not particularly limited, but from the viewpoint of more easily obtaining the desired selective reflection wavelength, the total solid content of the liquid crystal layer, Alternatively, it is preferably more than 1.0% by mass, more preferably 2.0% by mass or more, and even more preferably 3.0% by mass or more, relative to the total mass of the reflective layer.
  • the upper limit is not particularly limited, it is preferably 50% by mass or less, more preferably 48% by mass or less, and even more preferably 45% by mass or less in order to prevent phase separation from the liquid crystal compound.
  • a photosensitive chiral agent whose helical induced force changes upon light irradiation may be liquid crystalline or non-liquid crystalline.
  • a photosensitive chiral agent generally contains an asymmetric carbon atom in many cases.
  • the chiral agent A may be an axially asymmetric compound or planar asymmetric compound containing no asymmetric carbon atoms.
  • Photosensitive chiral agents include so-called photoreactive chiral agents.
  • a photoreactive chiral agent is a compound that has a chiral site and a photoreactive site that undergoes a structural change when irradiated with light, and that, for example, greatly changes the torsional force of a liquid crystal compound in accordance with the amount of irradiation.
  • Examples of photoreactive sites that undergo structural changes due to light irradiation include photochromic compounds (Kingo Uchida, Masahiro Irie, Kagaku Kogyo, vol.64, 640p, 1999, Kingo Uchida, Masahiro Irie, Fine Chemicals, vol.28(9), 15p , 1999).
  • the liquid crystal layer contains a component having a polymerizable group (for example, when it contains at least one of a cholesteric liquid crystal compound having a polymerizable group and a polymerizable chiral agent), the liquid crystal layer preferably contains a polymerization initiator.
  • the liquid crystal layer contains a component having a polymerizable group and a polymerization initiator, the liquid crystal layer is preferably photocurable, and the polymerization initiator is a photopolymerization initiator capable of initiating a polymerization reaction by irradiation with light. It is preferably an agent.
  • cross-linking agents include polyfunctional acrylate compounds such as dimethylol-tricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and pentaerythritol tri(meth)acrylate; glycidyl (meth)acrylate, ethylene glycol di(meth)acrylate; Epoxy compounds such as glycidyl ether; aziridine compounds such as 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate], 4,4-bis(ethyleneiminocarbonylamino)diphenylmethane; hexamethylene diisocyanate, biuret polyoxazoline compounds having oxazoline groups in side chains; and alkoxysilane compounds such as vinyltrimethoxysilane and N-(2-aminoethyl)3-aminopropyltrimethoxysilane.
  • polyfunctional acrylate compounds such as dimethylo
  • productivity can be improved in addition to improving the strength and durability of the reflective layer.
  • a commercial product may be used as the cross-linking agent, and examples thereof include “NK Ester A-DCP” (dimethylol-tricyclodecane diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. and the like.
  • the cross-linking agents may be used singly or in combination of two or more.
  • additives may be used singly or in combination of two or more.
  • the liquid crystal material preparation step is not particularly limited, and may be, for example, a step of forming a film (photopolymerizable reflective layer) by applying a photocurable liquid crystal composition containing a cholesteric liquid crystal compound to a substrate.
  • a photocurable liquid crystal composition containing a cholesteric liquid crystal compound for example, it may be a step of applying a liquid crystal composition to a substrate to form a coating film (liquid crystal layer).
  • the liquid crystal composition may contain a solvent.
  • the solvent is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of solubility, the solvent is preferably an organic solvent.
  • the method for preparing the liquid crystal composition is not particularly limited, and for example, the liquid crystal composition may be prepared by mixing each component such as a cholesteric liquid crystal compound.
  • the method of applying the liquid crystal composition to the substrate is not particularly limited, and examples thereof include spray coating, spin coating, blade coating, dip coating, casting, roll coating, bar coating, die coating, mist ink jet method, dispenser method, screen printing method, relief printing method, and intaglio printing method.
  • the liquid crystal composition When the liquid crystal composition contains a solvent, it may be dried after being applied to the substrate. Drying methods include, for example, drying by heating and drying under reduced pressure. In the case of drying by heating, the heating temperature and heating time may be appropriately adjusted according to the type of solvent. Moreover, you may perform heat drying as a part of following 1st heating process.
  • the first heating step is a step of heating the liquid crystal layer to form a cholesteric liquid crystal phase.
  • the cholesteric liquid crystal compound changes from the crystalline state to the oriented state, and further from the oriented state to the isotropic state.
  • the first heating step by heating the liquid crystal layer containing the cholesteric liquid crystal compound, the cholesteric liquid crystal compound is brought into an aligned state, and the liquid crystal layer becomes a cholesteric liquid crystal phase in which the cholesteric liquid crystal compound is aligned.
  • the heating temperature in the first heating step may be appropriately adjusted according to the type of cholesteric liquid crystal compound so that the cholesteric liquid crystal compound is aligned.
  • the heating time in the first heating step may be appropriately adjusted according to the heating temperature and the like.
  • the heating means is not particularly limited, and an oven, a hot plate, or the like may be used.
  • the first exposure and curing step is a step of irradiating a liquid crystal layer, preferably a liquid crystal layer in a cholesteric liquid crystal phase, with a first light to partially cure the liquid crystal layer.
  • a liquid crystal layer preferably a liquid crystal layer in a cholesteric liquid crystal phase
  • a part of the liquid crystal layer is cured with the cholesteric liquid crystal compound in an aligned state to emit right circularly polarized visible light. It becomes a reflective area or an area that reflects left circularly polarized visible light.
  • the exposure amount of the first light is not particularly limited, and when the first light is ultraviolet rays, it is preferably 0.1 mJ/cm 2 to 2,000 mJ/cm 2 , for example. From the viewpoint of controlling photocuring in the in-plane direction, the parallelism of ultraviolet rays is preferably 20° or less, more preferably 10° or less.
  • the first light may be irradiated through a first patterning mask having a plurality of regions with different transmittances for the first light.
  • a first patterning mask having a plurality of regions with different transmittances for the first light.
  • the type of light used in the torsion changing step is not particularly limited, but from the viewpoint of facilitating exposure of the photosensitive chiral agent, it is preferable to use ultraviolet light.
  • Ultra-high-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and light-emitting diodes (LEDs) are examples of ultraviolet light sources.
  • the wavelength range of the light used in the torsion changing step is not particularly limited, but is preferably a wavelength range in which the molar absorption coefficient of the photosensitive chiral agent is 100 times or more that of the photopolymerization initiator, such as 1,000 times. A wavelength range equal to or above is more preferable.
  • the wavelength range can be adjusted, for example, by a method using an optical filter, a method using two or more optical filters, or a method using a light source with a specific wavelength.
  • the uncured portion can be cured, and the curing of the region that reflects right-handed circularly polarized visible light or the region that reflects left-handed circularly polarized light formed in the first exposure step can be further accelerated.
  • the second light may be irradiated from the side of the substrate having the liquid crystal layer.
  • the second exposure step is performed in a low-oxygen atmosphere (preferably an oxygen concentration of 1,000 ppm or less, that is, an atmosphere containing no oxygen or an oxygen content of more than 0 ppm and 1,000 ppm or less) from the viewpoint of promoting curing. preferably in a nitrogen atmosphere, more preferably under a nitrogen atmosphere.
  • a low-oxygen atmosphere preferably an oxygen concentration of 1,000 ppm or less, that is, an atmosphere containing no oxygen or an oxygen content of more than 0 ppm and 1,000 ppm or less
  • a coating solution for forming an alignment layer having the composition described below was prepared.
  • UV-LED manufactured by CCS
  • CCS UV-LED
  • a reflective layer was formed by curing the liquid crystal layer with a liquid crystal.
  • the decorative film includes a region that reflects right-handed circularly polarized visible light and a region that reflects left-handed circularly polarized visible light in the thickness direction, and at least part of the in-plane direction reflects right-handed circularly polarized visible light. It includes a reflective region and a region that reflects left circularly polarized visible light.
  • a circularly polarized light-transmitting film was superimposed on the obtained decorative film and visually observed, and evaluated according to the following criteria. From the viewpoint of anti-counterfeiting properties, B is preferred, and A is more preferred. A: When the right-handed circularly polarized light-transmitting film is superimposed and visually recognized, a different color can be visually recognized from before being superimposed, and when the left-handed circularly polarized light-transmitting film is superimposed and visually recognized, a different color can be visually recognized from before being superimposed.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
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Abstract

L'invention concerne un film décoratif comprenant une couche de réflexion qui est une structure monocouche et qui comprend, dans au moins une partie de celui-ci, une région qui réfléchit la lumière visible à polarisation circulaire droite et une région qui réfléchit la lumière visible à polarisation circulaire gauche. La couche de réflexion est une couche qui comprend un composé de cristaux liquides aligné selon une forme hélicoïdale cholestérique, un agent chiral photosensible A qui induit la formation d'alignement hélicoïdal dans une première direction de torsion, et un agent chiral B qui induit la formation d'alignement hélicoïdal dans une direction de torsion opposée à la première direction de torsion, ou la couche de réflexion est une couche durcie obtenue par durcissement de la couche. L'invention concerne également : un corps moulé obtenu par moulage du film décoratif ; et un article pourvu du film décoratif ou du corps moulé.
PCT/JP2022/030787 2021-08-30 2022-08-12 Film décoratif, corps moulé et article WO2023032644A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003192808A (ja) * 2001-09-25 2003-07-09 Merck Patent Gmbh 異方性重合体フィルム
US20070246933A1 (en) * 2004-08-12 2007-10-25 Giesecke & Devrient Gmbh Security Element Comprising a Support
JP2009098454A (ja) * 2007-10-17 2009-05-07 Toppan Printing Co Ltd 光学素子、光学キット及びラベル付き印刷物
WO2018003359A1 (fr) * 2016-07-01 2018-01-04 富士フイルム株式会社 Filtre coloré stratifié, kit, procédé de fabrication de filtre coloré stratifié et capteur optique
WO2020196507A1 (fr) * 2019-03-28 2020-10-01 富士フイルム株式会社 Dispositif d'affichage à cristaux liquides de type à réflexion
WO2020262621A1 (fr) * 2019-06-28 2020-12-30 富士フイルム株式会社 Composition de cristaux liquides, couche de cristaux liquides cholestériques, produit durci, corps optiquement anisotrope et procédé de production de couche de cristaux liquides cholestériques

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003192808A (ja) * 2001-09-25 2003-07-09 Merck Patent Gmbh 異方性重合体フィルム
US20070246933A1 (en) * 2004-08-12 2007-10-25 Giesecke & Devrient Gmbh Security Element Comprising a Support
JP2009098454A (ja) * 2007-10-17 2009-05-07 Toppan Printing Co Ltd 光学素子、光学キット及びラベル付き印刷物
WO2018003359A1 (fr) * 2016-07-01 2018-01-04 富士フイルム株式会社 Filtre coloré stratifié, kit, procédé de fabrication de filtre coloré stratifié et capteur optique
WO2020196507A1 (fr) * 2019-03-28 2020-10-01 富士フイルム株式会社 Dispositif d'affichage à cristaux liquides de type à réflexion
WO2020262621A1 (fr) * 2019-06-28 2020-12-30 富士フイルム株式会社 Composition de cristaux liquides, couche de cristaux liquides cholestériques, produit durci, corps optiquement anisotrope et procédé de production de couche de cristaux liquides cholestériques

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