WO2022064776A1 - Film décoratif, son procédé de production, corps moulé à base de celui-ci et produit obtenu à partir de celui-ci - Google Patents

Film décoratif, son procédé de production, corps moulé à base de celui-ci et produit obtenu à partir de celui-ci Download PDF

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Publication number
WO2022064776A1
WO2022064776A1 PCT/JP2021/020827 JP2021020827W WO2022064776A1 WO 2022064776 A1 WO2022064776 A1 WO 2022064776A1 JP 2021020827 W JP2021020827 W JP 2021020827W WO 2022064776 A1 WO2022064776 A1 WO 2022064776A1
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Prior art keywords
liquid crystal
light
decorative film
layer
crystal layer
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PCT/JP2021/020827
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English (en)
Japanese (ja)
Inventor
千裕 増田
佑一 早田
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富士フイルム株式会社
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Priority to JP2022551140A priority Critical patent/JP7483026B2/ja
Publication of WO2022064776A1 publication Critical patent/WO2022064776A1/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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/02—Liquid crystal materials characterised by optical, electrical or physical properties of the components, in general
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • This disclosure relates to a decorative film, a manufacturing method thereof, a molded body, and an article.
  • decorative films are widely used to give designs to the surface of base materials used in the manufacture of electronic devices, home appliances, automobile parts, and the like.
  • a film utilizing wavelength selective reflectance due to multi-layer film interference is known, and various colors can be expressed by adjusting the reflectance of the surface thereof. Therefore, various techniques have been studied for adjusting the reflectance of the surface of a decorative film utilizing wavelength selective reflectance due to multilayer film interference to obtain a desired color.
  • International Publication No. 2018/186184 describes a decorative sheet containing a laminated body including a colored transmission layer and a reflection layer having wavelength selectivity for reflection.
  • an object to be solved by one embodiment of the present invention is to provide a decorative film whose reflectance can be controlled to an arbitrary reflectance.
  • An object to be solved by another embodiment of the present invention is to provide a method for producing the above-mentioned decorative film.
  • An object to be solved by another embodiment of the present invention is to provide a molded body obtained by molding the decorative film.
  • An object to be solved by another embodiment of the present invention is to provide an article provided with the above-mentioned molded body.
  • the reflective layer includes a plurality of regions in which the thickness of the light reflecting portion is different from each other in the in-plane direction.
  • the reflective layer includes a plurality of regions having different selective reflection wavelengths in the in-plane direction.
  • the plurality of regions having different selective reflection wavelengths differ from each other by 15 nm or more.
  • ⁇ 5> The decorative film according to any one of ⁇ 2> to ⁇ 4>, wherein the plurality of regions differ in maximum reflectance by 10% or more.
  • ⁇ 6> The decorative film according to any one of ⁇ 1> to ⁇ 5>, wherein the selective reflection wavelength of the reflective layer is 350 nm to 1200 nm.
  • the reflective layer is a cured product of the liquid crystal layer containing a cholesteric liquid crystal compound.
  • the light reflecting part is the cholesteric alignment part,
  • the translucent part is an isotropic part,
  • ⁇ 8> The decorative film according to ⁇ 7>, wherein the reflective layer includes a plurality of light reflecting portions in which the spiral pitch of the cholesteric liquid crystal compound differs by 10 nm or more in the in-plane direction.
  • the liquid crystal layer contains a photoisomerized chiral compound.
  • ⁇ 10> The decorative film according to any one of ⁇ 1> to ⁇ 9>, which contains a base material.
  • ⁇ 11> The decorative film according to any one of ⁇ 1> to ⁇ 10>, which includes a colored layer.
  • the liquid crystal layer contains a photoisomerized chiral compound and contains. Between the step of preparing the liquid crystal material and the step of curing a part of the liquid crystal layer, a step of irradiating the liquid crystal layer having a cholesteric liquid crystal phase with a third light to photoisomerize the photoisomerized chiral compound is included. , The method for producing a decorative film according to ⁇ 12> or ⁇ 13>. ⁇ 16> The addition according to ⁇ 15>, wherein in the step of photoisomerizing a photoisomerized chiral compound, the third light is irradiated through a second patterning mask having a plurality of regions having different transmittances of the third light.
  • the liquid crystal layer contains a photoradical polymerization initiator and contains.
  • the cholesteric liquid crystal compound comprises a cholesteric liquid crystal compound having a radically polymerizable group.
  • ⁇ 18> A molded body obtained by molding the decorative film according to any one of ⁇ 1> to ⁇ 11>.
  • ⁇ 20> The article according to ⁇ 19>, which is an electronic device.
  • a decorative film that can be controlled to an arbitrary reflectance.
  • a method for producing the decorative film there is provided a molded body obtained by molding the decorative film.
  • an article provided with the molded body is provided.
  • FIG. 1 is a schematic cross-sectional view showing an example of a decorative film according to the present disclosure.
  • FIG. 2 is a schematic cross-sectional view showing an example of a state in which the reflective layer is observed with a scanning electron microscope.
  • FIG. 3 is a schematic cross-sectional view showing an example of a liquid crystal material including a base material and a liquid crystal layer.
  • FIG. 4 is a schematic cross-sectional view showing an example of exposing the liquid crystal layer with the first light using the first patterning mask.
  • FIG. 5 is a schematic cross-sectional view showing an example of exposing the liquid crystal layer with the second light.
  • FIG. 6 is a schematic cross-sectional view showing an example of exposing the liquid crystal layer with the third light using the second patterning mask.
  • FIG. 7 is a schematic cross-sectional view showing an example of exposing the liquid crystal layer with the first light using the first patterning mask.
  • FIG. 8 is a schematic cross-sectional view showing an example of exposing the liquid crystal layer with the second light.
  • FIG. 9 is a schematic plan view showing the first patterning masks of Examples 1 to 3.
  • FIG. 10 is a schematic plan view showing the decorative film of Example 1.
  • FIG. 11 is a schematic cross-sectional view showing the decorative film of Example 1.
  • FIG. 12 is a schematic plan view showing the second patterning mask of the second embodiment.
  • FIG. 13 is a schematic plan view showing the decorative film of Example 2.
  • FIG. 14 is a schematic cross-sectional view showing the decorative film of Example 2.
  • FIG. 15 is a schematic plan view showing the decorative film of Example 3.
  • FIG. 16 is a schematic cross-sectional view showing the decorative film of Example 3.
  • FIG. 17 is a schematic plan view showing the glass member of the fourth embodiment.
  • FIG. 18 is a schematic cross
  • the numerical range indicated by using "-" in the present disclosure means a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in another stepwise description.
  • the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • the amount of each component means the total amount of a plurality of kinds of substances when there are a plurality of kinds of substances corresponding to each component, unless otherwise specified.
  • "light” is a concept including active energy rays such as ⁇ -rays, ⁇ -rays, electron rays, ultraviolet rays, and visible rays.
  • 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. ..
  • (meth) acrylic is a term used in a concept that includes both acrylic and methacrylic
  • (meth) acrylate is a term that is used as a concept that includes both acrylate and methacrylate.
  • Mw weight average molecular weight
  • the "total solid content” means the total mass of the components excluding the solvent from the total composition.
  • the “solid content” is a component obtained by removing the solvent from the entire composition, and may be, for example, a solid or a liquid at 25 ° C.
  • the decorative film according to the present disclosure includes a reflective layer composed of a single layer including a light reflecting portion having wavelength selective reflection and a translucent portion adjacent to the light reflecting portion in the thickness direction.
  • a decorative film that utilizes wavelength selective reflectance due to multi-layer film interference can express various colors by adjusting the reflectance of its surface.
  • a laminated body described in International Publication No. 2018/186184 it is necessary to paint and stack these layers separately.
  • a light reflecting portion having wavelength selective reflection and a light transmitting portion are provided in the reflecting layer composed of a single layer, and the light reflecting portion and the translucent portion are provided. And are arranged in the thickness direction so as to be adjacent to each other.
  • the reflective layer includes a light reflecting portion having wavelength selective reflection and a translucent portion adjacent to the light reflecting portion in the thickness direction, and is composed of a single layer.
  • the light reflecting unit having wavelength selective reflection property has a central wavelength of the selective reflection wavelength defined below (hereinafter, may be simply referred to as “selective reflection wavelength”).
  • the reflective layer including the light reflecting portion has wavelength selective reflection property derived from the light reflecting portion, and has the same selective reflection wavelength as the light reflecting portion. Therefore, when the reflective layer has wavelength selective reflectivity, the light reflecting portion also has wavelength selective reflectivity.
  • the "center wavelength of the selective reflection wavelength” is R max which is the maximum value and the maximum value (hereinafter, may be simply referred to as “maximum reflectance”) of the reflectance in the target object (member).
  • R max the maximum value and the maximum value (hereinafter, may be simply referred to as “maximum reflectance”) of the reflectance in the target object (member).
  • R 1/2 the average value of two wavelengths showing the half-value reflectance R 1/2 (%) expressed by the following formula.
  • one of the two wavelengths is the maximum wavelength in the wavelength range including a wavelength shorter than the wavelength indicating R max
  • the other wavelength of the two wavelengths is larger than the wavelength indicating R max .
  • the reflectance is the integrated reflectance measured by a spectrophotometer equipped with an integrating sphere device.
  • a spectrophotometer equipped with an integrating sphere device.
  • Commercially available products can be used as the spectrophotometer and the integrating sphere, and examples thereof include a spectrophotometer "V-670” manufactured by JASCO Corporation and a large-scale integrating sphere device "ILV-471" manufactured by JASCO Corporation.
  • the selective reflection wavelength and reflectance characterize the reflection spectrum and contribute to 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 having the same selective reflection wavelength may be referred to as "colors of the same system”
  • colors obtained from reflection spectra having different selective reflection wavelengths may be referred to as "colors of another system”. be.
  • by keeping the selective reflection wavelength constant and changing the reflectance it is possible to adjust the brightness and darkness with the same type of color. For example, 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 light and darkness with the same type of blue.
  • the selective reflection wavelength by changing the selective reflection wavelength, it is possible to obtain a color of another system. For example, by changing the selective reflection wavelength from 460 nm (blue) to 552 nm (green), green, which is a color of another system, can be obtained.
  • the thickness of the light reflecting portion and the translucent portion is not particularly limited, and may be appropriately adjusted so as to obtain a desired reflectance.
  • the thickness of the light reflecting portion and the translucent portion can be measured by observing the cross section of the reflecting layer with a scanning electron microscope (SEM).
  • the thickness of the reflective layer is not particularly limited, but is preferably 0.1 ⁇ m to 10 ⁇ m, more preferably 0.3 ⁇ m to 8 ⁇ m, and more preferably 0.5 ⁇ m to 0.5 ⁇ m from the viewpoint of obtaining a more appropriate reflectance. It is more preferably 6 ⁇ m.
  • the reflective layer may include a region having no translucent portion in addition to a region having a reflective portion and a translucent portion, and in a region having no translucent portion, the reflectance of the reflective layer is the reflection of the reflective portion. It becomes the same as the rate.
  • the reflective layer 10 includes a region a1 having a reflective portion 11 and a translucent portion 12, and a region a2 and a region a3 having no translucent portion 12. In this case, the reflectances of the regions a2 and a3 are the same as the reflectances of the light reflecting unit 11.
  • the reflective layer may include a plurality of regions having different thicknesses of the light reflecting portions in the in-plane direction. As a result, a plurality of regions having different reflectances can be provided in the in-plane direction, and the color can be changed in the in-plane direction.
  • the difference in thickness between the light reflecting portions is not particularly limited, and may be appropriately adjusted so as to obtain a desired reflectance.
  • the reflective layer may include a plurality of regions having different selective reflection wavelengths in the in-plane direction.
  • a plurality of regions having different selective reflection wavelengths can be provided in the in-plane direction, and the color can be changed in the in-plane direction.
  • the difference in the selective reflection wavelength between the regions is not particularly limited, and may be appropriately adjusted so that a desired selective reflection wavelength can be obtained.
  • the regions may differ in selective reflection wavelength by 15 nm or more, which allows the color to change more clearly in the in-plane direction.
  • the upper limit of the difference in the selective reflection wavelength may be, for example, 850 nm.
  • a plurality of regions having different thicknesses of the light reflecting portions may have different maximum reflectances of 10% or more. This makes it possible to change the color more clearly in the in-plane direction. Further, the maximum reflectance may be different by 10% or more in the plurality of regions having different selective reflection wavelengths. This makes it possible to change the color more clearly in the in-plane direction. For example, by setting a constant selective reflection wavelength and providing a plurality of regions having different maximum reflectances of 10% or more in the reflection layer, it is possible to obtain clearer light and shade with the same system of colors.
  • the upper limit of the difference in maximum reflectance is not particularly limited, and may be, for example, 90%.
  • the reflective layer is a cured product of the liquid crystal layer containing the cholesteric liquid crystal compound (detailed later)
  • the reflective layer reflects only the polarization corresponding to the twisting direction of the spiral of the cholesteric liquid crystal compound, so that the maximum reflectance is 50. % Is the upper limit.
  • the upper limit of the difference in the maximum reflectance is not particularly limited, and may be, for example, 40%.
  • the selective reflection wavelength of the reflective layer is preferably 350 nm to 1200 nm. Above all, 380 nm to 780 nm is more preferable.
  • the reflective layer is preferably a cured product of the liquid crystal layer containing a cholesteric liquid crystal compound.
  • the "cured product of the liquid crystal layer” includes a dried product and a polymerized cured product of the liquid crystal composition containing the components contained in the liquid crystal layer.
  • the light reflecting portion exhibiting wavelength selective reflectivity means a cholesteric oriented portion in which the cholesteric liquid crystal compound is oriented.
  • the translucent portion refers to a non-oriented isotropic portion in which the cholesteric liquid crystal compound does not have a constant orientation.
  • the presence or absence of orientation of the cholesteric liquid crystal compound in the reflective layer can be observed using SEM as follows.
  • the light reflecting portion 11 which is the cholesteric oriented portion in which the cholesteric liquid crystal compound is oriented is refracted. Due to the change in the rate, the bright part B and the dark part D are observed as a striped pattern in which the bright part B and the dark part D are alternately laminated in the thickness direction. On the other hand, no striped pattern is observed in the translucent portion 12 in which the cholesteric liquid crystal compound is an isotropic portion in which the cholesteric liquid crystal compound is non-oriented.
  • the portion where the striped pattern between the bright portion and the dark portion is observed is determined to be the light reflecting portion 11, and the other portion is determined to be the translucent portion 12.
  • One repeated cycle of the bright part B and the dark part D corresponds to 180 degrees of the twist of the cholesteric liquid crystal compound. Therefore, the repeated two cycles of the bright part B and the dark part D correspond to 360 degrees of the twist of the cholesteric liquid crystal compound. That is, the width P between these two bright portions B and the two dark portions D is the spiral pitch of the cholesteric liquid crystal compound (hereinafter, may be simply referred to as "spiral pitch").
  • the spiral pitch contributes to the selective reflection wavelength of the light reflecting portion. That is, when the spiral pitch becomes long, the selective reflection wavelength becomes long, while when the spiral pitch becomes short, the selective reflection wavelength becomes short. Therefore, by adjusting the spiral pitch, the selective reflection wavelength can be controlled, and the color of a desired system can be obtained more easily.
  • the reflective layer may include a plurality of regions having different spiral pitches of 10 nm or more in the in-plane direction. This makes it possible to change the color more clearly while providing a region having a different system of color in the in-plane direction.
  • the upper limit of the difference in the spiral pitch is not particularly limited and may be, for example, 850 nm.
  • the decorative film may contain a substrate. As a result, the strength of the decorative film can be increased, which makes it easier to handle.
  • the decorative film contains a base material
  • the base material can be used as a member constituting the molded body obtained by molding the decorative film.
  • the shape and material of the base material are not particularly limited, and may be appropriately selected as desired.
  • the base material is preferably a resin base material from the viewpoint of ease of molding.
  • Polyimide PI
  • Polymethylmethacrylate PMMA
  • Polycarbonate PC
  • Acrylic-Polycarbonate Resin Polyacrylate, Polymethacrylate, Polypropylene (PP), Polystyrene (PS), Polyacrylonitrile-butadiene-styrene copolymer (ABS), cyclic olefin-polymer (COC), cycloolefin polymer (COP), triacetyl cellulose (TAC), urethane resin, and urethane-acrylic resin.
  • the thickness of the base material is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, and more preferably 20 ⁇ m or more, from the viewpoint of the strength of the decorative film and the molding processability when molding the decorative film. More preferred. From the same viewpoint, the thickness of the base material is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, and further preferably 150 ⁇ m or less.
  • the position of the colored layer is not particularly limited and may be provided at a desired position.
  • the colored layer may be provided on the reflective layer.
  • the decorative film may be provided on the side opposite to the side on which the reflective layer of the base material is formed, and the decorative film containing the base material is peeled off from the base material. It may be a decorative film and may be provided on the decorative film after the base material is peeled off.
  • Examples of the inorganic pigment include the inorganic pigments described in paragraphs 0015 and 0114 of JP-A-2005-7765.
  • the pigment may be a pigment having light transmission and light reflection (so-called brilliant pigment).
  • brilliant pigment examples include aluminum, copper, zinc, iron, nickel, tin, aluminum oxide, and metal brilliant pigments of these alloys, interfering mica pigments, white mica pigments, graphite pigments, and glass flake pigments. Can be mentioned.
  • the bright pigment may be uncolored or colored.
  • colorant one type may be used alone, or two or more types may be used in combination.
  • an inorganic pigment and an organic pigment may be combined.
  • the content of the colorant is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 50% by mass, based on the total amount of the colored layer, from the viewpoint of the desired color development. It is particularly preferably 10% by mass to 40% by mass.
  • binder resin examples include acrylic resin, silicone resin, polyester, polyurethane, and polyolefin.
  • the binder resin may be a homopolymer or a copolymer.
  • binder resin one type may be used alone, or two or more types may be used in combination.
  • the content of the binder resin is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and 20% by mass, based on the total amount of the colored layer. It is particularly preferably from mass% to 60% by mass.
  • the colored layer may contain a dispersant.
  • the inclusion of the dispersant improves the dispersibility of the colorant in the colored layer. 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.
  • the polymer dispersant 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.
  • one type may be used alone, or two or more types may be used in combination.
  • the colored layer may contain additives, if necessary, in addition to the above-mentioned components.
  • the additive is not particularly limited, and is described in, for example, 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; Examples thereof include thermal polymerization inhibitors (also referred to as polymerization inhibitors, preferably phenothiazines); and additives described in paragraphs 0058 to 0071 of JP-A-2000-310706.
  • a method of forming a colored layer using a colored layer forming composition a method of applying a colored layer forming composition to form a colored layer, for example, printing a colored layer forming composition to form a colored layer.
  • the method of forming is mentioned.
  • Examples of the printing method include 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 type of each component may be the one described above for the colored layer.
  • the content of the colorant 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 the colored layer. It is particularly preferably% to 40% by mass.
  • the content of the binder resin is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and 20% by mass, based on the total solid content of the composition for forming the colored layer. It is particularly preferably% to 60% by mass.
  • the content of the dispersant is preferably 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the colorant.
  • the content of the organic solvent is preferably 5% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, based on the total amount of the composition for forming the colored layer.
  • the alignment layer is provided, for example, by a rubbing treatment of an organic compound (preferably a polymer), an orthorhombic deposition of an inorganic compound, a layer having microgrooves, or the like.
  • an alignment layer in which an alignment function is generated by applying an electric field, applying a magnetic field, or irradiating light is also known.
  • -Rubbing treatment alignment layer- A rubbing treatment is performed on the surface of the base to which the liquid crystal composition is applied.
  • the rubbing treatment can be performed, for example, 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 Maruzensha, October 30, 2000).
  • Examples of the polymer for the orientation layer forming the film containing the polymer as the main component as described above include the methacrylate-based copolymer, the styrene-based copolymer, and the polyolefin described in paragraph 0022 of JP-A-8-338913.
  • Examples thereof include polyvinyl alcohol, modified polyvinyl alcohol, poly (N-methylolacrylamide), polyester, polyimide, vinyl acetate copolymer, carboxymethyl cellulose, and polycarbonate.
  • the polymer for the alignment layer may be a silane coupling agent.
  • the polymer for the alignment layer is preferably a water-soluble polymer (for example, poly (N-methylolacrylamide), carboxymethyl cellulose, gelatin, polyvinyl alcohol, or modified polyvinyl alcohol), more preferably gelatin, polyvinyl alcohol or modified polyvinyl alcohol, and polyvinyl alcohol.
  • modified polyvinyl alcohol is particularly preferable.
  • N is the number of rubbing
  • l is the contact length of the rubbing roller
  • r is the radius of the roller
  • n is the rotation speed of the roller (rpm; revolutions per minute)
  • v is the stage moving speed (speed per second).
  • Examples thereof include photocrosslinkable polyimides, polyamides, and esters described in Japanese Patent Publication No.
  • the photoalignment material is preferably an azo compound, a photocrosslinkable polyimide, a polyamide, or an ester.
  • linearly polarized irradiation is an operation for causing a photoreaction in a photo-aligned material.
  • the wavelength of the 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 light used for light irradiation is preferably light having a peak wavelength of 200 nm to 700 nm, and more preferably ultraviolet light having a peak wavelength of 400 nm or less.
  • 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 and other lamps, and various lasers (for example, semiconductor lasers, etc.). Examples include helium neon lasers, argon ion lasers, helium cadmium lasers, or YAG lasers), light emitting diodes, and cathode wire tubes.
  • the light to be irradiated is linearly polarized light
  • a method of irradiating light from the upper surface or the back surface of the alignment layer in a direction perpendicular to the surface of the alignment layer or in an oblique direction can be mentioned.
  • the incident angle of light varies depending on the photoalignment material, but is preferably 0 ° to 90 ° (perpendicular) and more preferably 40 ° to 90 ° with respect to the alignment layer.
  • the decorative film may have other layers other than the colored layer and the oriented layer.
  • a protective layer an adhesive layer, an ultraviolet absorbing layer, a reflective layer, a self-repairing layer, an antistatic layer, an antifouling layer, an electromagnetic waveproof layer, a conductive layer, and the like, which are known layers in decorative films. Can be mentioned.
  • layers can be formed by a known method. For example, a method of applying a composition containing the components contained in these layers (layer-forming composition) in a layered manner and drying the composition can be mentioned.
  • the method for producing the decorative film is not particularly limited, but the decorative film is preferably produced using the photocurable liquid crystal composition containing the cholesteric liquid crystal compound by the method for producing the decorative film according to the present disclosure described below. can do.
  • a step of heating the liquid crystal layer after irradiation with the first light to make the uncured portion of the liquid crystal layer an isotropic phase (hereinafter, may be referred to as a "second heating step”).
  • a step of irradiating an uncured portion having at least an isotropic phase with a second light to cure the uncured portion (hereinafter, may be referred to as a “second exposure step”). including.
  • the liquid crystal material preparation step is a step of preparing a liquid crystal material having a base material and a photocurable liquid crystal layer containing a cholesteric liquid crystal compound.
  • Base material As the base material, those described above can be used.
  • the liquid crystal layer contains a cholesteric liquid crystal compound, and may contain other components such as a chiral compound described later, if necessary.
  • 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 more easily fixing the helical structure of the cholesteric liquid crystal compound, the cholesteric liquid crystal compound preferably contains a cholesteric liquid crystal compound having a reactive group.
  • the reactive group include a vinyl group, a (meth) acryloyl group, an epoxy group, an oxetanyl group, a vinyl ether group, a hydroxy group, a carboxy group, and an amino group.
  • the cross-linking mechanism of the reactive group include condensation reaction, 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 as a combination of the polymerizable groups.
  • the combination is 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-shaped cholesteric liquid crystal compound or a disc-shaped cholesteric liquid crystal compound.
  • the cholesteric liquid crystal compound is preferably a rod-shaped cholesteric liquid crystal compound from the viewpoint of more easily adjusting the spiral pitch of the cholesteric alignment portion and more easily suppressing the change in reflectance and color with time.
  • rod-shaped cholesteric liquid crystal compound 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).
  • disc-shaped cholesteric liquid crystal compound examples include a low molecular weight disc-shaped cholesteric liquid crystal compound such as a monomer and a polymerizable disc-shaped cholesteric liquid crystal compound.
  • disc-shaped cholesteric liquid crystal compounds examples include C.I. Research report by Destrade et al., Mol. Cryst. Benzene derivatives described in Vol. 71, p. 111 (1981); C.I. Research report by Destrade et al., Mol. Cryst. The tolucene derivative described in Volume 122, page 141 (1985), Physiclett, A, Volume 78, page 82 (1990); B. et al. Research report by Kohne et al., Angew. Chem. Cyclohexane derivatives described in Vol. 96, p. 70 (1984); M. Research report by Lehn et al., J. Mol. Chem. Commun.
  • cholesteric liquid crystal compound having a reactive group When a disk-shaped cholesteric liquid crystal compound having a reactive group is used as the cholesteric liquid crystal compound, it may be fixed in any of horizontal orientation, vertical orientation, inclined orientation, and torsional orientation in the cured liquid crystal film. ..
  • the content of the cholesteric liquid crystal compound is preferably 30% by mass to 100% by mass, preferably 40% by mass to 95% by mass, based on the total solid content of the liquid crystal layer, from the viewpoint of further increasing the reflectance of the reflective layer. It is more preferably 50% by mass to 90% by mass.
  • the liquid crystal layer preferably contains a chiral compound (that is, an optically active compound) from the viewpoint of ease of forming a cholesteric alignment layer and easiness of adjusting the spiral pitch.
  • the chiral compound has a function of inducing a helical structure for a cholesteric liquid crystal compound.
  • the chiral compound may be selected according to the purpose because the twisting direction or the spiral pitch of the induced spiral differs depending on the liquid crystal compound.
  • the chiral compound is not particularly limited, and a known compound (for example, "Liquid Crystal Device Handbook", Chapter 3, Section 4-3, TN (twisted nematic), STN (Super-twisted nematic) chiral agent, p.
  • the content of the chiral compound may be 1% by mass to 20% by mass with respect to the total solid content of the liquid crystal layer from the viewpoint of more easily obtaining the target reflection wavelength. It is preferably 1% by mass to 15% by mass, more preferably 1% by mass to 10% by mass.
  • the compound represented by the following formula (CH1) can change the orientation structure such as the spiral pitch (twisting force, spiral twisting angle) of the cholesteric liquid crystal phase according to the exposure amount at the time of exposure.
  • 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.
  • the aryl group in Ar CH1 and Ar CH2 of the formula (CH1) may have a substituent, preferably has a total carbon number of 6 to 40, and more preferably has a total carbon number of 6 to 30.
  • the substituent is 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 heterocyclic group.
  • 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.
  • Ar CH1 and Ar CH2 are preferably aryl groups represented by the following formula (CH2) or formula (CH3), and more preferably aryl groups represented by the following formula (CH2).
  • 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).
  • L CH1 and L CH2 in the formula (CH2) and the formula (CH3) are independently alkoxy groups having 1 to 10 carbon atoms or hydroxy groups, respectively.
  • NCH2 in the formula (CH3) is preferably 0 or 1, more preferably 0.
  • the complex aromatic ring group in Ar CH1 and Ar CH2 of the formula (CH1) may have a substituent, preferably has a total carbon number of 4 to 40, and more preferably has a total carbon number of 4 to 30. preferable.
  • 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.
  • the following compounds are preferably mentioned as the compound represented by the formula (CH1).
  • the following compounds are compounds in which the molecular configuration of each ethylenically unsaturated bond changes with exposure.
  • photoisomerized chiral compound one type may be used alone, or two or more types may be used in combination.
  • the content of the photoisomerized chiral compound is 0.5% by mass with respect to the total solid content of the liquid crystal layer from the viewpoint of more easily obtaining the target reflection wavelength. It is preferably ⁇ 15% by mass, more preferably 1% by mass to 10% by mass, and even more preferably 2% by mass to 7% by mass.
  • Examples of the polymerizable group of the polymerizable chiral compound include a radical polymerizable group and a cationically polymerizable group.
  • the polymerizable group is preferably an ethylenically unsaturated group, an epoxy group or an aziridinyl group, and more preferably an ethylenically unsaturated group.
  • the polymerizable chiral compound is preferably a compound containing an asymmetric carbon atom, but may be an axial asymmetric compound or a planar asymmetric compound that does not contain an asymmetric carbon atom.
  • axial or asymmetric compounds include binaphthyl, helicene, paracyclophane and derivatives thereof.
  • the polymerizable chiral compound preferably contains a polymerizable group of the same type as the polymerizable group of the cholesteric liquid crystal compound.
  • the polymerizable chiral compound also contains a radically polymerizable group.
  • the polymerizable chiral compound is preferably an isosorbide derivative, an isomannide derivative, or a binaphthyl derivative.
  • isosorbide derivatives include "Paliocolor LC756" manufactured by BASF.
  • the content of the polymerizable chiral compound is 0.5% by mass to 8% by mass with respect to the total solid content of the liquid crystal layer from the viewpoint of more easily obtaining the target reflection wavelength. It is preferably by mass, more preferably 1% by mass to 10% by mass, and even more preferably 1% by mass to 5% by mass.
  • 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 compound), 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 can initiate a polymerization reaction by irradiation with light. It is preferably an agent.
  • photopolymerization initiator examples include ⁇ -carbonyl compounds (for example, described in US Pat. Nos. 2,376,661 and US Pat. No. 2,376,670) and acidoin ether compounds (for example, US Pat. No. 2,448,828). ), ⁇ -hydrogen-substituted aromatic acidoine compounds (eg, described in US Pat. No. 2,225,512), polynuclear quinone compounds (eg, US Pat. No. 3,46127, US Pat. No. 2,951,758. ), Combination of triarylimidazole dimer and p-aminophenylketone (eg, described in US Pat. No.
  • the photopolymerization initiator may be a photoradical polymerization initiator or a photocationic polymerization initiator.
  • Preferred examples of the photoradical polymerization initiator include ⁇ -hydroxyacetophenone compound, ⁇ -aminoalkylphenone compound, acylphosphine oxide compound, thioxanthone compound, and oxime ester compound.
  • a commercially available product may be used as the photoradical polymerization initiator, and as a commercially available product, for example, IGM Resins B.I. V. Examples thereof include "Omnirad 907" (2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one) manufactured by the same company.
  • photocationic polymerization initiator examples include an iodonium salt compound and a sulfonium salt compound.
  • the liquid crystal layer contains a photoradical polymerization initiator and the cholesteric liquid crystal compound contains a cholesteric liquid crystal compound having a radical polymerizable group.
  • polymerization initiator one type may be used alone, or two or more types may be used in combination.
  • the content of the polymerization initiator can be appropriately selected depending on the structure of the cholesteric liquid crystal compound and the like, but from the viewpoint of curability, the content of the polymerization initiator is relative to the total solid content of the liquid crystal layer. , 0.1% by mass to 5% by mass, more preferably 0.2% by mass to 3% by mass, and even more preferably 0.3% by mass to 1.5% by mass.
  • the liquid crystal layer may contain a cross-linking agent from the viewpoint of improving the strength and durability of the liquid crystal film.
  • the cross-linking agent is preferably a compound whose reaction proceeds by ultraviolet rays, heat, humidity and the like.
  • cross-linking agent examples include polyfunctional acrylate compounds such as dimethylol-tricyclodecandi (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate; glycidyl (meth) acrylate and ethylene glycol di.
  • Epoxy compounds such as glycidyl ether; aziridine compounds such as 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], 4,4-bis (ethyleneiminocarbonylamino) diphenylmethane; hexamethylenediisocyanate, biuret
  • isocyanate compounds such as type isocyanates
  • polyoxazoline compounds having an oxazoline group in the side chain
  • alkoxysilane compounds such as vinyltrimethoxysilane and N- (2-aminoethyl) 3-aminopropyltrimethoxysilane.
  • a commercially available product may be used as the cross-linking agent, and examples of the commercially available product include "NK ester A-DCP" (dimethylol-tricyclodecanediacrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
  • cross-linking agent one type may be used alone, or two or more types may be used in combination.
  • the content of the cross-linking agent is preferably 0.1% by mass to 6% by mass with respect to the total solid content of the liquid crystal layer from the viewpoint of the orientation of the cholesteric liquid crystal compound. , 0.5% by mass to 5% by mass, more preferably 1% by mass to 4% by mass.
  • the liquid crystal layer may contain other additives other than the above-mentioned components, if necessary.
  • Other additives include, for example, surfactants, polymerization inhibitors, antioxidants, horizontal orientation agents, UV absorbers, light stabilizers, colorants, and metal oxide particles.
  • one type may be used alone, or two or more types may be used in combination.
  • the liquid crystal material preparation step is not particularly limited, and may be, for example, a step of applying a photocurable liquid crystal composition containing a cholesteric liquid crystal compound to a substrate to form a film (liquid crystal layer), for example, a liquid crystal composition. It may be a step of applying an object 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 intended purpose.
  • the solvent is preferably an organic solvent from the viewpoint of solubility.
  • organic solvent examples include ketones such as methyl ethyl ketone and methyl isobutyl ketone; alkyl halides, amides, sulfoxides, heterocyclic compounds, hydrocarbons, esters, ethers, and alcohols. Of these, ketones are preferable from the viewpoint of solubility of the cholesteric liquid crystal compound and consideration for environmental load.
  • one type may be used alone, or two or more types may be used in combination.
  • 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 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 cholesteric liquid crystal compound.
  • the method of applying the liquid crystal composition to the substrate is not particularly limited, and for example, a spray coating method, a spin coating method, a blade coating method, a dip coating method, a casting method, a roll coating method, a bar coating method, a die coating method, and a mist method. , Inkjet method, dispenser method, screen printing method, letterpress printing method, and intaglio printing method.
  • the liquid crystal composition may be applied to the substrate and then dried.
  • drying method include heat drying and vacuum drying.
  • the heating temperature and the heating time may be appropriately adjusted according to the type of solvent. Further, the heating and drying may be performed as a part of the first heating step described below.
  • 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 a crystalline state to an oriented state, and further from an oriented state to an isotropic state.
  • the liquid crystal layer containing the cholesteric liquid crystal compound is heated so that the cholesteric liquid crystal compound is in the oriented state and the liquid crystal layer is the cholesteric liquid crystal phase in which the cholesteric liquid crystal compound is oriented.
  • the heating temperature in the first heating step may be appropriately adjusted according to the type of the cholesteric liquid crystal compound so that the cholesteric liquid crystal compound is in the oriented state.
  • 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 step is a step of irradiating the liquid crystal layer having the cholesteric liquid crystal phase with the first light to cure a part of the liquid crystal layer.
  • a part of the liquid crystal layer is cured in the oriented state of the cholesteric liquid crystal compound to become a light reflecting portion.
  • the photocuring of the liquid crystal layer progresses in the thickness direction of the reflecting layer, the light reflecting portion becomes thicker.
  • a mask including a region for reducing the transmittance of the first light is used as a means for curing a part of the liquid crystal layer without completely curing the liquid crystal layer.
  • a method of reducing the exposure amount of the first light a mask including a region for reducing the transmittance of the first light is used. Examples thereof include a method of exposing the first light, a method of absorbing light by a compound contained in the liquid crystal layer, a method of suppressing polymerization by a polymerization inhibitor, a method of suppressing polymerization by oxygen, and a combination thereof.
  • the type of the first light is not particularly limited, but it is preferable to use ultraviolet rays in consideration of the reactivity of the components that can be contained in the liquid crystal compound.
  • Examples of the light source of ultraviolet rays include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and a light emitting diode (LED; Light Mission Diode).
  • the wavelength range of the first light is not particularly limited, but when the first light is ultraviolet light, it is preferably 400 nm or less, more preferably 360 nm or less, and further preferably 300 nm or less. When light of 300 nm or less is used, the light absorption of the cholesteric liquid crystal compound makes it easier to control the photocuring in the thickness direction.
  • the wavelength range can be adjusted by, for example, a method using an optical filter, a method using two or more types of optical filters, or a method using a light source having a specific wavelength.
  • the exposure amount of the first light is not particularly limited, and when the first light is ultraviolet rays, it may be, for example, 0.1 mJ / cm 2 to 2,000 mJ / cm 2 . From the viewpoint of controlling photocuring in the in-plane direction, the parallelism of ultraviolet rays is preferably 20 ° or less, and more preferably 10 ° or less.
  • the reflective layer may include the light reflecting portion and the translucent portion in any order with respect to the base material. That is, the reflective layer may include the light reflecting portion and the light transmitting portion in order from the base material side, and may include the light transmitting portion and the light reflecting portion in order from the base material side. From the viewpoint of controlling photocuring by oxygen concentration, which will be described later, it is more preferable that the reflective layer includes a light reflecting portion and a translucent portion in order from the substrate side.
  • the first exposure step exposes the base material from the side opposite to the side having the liquid crystal layer.
  • the first exposure step is to expose from the side having the liquid crystal layer of the base material.
  • the first exposure step is a low oxygen atmosphere when the substrate is exposed from the side opposite to the side having the liquid crystal layer. It may be carried out in an oxygen concentration of 1,000 ppm or less, that is, an atmosphere containing no oxygen or an oxygen of more than 0 ppm and 1,000 ppm or less, and in an atmosphere containing oxygen (atmosphere or containing 1000 ppm or more and less than 21% oxygen). It is more preferable that it is performed in an atmosphere). Since radical polymerization is inhibited by oxygen, it becomes easier to control photocuring in the thickness direction.
  • the first exposure step is performed in a low oxygen atmosphere (preferably oxygen concentration 1) from the viewpoint of promoting the curing of the light-reflecting portion. It is preferably carried out in an atmosphere of 000 ppm or less, that is, an atmosphere containing no oxygen or containing oxygen of more than 0 ppm and 1,000 ppm or less), and more preferably carried out in a nitrogen atmosphere.
  • a low oxygen atmosphere preferably oxygen concentration 1
  • the first light may be irradiated through the first patterning mask having a plurality of regions having different transmittances of the first light.
  • the first patterning mask having a plurality of regions having different transmittances of the first light.
  • the first patterning mask examples include a photomask in which patterns in a plurality of regions having different transmittances of the first light are formed.
  • pattern printing is performed using, for example, a photomask in which a pattern is formed by etching a metal film, and various printing methods (for example, printing by a laser printer or an inkjet printer, gravure printing, screen printing).
  • Photo masks can be mentioned.
  • a photomask in which a pattern is formed by etching a metal film can be obtained, for example, by forming a metal chromium film on a quartz substrate by sputtering and then patterning with a photoresist.
  • the first patterning mask When the first patterning mask is used to irradiate the first light, the first patterning mask may be arranged on the side opposite to the side having the liquid crystal layer of the base material, and may be arranged on the side having the liquid crystal layer of the base material. It's okay.
  • the first patterning mask When the first patterning mask is arranged on the side having the liquid crystal layer of the base material, the first patterning mask may be brought into contact with the liquid crystal layer to irradiate the first light, and a gap between the liquid crystal layer and the first patterning mask may be applied. May be provided to irradiate the first light.
  • the first patterning mask is arranged on the side opposite to the side having the liquid crystal layer of the base material, it is preferable to use a translucent base material because the liquid crystal layer is exposed by the first light through the base material.
  • the transmittance of the first light is not particularly limited, but a higher value is preferable from the viewpoint of more easily curing the liquid crystal layer.
  • only one type of the first patterning mask may be used, or two or more types may be used.
  • the second heating step is a step of heating the liquid crystal layer after irradiation with the first light to make the uncured portion of the liquid crystal layer an isotropic phase.
  • the cholesteric liquid crystal compound becomes an isotropic state.
  • the liquid crystal layer including the uncured portion that is not cured in the first exposure step is heated so that the cholesteric liquid crystal compound contained in the uncured portion is in an isotropic state, and the uncured portion is cholesteric.
  • the liquid crystal compound has a non-oriented isotropic phase.
  • the heating temperature in the second heating step may be appropriately adjusted according to the type of the cholesteric liquid crystal compound so that the cholesteric liquid crystal compound is in an isotropic state.
  • the heating time in the second 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 second exposure step is a step of irradiating the uncured portion having at least an isotropic phase with the second light to cure the uncured portion.
  • the uncured portion is cured in an isotropic state of the cholesteric liquid crystal compound to become a translucent portion.
  • a reflective layer composed of a single layer including the light reflecting portion and the translucent portion adjacent to the light reflecting portion in the thickness direction is formed.
  • the second exposure step not only the uncured portion but the entire liquid crystal layer may be exposed. This makes it possible to cure the uncured portion and further accelerate the curing of the light reflecting portion formed in the first exposure step.
  • the second light may be irradiated from the side having the liquid crystal layer of the base material.
  • the type of the second light is not particularly limited, but it is preferable to use ultraviolet rays in consideration of the reactivity of the components that can be contained in the liquid crystal compound.
  • Examples of the light source of ultraviolet rays include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and light emitting diodes (LEDs).
  • the type of the second light is the same as the type of the first light.
  • the wavelength range of the second light is not particularly limited, and for example, light having a wavelength range of 250 nm to 400 nm can be used.
  • the wavelength range can be adjusted by, for example, a method using an optical filter, a method using two or more types of optical filters, or a method using a light source having a specific wavelength.
  • the exposure amount of the second light is not particularly limited, and when the second light is ultraviolet light, it may be, for example, 5 mJ / cm 2 to 2,000 mJ / cm 2 .
  • 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 containing oxygen of more than 0 ppm and 1,000 ppm or less) from the viewpoint of accelerating curing. It is preferable that it is carried out, and it is more preferable that it is carried out in 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 containing oxygen of more than 0 ppm and 1,000 ppm or less
  • the substrate is translucent and
  • the first light is irradiated through the first patterning mask and the base material from the side opposite to the side having the liquid crystal layer of the base material.
  • the second light is irradiated from the side having the liquid crystal layer of the base material.
  • a liquid crystal material 200p having a base material 30 and a liquid crystal layer 10p is prepared (liquid crystal material preparation step), and the liquid crystal layer 10p is heated to obtain a cholesteric liquid crystal phase (first heating step). ..
  • one surface of the base material 30 is a first patterning mask 50 including a region 51 having a high transmittance of the first light and a region 52 having a low transmittance of the first light.
  • the light is emitted.
  • the reflective portion 11 is formed.
  • second heating step after heating the liquid crystal layer 10p to make the uncured portion 12p in the liquid crystal layer 10p an isotropic phase (second heating step), as shown in FIG. 5, from the side of the base material 30 having the liquid crystal layer 10p.
  • the uncured portion 12p is cured by irradiating the second light L2 (second exposure step) to form the translucent portion 12.
  • a decorative film including a reflective layer 10 composed of a single layer including a light reflecting portion 11 and a translucent portion 12 adjacent to the light reflecting portion 11 in the thickness direction. 200 can be manufactured.
  • the reflective layer 10 includes a light reflecting portion 11 and a light transmitting portion 12 in order from the base material 30 side.
  • the method for producing a decorative film according to the present disclosure uses a liquid crystal layer containing a photoisomerized chiral compound, and uses a liquid crystal layer having a cholesteric liquid crystal phase between the first heating step and the first exposure step. 3. It may include a step of irradiating with light to photoisomerize the photoisomerized chiral compound (hereinafter, may be referred to as a “third exposure step”).
  • the selective reflection wavelength can be changed to obtain a color of another system.
  • the type of the third light is not particularly limited, but it is preferable to use ultraviolet rays from the viewpoint of making the photoisomerized chiral compound more easily photoisomerized.
  • Examples of the light source of ultraviolet rays include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and light emitting diodes (LEDs).
  • the wavelength range of the third light is not particularly limited, and may be appropriately adjusted in consideration of the type of the photoisomerized chiral compound, the target selective reflection wavelength, the photoisomerization rate, and the like.
  • the third light is ultraviolet light, it is preferably 400 nm or less, more preferably 380 nm or less, and even more preferably 300 nm to 380 nm.
  • the wavelength range can be adjusted by, for example, a method using an optical filter, a method using two or more types of optical filters, or a method using a light source having a specific wavelength.
  • the wavelength range of the third light that photoisomerizes the photoisomerized chiral compound is set. It is preferably different from the wavelength range of the first light that photocures the liquid crystal composition. As a result, the photocuring of the liquid crystal composition by the third light can be suppressed, and the photoisomerized chiral compound can be photoisomerized more easily, so that the selective reflection wavelength can be more easily adjusted.
  • the exposure amount of the third light is not particularly limited, and may be appropriately adjusted in consideration of the type of the photoisomerized chiral compound, the target selective reflection wavelength, the photoisomerization rate, and the like.
  • the third light is ultraviolet light, it may be, for example, 0.1 mJ / cm 2 to 2000 mJ / cm 2 .
  • the third light may be irradiated through the second patterning mask having a plurality of regions having different transmittances of the third light.
  • the second patterning mask having a plurality of regions having different transmittances of the third light.
  • Examples of the second patterning mask include a photomask in which a pattern of a plurality of regions having different transmittances of the third light is formed.
  • pattern printing is performed using, for example, a photomask in which a pattern is formed by etching a metal film, and various printing methods (for example, printing by a laser printer or an inkjet printer, gravure printing, screen printing).
  • Photo masks can be mentioned.
  • a photomask in which a pattern is formed by etching a metal film can be obtained, for example, by forming a metal chromium film on a quartz substrate by sputtering and then patterning with a photoresist.
  • the second patterning mask When the second patterning mask is used to irradiate the third light, the second patterning mask may be arranged on the side opposite to the side having the liquid crystal layer of the base material, and may be arranged on the side having the liquid crystal layer of the base material. It's okay.
  • the second patterning mask When the second patterning mask is arranged on the side having the liquid crystal layer of the base material, the second patterning mask may be brought into contact with the liquid crystal layer to irradiate the third light, and a gap between the liquid crystal layer and the second patterning mask may be applied. May be provided to irradiate the third light.
  • the second patterning mask is arranged on the side opposite to the side having the liquid crystal layer of the base material, it is preferable to use a translucent base material because the liquid crystal layer is exposed by the second light through the base material.
  • the transmittance of the second light is not particularly limited, but a higher value is preferable from the viewpoint of making the photoisomerized chiral compound more easily photoisomerized.
  • only one type of the second patterning mask may be used, or two or more types may be used.
  • the method for producing a decorative film according to the present disclosure includes a third exposure step.
  • the substrate is translucent and
  • the third light is irradiated through the second patterning mask and the base material from the side opposite to the side having the liquid crystal layer of the base material.
  • the first exposure step the first light is irradiated through the first patterning mask and the base material from the side opposite to the side having the liquid crystal layer of the base material.
  • the second exposure step the second light is irradiated from the side having the liquid crystal layer of the base material.
  • the chiral agent can be isomerized by irradiation with a third light to change the spiral pitch.
  • the curing of the light reflecting portion can be promoted and the uncured portion can be formed, and when the second light is irradiated, the uncured portion having an isotropic phase is cured. It is possible to form a translucent portion.
  • a liquid crystal material 200p having a base material 30 and a liquid crystal layer 10p is prepared (liquid crystal material preparation step), and the liquid crystal layer 10p is heated to obtain a cholesteric liquid crystal phase (first heating step). .. Then, for example, as shown in FIG. 6, a second patterning mask 70 including a region 71 having a high third light transmittance and a region 72 having a low third light transmittance is attached to one surface of the base material 30 (FIG. 6).
  • the third light L3 is irradiated through the base material 30 and the second patterning mask 70 (third exposure step), and the photoisomerization rates of the photoisomerized chiral compounds are different from each other. It forms a region 101p and a region 102p.
  • a first patterning mask 50 including a region 51 having a high transmittance of the first light and a region 52 having a low transmittance of the first light is attached to one surface of the base material 30 (FIG. 7). 7 is arranged on the lower surface), and the first light L1 is irradiated through the base material 30 and the first patterning mask 50 to cure a part of the liquid crystal layer 10p (first exposure step).
  • the light reflecting unit 111 and the light reflecting unit 112 having different reflected wavelengths are formed.
  • the liquid crystal layer 10p was heated to make the uncured portion 121p and the uncured portion 122p in the liquid crystal layer 10p into isotropic phases (second heating step), and then, as shown in FIG. 8, the liquid crystal layer of the base material 30.
  • the translucent portion 121 and the translucent portion 122 are formed by irradiating the second light L2 from the side having 10p to cure the uncured portion 121p and the uncured portion 122p (second exposure step). As described above, for example, as shown in FIG.
  • the light reflecting unit 111 and the light reflecting unit 112 having different selective reflection wavelengths, and the light transmitting unit 121 and the light reflecting unit 112 adjacent to the light reflecting unit 111 are adjacent to each other. It is possible to manufacture a decorative film 200A including a reflective layer 10 made of a single layer including a translucent portion 122 in the thickness direction.
  • the reflective layer 10 includes a light reflecting portion 111 and a light reflecting portion 112, and a light transmitting portion 121 and a light transmitting portion 122 in this order from the base material 30 side.
  • the method for producing a decorative film according to the present disclosure may include other steps other than the above steps, if necessary.
  • a step of peeling the base material from the decorative film produced in a mode containing a base material can be mentioned, and a decorative film in a mode containing no base material can be produced.
  • examples of other steps include a colored layer forming step, an alignment layer forming step, and another layer forming step.
  • the details of the colored layer and the oriented layer and the forming method are as described above.
  • the details of the other layers are as described above, and a known method may be used as a method for forming the other layers.
  • the decorative film according to the present disclosure can be used for various purposes, and for example, the decorative film can be molded and used as a molded body.
  • Such molded bodies can be prepared for various articles, such as electronic devices such as smartphones, mobile phones, and tablets, automobiles, electrical appliances, packaging containers, and the like, among others. It can be suitably used for electronic devices.
  • the means for molding the decorative film to obtain the molded body is not particularly limited, and for example, a known method such as three-dimensional molding or insert molding may be used. Further, the means for applying the decorative film to the article is not particularly limited, and a known method may be appropriately used depending on the type of the article.
  • ⁇ Example 1> [Preparation of base material]
  • a technoloy C000 thickness 100 ⁇ m, polycarbonate resin single layer sheet, manufactured by Sumika Acrylic Sales Co., Ltd. having ultraviolet transparency was cut into 210 mm in the width direction and 300 mm in the longitudinal direction.
  • a coating liquid for forming an alignment layer having the composition described below was prepared.
  • -Composition of coating liquid for forming an alignment layer- -Modified polyvinyl alcohol with the structure shown below ... 10.00 parts by mass-Water ... 55.00 parts by mass-Methanol ... 35.00 parts by mass
  • modified polyvinyl alcohol is shown below.
  • the number at the bottom right of each building block represents the molar ratio.
  • the liquid crystal layer was formed by applying the coating liquid for forming the alignment layer to the substrate with a wire bar (count # 10) and drying at 100 ° C. for 2 minutes. Next, the formed liquid crystal layer was subjected to a rubbing treatment (rayon cloth, pressure 0.1 kgf, rotation speed 1,000 rpm, transfer speed 10 m / min) in a direction rotated 3 ° counterclockwise with respect to the short side direction of the base material. , Once). As a result, an orientation layer was formed on the substrate.
  • black mill base K Using the obtained black mill base K, a mixture of the following components was stirred at high speed to prepare an ink for mask printing.
  • -Black mill base K 9 parts by mass-N-vinyl caprolactam (manufactured by BASF) ... 25 parts by mass-Isobornyl acrylate (trade name: SR506, manufactured by Sartomer) ...
  • An inkjet printer (DMP-2831, manufactured by Fujifilm Co., Ltd.) was used in the center of the base material (Technoloy C000, thickness 100 ⁇ m, manufactured by Sumika Acrylic Sales Co., Ltd., A4 size), and the ink for mask printing was used in FIG.
  • the indicated mask pattern (area 51: gray scale 100% setting, area 52: gray scale 50% setting) was printed in gray scale. Since the mask printing ink is not applied to the region 51 printed with the gray scale set to 100%, the region 51 does not absorb the ultraviolet rays derived from the mask printing ink. Therefore, the transmittance of ultraviolet rays is higher in the region 51 than in the region 52.
  • the mask printing ink was cured by irradiating ultraviolet rays with an exposure amount of 300 mJ / cm 2 using a metal halide lamp (MAL625NAL, manufactured by GS Yuasa) from the surface side on which the mask pattern was printed.
  • a metal halide lamp MAL625NAL, manufactured by GS Yuasa
  • photoisomerized chiral compound Compound having the structure shown below ... 2.06 parts by mass
  • Cross-linking agent dimethylol-tricyclodecanediacrylate (product name “NK ester A-DCP”, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)... 0.88 parts by mass
  • Photopolymerization initiator 2-methyl -1- (4- (Methylthio) phenyl) -2-morpholinopropane-1-one (product name "Omnirad 907", manufactured by IGM Resins B.V.) ... 0.29 part by mass, surfactant 1: Below Compound having the structure shown ...
  • the structures of the liquid crystal compound 1, the liquid crystal compound 2, the liquid crystal compound 3, the polymerizable chiral compound, the photoisomerized chiral compound, the surfactant 1 and the surfactant 2 are shown.
  • the liquid crystal material was placed in a box kept at a temperature of 40 ° C., and the first patterning mask was brought into close contact with the side of the base material opposite to the side having the liquid crystal layer.
  • a UV (Ultra Violet) -LED manufactured by CCS
  • ultraviolet rays (first light) having a wavelength of 285 nm are irradiated through a substrate and a first patterning mask at an exposure amount of 300 mJ / cm 2 , and light is reflected. Formed a part.
  • the liquid crystal layer is heated on a hot plate at 120 ° C., and under a low oxygen atmosphere (oxygen concentration 1,000 ppm or less), UV-LED (UV-LED) from the side having the liquid crystal layer of the base material.
  • a reflective layer was formed by irradiating an ultraviolet ray (second light) having a wavelength of 285 nm with an exposure amount of 300 mJ / cm 2 using (manufactured by CCS) to cure the liquid crystal layer.
  • the decorative film 200B of Example 1 shown in FIGS. 10 and 11 (AA cross section of FIG. 10) was produced. As shown in FIG.
  • Example 2 [Making the first patterning mask]
  • the first patterning mask shown in FIG. 9 was prepared in the same manner as in Example 1.
  • the transmittance of ultraviolet rays is higher in the region 71 than in the region 72 and the region 73.
  • the mask printing ink was cured by irradiating ultraviolet rays with an exposure amount of 300 mJ / cm 2 using a metal halide lamp (MAL625NAL, manufactured by GS Yuasa) from the surface side on which the mask pattern was printed.
  • MAL625NAL metal halide lamp
  • the second patterning mask 70 (152 mm ⁇ 80 mm, region 71 width: 30 mm, region 72 width: 20 mm, region 73 width: 30 mm) having the region 71, the region 72, and the region 73 having different ultraviolet transmittances is provided. Made.
  • the liquid crystal material was placed in a box kept at a temperature of 40 ° C., and the second patterning mask was adhered to the side opposite to the side having the liquid crystal layer of the base material.
  • a UV-LED manufactured by CCS
  • ultraviolet rays (third light) having a wavelength of 365 nm are irradiated through a substrate and a second patterning mask with an exposure amount of 1.8 mJ / cm 2 , and photoisomerized chiral. Photoisomerization of the compound was performed.
  • the decorative film 200C of Example 2 shown in FIGS. 13 and 14 (cross section of BB in FIG. 13) was produced.
  • the decorative film 200C has a light reflecting portion 111 and a light reflecting portion 112, and a light transmitting portion 122 adjacent to the light reflecting portion 112 and a light transmitting portion 121 adjacent to the light reflecting portion 111.
  • the reflective layer 10 has a reflective layer 10 composed of a single layer including in the direction, and the reflective layer 10 includes a light reflecting portion 111 and a light reflecting portion 112, and a light transmitting portion 121 and a light transmitting portion 122 in order from the base material 30 side. It was. Further, the reflective layer 10 includes a plurality of regions (a6 to a11) in the in-plane direction.
  • Example 3 [Making the first patterning mask]
  • the first patterning mask shown in FIG. 9 was prepared in the same manner as in Example 1.
  • the liquid crystal material was placed in a box kept at a temperature of 40 ° C., and the first patterning mask was placed on the side of the base material having the liquid crystal layer with a gap between the liquid crystal layer and the first patterning mask.
  • a low oxygen atmosphere oxygen concentration of 1,000 ppm or less
  • ultraviolet rays having a wavelength of 285 nm with an exposure amount of 5 mJ / cm 2 are used through a first patterning mask using a UV-LED (manufactured by CCS). (1st light) was irradiated to form a light reflecting portion.
  • ultraviolet rays (second light) were irradiated to form a reflective layer.
  • the decorative film 200D of Example 3 shown in FIGS. 15 and 16 (C-C cross section of FIG. 15) was produced.
  • the decorative film 200D has a reflecting layer 10 composed of a single layer including a light reflecting portion 11 and a translucent portion 12 adjacent to the light reflecting portion 11 in the thickness direction, and reflects the light.
  • the layer 10 includes the translucent portion 12 and the light reflecting portion 11 in order from the base material 30 side.
  • the reflective layer 10 includes a plurality of regions (a12, a13) in the in-plane direction.
  • the maximum value and the maximum value of the reflectance are set to R max (%), and two values showing the half-value reflectance R 1/2 (%) represented by the following formula are shown.
  • the average value of the wavelengths was taken as the selective reflection wavelength.
  • Formula for calculating half-value reflectance: R 1/2 R max ⁇ 2
  • the reflective layer has selective reflectivity, and that a light reflecting portion having selective reflectivity is formed in the reflective layer.
  • a sample piece having a width of 5 mm and a length of 2 mm was cut out from the decorative film using a roller cutter.
  • the sample piece was embedded with an epoxy resin and cut in the thickness direction of the reflective layer using a microtom (product name "RM2265”, manufactured by Leica).
  • a scanning electron microscope (model “S-5500”, manufactured by Hitachi High-Technologies Corporation, observation magnification: 10000 times, acceleration voltage: 2.0 kV) was used to observe the SEM image of the sample cross section.
  • the part where the striped pattern between the bright part and the dark part is observed is determined to be the light reflecting part, and the other part is determined to be the translucent part, and the thickness of the light reflecting part and the thickness of the translucent part are measured. did.
  • SEM observation it was confirmed that the decorative film has a reflective layer composed of a single layer including a light reflecting portion and a translucent portion adjacent to the light reflecting portion in the thickness direction. Further, it was determined that the repeated two cycles of the bright part and the dark part corresponded to 360 degrees of the twist of the cholesteric liquid crystal compound, and the width between these two bright parts and the two dark parts was measured as a spiral pitch.
  • Table 1 shows the above evaluation results.
  • Table 2 shows the results of visual evaluation of colors.
  • the decorative films of Examples 1 to 3 could be controlled to have an arbitrary reflectance. As a result, as shown in Table 2, the color of the decorative film could be easily changed.
  • the selective reflection wavelength is 460 nm (blue), and the maximum reflectance is controlled between 23% (dark blue) and 48% (bright blue), so that the same type of blue is bright and dark. Was able to be adjusted.
  • the brightness of blue could be adjusted at a substantially constant selective reflection wavelength.
  • the selective reflection wavelength is changed from 460 nm (blue) to 552 nm (green) by photoisomerizing the photoisomerized chiral compound in the regions a7 and a10. I was able to obtain green, which is the color of the lineage.
  • the maximum reflectance is also controlled, and as a result, in addition to the color change of another system of blue and green, dark blue to light blue and dark green to light green. It was possible to add light and shade with the same type of color, and it was possible to obtain a complicated design.
  • Example 4 [Molded body] Using the decorative film of Example 1, a molded body was produced as follows.
  • the adhesive sheet After peeling off the protective film on one side of the adhesive sheet (G25, thickness 25 ⁇ m, manufactured by Nissei Shinka Co., Ltd.) having protective films on both sides of the adhesive layer, the adhesive sheet is attached to the colored layer of the decorative film and laminated (temperature). : 30 ° C., linear pressure 100 N / cm, transport speed 0.1 m / min).
  • a decorative film having a protective film, an adhesive layer, a colored layer, a reflective layer, and a base material in this order hereinafter, may be referred to as a "decorative film for molding" was obtained.
  • FIGS. 17 and 18 cross section of FIG. 17
  • a molded body was produced. Specifically, after the protective film is peeled off from the decorative film for molding, the decorative film for molding is attached to the glass member shown in FIG. It was vacuum formed at a heating temperature of 170 ° C. to form a molded body. In this way, it was possible to obtain a molded body having a blue light and dark design derived from the decorative film of Example 1.
  • This molded body can be preferably used for a smartphone, which is an electronic device.

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  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
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  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un film décoratif comprenant une couche réfléchissante comprenant une couche unique contenant, dans le sens de l'épaisseur, une section de réflexion de lumière dont la réflectivité est sélective en longueur d'onde et une section de transmission de lumière adjacente à la section de réflexion de lumière. La présente invention concerne également un procédé de production de celui-ci, un corps moulé à base de celui-ci et un produit obtenu à partir de celui-ci.
PCT/JP2021/020827 2020-09-23 2021-06-01 Film décoratif, son procédé de production, corps moulé à base de celui-ci et produit obtenu à partir de celui-ci WO2022064776A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004133179A (ja) * 2002-10-10 2004-04-30 Dainippon Printing Co Ltd 偏光素子およびその製造方法
WO2018212070A1 (fr) * 2017-05-19 2018-11-22 富士フイルム株式会社 Unité de rétroéclairage et dispositif d'affichage à cristaux liquides
WO2018230395A1 (fr) * 2017-06-13 2018-12-20 富士フイルム株式会社 Procédé de production d'un film à cristaux liquides et procédé de production d'un film fonctionnel
WO2019009252A1 (fr) * 2017-07-04 2019-01-10 富士フイルム株式会社 Demi-miroir
WO2020122245A1 (fr) * 2018-12-14 2020-06-18 富士フイルム株式会社 Procédé de fabrication d'un film décoratif pour moulage, procédé de moulage, film décoratif pour moulage, produit moulé, plaque extérieure d'automobile, et dispositif électronique

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017205987A (ja) 2016-05-20 2017-11-24 富士フイルム株式会社 加飾シートおよび物品

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004133179A (ja) * 2002-10-10 2004-04-30 Dainippon Printing Co Ltd 偏光素子およびその製造方法
WO2018212070A1 (fr) * 2017-05-19 2018-11-22 富士フイルム株式会社 Unité de rétroéclairage et dispositif d'affichage à cristaux liquides
WO2018230395A1 (fr) * 2017-06-13 2018-12-20 富士フイルム株式会社 Procédé de production d'un film à cristaux liquides et procédé de production d'un film fonctionnel
WO2019009252A1 (fr) * 2017-07-04 2019-01-10 富士フイルム株式会社 Demi-miroir
WO2020122245A1 (fr) * 2018-12-14 2020-06-18 富士フイルム株式会社 Procédé de fabrication d'un film décoratif pour moulage, procédé de moulage, film décoratif pour moulage, produit moulé, plaque extérieure d'automobile, et dispositif électronique

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