JP7177273B2 - DECORATIVE MOLDED PRODUCT, METHOD FOR MANUFACTURING DECORATIVE MOLDED BODY, DECORATIVE PANEL, AND ELECTRONIC DEVICE - Google Patents

Description

The present disclosure relates to a decorative molded body, a method for manufacturing a decorative molded body, a decorative panel, and an electronic device.

A decorative molded body is known in which a decorative film is placed on the surface of the resin molded body to color the surface of the resin molded body in a desired hue, or a desired pattern is provided on the surface of the resin molded body. there is The decorative molded product is obtained, for example, by placing a decorative film in advance in a mold and injecting a base resin into the mold, and the decorative film is integrated with the surface of the resin molded product. has a structured structure. Injection molding of a base resin after pre-arranging a decorative film in a mold is generally referred to as film insert molding or simply insert molding. Also, the decorated molded body may be produced by attaching a decorative film to the molded body after molding.

As a conventional hot stamp foil, JP-A-2001-105795 describes a hot stamp foil characterized in that a cholesteric liquid crystalline polymer layer having a selective reflection wavelength range in visible light is laminated as a transfer layer. It is Further, Japanese Patent Application Laid-Open No. 2017-97114 describes improving the retroreflectivity by applying unevenness processing to the cholesteric liquid crystal layer.

A problem to be solved by an embodiment of the present disclosure is to provide a decorative molding that has high brilliance and expresses a uniform color regardless of the viewing direction.
A problem to be solved by another embodiment of the present disclosure is to provide a method for manufacturing a decorative molding that has high brilliance and expresses a uniform color regardless of the viewing direction.
A problem to be solved by another embodiment of the present disclosure is to provide a decorative panel using the decorative molding.
A problem to be solved by another embodiment of the present disclosure is to provide an electronic device using the decorative panel.

The present disclosure includes the following aspects.
<1> A substrate, a reflective layer having a center wavelength of a selective reflection wavelength in the range of 300 nm or more and 1,500 nm or less and having an uneven structure, and a resin layer between the substrate and the reflective layer. , A decorative molded body including.
<2> The decorated molding according to <1>, wherein the uneven structure has a depth of 1 μm or more and a width of 5 μm or more.
<3> The decorative molding according to <1> or <2>, which contains a colored layer.
<4> The decorated molding according to any one of <1> to <3>, wherein the reflective layer is a layer containing cholesteric liquid crystal.
<5> A decorative film having at least a substrate, a reflective layer having a central wavelength of a selective reflection wavelength in the range of 300 nm or more and 1,500 nm or less, and a resin layer between the substrate and the reflective layer. <1>, comprising the step of preparing; The method for manufacturing the decorated molding according to any one of <4>.
<6> A step of preparing a decorative film having at least a base material and a reflective layer having a central wavelength of a selective reflection wavelength in the range of 300 nm or more and 1,500 nm or less, and a transparent body having a surface having an uneven structure. The reflective layer is brought into contact with the surface having the uneven structure by overlapping the decorative film, and a pressure of 0.01 MPa or more is applied to the reflective layer to impart the uneven structure to the reflective layer. The method for manufacturing the decorated molding according to any one of <1> to <4>, comprising the steps of:
<7> A decorative panel comprising the decorative molding according to any one of <1> to <4>.
<8> An electronic device including the decorative panel according to <7>.

According to one embodiment of the present disclosure, there is provided a decorative molding that has high brilliance and expresses a uniform color regardless of the viewing direction.
According to an embodiment of the present disclosure, there is provided a method for manufacturing a decorative molding that has high brilliance and expresses uniform color regardless of viewing direction.
According to another embodiment of the present disclosure, a decorative panel using the decorative film is provided.
According to another embodiment of the present disclosure, an electronic device using the decorative panel 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 the decorative film according to the present disclosure. FIG. 3 is a schematic cross-sectional view showing an example of the decorative molding according to the present disclosure. FIG. 4 is a schematic cross-sectional view showing an example of the decorative molding according to the present disclosure. FIG. 5 is a schematic cross-sectional view showing an example of the decorative molding according to the present disclosure. FIG. 6 is a schematic cross-sectional view showing an example of a decorative panel according to the present disclosure. FIG. 7 is a schematic plan view showing an example of an uneven pattern (A) according to the present disclosure. FIG. 8 is a schematic perspective view of the concavo-convex pattern (A) shown in FIG. FIG. 9 is a schematic plan view showing an example of the uneven pattern (B) according to the present disclosure. 10 is a schematic perspective view of the uneven pattern (B) shown in FIG. 9. FIG.

Embodiments of the present disclosure will be described below. However, the present disclosure is by no means limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the purpose of the present disclosure. When describing the embodiments of the present disclosure with reference to the drawings, descriptions of overlapping components and reference numerals may be omitted. Components shown using the same reference numerals in the drawings mean the same components. The dimensional ratios in the drawings do not necessarily represent the actual dimensional ratios.

Regarding the notation of groups (atomic groups) in the present disclosure, notations that do not describe substitution and unsubstituted include not only those not having substituents but also those having substituents. For example, 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.
The term "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.
The term "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.
In the present disclosure, the term “~” is used to include the numerical values before and after it as lower and upper limits.

In this disclosure, (meth)acrylate refers to acrylate and methacrylate, and (meth)acryl refers to acrylic and methacrylic.
In the present disclosure, 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. GPC measurement by (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1 .0 mL/min, detector: defined as polystyrene conversion value by Refractive Index Detector).

In the present disclosure, 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.
In the present disclosure, the term "process" includes not only an independent process, but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.
In the present disclosure, "total solid content" refers to the total mass of components excluding the solvent from the total composition of the composition. In addition, the “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.
In the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Moreover, in the present disclosure, a combination of two or more preferred aspects is a more preferred aspect.

(decorative film)
A decorative film according to an embodiment of the present disclosure has a base material and a reflective layer having a central wavelength of a selective reflection wavelength in the range of 300 nm or more and 1,500 nm or less. Applications of the decorative film according to an embodiment of the present disclosure are not particularly limited, for example, electronic devices (e.g., wearable devices and smartphones), home appliances, audio products, computers, displays, in-vehicle products, watches, It can be used to decorate accessories, optical parts, doors, windows, and building materials. Among them, the decorative film according to an embodiment of the present disclosure can be suitably used for decorating electronic devices (for example, wearable devices and smartphones). In addition, since the decorative film according to an embodiment of 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 decorative film for molding.

Conventionally, printing, painting, vapor deposition, or plating, for example, has been used for surface decoration used in articles such as home appliances, electronic devices, and mobile phones. However, from the standpoints of, for example, providing functionality, environmental impact, and reupholstery, decoration techniques using decorative films have come to be widely used. On the other hand, due to the spread of users' tastes, novel designs are required. In particular, changes in color (for example, tint and fine hues) depending on the viewing angle are one of the sought after designs, and there has been a demand for the introduction of decorative techniques to obtain such designs. . In addition, Japanese Patent Application Laid-Open No. 2001-105795 describes a hot stamp foil in which a cholesteric liquid crystalline polymer layer is laminated as a transfer layer. Couldn't get a taste. In addition, JP-A-2017-97114 describes that retroreflectivity is improved by applying unevenness processing to the cholesteric liquid crystal layer, but the use as a decorative film and its effect are mentioned. do not have.

As a result of intensive studies by the present inventors, the decorative film containing the above-described structure has high brilliance and is useful as a material for a decorative molding that exhibits a uniform color regardless of the viewing direction. found to be provided. In the present disclosure, "expressing a uniform color tone regardless of the viewing direction" means, for example, when the object is viewed from an angle perpendicular to the surface direction of the object, and when the object is viewed from the surface direction This means that the color change is small when the object is viewed from an angle of 45°. The above effect is preferable in that the desired design can be visually recognized regardless of the viewing angle.

The decorative film according to the present disclosure will be described in detail below.

<Base material>
A decorative film according to an embodiment of the present disclosure has a substrate. A substrate may be a support. As the base material, for example, conventionally known base materials used for molding such as three-dimensional molding and insert molding can be used without particular limitation, and may be appropriately selected according to suitability for molding. Moreover, the shape and material of the substrate are not particularly limited, and may be appropriately selected as desired. From the viewpoint of moldability and chipping resistance, the substrate is preferably a resin substrate, and more preferably a resin film.

Specific substrates include, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), acrylic resin, urethane resin, urethane-acrylic resin, polycarbonate (PC), acrylic-polycarbonate resin, triacetyl cellulose (TAC). , cycloolefin polymers (COP), and acrylonitrile/butadiene/styrene copolymer resins (ABS resins). Among them, the substrate is preferably polyethylene terephthalate (PET), acrylic resin, polycarbonate, or polypropylene from the viewpoint of molding processability and strength, and polyethylene terephthalate (PET), acrylic resin, or polycarbonate. It is more preferable to have Also, the substrate may be a laminated resin substrate having two or more layers. For example, a laminate film containing an acrylic resin layer and a polycarbonate layer is preferably used.

The base material may contain additives, if necessary. Such additives include, for example, lubricants (such as mineral oils, hydrocarbons, fatty acids, alcohols, fatty acid esters, fatty acid amides, metallic soaps, natural waxes, and silicones), inorganic flame retardants (such as magnesium hydroxide, and aluminum hydroxide), halogen-based organic flame retardants, phosphorus-based organic flame retardants, organic or inorganic fillers (e.g., metal powder, talc, calcium carbonate, potassium titanate, glass fiber, carbon fiber, and wood powder ), antioxidants, UV inhibitors, lubricants, dispersants, coupling agents, foaming agents, coloring agents, and engineering plastics other than the above resins. Engineering plastics include, for example, polyolefins, polyesters, polyacetals, polyamides, and polyphenylene ethers.

A commercially available product may be used as the base material. Commercially available products include, for example, the Technolloy (registered trademark) series (acrylic resin film or acrylic resin/polycarbonate resin laminated film, manufactured by Sumitomo Chemical Co., Ltd.), ABS film (manufactured by Okamoto Co., Ltd.), ABS sheet (Sekisui Seisei Kogyo Co., Ltd.), Teflex (registered trademark) series (PET film, manufactured by Teijin Film Solutions Co., Ltd.), Lumirror (registered trademark) easy-molding type (PET film, manufactured by Toray Industries, Inc.), and Pure Thermo (polypropylene) film, manufactured by Idemitsu Unitech Co., Ltd.).

The thickness of the substrate is determined according to, for example, the use and handleability of the molding to be produced, and is not particularly limited. The lower limit of the thickness of the substrate is preferably 1 μm or more, more preferably 10 μm or more, still more preferably 20 μm or more, and particularly preferably 30 μm or more. The upper limit of the thickness of the substrate is preferably 500 µm or less, more preferably 200 µm or less, and particularly preferably 100 µm or less.

<Reflective layer>
A decorative film according to an embodiment of the present disclosure has a reflective layer. The reflective layer has a central wavelength of a selective reflection wavelength in the range of 300 nm or more and 1,500 nm or less. Examples of the reflective layer include a layer containing cholesteric liquid crystal (hereinafter also referred to as a "cholesteric liquid crystal layer"), a layer containing flat metal particles, an optical multilayer film, and a layer containing a chromic material. Among the reflective layers described above, a cholesteric liquid crystal layer or a layer containing flat metal particles is preferable, and a cholesteric liquid crystal layer is more preferable, from the viewpoint of moldability and impact resistance.

<< liquid crystal composition >>
A cholesteric liquid crystal layer is a layer formed by curing a liquid crystal composition. A liquid crystal composition is a composition containing a liquid crystal compound. As the liquid crystal compound used in the present disclosure, from the viewpoint of moldability, it is preferable to use at least a cholesteric liquid crystal compound having one ethylenically unsaturated group or one cyclic ether group. The liquid crystal composition for forming the cholesteric liquid crystal layer includes, for example, a cholesteric liquid crystal compound having one ethylenically unsaturated group or one cyclic ether group, and 25 mass of the total solid content of the liquid crystal composition. % or more, and may further contain other components (for example, a chiral agent, an alignment control agent, a polymerization initiator, and an alignment aid).

-Cholesteric liquid crystal compound having one ethylenically unsaturated group or one cyclic ether group-
The liquid crystal composition may contain 25% by mass or more of a cholesteric liquid crystal compound having one ethylenically unsaturated group or one cyclic ether group (hereinafter also referred to as "specific liquid crystal compound") as a liquid crystal compound. preferable.

The ethylenically unsaturated group in the specific liquid crystal compound is not particularly limited, but examples thereof include (meth)acryloxy, (meth)acrylamide, vinyl, vinyl ester and vinyl ether groups. From the viewpoint of reactivity, the ethylenically unsaturated group is preferably a (meth)acryloxy group, a (meth)acrylamide group, or an aromatic vinyl group, and a (meth)acryloxy group or a (meth)acrylamide group. is more preferred, and a (meth)acryloxy group is particularly preferred.

The cyclic ether group in the specific liquid crystal compound is not particularly limited, but from the viewpoint of reactivity, it is preferably an epoxy group or an oxetanyl group, particularly preferably an oxetanyl group.

The specific liquid crystal compound is preferably a cholesteric liquid crystal compound having one ethylenically unsaturated group, from the viewpoints of reactivity and suppression of changes in reflectance and color change after molding. The liquid crystal composition more preferably contains a cholesteric liquid crystal compound having one ethylenically unsaturated group in an amount of 25% by mass or more relative to the total solid content of the liquid crystal composition.

The specific liquid crystal compound may have both an ethylenically unsaturated group and a cyclic ether group in one molecule. is one. Further, when the number of ethylenically unsaturated groups in the specific liquid crystal compound is one, for example, the specific liquid crystal compound is a compound having one ethylenically unsaturated group and one or more cyclic ether groups, good too.

When the liquid crystal composition contains a cholesteric liquid crystal compound having one ethylenically unsaturated group, the liquid crystal composition may contain a radical polymerization initiator from the viewpoint of suppressing reflectance change and color change after molding. More preferably, it contains a radical photopolymerization initiator.

When the liquid crystal composition contains a cholesteric liquid crystal compound having one cyclic ether group, the liquid crystal composition may contain a cationic polymerization initiator from the viewpoint of suppressing reflectance change and color change after molding. More preferably, it contains a photocationic polymerization initiator.

The specific liquid crystal compound is preferably a cholesteric liquid crystal compound having both an ethylenically unsaturated group and a cyclic ether group, from the viewpoint of suppressing change in reflectance and suppressing color change after molding. A cholesteric liquid crystal compound having a saturated group and one cyclic ether group is more preferred.

The specific liquid crystal compound may be a rod-like liquid crystal compound or a discotic liquid crystal compound as long as it is a compound having a liquid crystal structure. The specific liquid crystal compound is preferably a rod-like liquid crystal compound from the viewpoints of ease of adjustment of the pitch of the helical structure in the cholesteric liquid crystal layer and suppression of change in reflectance and change in color tone after molding.

Rod-shaped liquid crystal compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, Phenyldioxanes, tolanes or alkenylcyclohexylbenzonitriles are preferably used. Not only low-molecular-weight liquid crystal compounds as described above, but also liquid-crystalline polymer compounds can be used. Chem., 190, 2255 (1989), Advanced Materials 5, 107 (1993), U.S. Pat. No. 4,683,327, U.S. Pat. , U.S. Patent No. 5,770,107, WO 1995/022586, WO 1995/024455, WO 1997/000600, WO 1998/023580, WO 1998/052905, Patent Among the compounds described in JP-A-1-272551, JP-A-6-16616, JP-A-7-110469, JP-A-11-80081, and JP-A-2001-328973, ethylenically unsaturated Compounds with one saturated group or one cyclic ether group can be used. Furthermore, as the rod-like liquid crystal compound, for example, among the compounds described in JP-A-11-513019 and JP-A-2007-279688, one having one ethylenically unsaturated group or one cyclic ether group can be preferably used. The cholesteric liquid crystal layer is more preferably a layer in which the orientation is fixed by polymerization of a rod-like liquid crystal compound.

As the discotic liquid crystal compound, for example, among the compounds described in JP-A-2007-108732 or JP-A-2010-244038, compounds having one ethylenically unsaturated group or having one cyclic ether group can be preferably used.

Specific examples of the specific liquid crystal compound preferably include the compounds shown below, but needless to say, the compound is not limited to these.

The liquid crystal composition may contain one type of specific liquid crystal compound alone, or may contain two or more types thereof. The content of the specific liquid crystal compound is preferably 25% by mass or more with respect to the total solid content of the liquid crystal composition. When the content of the specific liquid crystal compound is 25% by mass or more, a decorative film with a small change in reflectance after molding can be obtained. In addition, the content of the specific liquid crystal compound is preferably 30% by mass or more, preferably 40% by mass or more, based on the total solid content of the liquid crystal composition, from the viewpoint of suppressing change in reflectance and suppressing color change after molding. is more preferably 60% by mass or more and 99% by mass or less, and particularly preferably 80% by mass or more and 98% by mass or less.

-Other Cholesteric Liquid Crystal Compounds-
The liquid crystal composition may contain a cholesteric liquid crystal compound other than the specific liquid crystal compound (hereinafter also simply referred to as "another liquid crystal compound"). Other liquid crystal compounds include, for example, cholesteric liquid crystal compounds having no ethylenically unsaturated groups and cyclic ether groups, cholesteric liquid crystal compounds having two or more ethylenically unsaturated groups and no cyclic ether groups, A cholesteric liquid crystal compound having two or more cyclic ether groups and no ethylenically unsaturated groups, and a cholesteric liquid crystal compound having two or more ethylenically unsaturated groups and two or more cyclic ether groups mentioned. Other liquid crystal compounds are cholesteric liquid crystal compounds that do not have ethylenically unsaturated groups and cyclic ether groups, and have two or more ethylenically unsaturated groups, from the viewpoint of suppressing reflectance change and color change after molding. And at least one selected from the group consisting of cholesteric liquid crystal compounds having no cyclic ether groups, and cholesteric liquid crystal compounds having two or more cyclic ether groups and no ethylenically unsaturated groups It is preferably a compound, a cholesteric liquid crystal compound having no ethylenically unsaturated groups and cyclic ether groups, a cholesteric liquid crystal compound having two ethylenically unsaturated groups and having no cyclic ether groups, and two It is more preferably at least one compound selected from the group consisting of cholesteric liquid crystal compounds having a cyclic ether group and no ethylenically unsaturated group, having an ethylenically unsaturated group and a cyclic ether group. and at least one compound selected from the group consisting of a cholesteric liquid crystal compound having two ethylenically unsaturated groups and no cyclic ether group is particularly preferable.

As another liquid crystal compound, a known cholesteric liquid crystal compound can be used. Rod-shaped liquid crystal compounds in other liquid crystal compounds include, for example, "Makromol. Chem., Vol. 190, p. 2255 (1989), Advanced Materials Vol. 5, p. US Pat. No. 5,622,648, US Pat. No. 5,770,107, WO 1995/022586, WO 1995/024455, WO 1997/000600, WO 1998/023580, WO No. 1998/052905, JP-A-1-272551, JP-A-6-16616, JP-A-7-110469, JP-A-11-80081, and JP-A-2001-328973 compounds can be used. Furthermore, as a rod-like liquid crystal compound among other liquid crystal compounds, for example, compounds described in JP-A-11-513019 or JP-A-2007-279688 can be preferably used. As the discotic liquid crystal compound among other liquid crystal compounds, for example, compounds described in JP-A-2007-108732 or JP-A-2010-244038 can be preferably used.

The liquid crystal composition may contain other liquid crystal compounds singly or in combination of two or more. The content of the other liquid crystal compound is preferably 70% by mass or less, preferably 60% by mass or less, based on the total solid content of the liquid crystal composition, from the viewpoint of suppressing reflectance change and suppressing color change after molding. It is more preferably 40% by mass or less, and particularly preferably 5% by mass or less. In addition, the lower limit of the content of other liquid crystal compounds is 0% by mass.

- Chiral agent (optically active compound) -
The liquid crystal composition preferably contains a chiral agent (that is, an optically active compound) from the viewpoints of facilitating the formation of a cholesteric liquid crystal layer and facilitating adjustment of the pitch of the helical structure. A chiral agent has a function of inducing a helical structure in a cholesteric liquid crystal layer. The chiral agent may be selected depending on the purpose, since the direction of helical twist or helical pitch induced by the liquid crystal compound differs. The chiral agent is not particularly limited, and may be a known compound (for example, "Liquid Crystal Device Handbook", Chapter 3, Section 4-3, chiral agent for TN (twisted nematic), STN (super-twisted nematic), page 199, 142nd Committee, Japan Society for the Promotion of Science, 1989), isosorbide, and isomannide derivatives can be used. A chiral agent generally contains an asymmetric carbon atom, but an axially chiral compound or planar chiral compound that does not contain an asymmetric carbon atom can also be used as the chiral agent. Examples of axially asymmetric compounds or planar asymmetric compounds preferably include binaphthyl compounds, helicene compounds, and paracyclophane compounds.

From the viewpoint of suppressing change in reflectance after molding, the liquid crystal composition preferably contains a chiral agent having a polymerizable group as a chiral agent. It is more preferable to contain an agent. The polymerizable group is not particularly limited as long as it is a polymerizable group, but from the viewpoint of reactivity and suppression of change in reflectance after molding, an ethylenically unsaturated group or a cyclic ether group is preferred. Preferably, it is an ethylenically unsaturated group. Preferred aspects of the ethylenically unsaturated group and the cyclic ether group in the chiral agent are the same as those of the ethylenically unsaturated group and the cyclic ether group in the specific liquid crystal compound described above.

When the chiral agent has an ethylenically unsaturated group or a cyclic ether group, the ethylenically unsaturated group or cyclic ether group possessed by the specific liquid crystal compound is used from the viewpoint of reactivity and suppression of reflectance change after molding. and the ethylenically unsaturated group or cyclic ether group possessed by the chiral agent are preferably the same group (e.g., an ethylenically unsaturated group, preferably a (meth)acryloxy group), and are the same group. is more preferred.

The chiral agent having a polymerizable group is preferably a chiral agent having two or more polymerizable groups from the viewpoint of reactivity and suppression of change in reflectance after molding. A chiral agent having a group or a chiral agent having two or more cyclic ether groups is more preferable, and a chiral agent having two or more ethylenically unsaturated groups is particularly preferable.

The chiral agent may be a cholesteric liquid crystal compound.

As will be described later, when controlling the size of the helical pitch of the cholesteric liquid crystal layer by light irradiation when manufacturing the cholesteric liquid crystal layer, the liquid crystal composition changes the helical pitch of the cholesteric liquid crystal layer in response to light. It is preferable to include a chiral agent (hereinafter also referred to as a “photosensitive chiral agent”) that allows the photosensitivity. A photosensitive chiral agent is a compound that changes its structure by absorbing light and can change the helical pitch of the cholesteric liquid crystal layer. As such a compound, a compound that causes at least one of a photoisomerization reaction, a photodimerization reaction, and a photodecomposition reaction is preferable. A compound that undergoes a photoisomerization reaction refers to a compound that undergoes stereoisomerization or structural isomerization under the action of light. Compounds that cause photoisomerization include, for example, azobenzene compounds and spiropyran compounds. Further, a compound that causes a photodimerization reaction refers to a compound that undergoes an addition reaction between two groups and is cyclized by irradiation with light. Compounds that cause photodimerization include, for example, cinnamic acid derivatives, coumarin derivatives, chalcone derivatives, and benzophenone derivatives. Moreover, the light is not particularly limited, and examples thereof include ultraviolet light, visible light, and infrared light.

As the photosensitive chiral agent, a chiral agent represented by the following formula (CH1) is preferably exemplified. The chiral agent represented by the following formula (CH1) can change the orientation structure such as the helical pitch (eg, helical period and twist period) of the cholesteric liquid crystal phase depending on the amount of light irradiated.

In formula (CH1), Ar ^CH1 and Ar ^CH2 each independently represent an aryl group or a heteroaromatic ring group, and R ^CH1 and R ^CH2 each independently represent a hydrogen atom or a cyano group.

Ar 4 ^CH1 and Ar 4 ^CH2 in formula (CH1) are each independently preferably an aryl group. The total carbon number of the aryl groups in Ar 2 ^CH1 and Ar 2 ^CH2 of formula (CH1) is preferably 6-40, more preferably 6-30. The aryl group may have a substituent. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, hydroxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, carboxy groups, cyano groups, or heterocyclic rings. A group is preferred, and a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an acyloxy group, an alkoxycarbonyl group, or an aryloxycarbonyl group is more preferred.

Ar ^CH1 and Ar ^CH2 are preferably aryl groups represented by the following formula (CH2) or (CH3).

In formula (CH2) and formula (CH3), R ^CH3 and R ^CH4 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, a hydroxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carboxy group, or a cyano group, L ^CH1 and L ^CH2 each independently represent a halogen atom, an alkyl group, an alkoxy group, or a hydroxy group, nCH1 represents an integer of 0 to 4, nCH2 represents an integer of 0 to 6, and * represents a bonding position with C forming an ethylenically unsaturated bond in formula (CH1).

R ^CH3 and R ^CH4 in formula (CH2) and formula (CH3) are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, Alternatively, it is preferably an acyloxy group, more preferably an alkoxy group, a hydroxy group, or an acyloxy group, and particularly preferably an alkoxy group.
L ^CH1 and L ^CH2 in the formulas (CH2) and (CH3) are each independently preferably an alkoxy group having 1 to 10 carbon atoms or a hydroxy group.
nCH1 in formula (CH2) is preferably 0 or 1.
nCH2 in formula (CH3) is preferably 0 or 1.

The total carbon number of the heteroaromatic ring groups in Ar 2 ^CH1 and Ar 2 ^CH2 of formula (CH1) is preferably 4-40, more preferably 4-30. The heteroaromatic ring group may have a substituent. Preferred substituents include, for example, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, a hydroxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, or a cyano group. Halogen atoms, alkyl groups, alkenyl groups, aryl groups, alkoxy groups, or acyloxy groups are more preferred. The heteroaromatic ring group is preferably a pyridyl group, a pyrimidinyl group, a furyl group or a benzofuranyl group, more preferably a pyridyl group or a pyrimidinyl group.

In formula (CH1), R ^CH1 and R ^CH2 are each independently preferably a hydrogen atom.

The liquid crystal composition may contain one chiral agent alone or two or more chiral agents. The content of the chiral agent can be appropriately selected according to the structure of the specific liquid crystal compound used and the desired pitch of the helical structure. The content of the chiral agent is 1% by mass based on the total solid content of the liquid crystal composition, from the viewpoints of facilitating the formation of the cholesteric liquid crystal layer, facilitating adjustment of the pitch of the helical structure, and suppressing changes in reflectance after molding. It is preferably 20% by mass or more, more preferably 2% by mass or more and 15% by mass or less, and particularly preferably 3% by mass or more and 10% by mass or less.

In the case where the liquid crystal composition contains a chiral agent having a polymerizable group as a chiral agent, the content of the chiral agent having a polymerizable group is, from the viewpoint of suppressing change in reflectance after molding, the total solid content of the liquid crystal composition. On the other hand, it is preferably 0.2% by mass or more and 15% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, and even more preferably 1% by mass or more and 8% by mass or less. It is particularly preferable to be 1.5% by mass or more and 5% by mass or less.

When the liquid crystal composition contains a chiral agent that does not have a polymerizable group as a chiral agent, the content of the chiral agent that does not have a polymerizable group should be within the total solid content of the liquid crystal composition from the viewpoint of suppressing changes in reflectance after molding. It is preferably 0.2% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 15% by mass or less, and 1.5% by mass or more and 10% by mass or less. is particularly preferred.

In addition, the pitch of the helical structure of the cholesteric liquid crystal in the cholesteric liquid crystal layer, and the selective reflection wavelength and its range described later can be easily adjusted not only by the type of liquid crystal compound used but also by adjusting the content of the chiral agent. can be changed. Although it cannot be generalized, if the content of the chiral agent in the liquid crystal composition is doubled, the pitch may be halved and the central value of the selective reflection wavelength may also be halved.

-Polymerization initiator-
The liquid crystal composition preferably contains a polymerization initiator, more preferably a photopolymerization initiator.

When the liquid crystal composition contains a cholesteric liquid crystal compound having one ethylenically unsaturated group, the liquid crystal composition may contain a radical polymerization initiator from the viewpoint of suppressing reflectance change and color change after molding. More preferably, it contains a radical photopolymerization initiator.

When the liquid crystal composition contains a cholesteric liquid crystal compound having one cyclic ether group, the liquid crystal composition may contain a cationic polymerization initiator from the viewpoint of suppressing reflectance change and color change after molding. More preferably, it contains a photocationic polymerization initiator.

The liquid crystal composition preferably contains only one of a radical polymerization initiator and a cationic polymerization initiator as a polymerization initiator.

A known polymerization initiator can be used as the polymerization initiator. Moreover, the polymerization initiator is preferably a photopolymerization initiator capable of initiating a polymerization reaction by ultraviolet irradiation. Examples of photoinitiators include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether compounds (described in US Pat. No. 2,448,828), α- Hydrocarbon-substituted aromatic acyloin compounds (described in US Pat. No. 2,722,512), polynuclear quinone compounds (described in US Pat. Nos. 3,046,127 and 2,951,758), triarylimidazole dimers and p-aminophenyl Combinations with ketones (described in US Pat. No. 3,549,367), acridine compounds and phenazine compounds (described in JP-A-60-105667 and US Pat. No. 4,239,850), and oxadiazole compounds (described in US Pat. No. 4212970).

As the radical photopolymerization initiator, a known radical photopolymerization initiator can be used. As the radical photopolymerization initiator, α-hydroxyalkylphenone compounds, α-aminoalkylphenone compounds, and acylphosphine oxide compounds are preferred.

A known photocationic polymerization initiator can be used as the photocationic polymerization initiator. As the photocationic polymerization initiator, an iodonium salt compound or a sulfonium salt compound is preferably used.

The liquid crystal composition may contain one polymerization initiator alone, or may contain two or more polymerization initiators. The content of the polymerization initiator can be appropriately selected according to the structure of the specific liquid crystal compound to be used and the desired pitch of the helical structure. The content of the polymerization initiator is 0 with respect to the total solid content of the liquid crystal composition, from the viewpoints of ease of forming the cholesteric liquid crystal layer, ease of adjusting the pitch of the helical structure, polymerization rate, and strength of the cholesteric liquid crystal layer. It is preferably 0.05% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less, even more preferably 0.1% by mass or more and 2% by mass or less. .2 mass % or more and 1 mass % or less is particularly preferable.

-Crosslinking agent-
The liquid crystal composition may contain a cross-linking agent in order to improve the strength and durability of the cured cholesteric liquid crystal layer. As the cross-linking agent, for example, a cross-linking agent that cures with ultraviolet rays, heat, or moisture can be preferably used. The cross-linking agent is not particularly limited and can be appropriately selected depending on the purpose. Examples include polyfunctional acrylate compounds such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate; epoxy compounds such as acrylates and ethylene glycol diglycidyl ether; aziridine compounds such as 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate] and 4,4-bis(ethyleneiminocarbonylamino)diphenylmethane; isocyanate compounds such as hexamethylene diisocyanate and biuret-type isocyanate; polyoxazoline compounds having oxazoline groups in side chains; and alkoxysilane compounds such as vinyltrimethoxysilane and N-(2-aminoethyl)3-aminopropyltrimethoxysilane. mentioned. Also, a known catalyst can be used depending on the reactivity of the cross-linking agent, and productivity can be improved in addition to improving the strength and durability of the cholesteric liquid crystal layer.

The liquid crystal composition may contain a single cross-linking agent or two or more cross-linking agents. From the viewpoint of the strength and durability of the cholesteric liquid crystal layer, the content of the cross-linking agent is preferably 1% by mass or more and 20% by mass or less, and 3% by mass or more and 15% by mass or less, based on the total solid content of the liquid crystal composition. The following are more preferable.

- Polyfunctional polymerizable compound -
From the viewpoint of suppressing changes in reflectance after molding, the liquid crystal composition preferably contains a polyfunctional polymerizable compound, and more preferably contains a polyfunctional polymerizable compound having the same type of polymerizable group. As the polyfunctional polymerizable compound, a cholesteric liquid crystal compound having two or more ethylenically unsaturated groups and not having a cyclic ether group in the other cholesteric liquid crystal compounds described above, and two or more cyclic ether groups. and a cholesteric liquid crystal compound having no ethylenically unsaturated groups, a cholesteric liquid crystal compound having two or more ethylenically unsaturated groups and two or more cyclic ether groups, and two or more of the above chiral agents and the above-mentioned cross-linking agents.

The liquid crystal composition includes, as polyfunctional polymerizable compounds, a cholesteric liquid crystal compound having two or more ethylenically unsaturated groups and no cyclic ether group, a cholesteric liquid crystal compound having two or more cyclic ether groups and ethylene It preferably contains at least one compound selected from the group consisting of a cholesteric liquid crystal compound having no polyunsaturated group and a chiral agent having two or more polymerizable groups, and two or more polymerizable groups. It is more preferable to include a chiral agent having

The liquid crystal composition may contain one type of polyfunctional polymerizable compound alone, or two or more types thereof. From the viewpoint of suppressing change in reflectance after molding, the content of the polyfunctional polymerizable compound is preferably 0.5% by mass or more and 70% by mass or less, and 1% by mass, based on the total solid content of the liquid crystal composition. It is more preferably at least 50% by mass, still more preferably at least 1.5% by mass and at most 20% by mass, and particularly preferably at least 2% by mass and not more than 10% by mass.

-Other additives-
The liquid crystal composition may contain additives other than the components described above, if necessary. Other additives that can be used include known additives, such as surfactants, polymerization inhibitors, antioxidants, horizontal alignment agents, UV absorbers, light stabilizers, colorants, and metal oxide particles can be mentioned.

Moreover, the liquid crystal composition may contain a solvent. The solvent is not particularly limited and can be appropriately selected depending on the intended purpose, but an organic solvent is preferably used. The organic solvent is not particularly limited and can be appropriately selected depending on the intended purpose. Included are hydrocarbons, esters, and ethers. A solvent may be used individually by 1 type, and may use 2 or more types together. Among these, ketones are particularly preferable in consideration of the load on the environment. Moreover, the above-mentioned component may function as a solvent.

The content of the solvent in the liquid crystal composition is not particularly limited, and may be adjusted so that the desired coatability can be obtained. The content of solids relative to the total mass of the liquid crystal composition is not particularly limited, but is preferably 1% by mass to 90% by mass, more preferably 5% by mass to 80% by mass, and 10% by mass. It is particularly preferred to be ∼80% by mass. The content of the solvent in the liquid crystal composition during curing for forming the cholesteric liquid crystal layer is preferably 5% by mass or less, more preferably 3% by mass or less, based on the total solid content of the liquid crystal composition. It is preferably 2% by mass or less, more preferably 1% by mass or less. The content of the solvent in the cholesteric liquid crystal layer obtained by curing the liquid crystal composition is preferably 5% by mass or less, more preferably 3% by mass or less, relative to the total mass of the cholesteric liquid crystal layer. It is more preferably 2% by mass or less, and particularly preferably 1% by mass or less.

- Application and curing of liquid crystal composition -
In forming the cholesteric liquid crystal layer, the liquid crystal composition is used, for example, by being applied onto an object (eg, the base material described above and the orientation layer described later). Application of the liquid crystal composition can be carried out, for example, by making the liquid crystal composition into a solution state with a solvent, or by making it into a liquid state such as a melt by heating, and then by an appropriate method such as a roll coating method, a gravure printing method, or a spin coating method. It can be carried out. Application of the liquid crystal composition can also be performed by various methods such as wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating, and die coating. A coating film (meaning a film-like liquid crystal composition formed by coating) can also be formed by ejecting a liquid crystal composition from a nozzle using an inkjet device.

After application of the liquid crystal composition, a cholesteric liquid crystal layer is formed by curing the liquid crystal composition. By curing the liquid crystal composition, the orientation state of the molecules of the liquid crystal compound (for example, the specific liquid crystal compound described above) is maintained and fixed. Curing of the liquid crystal composition is preferably carried out by a polymerization reaction of a polymerizable group (for example, an ethylenically unsaturated group or a cyclic ether group) possessed by the liquid crystal compound. When a solvent is used as a component of the liquid crystal composition, it is preferable to dry the coating film by a known method after coating the liquid crystal composition and before polymerization reaction for curing. For example, the coating film may be dried by standing, or may be dried by heating. It is sufficient that the liquid crystal compound in the liquid crystal composition is aligned after the liquid crystal composition is applied and dried.

-Layer structure of cholesteric liquid crystal layer-
The decorative film according to an embodiment of the present disclosure preferably has two or more cholesteric liquid crystal layers from the viewpoint of suppressing changes in reflectance after molding. Also, the compositions of two or more cholesteric liquid crystal layers may be the same or different. When the decorative film according to an embodiment of the present disclosure has two or more cholesteric liquid crystal layers, the decorative film according to an embodiment of the present disclosure has one ethylenically unsaturated group or a cyclic ether group. At least one layer obtained by curing a liquid crystal composition containing one cholesteric liquid crystal compound (that is, a specific liquid crystal compound) in an amount of 25% by mass or more with respect to the total solid content of the liquid crystal composition may be provided. From the viewpoint of suppressing change in reflectance after molding, a cholesteric liquid crystal compound in which each of the two or more cholesteric liquid crystal layers has one ethylenically unsaturated group or one cyclic ether group is added to the entire liquid crystal composition. It is preferably a layer obtained by curing a liquid crystal composition containing 25% by mass or more of the solid content.

Further, for example, when the decorative film according to an embodiment of the present disclosure has two cholesteric liquid crystal layers, from the viewpoint of suppressing reflectance change after molding, each surface of the base material has a cholesteric liquid crystal layer. It is preferable to have

<<Selective Reflectivity of Reflective Layer>>
The reflective layer has a central wavelength of a selective reflection wavelength in the range of 300 nm or more and 1,500 nm or less. In the present disclosure, the “center wavelength of the selective reflection wavelength” means the following when T _min (unit: %) is the minimum value and minimum value of light transmittance in a target object (for example, a reflective layer). An average value of two wavelengths showing the half-value transmittance T _1/2 (unit: %) represented by the formula. However, the first wavelength of the two wavelengths is the maximum wavelength in a wavelength range including a wavelength shorter than the wavelength indicating the T _min , and the second wavelength of the two wavelengths is the T _min . shall be the minimum wavelength in the wavelength region including the wavelengths longer than the wavelength indicating The transmittance is measured using a spectrophotometer (eg, spectrophotometer UV-2100 manufactured by Shimadzu Corporation and spectrophotometer V-670 manufactured by JASCO Corporation). The central wavelength of the selective reflection wavelength may be included in the range of 380 nm or more and 780 nm or less, or the range of more than 780 nm and 1,500 nm or less.
Formula for calculating half-value transmittance: T _1/2 = 100-(100-T _min )/2

The reflective layer preferably has a maximum reflective wavelength in the wavelength range of 380 nm to 1,500 nm. The wavelength range including the maximum reflection wavelength is preferably 380 nm to 1,200 nm, more preferably 400 nm to 1,000 nm, and more preferably 420 nm to 900 nm, from the viewpoint of use for decorative films. Especially preferred.

<Orientation layer>
A decorative film according to an embodiment of the present disclosure may have an alignment layer in contact with the cholesteric liquid crystal layer. The alignment layer is used to align the molecules of the liquid crystal compound in the liquid crystal composition when forming a layer containing the liquid crystal compound (hereinafter also referred to as "liquid crystal layer"). Since the alignment layer is used, for example, in forming the liquid crystal layer, the decorative film that does not contain the liquid crystal layer may or may not contain the alignment layer.

The alignment layer can be provided, for example, by rubbing an organic compound (preferably a polymer), oblique deposition of an inorganic compound (eg SiO ₂ ), or formation of a layer with microgrooves. Furthermore, an orientation layer is also known in which an orientation function is produced by application of an electric field, application of a magnetic field, or light irradiation. Depending on the material of the lower layer such as the support and the liquid crystal layer, the lower layer can be made to function as an orientation layer by direct orientation treatment (for example, rubbing treatment) without providing an orientation layer. An example of such an underlayer support is polyethylene terephthalate (PET). In addition, when a layer (hereinafter referred to as "upper layer" in this paragraph) is directly laminated on the liquid crystal layer, the lower liquid crystal layer acts as an alignment layer and can align the liquid crystal compound for the production of the upper layer. There is also In such a case, the liquid crystal compound in the upper layer can be aligned without providing an alignment layer or performing a special alignment treatment (for example, rubbing treatment).

Hereinafter, a rubbing treatment alignment layer and a photo-alignment layer will be described as preferable examples of the alignment layer.

<<Rubbing treatment alignment layer>>
The rubbing treatment orientation layer is an orientation layer to which orientation is imparted by rubbing treatment. Examples of polymers that can be used for the rubbing treatment alignment layer include, for example, methacrylate copolymers, styrene copolymers, polyolefins, polyvinyl alcohols and modified polyvinyl alcohols described in paragraph 0022 of JP-A-8-338913; and poly(N-methylolacrylamide), polyesters, polyimides, vinyl acetate copolymers, carboxymethylcellulose, and polycarbonates. A silane coupling agent can be used as the polymer. Polymers that can be used in the rubbing treatment alignment layer are preferably water-soluble polymers (e.g., poly(N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol), and gelatin, polyvinyl alcohol, or modified polyvinyl alcohol. Alcohol is more preferred, and polyvinyl alcohol or modified polyvinyl alcohol is particularly preferred.

In the method of aligning a liquid crystal compound using a rubbing alignment layer, for example, a composition for forming a cholesteric liquid crystal layer (one form of a liquid crystal composition) is applied to the rubbing surface of the rubbing alignment layer, Orient the molecules of the liquid crystal compound. Thereafter, if necessary, the polymer contained in the alignment layer and the polyfunctional monomer contained in the cholesteric liquid crystal layer are reacted, or the polymer contained in the alignment layer is crosslinked using a cross-linking agent to obtain the cholesteric liquid crystal. Layers can be formed. The film thickness of the alignment layer is preferably in the range of 0.1 μm to 10 μm.

－Rubbing treatment－
The surface of the alignment layer, support, or other layer to which the composition for forming a cholesteric liquid crystal layer is applied may be subjected to a rubbing treatment, if necessary. The rubbing treatment can generally be carried out by rubbing the surface of the film containing a polymer as a main component with paper or cloth in one direction. A general rubbing method is described, for example, in "Liquid Crystal Handbook" (published by Maruzen Co., Ltd., Oct. 30, 2000).

As a method for changing the rubbing density, a method described in "Liquid Crystal Handbook" (published by Maruzen Co., Ltd.) can be used. The rubbing density (L) is quantified by the following formula (A).
Formula (A): L=Nl(1+2πrn/60v)
In formula (A), N is the number of rubbing times, l is the contact length of the rubbing roller, π is the circular constant, r is the radius of the roller, n is the rotation speed of the roller (rpm: revolutions per minute), and v is the stage moving speed. (per second).

In order to increase the rubbing density, the number of times of rubbing can be increased, the contact length of the rubbing roller can be increased, the radius of the roller can be increased, the rotation speed of the roller can be increased, or the stage movement speed can be decreased. In order to lower the rubbing density, the opposite should be done. Further, the description in Japanese Patent No. 4052558 can be referred to as the conditions for the rubbing treatment.

<<Photo-alignment layer>>
The photo-alignment layer is an alignment layer imparted with alignment properties by light irradiation. The photo-alignment material used for the photo-alignment layer is described in many documents. As the photo-alignment material, JP-A-2006-285197, JP-A-2007-76839, JP-A-2007-138138, JP-A-2007-94071, JP-A-2007-121721, JP-A-2007- 140465, JP 2007-156439, JP 2007-133184, JP 2009-109831, JP 3883848, and the azo compounds described in JP 4151746, JP 2002- Aromatic ester compounds described in JP-A-229039, JP-A-2002-265541, and maleimide and/or alkenyl-substituted nadimide compounds having photoalignable units described in JP-A-2002-317013, Japanese Patent No. 4205195, And the photocrosslinkable silane derivative described in Japanese Patent No. 4205198, and the photocrosslinkable polyimide, polyamide, or ester described in Japanese Patent Publication No. 2003-520878, Japanese Patent Publication No. 2004-529220, and Japanese Patent No. 4162850. is mentioned as a preferable example. Particularly preferred are azo compounds, photocrosslinkable polyimides, polyamides, and esters.

For example, a layer formed from the above materials is subjected to linearly polarized or unpolarized irradiation to produce a photo-alignment layer. In the present disclosure, "linearly polarized light irradiation" is an operation for causing a photoreaction in the photoalignment material. The wavelength of light to be used varies depending on the photo-alignment material to be used, and is not particularly limited as long as the wavelength is necessary for the photoreaction. The peak wavelength of light used for light irradiation is preferably 200 nm to 700 nm, and more preferably ultraviolet light with a peak wavelength of 400 nm or less.

The light source used for light irradiation is a light source that is commonly used, such as lamps (e.g., tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury xenon lamps, and carbon arc lamps), various lasers (e.g., semiconductor Lasers, helium neon lasers, argon ion lasers, helium cadmium lasers and YAG (Yttrium Aluminum Garnet) lasers), light emitting diodes, and cathode ray tubes may be mentioned.

As means for obtaining linearly polarized light, a method using a polarizing plate (e.g., an iodine polarizing plate, a dichroic dye polarizing plate, and a wire grid polarizing plate), a prism-based element (e.g., a Glan-Thompson prism), and a Brewster angle were used. A method using a reflective polarizer or a method using light emitted from a polarized laser light source can be employed. Alternatively, only light of a required wavelength may be selectively irradiated using a filter and a wavelength conversion element.

When the light to be irradiated is linearly polarized light, a method of irradiating light perpendicularly or obliquely to the upper surface or the lower surface of the alignment layer is adopted. The incident angle of light varies depending on the photo-alignment material, but is preferably 0° to 90° (perpendicular), more preferably 40° to 90°. When using non-polarized light, the upper or lower surface of the alignment layer is obliquely irradiated with non-polarized light. The angle of incidence of unpolarized light is preferably 10° to 80°, more preferably 20° to 60°, particularly preferably 30° to 50°. The irradiation time is preferably 1 minute to 60 minutes, more preferably 1 minute to 10 minutes.

<Resin layer>
The decorative film according to an embodiment of the present disclosure preferably has a resin layer between the substrate and the reflective layer. For example, when pressure is applied to the reflective layer to give it an uneven structure, the resin layer is deformed so that the reflective layer can easily follow the unevenness used as a mold.

The thickness of the resin layer is preferably 0.2 μm to 100 μm, more preferably 0.5 μm to 70 μm, even more preferably 1.0 μm to 50 μm.

The elastic modulus of the resin layer at 25° C. is preferably 0.000001 GPa to 3 GPa, more preferably 0.00001 to 1 GPa, even more preferably 0.0001 to 0.5 GPa. The elastic modulus is measured with a nanoindenter device (for example, Nanoindenter G200, manufactured by KLA).

The resin layer preferably contains a binder resin as a main component. The binder resin is not limited, and known resins can be applied. From the viewpoint of obtaining a desired color, the binder resin is preferably a transparent resin, and specifically, a resin having a total light transmittance of 80% or more is preferable. The total light transmittance can be measured with a spectrophotometer (eg, spectrophotometer UV-2100 manufactured by Shimadzu Corporation).

The binder resin is not limited, and known resins can be applied. Examples of binder resins include acrylic resins, silicone resins, polyesters, urethane resins, and polyolefins. The binder resin may be a homopolymer of a specific monomer, or a copolymer of a specific monomer and another monomer.

Binder resin may be used individually by 1 type, and may be used in combination of 2 or more type. The content of the binder resin in the resin layer is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, based on the total mass of the resin layer, from the viewpoint of moldability. is more preferable, and 20% by mass to 60% by mass is particularly preferable.

A known adhesive or adhesive can also be used as the resin layer.

<<Adhesive>>
Examples of adhesives include acrylic adhesives, rubber adhesives, and silicone adhesives. In addition, as an example of the adhesive, the acrylic adhesive described in ""Release paper, release film and adhesive tape characteristics evaluation and its control technology", Information Organization, 2004, Chapter 2", ultraviolet (UV) curing mold adhesives, and silicone adhesives. In the present disclosure, an acrylic pressure-sensitive adhesive refers to a pressure-sensitive adhesive containing a polymer of (meth)acrylic monomers (that is, a (meth)acrylic polymer). When the resin layer contains an adhesive, the resin layer may further contain a tackifier.

<<Adhesive>>
Examples of adhesives include urethane resin adhesives, polyester adhesives, acrylic resin adhesives, ethylene vinyl acetate resin adhesives, polyvinyl alcohol adhesives, polyamide adhesives, and silicone adhesives. A urethane resin adhesive or a silicone adhesive is preferable from the viewpoint of higher adhesive strength.

<<Method for Forming Resin Layer>>
A method for forming the resin layer is not limited. The resin layer can be formed using, for example, a composition for forming a resin layer. The resin layer-forming composition can be prepared, for example, by mixing raw materials for the resin layer. As a method of applying the resin layer-forming composition, for example, the same method as the method of applying the liquid crystal composition can be used.

<<Additives>>
The resin layer may contain additives, if necessary, in addition to the above components. Additives are not limited, and known additives can be applied. Examples of additives include surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Application Laid-Open No. 2009-237362, and thermal polymerization described in paragraph 0018 of Japanese Patent No. 4502784. Inhibitors (also called polymerization inhibitors, preferably phenothiazine), and additives described in paragraphs 0058 to 0071 of JP-A-2000-310706.

<Colored layer>
A decorative film according to an embodiment of the present disclosure preferably has a colored layer. In one embodiment, the decorative film is preferably a decorative film for visually recognizing the colored layer through the cholesteric liquid crystal layer. The colored layer may be a colored (that is, not colorless and transparent) layer. The colored layer is preferably an opaque colored layer (preferably a colored layer having a total light transmittance of 10% or less). Also, the color of the colored layer may be black, gray, white, red, orange, yellow, green, blue, or purple. A black colored layer is preferable because the intensity of the reflected light is low and the color change is more emphasized.

Moreover, the colored layer may be a layer obtained by curing a polymerizable compound, or a layer containing a polymerizable compound and a polymerization initiator. The colored layer is preferably a layer formed by curing a polymerizable compound from the viewpoint of storage stability and adhesion between the colored layer and other layers, and includes a urethane bond and a carbon number of 2 or 3. More preferably, the layer is formed by curing at least a bifunctional or trifunctional polymerizable compound having at least one partial structure selected from the group consisting of alkyleneoxy groups.

<<coloring agent>>
The colored layer preferably contains a coloring agent from the viewpoint of visibility, and more preferably contains a pigment as the coloring agent from the viewpoint of durability. The coloring agent is not particularly limited, and a coloring agent having a desired hue can be appropriately selected and used. Colorants include, for example, pigments and dyes, with pigments being preferred. Also, the pigment is preferably a particulate pigment. As the pigment, conventionally known various inorganic pigments and organic pigments can be used.

Examples of inorganic pigments include inorganic pigments described in paragraphs 0015 and 0114 of JP-A-2005-7765. Specific inorganic pigments include, for example, white pigments (e.g., titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, and barium sulfate), and black pigments (e.g., carbon black). , titanium black, titanium carbon, iron oxide, and graphite). Known chromatic pigments such as iron oxide, barium yellow, cadmium red, and chrome yellow can also be used.

Examples of organic pigments include organic pigments described in paragraph 0093 of JP-A-2009-256572. Specific organic pigments include, for example, C.I. I. Pigment Red 177, 179, 224, 242, 254, 255, 264, 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 a blue pigment such as C.I. I. Purple pigments such as Pigment Violet 23 may be mentioned.

In addition, the colored layer may contain, as a pigment, particles of a pigment having light transmittance and light reflectivity (so-called luster pigment). When the method for forming the colored layer includes the step of exposing the colored layer, the bright pigment is preferably used within a range that does not interfere with curing by exposure.

The colorants may be used singly or in combination of two or more. Also, inorganic pigment particles and organic pigment particles may be used in combination. The content of the coloring agent in the colored layer is, from the viewpoint of expressing the desired hue (e.g., suppressing whitening) and maintaining the shape conformability of the colored layer to the mold, relative to the total mass of the colored layer, It is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 50% by mass, and even more preferably 10% by mass to 40% by mass. Here, “whitening” in the present disclosure means that the colored layer changes so as to exhibit a whitish color that gives a matte feeling.

<<polymerizable compound>>
The colored layer used in the present disclosure may contain a polymerizable compound. A polymerizable compound is a compound having a polymerizable group.

Examples of the polymerizable group include an ethylenically unsaturated group and an epoxy group. From the viewpoint of curability and the like, an ethylenically unsaturated group is preferred, and a (meth)acryloxy group is more preferred. Moreover, as a polymerizable group, a radically polymerizable group is preferable.

The polymerizable compound has at least one partial structure selected from the group consisting of a urethane bond, a urea bond, an alkyleneoxy group having 2 or 3 carbon atoms, and a hydrocarbon group having 6 to 12 carbon atoms. A bifunctional or trifunctional polymerizable compound (hereinafter also referred to as a “specific polymerizable compound”) is preferred, and a compound containing a urethane bond in its partial structure is more preferred.

-Bifunctional or trifunctional polymerizable compound having a urethane bond-
A urethane oligomer is preferable as the bifunctional or trifunctional polymerizable compound having a urethane bond (hereinafter also referred to as “specific polymerizable compound 1”). The nitrogen atom in the urethane bond may be disubstituted (one of the groups on the nitrogen atom is a hydrogen atom) or trisubstituted. Moreover, the specific polymerizable compound 1 preferably has a urethane resin chain.

A urethane (meth)acrylate oligomer is preferable as the urethane oligomer. Urethane (meth)acrylate oligomers include, for example, aliphatic urethane (meth)acrylates and aromatic urethane (meth)acrylates. For details, refer to Oligomer Handbook (supervised by Junji Furukawa, The Chemical Daily Co., Ltd.), and the urethane oligomer described herein can be appropriately selected according to the purpose and used to form a colored layer. .

The molecular weight of the urethane oligomer, which is one type of the specific polymerizable compound 1, is preferably 800 to 2,000, more preferably 1,000 to 2,000.

As the urethane (meth)acrylate oligomer which is one type of the specific polymerizable compound 1, a commercially available product may be used. Examples of commercially available urethane (meth)acrylate oligomers include U-2PPA and UA-122P manufactured by Shin-Nakamura Chemical Co., Ltd.; ＣＮ９６５、ＣＮ９８２Ｂ８８、ＣＮ９８１、ＣＮ９８３、ＣＮ９９１、ＣＮ９９１ＮＳ、ＣＮ９９６、ＣＮ９９６ＮＳ、ＣＮ９００２、ＣＮ９００７、ＣＮ９１７８、及びＣＮ９８９３；並びにダイセル・オルネクス（株）製のＥＢＥＣＲＹＬ２３０、ＥＢＥＣＲＹＬ２７０、ＥＢＥＣＲＹＬ２８４、ＥＢＥＣＲＹＬ４８５８、ＥＢＥＣＲＹＬ２１０、ＥＢＥＣＲＹＬ８４０２、ＥＢＥＣＲＹＬ８８０４、及びＥＢＥＣＲＹＬ８８００ -20R (these are trade names). "EBECRYL" is a registered trademark.

<<Dispersant>>
From the viewpoint of improving the dispersibility of the pigment contained in the colored layer, the colored layer may contain a dispersant. By including a dispersant in the colored layer, the dispersibility of the pigment in the formed colored layer is improved, and the resulting decorative film can have a uniform hue.

The dispersant can be appropriately selected according to the type, shape, etc. of the pigment, and is preferably a polymer dispersant. Polymeric dispersants include, for example, silicone polymers, acrylic polymers, and polyester polymers.

When it is desired to impart heat resistance to the decorative film, it is suitable to use, for example, a silicone polymer such as a graft-type silicone polymer as the dispersant.

The weight average molecular weight of the dispersant is preferably 1,000 to 5,000,000, more preferably 2,000 to 3,000,000, and 2,500 to 3,000,000. is particularly preferred. When the weight average molecular weight is 1,000 or more, the dispersibility of the pigment is further improved.

A commercially available product may be used as the dispersant. Commercially available products include, for example, EFKA 4300 (acrylic polymer dispersant) manufactured by BASF Japan, Homogenol L-18, Homogenol L-95, and Homogenol L-100 manufactured by Kao Corporation, and Nippon Lubrizol Co., Ltd. DISPERBYK-110, DISPERBYK-164, DISPERBYK-180, and DISPERBYK-182 manufactured by BYK-Chemie Japan Co., Ltd.; "Homogenol", "Solsperse" and "DISPERBYK" are all registered trademarks.

When the colored layer contains a dispersant, the dispersant may contain only one dispersant, or may contain two or more dispersants. The content of the dispersant is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the colorant.

<<polymerization initiator>>
The colored layer may contain a polymerization initiator. As the polymerization initiator, a photopolymerization initiator is preferable from the viewpoint of enhancing the sensitivity to exposure. Examples of photopolymerization initiators include, for example, the polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716, and the oxime-based polymerization initiators described in paragraphs 0064 to 0081 of JP-A-2015-014783. agent can be used.

Specific photopolymerization initiators include, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) (eg, IRGACURE (registered trademark) OXE-01, BASF), [9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-one-1-(O-acetyloxime) (eg, IRGACURE (registered trademark) OXE -02, manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (for example, IRGACURE® ) 379EG, manufactured by BASF), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (for example, IRGACURE® 907, manufactured by BASF), 2-hydroxy-1 -{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methyl-propan-1-one (eg, IRGACURE® 127, manufactured by BASF), 2-benzyl- 2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (eg, IRGACURE (registered trademark) 369, manufactured by BASF), 2-hydroxy-2-methyl-1-phenylpropan-1-one (eg, , IRGACURE (registered trademark) 1173, manufactured by BASF), 1-hydroxycyclohexylphenyl ketone (e.g., IRGACURE (registered trademark) 184, manufactured by BASF), 2,2-dimethoxy-1,2-diphenylethan-1-one (for example, IRGACURE (registered trademark) 651, manufactured by BASF), trade name of oxime ester polymerization initiator: Lunar 6 (manufactured by DKSH Japan Co., Ltd.), 2,4-diethylthioxanthone (for example, Kayacure DETX-S , manufactured by Nippon Kayaku Co., Ltd.), and DFI-091 and DFI-020, which are fluorene oxime-based polymerization initiators (both manufactured by Daito Chemix Co., Ltd.).

Among them, it is preferable to use other initiators other than halogen-containing polymerization initiators such as trichloromethyltriazine-based compounds from the viewpoint of increasing curing sensitivity. Oxime-based polymerization initiators such as oxime-based compounds are more preferred.

The content of the polymerization initiator is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the polymerizable compound.

<<binder resin>>
The colored layer preferably contains a binder resin from the viewpoint of reducing cure shrinkage of the colored layer. The binder resin is not particularly limited, and can be appropriately selected from known resins. The binder resin is preferably a transparent resin in order to obtain the desired hue, and specifically, a resin having a total light transmittance of 80% or more is preferable. The total light transmittance can be measured with a spectrophotometer (eg, spectrophotometer UV-2100 manufactured by Shimadzu Corporation).

Examples of binder resins include acrylic resins, silicone resins, polyester resins, urethane resins, and olefin resins. Among them, from the viewpoint of transparency, acrylic resins, silicone resins, or polyester resins are preferable, and acrylic resins or silicone resins are more preferable. Furthermore, from the viewpoint of heat resistance, a silicone resin is preferable.

In the present disclosure, "acrylic resin" refers to a resin containing a structural unit derived from an acrylic monomer having a (meth)acryloyl group. A (meth)acryloyl group is a concept including a methacryloyl group and an acryloyl group. Acrylic resins include, for example, acrylic acid homopolymers, methacrylic acid homopolymers, acrylic acid ester homopolymers, methacrylic acid ester homopolymers, copolymers of acrylic acid and other monomers, methacrylic acid Copolymers of acids and other monomers, copolymers of acrylic acid esters and other monomers, copolymers of methacrylic acid esters and other monomers, and urethane-modified copolymers having urethane skeletons in side chains Consolidation is included. Examples of acrylic resins include glycidyl methacrylate adducts of cyclohexyl methacrylate/methyl methacrylate/methacrylic acid copolymers, benzyl methacrylate/methacrylic acid random copolymers, allyl methacrylate/methacrylic acid copolymers, and benzyl methacrylate/methacrylic acid copolymers. Copolymers of acid/hydroxyethyl methacrylate are mentioned.

As the silicone resin, known silicone resins can be used, and examples thereof include methyl-based straight silicone resin, methylphenyl-based straight silicone resin, acrylic resin-modified silicone resin, ester resin-modified silicone resin, epoxy resin-modified silicone resin, and alkyd resin. Examples include modified silicone resins and rubber-based silicone resins. Among them, methyl-based straight silicone resin, methylphenyl-based straight silicone resin, acrylic resin-modified silicone resin, or rubber-based silicone resin is preferable, and methyl-based straight silicone resin, methylphenyl-based straight silicone resin, or rubber-based silicone. Resin is more preferred.

Commercially available silicone resins may be used, and examples of commercially available products include KR-300, KR-311, KR-251, X-40-2406M, and KR-282 manufactured by Shin-Etsu Chemical Co., Ltd. be done.

Examples of polyester resins include linear saturated polyesters synthesized from aromatic dibasic acids or ester-forming derivatives thereof and diols or ester-forming derivatives thereof. Specific examples of linear saturated polyesters include, for example, polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, poly(1,4-cyclohexylene dimethylene terephthalate), and polyethylene-2,6-naphthalate.

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 mass of the colored layer, in order to reduce curing shrinkage of the colored layer. % or more and 60% by mass is more preferable. Further, the ratio of the total amount of the binder resin to the total amount of the polymerizable compounds including the specific polymerizable compound, that is, the total amount of the polymerizable compounds/the total amount of the binder resin, is preferably 0.3 to 1.5. It is more preferably 5 to 1.0.

<<Other Ingredients>>
The colored layer may contain additives, if necessary, in addition to the above components. As the additive, known additives can be used, for example, paragraph 0017 of Japanese Patent No. 4502784, and paragraphs 0060 to 0071 of Japanese Patent Application Laid-Open No. 2009-237362, surfactants described in Japanese Patent No. 4502784 Thermal polymerization inhibitors (also referred to as polymerization inhibitors, preferably phenothiazine) described in paragraph 0018 of JP-A 2000-310706, and other additives described in paragraphs 0058 to 0071 of JP-A-2000-310706.

<<Formation of colored layer>>
Although the method for forming the colored layer is not particularly limited, it is preferably formed using a colored layer-forming composition. The colored layer-forming composition preferably contains a coloring agent, and more preferably contains a coloring agent and an organic solvent. Moreover, the composition for forming a colored layer may further contain the other components described above. The composition for forming a colored layer can be prepared, for example, by mixing an organic solvent and a component contained in the colored layer such as a colorant. The content of the components contained in the colored layer is described as the content (mass%) with respect to the total mass of the colored layer, but when these components are contained in the colored layer-forming composition, the content is , shall be read as the content (% by mass) relative to the total solid content of the composition for forming a colored layer.

Further, when the composition for forming a colored layer contains a pigment as a coloring agent, a pigment dispersion containing a pigment and a dispersant thereof is prepared in advance, and the composition for forming a colored layer is prepared using this pigment dispersion. is preferable from the viewpoint of further enhancing the uniform dispersibility and dispersion stability of the pigment.

The colored layer-forming composition may be prepared in advance by the above method, or may be a commercially available product, or the colored layer-forming composition may be prepared immediately before coating. .

-Organic solvent-
As the organic solvent, commonly used organic solvents can be used without particular limitation. Specific examples include organic solvents such as esters, ethers, ketones, and aromatic hydrocarbons. Also, the same methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, lactic acid as Solvents described in paragraphs 0054 and 0055 of US Patent Application Publication No. 2005/282073 Ethyl, methyl lactate, and the like can also be suitably used as the organic solvent in the colored layer-forming composition. Among them, 1-methoxy-2-propyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, diethylene glycol mono Ethyl ether acetate (ethyl carbitol acetate), diethylene glycol monobutyl ether acetate (butyl carbitol acetate), propylene glycol methyl ether acetate, methyl ethyl ketone and the like are preferably used as the organic solvent in the colored layer forming composition. These organic solvents may be used individually by 1 type, and may use 2 or more types together. The content of the organic solvent is not particularly limited, but is preferably 5% by mass to 90% by mass, preferably 30% by mass, based on the total mass of the composition for forming a colored layer (eg, coating liquid). It is more preferably ~70% by mass.

<Adhesive layer>
The decorative film according to an embodiment of the present disclosure preferably has an adhesive layer from the viewpoint of adhesion to the housing to which the decorative film is attached or adhesion between layers. The material for the adhesive layer is not particularly limited and can be appropriately selected according to the purpose. The adhesive layer includes, for example, a layer containing a known adhesive or adhesive.

<<Adhesive>>
Examples of adhesives include acrylic adhesives, rubber adhesives, and silicone adhesives. Also, as examples of adhesives, acrylic adhesives and ultraviolet (UV) curable adhesives described in Chapter 2 of "Release Paper/Release Film and Adhesive Tape Characteristic Evaluation and Control Technology", Information Organization, 2004 and silicone adhesives. When the adhesive layer contains an adhesive, the adhesive layer may further contain a tackifier.

<<Adhesive>>
Examples of adhesives include urethane resin adhesives, polyester adhesives, acrylic resin adhesives, ethylene vinyl acetate resin adhesives, polyvinyl alcohol adhesives, polyamide adhesives, and silicone adhesives. A urethane resin adhesive or a silicone adhesive is preferable from the viewpoint of higher adhesive strength.

In the decorative film according to one embodiment, the relationship among the thickness (T2) of the colored layer, the thickness (T3) of the reflective layer (preferably the cholesteric liquid crystal layer), and the thickness (T4) of the adhesive layer is T4<10 ( T2+T3) is preferably satisfied. By satisfying the above relationship, it is possible to obtain a decorative film that is thin and has excellent luster and visibility. More preferably, T4<8 (T2+T3), still more preferably T4<5 (T2+T3), particularly preferably T4<3 (T2+T3).

<<Method of Forming Adhesive Layer>>
The method of forming the adhesive layer is not particularly limited, and a protective film having an adhesive layer formed thereon is laminated so that the adhesive layer and an object (e.g., a reflective layer, an orientation layer, or a colored layer) are in contact, A method of laminating an adhesive layer alone so that it is in contact with an object (e.g., a reflective layer, an orientation layer, or a colored layer), and a composition containing a pressure-sensitive adhesive or adhesive to an object (e.g., a reflective layer, an orientation layer, or coloring layer). A known method can be used as the lamination method. The coating method is preferably the same as the coating method of the liquid crystal composition.

The thickness of the adhesive layer in the decorative film is preferably 2 μm to 40 μm, more preferably 3 μm to 25 μm, still more preferably 4 μm to 20 μm, and particularly preferably 4 μm to 15 μm, from the viewpoint of both adhesive strength and handling properties.

<Other layers>
A decorative film according to an embodiment of the present disclosure may have layers other than those described above. Other layers include, for example, a self-healing layer, an antistatic layer, an antifouling layer, an anti-electromagnetic layer, and a conductive layer, which are known layers in decorative films. Other layers in the decorative film according to one embodiment of the present disclosure can be formed by known methods. Examples thereof include a method of applying a composition (layer-forming composition) containing components contained in these layers in layers and drying the layers.

<< cover film >>
The decorative film according to an embodiment of the present disclosure may have a cover film as the outermost layer on the reflective layer side with respect to the substrate for the purpose of preventing contamination and the like. As the cover film, any material having flexibility and good releasability can be used without particular limitation, and examples thereof include resin films. Examples of resin films include polyethylene films. A cover film is introduced into the decorative film, for example, by attaching it to an object (eg, a reflective layer). The method of attaching the cover film is not particularly limited, and includes known attaching methods, such as a method of laminating the cover film on an object (eg, reflective layer).

<Layer structure of decorative film>
Here, examples of the structure of the layers of the decorative film will be described with reference to FIGS. 1 and 2, respectively. However, the layer structure of the decorative film is not limited to the layer structure shown in each drawing. FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of the decorative film according to the present disclosure. Decorative film 20 shown in FIG. 28 and an adhesive layer 30 .

FIG. 2 is a schematic cross-sectional view showing an example of the layer structure of the decorative film according to the present disclosure. Decorative film 50 shown in FIG. and a cholesteric liquid crystal layer 40 .

<Method for manufacturing decorative film>
A method for manufacturing a decorative film according to an embodiment of the present disclosure is not limited. For example, a decorative film having at least a substrate and a reflective layer can be produced by providing a reflective layer and, if necessary, a layer other than the reflective layer on the substrate. As a method for forming each layer, the method described above can be used. A decorative film may be produced by previously producing a plurality of laminates each including two or more layers and stacking the plurality of laminates.

(Decoration method and decoration)
A decorating method according to an embodiment of the present disclosure is not particularly limited as long as it is a decorating method using a decorative film according to an embodiment of the present disclosure. A decorating method according to an embodiment of the present disclosure includes, for example, a step of attaching a reflective layer side surface of a decorating film and an uneven surface of a transparent body having an uneven structure by a lamination or molding process. is preferred. A decorative object according to an embodiment of the present disclosure is a decorative object using a decorative film according to an embodiment of the present disclosure, and is a decorative object obtained by a decorating method according to an embodiment of the present disclosure. is preferred.

In the step of attaching the reflective layer side surface of the decorative film to the uneven surface of the transparent body having the uneven structure, the surface of the decorative film having the reflective layer and/or the transparent body having the uneven structure It is preferable to activate the uneven surface in advance. The pre-activation treatment improves adhesion. Examples of activation treatments include corona treatment, plasma treatment, and silane coupling agent treatment. Corona treatment is most preferred from the viewpoint of production process simplicity.

(Decorative molding)
A decorative molded article according to an embodiment of the present disclosure includes a base material and a reflective layer having a center wavelength of a selective reflection wavelength in the range of 300 nm or more and 1,500 nm or less and having an uneven structure. A decorative molding is one form of a decorative article. According to the above-described embodiment, a decorative molding that has high brilliance and develops a uniform color regardless of the viewing direction is provided. The reason why the decorative molding according to the embodiment of the present disclosure has the above effect is presumed as follows. The reflective layer has a central wavelength of a selective reflection wavelength in the range of 300 nm or more and 1,500 nm or less, and has an uneven structure, so that light having a specific wavelength as described above is reflected in multiple directions in the reflective layer. be done. On the other hand, scattering of light having a wavelength that is not reflected by the reflective layer is suppressed, so that the brilliance can be maintained. As a result, according to the decorative molding according to the embodiment of the present disclosure, it is presumed that the brilliance is high and a uniform color is exhibited regardless of the viewing direction. For example, by observing the decorative molding in the direction from the reflective layer toward the base material, the user can observe a highly brilliant and uniform color regardless of the viewing direction.

<Base material>
A decorative molded article according to an embodiment of the present disclosure includes a base material. As the base material, for example, the base material described in the above section of "decorative film" can be used. Preferred aspects of the base material are the same as the preferred aspects of the base material described in the above section "Decorative film". The substrate may have an uneven structure.

<Reflective layer>
A decorative molding according to an embodiment of the present disclosure includes a reflective layer. The reflective layer has a selective reflection wavelength center wavelength in the range of 300 nm or more and 1,500 nm or less, and has an uneven structure. As the reflective layer, the reflective layer described in the above section "Decorative Film" can be used. Preferred aspects of the reflective layer are the same as the preferred aspects of the reflective layer described in the above section "Decorative Film". In one embodiment, the reflective layer is preferably a layer containing cholesteric liquid crystals.

The reflective layer has a central wavelength of a selective reflection wavelength in the range of 300 nm or more and 1,500 nm or less. The center wavelength of the selective reflection wavelength in the reflective layer is as described in the section "Decorative Film" above.

The reflective layer has an uneven structure. Scattering of light of wavelengths not reflected by the reflective layer is suppressed, and brightness can be maintained. In appearance, the uneven structure may include only a plurality of protrusions, may include only a plurality of recesses, or may include a plurality of protrusions and recesses. As the uneven structure including only a plurality of protrusions, a structure in which hemispherical protrusions are formed can be exemplified, but is not particularly limited. For example, the concave-convex structure including a plurality of convex portions and concave portions may include a prism shape, a pyramid shape, or a corner cube shape.

It is preferable that the concave-convex structure has at least one of convex portions and concave portions at a periodic pitch. The pitch is the interval between adjacent protrusions in the uneven structure or the interval between adjacent recesses in the uneven structure. The distance between protrusions is the distance between the highest points of the protrusions and the highest points of the protrusions. The recess-to-recess spacing is the distance between the lowest point of the recess and the lowest point of the recess. For example, when the concave-convex structure has a hemispherical shape, the pitch corresponds to the distance between the apexes of the two nearest hemispherical protrusions. For example, when the concave-convex structure is in the shape of a corner cube, the pitch corresponds to the distance between the vertices of the two closest corner cube-shaped protrusions. For example, when the uneven structure is pyramidal, the pitch corresponds to the distance between the apexes of the two closest pyramidal protrusions.

The depth of the concave-convex structure is preferably 1 μm or more, more preferably 1 μm to 2,000 μm, more preferably 3 μm, in order to visually recognize a uniform color regardless of the viewing angle and from the viewpoint of brightness. It is more preferably ˜500 μm, particularly preferably 5 μm to 100 μm, and most preferably 8 μm to 50 μm. In the present disclosure, the in-plane average value of the height difference between adjacent maximum and minimum portions of the uneven surface obtained using a laser microscope (for example, VK-X1000 manufactured by Keyence Corporation) is adopted as the depth of the uneven structure. do. The surface to be measured is the surface of the exposed reflective layer with the uneven structure (that is, the uneven surface). However, if the layer covering the reflective layer has an uneven structure and the uneven structure of the layer covering the reflective layer can be considered to be substantially the same as the uneven structure of the reflective layer, the unevenness of the layer covering the reflective layer The depth of the structure may be employed as the depth of the uneven structure of the reflective layer.

The width of the concave-convex structure is preferably 5 μm or more, more preferably 10 μm to 5000 μm, more preferably 30 μm to 2000 μm, from the viewpoint of visual uniformity of color regardless of the viewing angle and brightness. It is more preferable to have a thickness of 50 μm to 500 μm. In the present disclosure, the in-plane average value of the distance between the adjacent minimal parts of the uneven surface obtained using a laser microscope (for example, VK-X1000 manufactured by Keyence Corporation) is adopted as the width of the uneven structure. do. The surface to be measured is the surface of the exposed reflective layer with the uneven structure (that is, the uneven surface). However, if the layer covering the reflective layer has an uneven structure and the uneven structure of the layer covering the reflective layer can be considered to be substantially the same as the uneven structure of the reflective layer, the unevenness of the layer covering the reflective layer The width of the structure may be employed as the width of the relief structure of the reflective layer.

The ratio of the width of the concave-convex structure to the depth of the concave-convex structure (width: depth) is 100: 1 to 1: 2 from the viewpoint of visually recognizing a uniform color regardless of the viewing angle and from the viewpoint of brightness. Preferably, 50:1 to 1:1 is more preferred.

The ratio of the depth H _D of the concave-convex structure of the reflective layer to the thickness H _T of the reflective layer is preferably 0.1<H _D /H _T , and 0.5<H _D /H _T <200. more preferably 1<H _D /H _T <100, and particularly preferably 5<H _D /H _T <50.

The method for forming the uneven structure in the reflective layer is not particularly limited. A method of transferring an uneven shape to a substrate on which a reflective layer having no methods are preferred. In either case, a resin layer, which will be described later, can be provided on the base material so that it can easily follow the uneven shape. The transfer method includes, for example, a method of pressing the mold directly against the substrate and a method of pressing using a vacuum laminator.

<Resin layer>
It is preferable that the decorative molding according to an embodiment of the present disclosure includes a resin layer between the substrate and the reflective layer. The resin layer particularly contributes to the formation of the uneven structure in the reflective layer. For example, the resin layer can improve the followability of the reflective layer to the surface having the rugged structure (that is, the rugged surface) used as a mold for imparting the rugged structure to the reflective layer. As a result, it is possible to easily impart a desired uneven structure to the reflective layer.

As the resin layer, the resin layer described in the above section "Decorative Film" can be used. Preferred aspects of the resin layer are the same as the preferred aspects of the resin layer described in the above section "Decorative Film". The resin layer may have an uneven structure. The resin layer preferably has the same uneven structure as that of the reflective layer.

The thickness of the resin layer is preferably 0.5 to 10 times, more preferably 0.8 to 8 times, and 1 to 5 times the depth of the uneven structure of the reflective layer. is particularly preferred.

<Colored layer>
It is preferable that the decorative molding according to an embodiment of the present disclosure includes a colored layer. As the colored layer, the colored layer described in the above section "Decorative Film" can be used. Preferred embodiments of the colored layer are the same as the preferred embodiments of the colored layer described in the section "Decorative Film" above. The colored layer may have an uneven structure.

The position of the colored layer is not restricted. In one embodiment, the colored layer is preferably arranged between the substrate and the reflective layer. That is, it is preferable that the decorative molding according to one embodiment includes a substrate, a colored layer, and a reflective layer in this order. In one embodiment, the colored layer is preferably located on the opposite side of the substrate from the reflective layer. That is, it is preferable that the decorative molding according to one embodiment includes a colored layer, a substrate, and a reflective layer in this order.

<Orientation layer>
A decorative molded body according to an embodiment of the present disclosure may include an orientation layer. Preferably, the alignment layer is in contact with the reflective layer (preferably the cholesteric liquid crystal layer). As the orientation layer, the orientation layer described in the above section "Decorative Film" can be used. Preferred aspects of the orientation layer are the same as the preferred aspects of the orientation layer described in the above section "Decorative Film". The alignment layer may have an uneven structure.

<Adhesive layer>
A decorative molded body according to an embodiment of the present disclosure may include an adhesive layer. The adhesive layer may be arranged on the surface of the decorative molding. The adhesive layer may be arranged between any two layers included in the decorative molding. As the adhesive layer, the adhesive layer described in the above section "Decorative Film" can be used. Preferred aspects of the adhesive layer are the same as the preferred aspects of the adhesive layer described in the above section "Decorative Film". The adhesive layer may have an uneven structure.

<Other layers>
A decorative molded body according to an embodiment of the present disclosure may include layers other than the layers described above. As other layers, for example, the other layers described in the above section "Decorative Film" can be used.

A decorative molded body according to an embodiment of the present disclosure may include a transparent body having a surface having an uneven structure (that is, an uneven surface). In one embodiment, the decorative molded body preferably includes a base material, a reflective layer, and a transparent body having a surface having an uneven structure in this order. For example, by observing the decorative molding in the direction from the transparent body to the base material, the user can observe a highly brilliant and uniform color regardless of the viewing direction. Preferably, the transparent body is in contact with the reflective layer (preferably the cholesteric liquid crystal layer). The transparent body may contact the reflective layer through another layer (eg, an alignment layer). The uneven surface of the transparent body preferably faces the reflective layer. Examples of the transparent body include transparent resin and glass.

<Layer structure of decorative molding>
An example of the layer structure of the decorative molding will be described with reference to FIGS. 3, 4, and 5, respectively. However, the layer structure of the decorative molding is not limited to the layer structure shown in each drawing.

FIG. 3 is a schematic cross-sectional view showing an example of a decorative molding according to the present disclosure. The decorative molding 70 shown in FIG. 3 comprises a substrate 22, a colored layer 24, an alignment layer 26, a cholesteric liquid crystal layer 28, an adhesive layer 30, and a transparent body 60 having an uneven structure in this order. have. The transparent body 60 is one form of transparent body.

FIG. 4 is a schematic cross-sectional view showing an example of the decorative molding according to the present disclosure. The decorative molding 80 shown in FIG. 4 comprises a colored layer 32, a base material 34, a resin layer 36, an alignment layer 38, a cholesteric liquid crystal layer 40, and a transparent body 60 having an uneven structure in this order. have.

FIG. 5 is a schematic cross-sectional view showing an example of the decorative molding according to the present disclosure. The decorative molded body 90 shown in FIG. 5 comprises a colored layer 32, a base material 34, a resin layer 36, a cholesteric liquid crystal layer 40, an alignment layer 38, and a transparent body 60 having an uneven structure in this order. have.

<Manufacturing method of decorative molding>
A method for manufacturing a decorated molded body according to an embodiment of the present disclosure is preferably a method using a decorative film according to an embodiment of the present disclosure. In the method for manufacturing a decorative molded body according to an embodiment of the present disclosure, the step of attaching the decorative film to a transparent body having an uneven structure on the reflective layer side is preferable. The decorative film according to an embodiment of the present disclosure is also excellent in three-dimensional moldability, so it can be suitably used for manufacturing a decorative molded body, for example, it is selected from the group consisting of three-dimensional molding and insert molding. It is particularly suitable for producing a decorative molding by at least one molding. In addition, according to the decorative film according to the embodiment of the present disclosure, it is possible to form a decorative molded body by attaching it to the molded body after molding. By using the decorative film according to an embodiment of the present disclosure when producing a decorative molded body, it is possible to apply it to molds with more complicated shapes, smaller shapes, etc., and the range of applications of the decorative molded body can be expanded. The layer structure of the decorative molded product obtained using the decorative film reflects the layer structure of the decorative film. In other words, the decorated molding obtained using the decorative film includes each layer included in the decorative film.

Moreover, as molding, three-dimensional molding is also preferably exemplified. Suitable three-dimensional molding includes, for example, thermoforming, vacuum molding, air pressure molding, and vacuum pressure molding. The method of vacuum molding is not particularly limited, but a method of performing three-dimensional molding in a heated state under vacuum is preferred. Vacuum refers to a state in which the pressure inside the chamber is reduced to a degree of vacuum of 100 Pa or less. The temperature at which the three-dimensional molding is performed may be appropriately set according to the molding substrate to be used, but it is preferably in the temperature range of 60°C or higher, more preferably in the temperature range of 80°C or higher, and 100°C or higher. is more preferably in the temperature range of The upper limit of the temperature for three-dimensional molding is preferably 200°C. The temperature at the time of three-dimensional molding refers to the temperature of the molding substrate subjected to three-dimensional molding, and is measured by attaching a thermocouple to the surface of the molding substrate.

Vacuum forming can be performed using a vacuum forming technique widely known in the field of forming. For example, Formech 508FS manufactured by Nippon Seiki Kogyo Co., Ltd. may be used for vacuum forming.

A method for manufacturing a decorative molding will be specifically described below. A method for manufacturing a decorated molded body according to an embodiment of the present disclosure prepares a decorative film having at least a substrate and a reflective layer having a central wavelength of a selective reflection wavelength in the range of 300 nm or more and 1,500 nm or less. and applying a pressure of 0.01 MPa or more to the reflective layer to impart the rugged structure to the reflective layer. The surface having the uneven structure functions as a mold for providing the reflective layer with the uneven structure. By bringing the reflective layer into contact with the surface having the uneven structure and pressing the reflective layer, the reflective layer deforms along the surface having the uneven structure. As a result, the reflective layer is provided with an uneven structure.

The layer structure of the decorative film may be determined according to the layer structure of the intended decorative molding. For example, by using a decorative film having a substrate, a reflective layer, and a resin layer between the substrate and the reflective layer, the substrate, the resin layer, the reflective layer, is obtained in this order.

Textured surfaces are defined by exterior surfaces of various articles. The surface having an uneven structure may be, for example, the surface of a mold or the surface of an article other than the mold.

In the process of bringing the reflective layer into contact with the surface having the uneven structure, the reflective layer may be brought close to the surface having the uneven structure, or the surface having the uneven structure may be brought close to the reflective layer. The reflective layer may be brought into contact with the surface having the relief structure via another layer (for example, an alignment layer).

The pressure applied to the reflective layer is preferably 0.1 MPa or higher, more preferably 0.3 MPa or higher, and particularly preferably 0.5 MPa or higher. There is no upper limit to the pressure applied to the reflective layer. The upper limit of the pressure applied to the reflective layer may be determined, for example, according to the workability of the reflective layer and the thickness of the decorative film. The pressure applied to the reflective layer is preferably 10 MPa or less, more preferably 3 MPa or less, and particularly preferably 1 MPa or less.

A method for applying pressure to the reflective layer is not limited, and a known method can be used. Examples of the method of applying pressure include a method using compressed air and a method using a press machine.

In the method for producing a decorative molded body, the article having the uneven surface may be, for example, a transparent body having the uneven surface (that is, the uneven surface). For example, a method for manufacturing a decorated molded body according to an embodiment prepares a decorative film having at least a substrate and a reflective layer having a central wavelength of a selective reflection wavelength in the range of 300 nm or more and 1,500 nm or less. and a transparent body having a surface having an uneven structure and the decorative film are superimposed to bring the reflective layer into contact with the surface having the uneven structure, and a pressure of 0.01 MPa or more is applied to the reflective layer. is applied to provide the reflective layer with an uneven structure. After providing the reflective layer with the relief structure, the transparent body may or may not be removed. If the transparent body is not removed, it is for example arranged as an outer layer of the decorative molding.

<Application>
The use of the decorated molded body obtained as described above is not particularly limited, and the decorated molded body can be used for various articles. Applications of the decorated molded body include, for example, electronic devices ( For example, interiors and exteriors of wearable devices and smartphones), interiors and exteriors of automobiles, interiors and exteriors of electric appliances, and packaging containers are particularly suitable.

(decorative panel)
A decorative panel according to an embodiment of the present disclosure includes a decorative molding according to an embodiment of the present disclosure. The decorative molded body in the decorative panel is synonymous with the decorative molded body described in the section "Decorated molded body" above.

The decorative panel can be manufactured, for example, by bonding the surface of the decorative molding on the side of the reflective layer and the surface of the member that will be the surface layer portion of the decorative panel. Examples of the member that becomes the surface layer of the decorative panel include a glass panel. For example, the above-described adhesive layer can be used for adhesion between the decorative molded body and the member that forms the surface layer of the decorative panel. The decorative molded body may be used alone as a decorative panel without combining the decorative molded body with other members.

An example of the layer structure of the decorative panel will be described with reference to FIG. However, the layer structure of the decorative panel is not limited to the layer structure shown in FIG. FIG. 6 is a schematic cross-sectional view showing an example of a decorative panel according to the present disclosure. A decorative panel 100 shown in FIG. , and the glass panel 44 in this order.

The shape of the decorative panel is not restricted. The shape of the decorative panel may be determined, for example, according to the application. The decorative panel may be flat, for example. Also, the decorative panel may have a curved surface.

Decorative panels can be used, for example, for the interior and exterior of various articles (eg, electronic devices, automobiles, and electric appliances). For example, when the decorative panel 100 shown in FIG. 6 is used as a housing for an electronic device, the colored layer 32, the base material 34, the resin layer 36, the cholesteric liquid crystal layer 40, and the alignment layer are arranged from the inside to the outside of the housing. 38. Preferably, a transparent body 60 having an uneven structure, an adhesive layer 42, and a glass panel 44 are arranged. By observing the decorative panel 100 in the direction from the glass panel 44 toward the colored layer 32, the user can observe a highly brilliant and uniform color regardless of the viewing direction.

(electronic device)
An electronic device according to an embodiment of the present disclosure includes a decorative panel according to an embodiment of the present disclosure. Electronic devices include, for example, wearable devices and smart phones. The decorative panel in the electronic device has the same meaning as the decorative panel described in the above section "Decorative panel". The decorative panel is preferably used as a housing for electronic devices.

The method of manufacturing the electronic device is not limited, and known methods can be used. When a decorative panel is used as a housing of an electronic device, the electronic device including the decorative panel can be manufactured by housing various electronic components of the electronic device inside the housing containing the decorative panel.

EXAMPLES The present disclosure will be described more specifically with reference to examples below. The scope of the present disclosure is not limited to the specific examples shown below.

(Reference example 1)
<Preparation of support>
Technoloy S001 (acrylic film, thickness: 125 μm, manufactured by Sumika Acrylic Co., Ltd.) was prepared as a support.

<Preparation of black pigment dispersion>
Carbon black, a dispersant, a polymer and a solvent were mixed so as to have the following composition of a black pigment dispersion, and a black pigment dispersion was obtained using a triple roll and a bead mill. The average particle size of carbon black measured using Microtrac FRA (Honeywell) was 163 nm.

-Composition of black pigment dispersion-
・ Resin-coated carbon black prepared according to paragraphs 0036 to 0042 of Japanese Patent No. 5320652: 20.0% by mass
- Dispersant 1 (structure below): 1.0% by mass
・ Polymer (random copolymer of benzyl methacrylate/methacrylic acid = 72/28 (molar ratio), weight average molecular weight: 30,000): 6.0% by mass
・Propylene glycol monomethyl ether acetate: 73.0% by mass

<Composition of Colored Layer Forming Coating Liquid 1>
・Black dispersion: 30 parts by mass ・Polymerizable compound 1: Sartomer Japan Co., Ltd., urethane acrylate oligomer, CN-996NS: 25 parts by mass ・Binder resin 3: Urethane-modified acrylic polymer (containing polyol) 35% by mass acetic acid Ethyl / ethyl methyl ketone / isopropyl alcohol solution: 25 parts by mass Photoinitiator (Irgacure 2959, manufactured by BASF): 1.0 parts by mass Methyl ethyl ketone: 19 parts by mass

<Formation of colored layer 1>
The colored layer forming coating solution 1 was applied onto the support using a wire bar coater and dried at 100° C. for 10 minutes. A colored layer 1 (black colored layer) having a layer thickness of 4 μm was formed by exposing the entire surface of the colored layer of the formed laminate to an exposure amount of 500 mJ/cm ² (i-line).

<Formation of alignment layer 1>
The orientation layer-forming coating solution 1 was applied onto the colored layer 1 using a wire bar coater. Thereafter, the applied coating liquid 1 for forming an alignment layer was dried at 100° C. for 120 seconds to prepare an alignment layer 1 having a layer thickness of 0.5 μm.

[Composition of coating liquid 1 for forming alignment layer]
Modified polyvinyl alcohol shown below: 28 parts by mass Citric acid ester (AS3, manufactured by Sankyo Chemical Co., Ltd.): 1.2 parts by mass Photoinitiator (Irgacure 2959, manufactured by BASF): 0.84 parts by mass・Glutaraldehyde: 2.8 parts by mass ・Water: 699 parts by mass ・Methanol: 226 parts by mass

・Modified polyvinyl alcohol (the following compounds, the number on the lower right of each structural unit represents the molar ratio.)

<Formation of cholesteric liquid crystal layer 1>
Rubbing treatment (rayon cloth, pressure: 0.1 kgf (0.98 N), Rotation speed: 1,000 rpm (revolutions per minute), conveying speed: 10 m/min, number of reciprocations: 1). Components contained in coating liquid 1 for forming cholesteric liquid crystal layer shown below were stirred and dissolved in a container kept at 25° C. to prepare coating liquid 1 for forming cholesteric liquid crystal layer (liquid crystal composition 1). .

[Composition of coating liquid 1 for forming cholesteric liquid crystal layer]
・Methyl ethyl ketone: 150.6 parts by mass ・Liquid crystal compound 1 (rod-shaped liquid crystal compound): 92 parts by mass ・Photopolymerization initiator A (IRGACURE 907, manufactured by BASF): 0.50 parts by mass ・Chiral agent A: 4.00 parts by mass parts Chiral agent B: 4.00 parts by mass Surfactant F1 below: 0.027 parts by mass

Liquid crystal compound 1 (monofunctional): The following rod-like liquid crystal compound. In the case of a radical polymerization system, even if it has an oxetanyl group (cationically polymerizable functional group), it has only one acryloxy group (radical polymerizable group), so it is defined as monofunctional. The same applies to cationic polymerization systems.

Chiral agent A (bifunctional): the following compound

Chiral agent B (0-functional): the following compound. In the compounds below, Bu represents an n-butyl group.

Surfactant F1: the following compound

The prepared coating solution 1 for forming a cholesteric liquid crystal layer was applied to the rubbed surface of the alignment layer 1 with a wire bar coater and dried at 85° C. for 120 seconds. The entire surface of the cholesteric liquid crystal layer of the laminate thus formed was exposed with an exposure amount of 70 mJ/cm ² (i-line) to prepare a cholesteric liquid crystal layer 1 having a layer thickness of 3.0 μm.

<Formation of adhesive layer 1>
On the cholesteric liquid crystal layer 1, an acrylic adhesive liquid (SK Dyne SG-50Y, manufactured by Soken Chemical Co., Ltd.) is applied using a comma coater and dried at 120 ° C. for 2 minutes. An adhesive layer 1 of 5 μm was formed. Through the above procedure, a laminate 1 (that is, a decorative film) having the support, the colored layer 1, the alignment layer 1, the cholesteric liquid crystal layer 1, and the adhesive layer 1 in this order was produced.

<Molding process>
A transparent body (thickness: 2 mm, width: 70 mm, length: 150 mm) having an uneven pattern (A) shown in FIGS. The surface of the adhesive layer 1 of the laminate 1 was brought into contact with the surface, and pressure molding (TOM molding, TOM: Three dimension overlay method) was performed to obtain a molded body 1 (that is, a decorated molded body). A TOM molding machine NGF-0510-R (manufactured by Fuse Vacuum Co., Ltd.) was used for air pressure molding, the molding temperature was 120° C., and the draw ratio was 30% at the highest point. The pressure in the pressure molding process was 0.1 MPa.

<Performance evaluation>
- Reflection characteristics -
The reflectance of molded body 1 was measured using a spectrophotometer V-670 manufactured by JASCO Corporation, from the side of the transparent body and from the direction perpendicular to the surface of the transparent body, in the wavelength range of 380 nm to 1,100 nm. It was measured. Reflectance indicates the highest of the maxima in the reflectance spectrum. As an evaluation result, C is preferable, B is more preferable, and A is particularly preferable.
<<Evaluation Criteria>>
A: The reflectance is 20% or more.
B: The reflectance is 10% or more and less than 20%.
C: The reflectance is 5% or more and less than 10%.
D: The reflectance is less than 5%.

-Luminousness-
The resulting molded product 1 was visually evaluated for its brilliance when viewed from the transparent body side. The evaluation was performed from a position 50 cm away from the plane of the transparent body at 90° C. in the vertical direction. The evaluation result is preferably C, more preferably B, and particularly preferably A.
<<Evaluation Criteria>>
A: High brightness can be confirmed.
B: Brightness can be confirmed, but it looks a little cloudy as a whole.
C: Glitter can be slightly confirmed D: Glitter is difficult to confirm.

- Uniformity of color (evaluation of whether uniform color can be obtained regardless of viewing angle) -
Regarding the obtained molded body 1, when the direction perpendicular to the surface direction of the molded body 1 is 0 °, the change in color when viewed from angles of 0 ° and 45 ° (for example, yellow at 0 ° direction, 45 ° ° direction) was evaluated. As an evaluation result, C is preferable, B is more preferable, and A is particularly preferable.
<<Evaluation Criteria>>
A: No color change when viewed from 0° direction and 45° direction B: Color change when viewed from 0° direction and 45° direction is slightly confirmed.
C: When viewed from the direction of 0° and when viewed from the direction of 45°, a change in color is observed, but the colors are similar.
D: A large change in color is observed between when viewed from the direction of 0° and when viewed from the direction of 45°.

The evaluation results are collectively shown in Table 1.

(Reference Examples 2 to 13, and Comparative Example 1)
A molded body was produced in the same manner as in Reference Example 1, except that the uneven pattern (A or B), depth, and width of the transparent body were changed according to the items listed in Table 1. The same performance evaluation as the performance evaluation of Reference Example 1 was performed using the obtained molded body. The evaluation results are collectively shown in Table 1.

The column of "concavo-convex pattern" in Table 1 represents the type of concavo-convex pattern. "A" described in the column of "convex pattern" represents the concavo-convex pattern (A) shown in FIGS. "B" described in the column of "convex pattern" represents the concavo-convex pattern (B) shown in FIGS.

The column of "Depth" in Table 1 represents the depth of the uneven structure of the uneven pattern. The numerical value described in the column of "Depth" is the same as the depth of the concave-convex structure of the reflective layer.

The "width" column in Table 1 represents the width of the uneven structure of the uneven pattern. The numerical value described in the "width" column is the same as the width of the concave-convex structure of the reflective layer.

From the results shown in Table 1, in Reference Examples 1 to 13, decorative moldings were obtained which were excellent in terms of brilliance and uniform tint irrespective of viewing direction. On the other hand, in Comparative Example 1, in which unevenness was not formed, a uniform color was not developed regardless of the viewing direction.

(Example 14)
[Composition of Resin Layer Coating Liquid 14]
・Methyl ethyl ketone: 45 parts by mass ・Acryt 8UA-146 (urethane-modified acrylic polymer (hereinafter sometimes referred to as “urethane acrylic resin”), methyl ethyl ketone (MEK) / isopropyl alcohol (IPA) diluted solution, solid content: 29% by mass ): 50 parts by mass Surfactant (F551-A): 0.1 parts by mass

<Formation of resin layer 14>
The resin layer forming coating solution 14 was applied onto the support using a percoater and dried at 120° C. for 2 minutes to form a resin layer 14 having a layer thickness of 15 μm.

<Formation of alignment layer 14>
The alignment layer-forming coating solution 1 was applied onto the resin layer 14 using a wire bar coater. After that, the applied coating liquid 1 for forming an alignment layer was dried at 100° C. for 120 seconds to prepare an alignment layer 14 having a layer thickness of 0.5 μm.

Rubbing treatment (rayon cloth, pressure: 0.1 kgf (0.98 N), Rotation speed: 1,000 rpm (revolutions per minute), conveying speed: 10 m/min, number of reciprocations: 1).

<Formation of cholesteric liquid crystal layer 14>
The prepared coating liquid 1 for forming a cholesteric liquid crystal layer was applied to the surface of the alignment layer 14 subjected to the rubbing treatment using a wire bar coater and dried at 85° C. for 120 seconds. A cholesteric liquid crystal layer 14 having a layer thickness of 3.0 μm was formed by exposing the entire surface of the cholesteric liquid crystal layer of the formed laminate to an exposure amount of 70 mJ/cm ² (i-line).

<Formation of colored layer 14>
The colored layer-forming coating solution 1 was applied on the support opposite to the side on which the cholesteric liquid crystal layer was formed, using a wire bar coater, and dried at 100° C. for 10 minutes. The entire surface of the colored layer of the formed laminate was exposed with an exposure amount of 500 mJ/cm ² (i-line) to form a colored layer 14 (black colored layer) having a layer thickness of 4 μm. Through the above procedure, a laminate 14 (that is, a decorative film) having the colored layer 14, the support, the resin layer 14, the alignment layer 14, and the cholesteric liquid crystal layer 14 in this order was formed.

<Molding process>
Corona treatment was performed on the surface of the cholesteric liquid crystal layer 14 of the laminate 14 using a desktop corona treatment device (TEC-8XA, manufactured by Kasuga Seiki Co., Ltd., set output: 70 W, operation speed: 1 m/min, number of times: 5 reciprocations). After that, a transparent body (thickness: 2 mm, width: 70 mm, length: 150 mm) having an uneven pattern (A) shown in FIGS. The surface of the adhesive layer 1 was brought into contact with the adhesive layer 1, and air pressure molding (TOM molding) was performed to obtain a molded body 14 (that is, a decorated molded body). A TOM molding machine NGF-0510-R (manufactured by Fuse Vacuum Co., Ltd.) was used for air pressure molding, the molding temperature was 120° C., and the draw ratio was 30% at the highest point. The pressure in the pressure molding process was 0.1 MPa.

(Example 15)
<Preparation of support>
As a support, two sheets of COSMOSHINE A4100 (PET, thickness: 50 μm, film having an easy-adhesion layer on one side, manufactured by Toyobo Co., Ltd., A4 size) were prepared. The two supports are hereinafter referred to as support 15A and support 15B, respectively.

<Production of laminate 15-1>
The alignment layer-forming coating liquid 1 was applied by a wire bar coater to the surface of the support 15A on which the easy-adhesion layer was not formed. After that, the applied coating liquid 1 for forming an alignment layer was dried at 100° C. for 120 seconds to prepare an alignment layer 15 having a layer thickness of 0.5 μm.

Rubbing treatment (rayon cloth, pressure: 0.1 kgf (0.98 N), Rotation speed: 1,000 rpm (revolutions per minute), conveying speed: 10 m/min, number of reciprocations: 1).

The prepared coating liquid 1 for forming a cholesteric liquid crystal layer was applied to the surface of the alignment layer 15 subjected to the rubbing treatment using a wire bar coater and dried at 85° C. for 120 seconds. By exposing the entire surface of the cholesteric liquid crystal layer of the formed laminate with an exposure amount of 70 mJ/cm ² (i-line), a cholesteric liquid crystal layer 15 having a layer thickness of 3.0 μm is formed. 15-1 was formed. The laminate 15-1 has a support 15A, an alignment layer 15, and a cholesteric liquid crystal layer 15 in this order.

<Production of laminate 15-2>
An acrylic pressure-sensitive adhesive (SK Dyne SG-50Y, manufactured by Soken Chemical Co., Ltd.) was applied to the separately prepared surface of Cosmoshine A4100 (that is, support 15B) on which the easy-adhesion layer was formed using a comma coater. It was applied and dried at 120° C. for 2 minutes to form a resin layer 15 (adhesive layer) having a layer thickness of 20 μm, thereby forming a laminate 15-2. The laminate 15-2 has a support 15B and a resin layer 15. As shown in FIG.

<Production of laminate 15-3>
The laminated body 15-1 and the laminated body 15-2 were laminated by a laminator so that the resin layer 15 and the cholesteric liquid crystal layer 15 were in contact with each other. By peeling off the PET film (that is, the support 15A) on the side of the laminate 15-1, the laminate 15- in which the support 15B/resin layer 15/cholesteric liquid crystal layer 15/orientation layer 15 are laminated in this order. got 3.

<Production of laminate 15>
The colored layer forming coating solution 1 was applied onto the support 15B of the laminate 15-3 using a wire bar coater and dried at 100° C. for 10 minutes. The entire surface of the colored layer of the formed laminate is exposed with an exposure amount of 500 mJ/cm ² (i-line) to form a colored layer 15 (black colored layer) having a layer thickness of 4 μm. A body 15 (that is, a decorative molded body) was formed. The laminate 15 has a colored layer 15, a support 15B, a resin layer 15, a cholesteric liquid crystal layer 15, and an alignment layer 15 in this order.

<Molding process>
The surface of the alignment layer 15 of the laminate 15 was subjected to corona treatment using a desktop corona treatment device (TEC-8XA, manufactured by Kasuga Seiki Co., Ltd., set output 70 W, operation speed 1 m/min, number of times: 5 reciprocations), A transparent body (thickness: 2 mm, width: 70 mm, length: 150 mm) having an uneven pattern (A) shown in FIGS. The surfaces of 15 were brought into contact with each other, and pressure-air molding (TOM molding) was performed to obtain molded body 15 (that is, decorated molded body). A TOM molding machine NGF-0510-R (manufactured by Fuse Vacuum Co., Ltd.) was used for air pressure molding, the molding temperature was 120° C., and the draw ratio was 30% at the highest point. The pressure in the pressure molding process was 0.1 MPa.

(Example 16)
Molded body 16 (that is, decorative molding body) was formed. The elastic modulus of the resin layer of the molded body 16 was 0.01 GPa.

(Example 17)
Molded body 17 (that is, molded article 17) was prepared in the same manner as in Example 15, except that the acrylic adhesive liquid used for forming the resin layer was changed to TM-51K (urethane reactive adhesive, manufactured by Toyo Ink Co., Ltd.). A decorative molding) was formed. The elastic modulus of the resin layer of the molded body 17 was 0.001 GPa.

(Example 18)
A molding 18 (that is, a decorative molding) was formed in the same manner as in Example 15, except that the resin layer 15 was changed to a resin layer 18 formed by the following method.

[Composition of Resin Layer Forming Coating Liquid 18]
・Methyl ethyl ketone: 45 parts by mass ・Acryt 8UA-146 (urethane-modified acrylic polymer, methyl ethyl ketone / isopropanol diluted solution, solid content: 29% by mass): 30 parts by mass ・Polylite OD-X-2523 (manufactured by DIC): 20 parts by mass・Surfactant (F551-A): 0.1 part by mass

<Formation of resin layer 18>
The resin layer forming coating solution 18 was applied onto a support (meaning the support 15B used in Example 15) using a percoater and dried at 120° C. for 2 minutes to give a layer thickness of 25 μm. of the resin layer 18 was formed. The elastic modulus of the resin layer was 0.00001 GPa.

(Example 19)
A molding 19 (that is, a decorative molding) was formed in the same manner as in Example 15, except that the resin layer 15 was changed to a resin layer 19 formed by the following method.

[Composition of Resin Layer Forming Coating Liquid 19]
· A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd.): 75 parts by mass · Ethanol: 20 parts by mass · Photopolymerization initiator (Irgacure127): 4.9 parts by mass · Surfactant (F551-A): 0 .1 part by mass

<Formation of Resin Layer 19>
The resin layer forming coating solution 19 was applied onto a support (meaning the support 15B used in Example 15) using a percoater, dried at 120° C. for 2 minutes, and coated with a metal halide lamp. , and photocuring at an integrated exposure amount of 200 mJ/cm ² to form an adhesive layer 19 having a layer thickness of 25 μm. The elastic modulus of the resin layer 19 was 0.5 GPa.

(Example 20)
A molding 20 (that is, a decorative molding) was formed in the same manner as in Example 15, except that the resin layer 15 was changed to a resin layer 20 formed by the following method.

[Composition of Resin Layer Coating Liquid 20]
· A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd.): 35 parts by mass · DPHA (manufactured by Shin-Nakamura Chemical Co., Ltd.): 40 parts by mass · Ethanol: 20 parts by mass · Photoinitiator (Irgacure 127): 4.9 Parts by mass Surfactant (F551-A): 0.1 parts by mass

<Formation of resin layer 20>
The resin layer forming coating liquid 20 was applied onto a support (meaning the support 15B used in Example 15) using a percoater, dried at 120° C. for 2 minutes, and coated with a metal halide lamp. , and a cumulative exposure amount of 500 mJ/cm ² to form a resin layer 20 having a layer thickness of 25 μm. The elastic modulus of the resin layer 20 was 2.0 GPa.

(Examples 21-26)
Molded bodies 21 to 26 were formed in the same manner as in Example 15, except that the thickness of the resin layer was changed according to Table 2. The thickness of each resin layer was adjusted by changing the coating amount of the coating liquid for forming the resin layer.

(Example 27)
After forming a resin layer on the support based on each method for forming the resin layer 14 and the colored layer 14 described in Example 14, the surface of the support opposite to the surface on which the resin layer is arranged is colored. formed a layer. By the above method, a laminate 27 having a resin layer, a support, and a colored layer in this order was produced.

Next, using as a mold a transparent body (thickness: 2 mm, width: 70 mm, length: 150 mm) having the concave-convex pattern (A) shown in FIGS. Then, a 100 nm layer of silicon oxide (SiO ₂ ) was formed using a vacuum sputtering apparatus (VEP-1000, manufactured by ULVAC, Inc.). A niobium oxide (Nb ₂ O ₅ ) layer having a thickness of 100 nm was formed on the silicon oxide layer using the vacuum sputtering apparatus. By alternately repeating the formation of the silicon oxide layer and the formation of the silicon oxide layer, a total of six layers including alternating silicon oxide layers and niobium oxide layers were formed. The thickness of each layer was 100 nm. By the above method, a reflective layer exhibiting a red reflective color was formed on the uneven surface of the transparent body.

The molded body 27 was obtained by bringing the resin layer of the laminated body 27 into contact with the uneven surface of the obtained reflective layer and performing air pressure molding (TOM molding). A TOM molding machine NGF-0510-R (manufactured by Fuse Vacuum Co., Ltd.) was used for the pressure molding, and the molding temperature was 120°C. The pressure in the pressure molding process was 0.1 MPa.

(Examples 28-39)
Molded bodies 28 to 39 were produced in the same manner as in Example 15, except that the type, depth, and width of the uneven pattern for imparting the uneven structure to the reflective layer were changed according to the description in Table 4. .

(performance evaluation)
Reflectance, brilliance, color uniformity, and adhesion were evaluated for each of the moldings obtained in Examples 14 to 39 (ie, decorative moldings) according to the following methods. Table 2 shows the results.

－Reflection characteristics (reflectance)－
The reflectance of the molded body is measured from the side of the transparent body and from the direction perpendicular to the surface of the transparent body using a spectrophotometer V-670 manufactured by JASCO Corporation in the wavelength range of 380 nm to 1,100 nm. did. Reflectance indicates the highest of the maxima in the reflectance spectrum. As an evaluation result, C is preferable, B is more preferable, and A is particularly preferable.
<<Evaluation Criteria>>
A: The reflectance is 30% or more.
B: The reflectance is 15% or more and less than 30%.
C: The reflectance is 5% or more and less than 15%.
D: The reflectance is less than 5%.

- Glitter (regular reflectance) -
The specular reflectance of the obtained molding was measured in a wavelength range of 380 nm to 1,100 nm from the vertical direction using a spectrophotometer V-670 manufactured by JASCO Corporation. Specular reflectance indicates the highest of the maxima in the reflectance spectrum. The evaluation result is preferably C, more preferably B, and particularly preferably A.
<<Evaluation Criteria>>
A: The regular reflectance is 20% or more.
B: The regular reflectance is 10% or more and less than 20%.
C: The regular reflectance is 5% or more and less than 10%.
D: The regular reflectance is less than 5%.

- Uniformity of color (evaluation of whether uniform color can be obtained regardless of viewing angle) -
Regarding the obtained molded body, when the direction perpendicular to the surface direction of the molded body is 0 °, the change in color when viewed from angles of 0 ° and 45 ° (e.g., yellow at 0 ° direction, 45 ° direction (blue, etc.) was evaluated. As an evaluation result, C is preferable, B is more preferable, and A is particularly preferable.
<<Evaluation Criteria>>
A: There is almost no change in color when viewed from the direction of 0° and when viewed from the direction of 45°.
B: A slight change in color is observed between when viewed from the 0° direction and when viewed from the 45° direction.
C: When viewed from the direction of 0° and when viewed from the direction of 45°, a change in color is observed, but the colors are similar.
D: A large change in color is observed between when viewed from the direction of 0° and when viewed from the direction of 45°.

-Adhesion evaluation-
A cross-cut pattern (width of 2 mm) with a depth of 70 μm was formed on the surface of the outermost layer (that is, the support or the colored layer) of the obtained molding. Specifically, 10 slits (meaning notches) were formed vertically and horizontally on the surface of the outermost layer of the molding to form a cross-cut pattern. A tape (Cellotape (registered trademark) No. 405, 24 mm width, manufactured by Nichiban Co., Ltd.) was applied so as to cover the cross-cut pattern, and then a peeling test was performed in which the tape was peeled off.
<<Evaluation Criteria>>
A: Peeling of the outermost layer does not occur (that is, only the tape is peeled).
B: Delamination occurs at a specific interface (ie, the interface between two adjacent layers).

The "Pattern" column in Tables 2 to 4 indicates the type of uneven pattern. "A" described in the "Pattern" column represents the concave-convex pattern (A) shown in FIGS. "B" written in the "Pattern" column represents the uneven pattern (B) shown in FIGS.

The column "Depth" in Tables 2 to 4 represents the depth of the concave-convex structure of the concave-convex pattern. The numerical value described in the column of "Depth" is the same as the depth of the concave-convex structure of the reflective layer.

The "width" column in Tables 2 to 4 represents the width of the uneven structure of the uneven pattern. The numerical value described in the "width" column is the same as the width of the concave-convex structure of the reflective layer.

The disclosure of Japanese Patent Application No. 2019-133165 filed on July 18, 2019 and Japanese Patent Application No. 2020-045755 filed on March 16, 2020 is herein incorporated by reference in its entirety. It is captured. All publications, patent applications and technical standards mentioned herein are to the same extent as if each individual publication, patent application and technical standard were specifically and individually indicated to be incorporated by reference. incorporated herein by reference.

Claims (11)

a substrate;
a reflective layer having a center wavelength of a selective reflection wavelength in the range of 300 nm or more and 1,500 nm or less and having an uneven structure;
a resin layer between the base material and the reflective layer;
including
The elastic modulus of the resin layer at 25° C. is 0.0001 GPa or more and 1 GPa or less,
The resin layer has a thickness of 0.5 μm or more and 200 μm or less,
The depth of the uneven structure in the reflective layer is 1 μm or more,
A decorative molding , wherein the ratio of the width to the depth (width:depth) of the concave-convex structure in the reflective layer is 100:1 to 1:2 . The decorative molding according to claim 1, wherein the resin layer has an elastic modulus of 0.0001 GPa or more and 0.5 GPa or less at 25°C. 3. The decorative molded body according to claim 1, wherein the depth of the concave-convex structure in the reflective layer is 1 [mu]m or more and 500 [mu]m or less. The decorative molding according to any one of claims 1 to 3, wherein the uneven structure has a width of 5 µm or more. Thickness H of the reflective layer _T. The depth H of the uneven structure of the reflective layer with respect to _D. ratio is 1<H _D. /H _T. The decorated molding according to any one of claims 1 to 4, which satisfies <100. The decorated molding according to any one of claims 1 to 5 , comprising a colored layer. The decorative molding according to any one of claims 1 to 6 , wherein the reflective layer is a layer containing cholesteric liquid crystal. A step of preparing a decorative film having at least a substrate, a reflective layer having a central wavelength of a selective reflection wavelength in the range of 300 nm or more and 1,500 nm or less, and a resin layer between the substrate and the reflective layer. When,
bringing the reflective layer into contact with a surface having an uneven structure, applying a pressure of 0.01 MPa or more to the reflective layer, and imparting an uneven structure to the reflective layer;
The method for manufacturing the decorated molding according to any one of claims 1 to 7 . preparing a decorative film having at least a substrate and a reflective layer having a central wavelength of a selective reflection wavelength in the range of 300 nm or more and 1,500 nm or less;
The reflective layer is brought into contact with the surface having the rugged structure by superimposing the transparent body having the surface having the rugged structure and the decorative film, and a pressure of 0.01 MPa or more is applied to the reflective layer. , and a step of imparting an uneven structure to the reflective layer;
The method for manufacturing the decorated molding according to any one of claims 1 to 7 . A decorative panel comprising the decorative molding according to any one of claims 1 to 7 . An electronic device comprising the decorative panel according to claim 10 .

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