TW202110618A - Decorative film, decorative panel and manufacturing method thereof, electronic device, wearable device, and smartphone - Google Patents

Abstract

Provided are a decorative film and applications thereof, said decorative film being a thin film and being capable of forming a decorative layer that, when viewed through a transparent housing, has superior luster, visibility, and color variation depending on viewing angle. A decorative film for viewing a colored layer via a cholesteric liquid crystal layer, and applications thereof, said decorative film having a temporary support body, said colored layer, and said cholesteric liquid crystal layer, wherein the relationships between the thickness (T1) of the temporary support body, the thickness (T2) of the colored layer, and the thickness (T3) of the cholesteric liquid crystal layer satisfy T1 > T2 > 0.1*T3 and T1 > T3, or T1 > T2 > T3.

Description

Decorative film, decorative panel, and manufacturing method of decorative panel, as well as electronic equipment, wearable equipment, and smart phone

The present disclosure relates to a decorative film, a decorative panel, and a manufacturing method of the decorative panel, as well as electronic equipment, wearable equipment and smart phones.

It is known that a decorative film is arranged on the surface of a resin molded body, and the surface is colored in a desired hue, or a decorative molded body is provided with a desired pattern on the surface. The decorative molded body has, for example, a structure in which a decorative molded film is pre-arranged in a mold and a base resin is injected into the mold, and the decorative film is integrated on the surface of the resin molded body. In the present disclosure, the decorative molding film refers to a molding substrate with a decorative film attached to it. Among them, after the decorative molding film is pre-arranged in the mold, the injection molding of the base resin is generally referred to as film embedding molding or simply embedding molding. In addition, the decorative molded body can be manufactured by pasting a decorative film on the molded body after molding.

In addition, as another method of decorating the surface of the resin molded body, there is a method of using a hot press foil. As a conventional hot-pressed foil, Japanese Patent Application Laid-Open No. 2001-105795 describes a hot-pressed foil characterized in that a cholesteric liquid crystal polymer layer having a selective reflection wavelength region in visible light is provided as a transfer layer.

The problem to be solved by one embodiment of the present disclosure is to provide a decorative film which is a film and can be formed with excellent brightness, visibility and color variability according to the direction of visual recognition through a transparent frame. The decorative layer. Other embodiments of the present disclosure are related to providing a decorative panel or a manufacturing method of a decorative panel using the above-mentioned decorative film. Another embodiment of the present disclosure relates to providing an electronic device, a wearable device, or a smart phone equipped with a decorative panel using the above-mentioned decorative film.

The present disclosure includes the following embodiments. <1> A decorative film having a dummy support, a colored layer, and a cholesteric liquid crystal layer, the thickness of the dummy support (T1), the thickness of the colored layer (T2), and the thickness of the cholesteric liquid crystal layer (T3) The relationship of satisfies T1>T2>0.1×T3, and is used to visually recognize the colored layer through the cholesteric liquid crystal layer. <2> A decorative film having a dummy support, a colored layer, and a cholesteric liquid crystal layer, the thickness of the dummy support (T1), the thickness of the colored layer (T2), and the thickness of the cholesteric liquid crystal layer (T3) The relationship of satisfies T1>T2>T3, and is used to visually recognize the colored layer through the cholesteric liquid crystal layer. <3> The decorative film according to <1> or <2>, wherein the elastic modulus at 25° C. of the colored layer is 0.0001 Gpa or more and less than 0.5 Gpa. <4> The decorative film according to any one of <1> to <3>, which further has a resin layer on the side opposite to the side having the pseudo support. <5> A decorative film having a pseudo support, a colored layer, a cholesteric liquid crystal layer, and an adhesive layer, the thickness of the colored layer (T2), the thickness of the cholesteric liquid crystal layer (T3), and the thickness of the adhesive layer (T4) The relationship satisfies T4<10 (T2+T3), and is used to visually recognize the colored layer through the cholesteric liquid crystal layer. <6> The decorative film according to <5>, wherein the elastic modulus at 25° C. of the colored layer is 0.0001 Gpa or more and less than 0.5 Gpa. <7> A decorative panel in which a transparent frame of 0.5 mm or more is pasted on the side opposite to the side of the pseudo support having the decorative film described in any one of <1> to <6> , And used to visually recognize the colored layer from the transparent frame side through the cholesteric liquid crystal layer. <8> The decorative panel according to <7>, wherein the main component of the transparent frame is glass. <9> The decorative panel according to <7> or <8>, wherein the transparent frame has a three-dimensional shape. <10> A method of manufacturing a decorative panel, which has at least a 0.5mm pasting on the side opposite to the side of the pseudo support having the decorative film described in any one of <1> to <6> After the above transparent frame, the process of peeling off the dummy support. <11> The method for manufacturing a decorative panel as described in <10>, wherein the process of laminating the transparent frame of 0.5 mm or more is a heat forming process at 60° C. or more. <12> An electronic device equipped with the decorative panel described in any one of <7> to <9>. <13> A wearable device equipped with the decorative panel described in any one of <7> to <9>. <14> A smart phone equipped with the decorative panel described in any one of <7> to <9>. [Effects of the invention]

According to an embodiment of the present disclosure, it is possible to provide a decorative film which is a film capable of forming a decorative layer having excellent brightness, visibility and color variability according to the visual recognition direction when visually recognized through a transparent frame. In addition, according to other embodiments of the present disclosure, it is possible to provide a decorative panel or a method of manufacturing a decorative panel using the above-mentioned decorative film. According to another embodiment of the present disclosure, it is possible to provide an electronic device, a wearable device, or a smart phone equipped with a decorative panel using the above-mentioned decorative film.

Hereinafter, an embodiment of the decorative film of the present disclosure and its application will be described. However, the present invention is not limited to the following embodiments in any way, and can be implemented with appropriate modifications within the scope of the purpose of the present disclosure.

Regarding the label of the group (atomic group) in the present disclosure, the label that does not indicate substituted and unsubstituted includes those that do not have a substituent, and includes those that have a substituent. For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl) but also substituted alkyl (substituted alkyl). The "light" in the present disclosure refers to actinic rays or radiation. The “actinic rays” or “radiation rays” in the present disclosure refer to, for example, the bright-line spectrum of mercury lamps, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays and electron beams ( EB: Electron Beam) and so on. Unless otherwise specified, the "exposure" in the present disclosure means not only exposure based on the bright line spectrum of mercury lamps, extreme ultraviolet, extreme ultraviolet, X-ray and EUV light represented by excimer lasers, but also exposure based on electrons Exposure of particle beams such as beams and ion beams.

In the present disclosure, "-" refers to the use of the meaning including the numerical values described before and after it as the lower limit and the upper limit. In the present disclosure, in the numerical range described in stages, the upper limit or the lower limit in one numerical range can be replaced with the upper limit or lower limit of the numerical range described in another stage. In addition, within the numerical range described in this disclosure, the upper limit or lower limit of the numerical range can be replaced with the values shown in the examples.

In this disclosure, (meth)acrylate means acrylate and methacrylate, and (meth)acrylic means acrylic and methacrylic acid.

In this 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 of the resin component (also referred to as molecular weight distribution) (Mw/Mn) are defined as using GPC (Gel Permeation Chromatography: Gel Permeation Chromatography) device (HLC-8120GPC manufactured by TOSOH CORPORATION) for GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection volume): 10μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, tube Column temperature: 40°C, flow rate: 1.0 mL/min, detector: polystyrene conversion value obtained by the Refractive Index Detector.

In this disclosure, regarding the amount of each component in the composition, when there are multiple substances corresponding to each component in the composition, unless otherwise specified, it refers to the total of the corresponding multiple substances present in the composition the amount. In the disclosure, the term "process" is not only an independent process, even when it cannot be clearly distinguished from other processes, as long as the desired purpose of the process can be achieved, it is also included in this term. In the present disclosure, the "total solid content" refers to the total mass of the components obtained by removing the solvent from the total composition of the composition. In addition, the "solid component" refers to a component that removes the solvent from the total composition of the composition. For example, at 25°C, it may be a solid or a liquid. In the present disclosure, "% by mass" is the same as "% by weight", and "parts by mass" is the same as "parts by weight". In addition, in this disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. When the embodiments of the present disclosure are described with reference to the drawings, descriptions of overlapping components and symbols will be omitted. Components denoted by the same symbols in the drawings refer to the same components. The size ratio in the illustration does not necessarily indicate the actual size ratio.

(Decorative film) One form of the decorative film of the present disclosure has a dummy support, a colored layer, a cholesteric liquid crystal layer, and the thickness of the dummy support (T1), the thickness of the colored layer (T2), and the thickness of the cholesteric liquid crystal layer The relationship of (T3) satisfies T1>T2>0.1×T3, and is used to visually recognize the colored layer through the cholesteric liquid crystal layer. The relationship between T1, T2, and T3 is preferably T1>T2>0.1×T3 and T1>T3.

The use of the decorative film of the present disclosure is not particularly limited. For example, it can be used in electronic devices such as smart phones, wearable devices, automobiles, home appliances, audio products, computers, displays, automotive products, watches, accessories, and optical components. , Doors, windows, glass and building materials.

Among them, the decorative film of the present disclosure can be preferably used as a decorative film used in electronic products such as smart phones and wearable devices.

In addition, the decorative film of the present disclosure is also excellent in three-dimensional moldability, so it is preferably used as a decorative film for molding used in molding such as three-dimensional molding and embedded molding, and is more preferable as a decorative film for three-dimensional molding.

For example, one form of the decorative film of the present disclosure is a form in which the adhesive layer described later is provided on the side opposite to the side having the pseudo support, and is preferably used for attaching the base material for molding described later After the adhesive layer side, the pseudo support is peeled off for use as a decorative molded film or after the molded body is attached to the adhesive layer side, the pseudo support is peeled off and used as a decorative molded body.

In the past, in the surface decoration of articles such as home appliances, electronic devices, and mobile phones, printing, painting, deposition, or plating were used, for example. However, in terms of functional provision, environmental load issues, and possibility of replacement, the decoration technology by using a decoration film has been widely used.

On the other hand, more sensors are introduced in electronic devices represented by smart phones, or with the expansion of wireless power supply, a metal design with radio wave permeability becomes necessary. In addition, electronic devices represented by smart phones are becoming thinner, so the decorative film on board also needs to be thinner. In addition, the user's preferences have expanded, so new designs are required. In particular, changes in colors (such as hue and subtle colors) based on the viewing angle are one of the required designs, requiring the introduction of decorative technology.

In addition, Japanese Patent Laid-Open No. 2001-105795 describes that the cholesteric liquid crystal polymer layer is used as a heat-pressing foil for the transfer laminate layer. However, regarding the decorative film of the present disclosure, the content of the colored layer is visually recognized through the cholesteric liquid crystal layer Not documented.

As a result of intensive research, the inventors have found that the decorative film of the above-mentioned structure can be formed into a film and has excellent brightness, visibility and color variability according to the direction of visual recognition through a transparent frame. The situation.

In the present disclosure, the use of a decorative film to form a film refers to the use of the decorative film of the present disclosure to provide a decorative layer with a relatively thin thickness of the entire decorative layer. In the present disclosure, the term of the decorative layer is used as a term to collectively refer to the remaining layers after peeling off the pseudo support from the decorative film of the present disclosure.

In particular, a decorative film having a laminated film including a cholesteric liquid crystal layer and a coloring layer obtains a thin decorative layer by peeling and removing the pseudo support. On the other hand, the laminated film containing the cholesteric liquid crystal layer and the coloring layer has the following problem. That is, when the pseudo support is peeled off after being disposed on the substrate as a decoration object, it is easy to cause a gap between the coloring layer and the cholesteric liquid crystal layer. The interface between the decorative film and the base material peels off or the cohesion failure caused by insufficient strength of the laminated film makes it difficult to peel off the pseudo support. The decorative film of the present disclosure solves the above problems by satisfying a specific relationship between the thickness of the pseudo support (T1), the thickness of the colored layer (T2), and the thickness (T3) of the cholesteric liquid crystal layer.

In addition, in the present disclosure, "brightness and visibility when visually recognized through the transparent frame" means that the decorative film is arranged on the transparent frame and the decorative layer is formed and molded, and then the decorative layer is viewed from the transparent frame side The brightness and visibility of the decorative layer at the time. It can be said that the greater the degree of brightness and visibility described above, a more attractive design can be realized.

In addition, in the present disclosure, the color variability according to the visual recognition direction refers to the case of visual recognition from an angle perpendicular to the surface direction of the decorative film (also referred to as "film surface direction") and the case of visual recognition from a 45° angle The color changes in the case. The greater the degree of change in the color, the more excellent the color variability according to the direction of visual recognition.

Although the mechanism of the above-mentioned effects is not clearly shown in detail, by having a pseudo support, a colored layer, and a cholesteric liquid crystal layer, and the thickness of the pseudo support (T1), the thickness of the colored layer (T2), and the cholesteric liquid crystal The relationship of the thickness (T3) of the layer satisfies T1>T2>0.1×T3, and good peeling characteristics of the pseudo support can be obtained, thereby obtaining a thin decorative layer. In addition, it is estimated that a uniform decorative layer is formed after peeling off the pseudo support, and when it is visually recognized through the transparent frame, the brightness, visibility, and color variability according to the visual recognition direction are excellent.

Hereinafter, the decorative film of the present disclosure will be described in detail.

[Layer order of each layer] The decorative film of the present disclosure has a pseudo support, a colored layer, and a cholesteric liquid crystal layer, and the colored layer is visually recognized through the cholesteric liquid crystal layer. Regarding the layering order, as long as the colored layer can be visually recognized through the cholesteric liquid crystal layer, it is not particularly limited, but it is preferable to laminate the pseudo support, the colored layer, and the cholesteric liquid crystal layer in this order.

[Preferred thickness of each layer] The decorative film of the present disclosure has a pseudo support, a colored layer, and a cholesteric liquid crystal layer, and the relationship between the thickness of the pseudo support (T1), the thickness of the colored layer (T2), and the thickness of the cholesteric liquid crystal layer (T3) satisfy T1> T2>0.1×T3.

The thickness of the pseudo support is not particularly limited, but from the standpoint of releasability, 10 μm to 500 μm is preferable, 20 μm to 300 μm is more preferable, and 50 μm to 150 μm is particularly preferable. The thickness of the colored layer is not particularly limited, but from the viewpoint of the peelability, visibility, and three-dimensional formability of the pseudo support, 0.5 μm or more is preferable, 3 μm or more is more preferable, and 3 μm to 50 μm is more preferable , 3μm～20μm is particularly preferred. From the standpoints of the peelability, visibility, and color variability of the pseudo support, the thickness of the cholesteric liquid crystal layer is preferably less than 4μm, more preferably 2μm or less, and 0.2μm～1.5μm is further Preferably, 0.4 μm to 1.2 μm is particularly preferred.

The relationship between the thickness of the pseudo support (T1), the thickness of the colored layer (T2) and the thickness of the cholesteric liquid crystal layer (T3) is T1>T2>0.1×T3, T1>T2>0.3×T3 is more preferable, T1> T2>0.5×T3 is further preferred, and T1>T2>T3 is particularly preferred. That is, one embodiment of the decorative film of the present disclosure includes the relationship between the thickness of the dummy support (T1), the thickness of the colored layer (T2), and the thickness (T3) of the cholesteric liquid crystal layer: T1>T2>T3. With T1, T2, and T3 satisfying the above relationship, when the pseudo support is peeled off, the stress applied to the colored layer and the cholesteric liquid crystal layer is dispersed, and the local concentration of the stress is suppressed, thereby suppressing the interface peeling and the aggregation failure of the film, thereby obtaining Good peeling characteristics of the pseudo support. With the good peeling characteristics of the pseudo support, the damage of the decoration layer obtained by the decoration film is effectively suppressed. The decoration film of the present disclosure is a film and can form the brightness, visibility and basis for visual recognition through the transparent frame A decorative layer with excellent color variability in the direction of visual recognition.

Regarding the thickness of each layer constituting the decorative film, the decorative film can be cut in a direction perpendicular to the surface of the film, the cut surface can be observed by a scanning electron microscope (SEM) or an optical microscope, and the cross-sectional observation method of measuring the thickness of the layer under this range can be used Determination. In addition, if the entire decorative film can be peeled off, the peeled layer can be measured by a direct measurement method such as a caliper or a film thickness meter.

〔Elastic modulus of each layer〕 The elastic modulus of each layer constituting the decorative film is preferably within the range shown below. The method for measuring the elastic modulus of each layer in the present disclosure is to use a dynamic ultramicro hardness meter (DUH-201S, manufactured by Shimadzu Corporation) to measure the push hardness of each layer.

The measurement conditions are as follows. ･Type of indenter: Vickers ･Test mode: load-unload test ･Test force: 40mN ･Load speed: 1.3239mN/sec ･Retention time: 5sec

In addition, the measurement of each layer can be measured on the cut section of the laminate, or the layer measured by cutting or the like can be exposed. The protective layer (that is, the outermost layer) and the adhesive layer can be measured on the surface.

In the decorative film of the present disclosure, the elastic modulus of the colored layer at 25° C. is preferably 0.0001 Gpa or more and less than 0.5 Gpa, and more preferably 0.001 Gpa or more and 0.08 Gpa or less. By setting it as the said range, the peelability of a pseudo support body from a decoration film is excellent, and a thin and uniform decoration layer can be obtained.

The modulus of elasticity of the pseudo support at 25° C. may be 0.01 Gpa or more and less than 6 Gpa, and preferably 0.5 Gpa or more and less than 6 Gpa. By setting it as the said range, the peelability of a pseudo support body from a decoration film is excellent, and a thin and uniform decoration layer can be obtained.

The elastic modulus of the liquid crystal layer at 25° C. is preferably 0.0001 Gpa or more and less than 0.1 Gpa, and more preferably 0.001 Gpa or more and 0.03 Gpa or less. By setting it as the said range, the peelability of a pseudo support body from a decoration film is excellent, and a thin and uniform decoration layer can be obtained.

In the decorative film of the present disclosure, when the elastic modulus of the pseudo support is set to (G1), the elastic modulus of the colored layer is set to (G2), and the elastic modulus of the liquid crystal layer is set to (G3), G1> The relationship of G2>G3 is better. Among the above, the peelability from the dummy support is more excellent.

In addition, in a form in which the decorative film has an adhesive layer, when the elastic modulus of the adhesive layer is set to (G4), the relationship of G1>G2>G3>G4 is preferable. Among the above, the releasability of the dummy support from the decorative film is more excellent.

〔Pseudo-support〕 The pseudo support is not particularly limited. A known resin film is used, and a film that is flexible and does not undergo significant deformation, shrinkage, or extension under pressure or pressure and heating can be preferably used. As a pseudo support, resin films such as cyclic olefin copolymer film, polyethylene terephthalate (PET) film, cellulose triacetate film, polystyrene film, polycarbonate film, polymethyl methacrylate film, etc. Preferably, a polyethylene terephthalate film is more preferable. In addition, from the viewpoint of excellent peelability of the pseudo support from the colored layer, an organic film with a peeling layer is more preferable. Commercial products of the pseudo support include, for example, "Unipeel (registered trademark)" series (manufactured by UNITIKA LTD.), "Serapeel (registered trademark)" series (manufactured by Toray Advanced Film Co., Ltd.), etc. Layer of PET film, etc.

-Total light transmittance- Regarding the pseudo support used in the present disclosure, when exposure is performed from the side of the pseudo support in the exposure process described later, the total light transmittance is preferably 80% or more, and more preferably 90% or more. The total light transmittance can be measured with a spectrophotometer (for example, a spectrophotometer UV-2100 manufactured by Shimadzu Corporation, a spectrophotometer V-670 manufactured by JASCO Corporation, etc.).

〔Peeling layer〕 In order to improve the peelability from the colored layer of the pseudo support, it is preferable to have a peeling layer on the colored layer side of the pseudo support. In addition, in order to improve the peelability between the pseudo support and the colored layer, the decorative film of the present disclosure preferably has a peeling layer between the pseudo support and the colored layer. In addition, when the decorative film of the present disclosure has the above-mentioned release layer, in order to prevent the occurrence of irregularities in the colored layer when the pseudo support is peeled off, and the occurrence of poor transfer in the bubble biting portion where bubbles are generated on the colored layer during transfer, It is preferable to perform peeling between the dummy support and the peeling layer.

It does not specifically limit as a peeling layer, A well-known peeling layer in the field, such as a transfer film, can be used. As the release layer, for example, a layer containing a thermoplastic resin can be cited, and the thermoplastic resin layer described in paragraph 0026 of Patent No. 4,502,784 is preferably used as the release layer. When the pseudo support has a peeling layer, it is preferable that the colored layer is formed on the peeling layer in the process of forming the colored layer.

〔Colored layer〕 The decorative film of the present disclosure is a decorative film that has a colored layer and is used to visually recognize the colored layer through the cholesteric liquid crystal layer.

The color of the colored layer is not particularly limited, as long as it is a colored (that is, not colorless and transparent), and an opaque colored layer (preferably a colored layer with a total light transmittance of 10% or less) is preferred. In addition, the colored layer can be in various colors such as black, gray, white, red, orange, yellow, green, blue, purple, etc. If it is a black colored layer, the intensity of reflected light is smaller and the color change is more emphasized. Therefore it is better. For example, even if the colored layer is black, it can be set that by appropriately selecting the cholesteric liquid crystal layer, not only does the color change from black, but it is also visually recognized from any angle of the film surface on the cholesteric liquid crystal layer side, and the A decorative film in which the color of the colored layer itself is different, and the color further changes according to the angle. Also, for example, even if the colored layer is black, it can be made blue when viewed from an angle perpendicular to the surface direction of the decorative film, and visually recognized when viewed from a direction at 45° to the surface direction of the film. The decorative film is black, or even if the colored layer is black, it can be visually recognized as red when viewed from an angle perpendicular to the surface direction of the decoration film, and when viewed from a direction 45° to the surface direction of the film It is visually recognized as a yellow decorative film.

In addition, the colored layer may be a layer formed by curing a polymerizable compound, or may be a layer containing a polymerizable compound and a polymerization initiator. From the standpoint of preservability and adhesion between the colored layer and other layers, the colored layer is preferably a layer formed by curing a polymerizable compound, and more preferably a layer formed by curing at least a bifunctional or trifunctional polymerizable compound. The aforementioned bifunctional or trifunctional polymerizable compound has a partial structure of at least one selected from the group consisting of a urethane bond and an alkoxy group having 2 or 3 carbon atoms.

-Colorant- From the viewpoint of visibility, the colored layer preferably contains a colorant, and from the viewpoint of durability, it is more preferable to contain a pigment as the colorant. The coloring agent is not limited, and a coloring agent of the target hue can be appropriately selected and used. As a coloring agent, a pigment, a dye, etc. are mentioned, for example, and a pigment is preferable. In addition, pigments in the shape of pigment-based particles are preferable. As the pigment, various conventionally known inorganic pigments and organic pigments can be used. Examples of inorganic pigments include inorganic pigments described in paragraphs 0015 and 0114 of JP 2005-007765 A. Specific inorganic pigments include, for example, white pigments such as titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon black, aluminum oxide, aluminum hydroxide, and barium sulfate, as well as carbon black, titanium black, and titanium Black pigments such as carbon, iron oxide and graphite. For example, well-known color pigments such as iron oxide, barium yellow, cadmium red, and chrome yellow can also be used.

As an organic pigment, the organic pigment described in the 0093 paragraph of Unexamined-Japanese-Patent No. 2009-256572 can be mentioned, for example. Examples of specific organic pigments include red pigments such as CIPigment Red 177, 179, 224, 242, 254, 255, 264, yellow pigments such as CIPigment Yellow 138, 139, 150, 180, and 185, and CIPigment Orange 36 , 38, 71 and other orange pigments, CIPigment Green 7, 36, 58 and other green pigments, CIPigment Blue 15: 6 and other blue pigments, CIPigment Violet 23 and other purple pigments. In addition, as the pigment, particles of a pigment having translucency and light reflectivity (so-called bright pigment) may be included. When the forming method of the colored layer includes the process of exposing the colored layer, the bright pigment is preferably used within a range that does not hinder the hardening caused by exposure.

A coloring agent may be used individually by 1 type, respectively, and may use 2 or more types together. In addition, particles of inorganic pigments and particles of organic pigments may be used in combination.

From the viewpoints of the development of the target hue (for example, the suppression of whitening) and the maintenance of the shape followability of the mold with respect to the colored layer, the content of the coloring agent in the colored layer is 1% by mass to the total mass of the colored layer. 50% by mass is more preferable, 5% by mass to 50% by mass is more preferable, and 10% by mass to 40% by mass is still more preferable. Here, the "whitening" in the present disclosure means that the colored layer is changed into a whitish tone as if a matt feeling is imparted.

-Polymerizable compound- The coloring layer used in the present disclosure preferably contains a polymerizable compound. As the polymerizable group, an ethylenic unsaturated group, an epoxy group, etc. can be mentioned. From the viewpoint of curability and the like, an ethylenic unsaturated group is preferred, and a (meth)acryloxy group is more preferred. Moreover, as a polymerizable group, a radical polymerizable group is preferable.

As a polymerizable compound, a difunctional having at least one partial structure selected from the group consisting of a urethane bond, a urea bond, an alkoxy group having 2 or 3 carbons, and a hydrocarbon group having 6 to 12 carbons Or a trifunctional polymerizable compound (hereinafter also referred to as a "specific polymerizable compound") is preferably, having at least one selected from the group consisting of a urethane bond and an epoxyalkyl group having 2 or 3 carbon atoms Partially structured bifunctional or trifunctional polymerizable compounds are more preferable.

In the specific polymerizable compound, if necessary, it may have a linking group between the partial structure and the polymerizable group. In addition, the specific polymerizable compound may have two or more partial structures selected from the group consisting of a urethane bond, a urea bond, an alkoxy group having 2 or 3 carbons, and a hydrocarbon group having 6 to 12 carbons.

<Difunctional or trifunctional polymerizable compound with urethane bond> One form of the polymerizable compound is preferably a bifunctional or trifunctional polymerizable compound having a urethane bond (hereinafter also referred to as "specific polymerizable compound 1"). As the specific polymerizable compound 1, urethane Ester oligomers are preferred. The nitrogen atom in the urethane bond may be 2-substituted (one of the groups on the nitrogen atom is a hydrogen atom) or 3-substituted. Moreover, it is preferable that the specific polymerizable compound 1 has a urethane resin chain.

As the urethane oligomer, an urethane (meth)acrylate oligomer is preferred. As a urethane (meth)acrylate oligomer, aliphatic urethane (meth)acrylate, aromatic urethane (meth)acrylate, etc. are mentioned, for example. For details, please refer to the oligomer manual (supervised by Junji Furukawa, The Chemical Daily Co., Ltd.). The urethane oligomer described therein can be appropriately selected according to the purpose and used for the formation of the coloring layer in this process. . The molecular weight of the urethane oligomer, which is one of the specific polymerizable compounds 1, is preferably 800 to 2,000, and 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 can be used. Examples of commercially available products of urethane (meth)acrylate oligomers include U-2PPA and UA-122P manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.; CN964A85 manufactured by Sartomer Japan Inc. CN964, CN959, CN962, CN963J85, CN965, CN982B88, CN981, CN983, CN991, CN991NS, CN996, CN996NS, CN9002, CN9007, CN9178, CN9893; DAICEL-ALLNEX LTD. manufactured by DAICEL-ALLNEX LTD. EBECRYL230, EBECRYL270, EBECRYL284, EBECL840L4858, EBECRYL4858, EBECRYL4858 , EBECRYL8804, EBECRYL8800-20R, etc. (the above are product names). Furthermore, "EBECRYL" is a registered trademark.

<Difunctional or trifunctional polymerizable compound with urea bond> One form of the polymerizable compound is preferably a bifunctional or trifunctional polymerizable compound having a urea bond (hereinafter also referred to as "specific polymerizable compound 2"). As the specific polymerizable compound 1, a urea bond may be mentioned. The difunctional or trifunctional ethylenically unsaturated compound. The nitrogen atom in the urea bond may be 2-substituted (one of the groups on the nitrogen atom is a hydrogen atom) or 3-substituted. Moreover, it is preferable that the specific polymerizable compound 2 has a urea resin chain.

Specific examples of the bifunctional or trifunctional ethylenically unsaturated compound having a urea bond include a compound obtained by reacting an isocyanate compound having an ethylenically unsaturated group with an amine compound.

As the isocyanate compound having an ethylenically unsaturated group, for example, 2-isocyanoethyl methacrylate (as a commercially available product, there is Karenz MOI (registered trademark) manufactured by Showa Denko Gas Products Co., Ltd.) , The isocyanate group of 2-isocyanoethyl methacrylate is blocked by methyl ethyl ketoxime (2-(O-[1'-methyl propylene amino] carboxyamino) methyl Ethyl acrylate, as a commercially available product, is Karenz MOI-BM (registered trademark) manufactured by Showa Denko Gas Products Co., Ltd., and isocyanate group of 2-isocyanoethyl methacrylate is sealed by pyrazole. Terminator (2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate, as a commercially available product, there is Karenz MOI manufactured by Showa Denko Gas Products Co., Ltd. -BP (registered trademark)) etc.

In addition, as the amine compound, for example, an amine compound having two or more active hydrogen atoms can be used. Specifically, dimethylamine, trimethylamine, triethylamine, diisopropylamine, and diethylenetriamine can be used. Amine, ethylenetetramine, etc. In addition, the specific polymerizable compound 2 is not limited to those obtained by this method.

Specific examples of the specific polymerizable compound 2 include ethoxylated isocyanuric acid diacrylate, ethoxylated isocyanuric acid triacrylate, and ε-caprolactone modified tris(2- Acrylic oxyethyl) trimeric isocyanate, etc. Among them, ethoxylated isocyanuric acid diacrylate, ethoxylated isocyanuric acid triacrylate and ε-caprolactone modified tris(2-propylene oxyethyl) cyanuric acid ester series have Vinyloxy compounds.

The specific polymerizable compound 2 can be obtained as a commercially available product. As specific examples of commercially available products, for example, NK ester A-9300 and A-9300-1CL manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.; ARONIX (registered trademark) M-215 manufactured by TOAGOSEI CO., LTD. , 313, 315 (the above are product names), etc.

<Difunctional or trifunctional polymerizable compound having an alkoxy group having 2 or 3 carbons> One form of the polymerizable compound is an alkoxy group having 2 or 3 carbons (also referred to as "alkylene oxide" .) bifunctional or trifunctional polymerizable compound (hereinafter, also referred to as "specific polymerizable compound 3".) is preferably, the specific polymerizable compound 3 has, for example, one or more vinyloxy groups or stretches in one molecule A propoxy group has 2 or 3 polymerizable groups at the end of the molecule. The propoxyl group may be -CH ₂ -CH ₂ -CH ₂ -O-, -CH ₂ -CH(CH ₃ )O- or -CH(CH ₃ )-CH ₂ O-, -CH ₂ -CH( CH ₃ )O- or -CH(CH ₃ )-CH ₂ O- is preferred. Among them, as the polymerizable group in the specific polymerizable compound 3, for example, at least one selected from the group consisting of acryloxy group, acryloxy group, methacryloxy group, and methacryloxy group Ethylene unsaturated group.

Specific examples of the specific polymerizable compound 3 include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, and ethoxylate. Bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethyl Oxylated glycerol triacrylate, ethoxylated glycerol trimethacrylate, etc. From the viewpoint of improving the shape followability with respect to the mold, the number of ethyleneoxy or propoxyl groups in these compounds is preferably 3 or more, more preferably 9-40, and 15- 30 is particularly good.

In addition, from the viewpoint of improving the shape followability with respect to the mold, the specific polymerizable compound 3 has a polyvinyloxy group or a polypropyleneoxy group having two or more ethyleneoxy groups or propyleneoxy groups repeatedly. Better. The number of repetitions of the ethyleneoxy group or the propyleneoxy group in the polyvinyloxy group or the polypropyleneoxy group is preferably 3 or more, and particularly preferably 5 or more.

The specific polymerizable compound 3 can be obtained as a commercially available product. As specific examples of commercially available products, for example, NK esters A-200, A-400, A-600, A-1000, 1G, 2G, 3G, 4G, 9G, manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD. 14G, 23G, ABE-300, A-BPE-4, A-BPE-6, A-BPE-10, A-BPE-20, A-BPE-30, BPE-80N, BPE-100N, BPE-200, BPE-500, BPE-900, BPE-1300N, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-TMPT-3EO, A-TMPT-9EO; manufactured by NIPPON KAYAKU Co, Ltd. PEG400DA; ARONIX (registered trademark) M-220, M-350 manufactured by TOAGOSEI CO., LTD.; SR415, SR454, SR9035 manufactured by Sartomer Japan Inc. (the above are product names), etc.

<Difunctional or trifunctional polymerizable compound having a C6-12 hydrocarbon group> One form of the polymerizable compound is a bifunctional or trifunctional polymerizable compound having a hydrocarbon group with 6 to 12 carbons (hereinafter also referred to as "specific polymerizable compound 4"). In the specific polymerizable compound 4, carbon The number is 6 to 12, and it has any of chain, cyclic, and branched hydrocarbon groups and 2 or 3 polymerizable groups. Among them, the hydrocarbon group in the specific polymerizable compound 4 is specifically a hydrocarbon chain having 6 to 12 carbon atoms, which may be a straight chain or a branched chain. Among them, from the viewpoint of improving the shape followability with respect to the mold, as the hydrocarbon group, a straight-chain one is preferred. In addition, as the polymerizable group, for example, at least one ethylenically unsaturated group selected from the group containing an acryloxy group, an acryloxy group, a methacryloxy group, and a methacryloxy group can be mentioned.

Specific examples of the specific polymerizable compound 4 include 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, and 1,8-octanediol Di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,4-cyclohexanediol di(methyl) ) Acrylate, tricyclodecane dimethanol di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, hydrogenated bisphenol F di(meth)acrylate. Among the above compounds, tricyclodecane dimethanol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate are preferably used , 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate.

From the viewpoint of improving the three-dimensional formability by improving the flexibility during heating, etc., the polymerizable compound has one selected from the group consisting of a urethane bond and an epoxyalkyl group having 2 or 3 carbon atoms. At least one bifunctional or trifunctional polymerizable compound having a partial structure is preferred.

The colored layer may contain other polymerizable compounds in addition to the specific polymerizable compound. As the other polymerizable compound, as long as it is a compound containing the same polymerizable group as the specific polymerizable compound, it can be used without particular limitation.

From the viewpoint of improving the adhesion between layers and imparting flexibility to the colored layer, relative to the total mass of the uncured colored layer, the content of the polymerizable compound is preferably 10% to 50% by mass, and 20% to 40% by mass The quality% is better.

A specific polymerizable compound and another polymerizable compound may be used individually by 1 type, respectively, and may be used in combination of 2 or more types.

The polymerizable compound used in the present disclosure has a molecular weight (weight average molecular weight when having a molecular weight distribution) of 200 to 3,000, preferably 250 to 2,600, and particularly preferably 280 to 2,200.

-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 the dispersant, the dispersibility of the pigment in the formed coloring layer is improved, and the hue of the obtained decorative film is uniformized.

As the dispersant, it can be appropriately selected and used according to the type, shape, etc. of the pigment, and a polymer dispersant is preferred. Examples of polymer dispersants include silicone polymers, propylene polymers, and polyester polymers. In the case of imparting heat resistance to the decorative film, for example, as a dispersant, a silicone polymer such as a graft-type silicone polymer is preferably used.

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 particularly preferably 2,500 to 3,000,000. If the weight average molecular weight is 1,000 or more, the dispersibility of the pigment is further improved.

As the dispersant, a commercially available product can be used. Commercially available products include EFKA 4300 (acrylic polymer dispersant) manufactured by BASF Japan Ltd., HOMOGENOL L-18, HOMOGENOL L-95 and HOMOGENOL L-100 manufactured by Kao Corporation, Solsperse 20000 manufactured by The Lubrizol Corporation, and Solsperse24000 and DISPERBYK-110, DISPERBYK-164, DISPERBYK-180, DISPERBYK-182, etc. manufactured by BYK JAPAN KK. Furthermore, "HOMOGENOL", "Solsperse", and "DISPERBYK" are all registered trademarks.

When the colored layer contains a dispersant, it may contain only one type of dispersant, or may contain two or more types of dispersant. The content of the dispersant is preferably 1 part by mass to 30 parts by mass relative to 100 parts by mass of the coloring agent.

-Polymerization initiator- In order to increase the curing sensitivity and further improve the adhesion between layers, the colored layer preferably contains a polymerization initiator, and more preferably contains a polymerizable compound and a polymerization initiator. From the viewpoint of improving the sensitivity to exposure, as the polymerization initiator, a photopolymerization initiator is preferred. As the photopolymerization initiator, the polymerization initiator described in paragraphs 0031 to 0042 of Japanese Patent Application Publication No. 2011-095716, and the oxime polymerization initiator described in paragraphs 0064 to 0081 of Japanese Patent Application Publication No. 2015-014783 can be used. Beginner.

As the photopolymerization initiator, specifically, for example, 1-[4-(phenylthio)]-1,2-octanedione-2-(orthobenzyl oxime) (for example, IRGACURE ( Registered trademark) OXE-01, manufactured by BASF Corporation), [9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethane-1-one-1-( O-Acetyl oxime) (for example, IRGACURE (registered trademark) OXE-02, manufactured by BASF Corporation), 2-(dimethylamino)-2-[(4-tolyl)methyl]-1-[4- (4-morpholinyl)phenyl]-1-butanone (for example, IRGACURE (registered trademark) 379EG, manufactured by BASF Corporation), 2-methyl-1-(4-methylthiophenyl)-2-methanone Phytopropan-1-one (for example, IRGACURE (registered trademark) 907, manufactured by BASF Corporation), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanyl)benzyl]benzene 2-methyl-propane-1-one (for example, IRGACURE (registered trademark) 127, manufactured by BASF Corporation), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) Butanone-1 (for example, IRGACURE (registered trademark) 369, manufactured by BASF Corporation), 2-hydroxy-2-methyl-1-phenylpropane-1-one (for example, IRGACURE (registered trademark) 1173, manufactured by BASF Corporation) ), 1-hydroxycyclohexyl phenyl ketone (for example, IRGACURE (registered trademark) 184, manufactured by BASF Corporation), 2,2-dimethoxy-1,2-diphenylethane-1-one (for example, IRGACURE (registered trademark) 651, manufactured by BASF Corporation), product names of oxime ester polymerization initiators: Lunar 6 (manufactured by dksh japan kk), 2,4-diethyl thioxanthone (for example, KAYACURE DETX-S , Nippon Kayaku Co., Ltd.), DFI-091 and DFI-020 (all manufactured by DAITO CHEMIX Co., Ltd.), fluorenoxime polymerization initiators.

Among them, from the viewpoint of improving the curing sensitivity, it is preferable to use other initiators other than the halogen-containing polymerization initiators such as trichloromethyl tris-based compounds, and α-aminoalkyl phenone-based compounds , Alpha-hydroxyalkyl phenone compounds, oxime ester compounds and other oxime polymerization initiators are more preferred.

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

-Binder resin- From the viewpoint of reducing the curing shrinkage of the colored layer, etc., the colored layer preferably contains a binder resin. It does not specifically limit as a binder resin, A well-known resin can be selected suitably. As the binder resin, from the viewpoint of obtaining the target hue, a transparent resin is preferable, and specifically, a resin having a total light transmittance of 80% or more is preferable. The total light transmittance can be measured with a spectrophotometer (for example, a spectrophotometer UV-2100 manufactured by Shimadzu Corporation).

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

In the present disclosure, "acrylic resin" refers to a resin containing structural units derived from acrylic monomers having (meth)acrylic groups. (Meth)acrylic acid group refers to the concept including methacrylic acid group and acrylic acid group. Acrylic resins include, for example, homopolymers of acrylic acid, homopolymers of methacrylic acid, homopolymers of acrylates, homopolymers of methacrylates, copolymers of acrylic acid and other monomers, methacrylic acid and other monomers Copolymers, copolymers of acrylate and other monomers, copolymers of methacrylate and other monomers, urethane-modified copolymers with urethane backbone in the side chain, etc. Examples of acrylic resins include glycidyl methacrylate adducts of cyclohexyl methacrylate/methyl methacrylate/methacrylic acid copolymers, and random copolymers of benzyl methacrylate/methacrylic acid. , Allyl methacrylate/methacrylic acid copolymer, benzyl methacrylate/methacrylic acid/hydroxyethyl methacrylate copolymer, etc.

As the silicone resin, well-known silicone resins can be used. Examples include methyl-based linear silicone resins, tolyl-based linear silicone resins, acrylic resin-modified silicone resins, ester resin-modified silicone resins, and cyclic silicone resins. Oxygen resin modified silicone resin, alkyd resin modified silicone resin and rubber silicone resin. Among them, methyl-based linear silicone resins, tolyl-based linear silicone resins, acrylic resin modified silicone resins or rubber-based silicone resins are preferred, methyl-based linear silicone resins, tolyl-based linear silicone resins Resin or rubber-like silicone resin is more preferable.

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

Examples of polyester resins include linear saturated polyesters synthesized from aromatic dibasic acids or their ester-forming derivatives and diols or their ester-forming derivatives. Specific examples of linear saturated polyesters include polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, and polytetramethylene terephthalate. Adipate, poly-2,6-naphthalene carboxyethylene glycol, etc.

From the viewpoint of reducing the curing shrinkage of the colored layer, relative to the total mass of the colored layer, the content of the binder resin is preferably 5 mass% to 70 mass%, more preferably 10 mass% to 60 mass%, and 20 mass% % Or more and 60% by mass are more preferable. In addition, the ratio of the total amount of binder resin to the total amount of polymerizable compounds containing the specific polymerizable compound, that is, the total amount of polymerizable compounds/the total amount of binder resin is preferably 0.3 to 1.5, 0.5 to 0.5 1.0 is better.

-Other ingredients- In addition to the above-mentioned components, the colored layer may contain additives as necessary. As the additives, known additives can be used, for example, the surfactants described in paragraph 0017 of Patent No. 4502784, paragraphs 0060 to 0071 of JP 2009-237362, and paragraph 0018 of Patent No. 4502784 The thermal polymerization inhibitor described in (also referred to as a polymerization inhibitor. Preferably it is phenanthrene), and other additives described in paragraphs 0058 to 0071 of JP 2000-310706 A.

-Formation of colored layer- The method of forming the colored layer is not particularly limited, but it is preferable to use a composition for forming a colored layer. The composition for forming a colored layer preferably contains a colorant, and more preferably contains a colorant and an organic solvent. In addition, the composition for forming a colored layer may contain the above-mentioned other components. The composition for forming a colored layer can be prepared, for example, by mixing components contained in the colored layer such as an organic solvent and a coloring agent. The content of the components contained in the colored layer is described as the content (mass %) relative to the total mass of the colored layer. However, when these components are contained in the composition for forming the colored layer, the content is replaced with the content relative to the colored layer. The total solid content (mass%) of the layer forming composition.

In addition, when the colored layer forming composition contains a pigment as a colorant, a pigment dispersion containing the pigment and its dispersant is prepared in advance, and the pigment dispersion is used to prepare the colored layer forming composition to further improve the uniformity of the pigment. It is preferable from the viewpoint of dispersibility and dispersion stability.

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

＜Organic solvent＞ As the organic solvent, commonly used organic solvents can be used without particular limitation. Specifically, for example, organic solvents such as esters, ethers, ketones, and aromatic hydrocarbons can be cited. In addition, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone are the same as Solvent (solvent) described in paragraphs 0054 and 0055 of the specification of U.S. Patent Application Publication No. 2005/282073 , Cyclohexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate, etc. can also be preferably used as an organic solvent in the composition for forming a colored layer. Among them, 1-methoxy-2-propyl acetate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethyl cellosolve acetate, ethyl lactate, acetic acid Butyl ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, diethylene glycol monoethyl ether acetate (ethyl carbitol acetate), diethylene glycol monobutyl ether ethyl An acid ester (butyl carbitol acetate), propylene glycol methyl ether acetate, methyl ethyl ketone, and the like are preferably used as the organic solvent in the composition for forming a colored layer. These organic solvents may be used individually by 1 type, and may use 2 or more types together. In addition, the content of the organic solvent is not particularly limited, but it is preferably 5% to 90% by mass relative to the total mass of the composition (coating liquid) for forming a colored layer, and more preferably 30% to 70% by mass.

〔Cholesterol type liquid crystal layer〕 The decorative film of the present disclosure has a cholesteric liquid crystal layer on the pseudo support. From the viewpoint of further exerting the effects of the present disclosure, the decorative film of the present disclosure is used for a decorative film that is visually recognized through the above-mentioned cholesteric liquid crystal layer. In addition, the cholesteric liquid crystal layer in the decorative film of the present disclosure only needs to be on the pseudo support, and it can be directly connected to the pseudo support, or it can be laminated on the pseudo support via other layers such as the above-mentioned colored layer.

The decorative film of the present disclosure can adjust the color change and progress based on the angle of visual recognition by changing at least one selected from the group consisting of the pitch, refractive index, and thickness of the spiral structure in the cholesteric liquid crystal layer. The visually recognized color itself. The pitch of the above-mentioned spiral structure can be easily adjusted by changing the addition amount of the chiral agent. Specifically, it is described in detail in Fuji Film Research Report No.50 (2005) p.60-63. In addition, the pitch of the above-mentioned spiral structure can also be adjusted using conditions such as temperature, luminosity, and irradiation time when the cholesteric orientation state is fixed.

The cholesteric liquid crystal layer preferably fixes the liquid crystal compound in a cholesteric alignment state. The cholesteric orientation state may be an orientation state that reflects right circular polarization, or an orientation state that reflects left circular polarization, or both. The liquid crystal compound is not particularly limited, and various known ones can be used.

＜＜Liquid crystal composition＞＞ The cholesteric liquid crystal layer is a layer formed by curing a liquid crystal composition. As the liquid crystal compound used in the present disclosure, from the viewpoint of molding processability and pseudo-support peelability, it is better to use a cholesteric liquid crystal compound having at least one ethylenically unsaturated group or one cyclic ether group. good. The liquid crystal composition used to form the cholesteric liquid crystal layer includes, for example, 25% by mass or more of the cholesteric liquid crystal compound having one ethylenically unsaturated group or having a cyclic ether group with respect to the total solid content of the liquid crystal composition, In addition, other components such as chiral agents, orientation control agents, polymerization initiators, and orientation aids may also be contained.

-Cholesterol type liquid crystal compound with 1 ethylenically unsaturated group or 1 cyclic ether group- In the above-mentioned liquid crystal composition, a content of 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") is preferably contained. .

The ethylenic unsaturated group in the specific liquid crystal compound is not particularly limited, and examples thereof include (meth)acryloxy groups, (meth)acrylamide groups, vinyl groups, vinyl ester groups, and vinyl ether groups. Wait. Among them, from the viewpoint of reactivity, (meth)acryloxy group, (meth)acrylamide group or aromatic vinyl group is preferred, (meth)acryloxy group or (meth)propylene group The amide group is more preferable, and the (meth)acryloxy group is particularly preferable.

The cyclic ether group in the specific liquid crystal compound is not particularly limited. From the viewpoint of reactivity, an epoxy group or an oxetanyl group is preferable, and an oxetanyl group is particularly preferable. In addition, from the viewpoints of reactivity, suppression of reflectance change after molding, and suppression of color change, it is preferable that the specific liquid crystal compound is a compound having one ethylenically unsaturated group. It is more preferable that the total solid content of the product contains 25% by mass or more of a cholesteric liquid crystal compound having one ethylenically unsaturated group.

Furthermore, the specific liquid crystal compound may have both ethylenic unsaturated groups and cyclic ether groups in one molecule, but the number of ethylenic unsaturated groups is one or the number of cyclic ether groups is one. . In addition, if the number of ethylenically unsaturated groups in the specific liquid crystal compound is one, for example, the specific liquid crystal compound may be a compound having one ethylenically unsaturated group and one or more cyclic ether groups.

In the case of containing a specific liquid crystal compound having one ethylenically unsaturated group, from the viewpoints of suppressing the change in reflectance after molding and suppressing the change in color tone, it is preferable that the liquid crystal composition includes a radical polymerization initiator. The photo-radical polymerization initiator is more preferable. In the case of containing a specific liquid crystal compound having one cyclic ether group, from the viewpoints of suppressing the change in reflectance after molding and suppressing the change in color tone, it is preferable that the liquid crystal composition includes a radical polymerization initiator, including light. A radical polymerization initiator is more preferable. In addition, from the viewpoints of suppressing the change in reflectance after molding and suppressing the change in color tone, as the specific liquid crystal compound, a compound having both an ethylenic unsaturated group and a cyclic ether group is preferable, and it has one ethylenic A compound with an unsaturated group and one cyclic ether group is more preferable.

The specific liquid crystal compound may be a compound having a liquid crystal structure, and may be a rod-shaped liquid crystal compound or a disc-shaped liquid crystal compound. Among them, the rod-shaped liquid crystal compound is preferable from the viewpoints of the ease of adjustment of the pitch of the spiral structure in the cholesteric liquid crystal layer, the suppression of the reflectance change after molding, and the suppression of the color tone change.

As the rod-shaped liquid crystal compound, azomethines, azo oxides, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, phenyl cyclohexanecarboxylic acid esters, Cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, diphenylacetylenes, or alkenylcyclohexylbenzonitrile. Not only the above low-molecular liquid crystal compounds but also liquid crystal polymer compounds can be used. The above-mentioned cholesteric liquid crystal layer is preferably a layer formed by polymerizing rod-shaped liquid crystal compounds to fix the orientation. As the rod-shaped liquid crystal compound, Makromol. Chem., Vol. 190, 2255 (1989), Advanced Materials Vol. 5, 107 (1993), U.S. Patent No. 4683327, U.S. Patent No. 5622648, U.S. Patent No. 5770107 Specification, International Publication No. 95/022586, International Publication No. 95/024455, International Publication No. 97/000600, International Publication No. 98/023580, International Publication No. 98/052905, Japanese Patent Application Publication No. 1 -272551, Japanese Patent Application Publication No. 6-016616, Japanese Patent Application Publication No. 7-110469, Japanese Patent Application Publication No. 11-080081, Japanese Patent Application Publication No. 2001-328973, etc. have one ethylene Sexually unsaturated groups or those having one cyclic ether group. In addition, as the rod-shaped liquid crystal compound, for example, those described in Japanese Patent Application Publication No. 11-513019 and Japanese Patent Application Publication No. 2007-279688 have one ethylenically unsaturated group or have one cyclic ring. Ether-based.

As the discotic liquid crystal compound, for example, those described in JP 2007-108732 A or 2010-244038 have one ethylenically unsaturated group or one cyclic ether group. By.

Specifically, as the specific liquid crystal compound, the compounds shown below are preferably exemplified, and needless to say, they are not limited to these.

[化學式1]

[Chemical formula 1]

[Chemical formula 2]

[Chemical formula 3]

[Chemical formula 4]

[Chemical formula 5]

[Chemical formula 6]

[Chemical formula 7]

The above-mentioned liquid crystal composition may include one specific liquid crystal compound alone, or may include two or more specific liquid crystal compounds. The content of the specific liquid crystal compound is 25% by mass or more with respect to the total solid content of the liquid crystal composition. When it is 25% by mass or more, a decorative film for molding with little change in reflectance after molding can be obtained. In addition, from the viewpoint of suppressing the change in reflectance after molding and suppressing the change in color tone, relative to the total solid content of the liquid crystal composition, the content of the specific liquid crystal compound is preferably 30% by mass or more, and more preferably 40% by mass or more , 60% by mass or more and 99% by mass or less are more preferable, and 80% by mass or more and 98% by mass or less are particularly preferable.

-Other cholesteric liquid crystal compounds- The above-mentioned liquid crystal composition may include other cholesteric liquid crystal compounds (hereinafter, also referred to simply as "other liquid crystal compounds") in addition to the specific liquid crystal compound. As other liquid crystal compounds, 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, and A cholesteric liquid crystal compound having two or more cyclic ether groups and no ethylenically unsaturated group and a cholesteric liquid crystal compound having two or more ethylenic unsaturated groups and two or more cyclic ether groups.

Among them, from the viewpoint of suppressing change in reflectance after molding and suppressing color change, other liquid crystal compounds are selected from cholesteric liquid crystal compounds that do not have ethylenically unsaturated groups and cyclic ether groups, and have two or more ethylene groups. At least one compound in the group of a cholesteric liquid crystal compound having a cyclic ether group without a cyclic ether group and a cholesteric liquid crystal compound having two or more cyclic ether groups without an ethylenically unsaturated group is preferred , Selected from cholesteric liquid crystal compounds containing no ethylenically unsaturated groups and cyclic ether groups, cholesteric liquid crystal compounds having 2 ethylenically unsaturated groups and no cyclic ether groups, and 2 cyclic ether groups At least one compound in the group of cholesteric liquid crystal compounds without ethylenically unsaturated groups is more preferred, and is selected from the group consisting of cholesteric liquid crystal compounds without ethylenic unsaturated groups and cyclic ether groups, and those having 2 At least one compound in the group of cholesteric liquid crystal compounds having an ethylenically unsaturated group and no cyclic ether group is particularly preferred.

As other liquid crystal compounds, well-known cholesteric liquid crystal compounds can be used. As the rod-shaped liquid crystal compound among other liquid crystal compounds, Makromol. Chem., volume 190, page 2255 (1989), Advanced Materials volume 5, page 107 (1993), specification of U.S. Patent No. 4,683,327, and U.S. Patent No. Specification No. 5622648, Specification of U.S. Patent No. 5770107, International Publication No. 95/022586, International Publication No. 95/024455, International Publication No. 97/000600, International Publication No. 98/023580, International Publication No. 98/052905 , Japanese Patent Application Publication No. 1-725551, Japanese Patent Application Publication No. 6-016616, Japanese Patent Application Publication No. 7-110469, Japanese Patent Application Publication No. 11-080081, Japanese Patent Application Publication No. 2001-328973, etc. . In addition, as the rod-shaped liquid crystal compound, for example, those described in Japanese Patent Application Publication No. 11-513019 or Japanese Patent Application Publication No. 2007-279688 can be preferably used. As the discotic liquid crystal compound among other liquid crystal compounds, for example, those described in Japanese Patent Application Publication No. 2007-108732 or Japanese Patent Application Publication No. 2010-244038 can be preferably used.

The above-mentioned liquid crystal composition may include one type of other liquid crystal compound alone, or may include two or more types of other liquid crystal compounds. From the viewpoint of suppressing the change in reflectance after molding and suppressing the change in color tone, relative to the total solid content of the liquid crystal composition, the content of other liquid crystal compounds is preferably 70% by mass or less, and more preferably 60% by mass or less. Mass% or less is more preferable, and 5 mass% or less is particularly preferable. In addition, the lower limit of the content of other liquid crystal compounds is 0% by mass.

-Chiral reagents (optically active compounds)- From the viewpoint of the ease of forming the cholesteric liquid crystal layer and the ease of adjusting the pitch of the helical structure, it is preferable that the liquid crystal composition contains a chiral agent (optically active compound). The chiral reagent has the function of inducing the helical structure in the cholesteric liquid crystal layer. Regarding the chiral reagent, the twisting direction or the pitch of the helix induced by the liquid crystal compound is different, so it can be selected according to the purpose. The chiral reagent is not particularly limited, and known compounds (for example, "Handbook of Liquid Crystal Devices", Chapter 3 Item 4-3, TN (twisted nematic: twisted nematic liquid crystal), STN (Super-twisted nematic) can be used. : Super-twisted nematic liquid crystal) Chiral reagent, 199 pages, prepared by the 142nd Committee of Japan Society for the Promotion of Science, documented in 1989), isosorbide and isomannitol derivatives. Chiral reagents generally contain asymmetric carbon atoms, but axially asymmetric compounds or surface asymmetric compounds that do not contain asymmetric carbon atoms can also be used as chiral reagents. Examples of the axial asymmetric compound or the planar asymmetric compound may preferably include a binaphthyl compound, a spiro dimer compound, or a p-xylene dimer compound.

From the viewpoint of suppressing the change in reflectance after forming, as the chiral agent, it is preferable that the liquid crystal composition includes a chiral agent having a polymerizable group, including a chiral agent having a polymerizable group and a chiral agent having no polymerizable group. The chiral reagent is better. The polymerizable group is not particularly limited as long as it is a polymerizable group, but from the viewpoint of reactivity and suppression of reflectance change after molding, an ethylenically unsaturated group or a cyclic ether group is preferred. Ethylene unsaturated groups are more preferred. The preferred forms of the ethylenic unsaturated group and the cyclic ether group in the chiral reagent are the same as the preferred forms of the ethylenic unsaturated group and the cyclic ether group in the above-mentioned specific liquid crystal compound, respectively.

In addition, when the chiral reagent has an ethylenically unsaturated group or a cyclic ether group, the ethylenicity possessed by the specific liquid crystal compound in the above-mentioned liquid crystal composition from the viewpoint of reactivity and suppression of reflectance change after molding The unsaturated group or cyclic ether group and the ethylenically unsaturated group or cyclic ether group possessed by the chiral reagent are the same type of group (for example, an ethylenically unsaturated group, preferably (meth)acryloyloxy) ) Is preferable, and the same group is more preferable.

In addition, from the viewpoint of reactivity and suppression of reflectance change after forming, a chiral reagent having a polymerizable group is preferably a chiral reagent having two or more polymerizable groups, and has two or more ethylenic unsaturations. A chiral reagent with a base or a chiral reagent with more than two cyclic ether groups is more preferable, and a chiral reagent with more than two ethylenically unsaturated groups is particularly preferable. In addition, the chiral reagent may be a cholesteric liquid crystal compound.

Furthermore, as will be described later, when the cholesteric liquid crystal layer is manufactured by light irradiation to suppress the spiral pitch of the cholesteric liquid crystal layer, it includes a device that is sensitive to light and can change the spiral pitch of the cholesteric liquid crystal layer. A sex reagent (hereinafter, also referred to as a "photosensitive chiral reagent") is preferable. Photosensitive chiral reagent refers to a compound whose structure changes 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 photolysis reaction is preferred. A compound that causes a photoisomerization reaction refers to a compound that causes stereoisomerization or structural isomerization under the action of light. As a photoisomerization compound, an azobenzene compound, a spiropiperan compound, etc. are mentioned, for example. In addition, a compound that causes a photodimerization reaction refers to a compound that causes an additional reaction between two groups by light irradiation to cyclize. Examples of the photodimerization compound include cinnamic acid derivatives, coumarin derivatives, chalcone derivatives, and benzophenone derivatives. Moreover, as said light, there is no restriction|limiting in particular, Ultraviolet light, visible light, infrared light, etc. are mentioned.

As the above-mentioned photosensitive chiral reagent, a chiral reagent represented by the following formula (CH1) can be preferably used. The chiral reagent represented by the following formula (CH1) can change the orientation structure of the cholesteric liquid crystal phase such as the spiral pitch (spiral period, twist period) according to the amount of light during light irradiation.

[Chemical formula 8]

In the 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.

^{Preferably, Ar CH1} and Ar ^CH2 in formula (CH1) are independently aryl groups. ^{The aryl groups in Ar CH1} and Ar ^CH2 of formula (CH1) may have substituents, and the total carbon number is preferably 6-40, and the total carbon number is more preferably 6-30. As the substituent, for example, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a hydroxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carboxyl group, a cyano group or a heterocyclic group are more preferred. Preferably, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an acyloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group is more preferable. ^{Preferably, R CH1} and R ^CH2 in the formula (CH1) are independently hydrogen atoms.

Among them, as Ar ^CH1 and Ar ^CH2 , an aryl group represented by the following formula (CH2) or formula (CH3) is preferred.

[Chemical formula 9]

In formula (CH2) and formula (CH3), R ^CH3 and R ^CH4 each independently represent 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 hydroxyl group, and an acyl group , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, carboxyl group or cyano group, L ^CH1 and L ^CH2 each independently represent a halogen atom, an alkyl group, an alkoxy group or a hydroxyl group, nCH1 represents an integer from 0 to 4, nCH2 It represents an integer of 0-6, and * represents the bonding position with the 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 hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group or An oxy group is preferable, and an alkoxy group, a hydroxy group, or an oxy group is more preferable, and an alkoxy group is particularly preferable. ^{It is preferred that L CH1} and L ^CH2 in the formula (CH2) and the formula (CH3) are independently an alkoxy group having 1 to 10 carbon atoms or a hydroxyl group. Preferably, nCH1 in formula (CH2) is 0 or 1. Preferably, nCH2 in formula (CH3) is 0 or 1.

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

The above-mentioned liquid crystal composition may include one type of chiral reagent alone, or may include two or more types of chiral reagents.

Regarding the content of the chiral reagent, it can be appropriately selected according to the structure of the specific liquid crystal compound used or the desired pitch of the helical structure, but the ease of formation from the cholesteric liquid crystal layer, the ease of adjustment of the pitch of the helical structure, and the suppression From the viewpoint of reflectance change after molding, relative to the total solid content of the liquid crystal composition, 1% by mass or more and 20% by mass or less is preferable, and 2% by mass or more and 15% by mass or less are more preferable, and 3% by mass % Or more and 10% by mass or less are particularly preferred.

In addition, when a chiral reagent having a polymerizable group is contained as a chiral reagent, from the viewpoint of suppressing the change in reflectance after molding, it has the chirality of the polymerizable group relative to the total solid content of the liquid crystal composition. The content of the reagent 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, more preferably 1% by mass or more and 8% by mass or less, 1.5% by mass or more and 5 The mass% or less is particularly good.

In addition, when the chiral reagent contains a chiral reagent that does not have a polymerizable group, from the viewpoint of suppressing the change in reflectance after molding, the liquid crystal composition does not have a polymerizable group relative to the total solid content of the liquid crystal composition. The content of the chiral reagent 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 particularly preferably 1.5% by mass or more and 10% by mass or less.

In addition, the pitch of the cholesteric liquid crystal helical structure in the cholesteric liquid crystal layer and the selective reflection wavelength and 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 reagent. change. Although it cannot be generalized, if the content of the chiral agent in the liquid crystal composition is doubled, the pitch may become 1/2 and the center value of the selective reflection wavelength may also become 1/2.

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

In addition, when the liquid crystal composition includes a specific liquid crystal compound having one ethylenically unsaturated group, from the viewpoint of suppressing the change in reflectance after molding and suppressing the change in color tone, the liquid crystal composition includes a radical polymerization initiator. The agent is preferable, and it is more preferable to include a photoradical polymerization initiator. In addition, when the liquid crystal composition includes a specific liquid crystal compound having one cyclic ether group, from the viewpoint of suppressing the change in reflectance after molding and suppressing the change in color tone, the liquid crystal composition includes a cationic polymerization initiator. Preferably, it is more preferable to include a photocationic polymerization initiator. Moreover, as a polymerization initiator, it is preferable that the said liquid crystal composition contains only any one of a radical polymerization initiator or a cationic polymerization initiator.

As the polymerization initiator, a known polymerization initiator can be used. In addition, the polymerization initiator is preferably a photopolymerization initiator capable of starting the polymerization reaction by ultraviolet irradiation. Examples of photopolymerization initiators include α-carbonyl compounds (described in the specifications of U.S. Patent No. 2367661 and U.S. Patent No. 2367670), azoin ether compounds (described in U.S. Patent No. 2448828), and α-carbonyl compounds (described in the specifications of U.S. Patent No. 2367661 and U.S. Patent No. 2367670), Hydrocarbon-substituted aromatic azoin compounds (described in the specification of U.S. Patent No. 2722512), polynuclear quinone compounds (described in the specifications of U.S. Patent No. 3046127 and U.S. Patent No. 2951758), triarylimidazole dimer and p-aminobenzene Combinations of base ketones (described in the specification of U.S. Patent No. 3549367), acridine compounds and pheno compounds (described in Japanese Patent Laid-Open No. 60-105667 and U.S. Patent No. 4239850), oxadiazole compounds (described in the specification of U.S. Patent Instruction No. 4212970) and so on.

In addition, as the photoradical polymerization initiator, a known one can be used. As the photoradical polymerization initiator, preferably, an α-hydroxyalkylphenone compound, an α-aminoalkylphenone compound, an acylphosphine oxide compound, and the like are mentioned. Moreover, as a photocationic polymerization initiator, a well-known thing can be used. As the photocationic polymerization initiator, preferably, an iodonium salt compound, a sulfonium salt compound, and the like are mentioned.

The above-mentioned liquid crystal composition may include one type of polymerization initiator alone, or may include two or more types of polymerization initiators.

The content of the polymerization initiator can be appropriately selected according to the structure of the specific liquid crystal compound used and the desired pitch of the helical structure. From the viewpoints of the ease of formation of the cholesteric liquid crystal layer, the ease of adjusting the pitch of the helical structure, the polymerization rate, and the strength of the cholesteric liquid crystal layer, the polymerization initiator is less than the total solid content of the liquid crystal composition. The content 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, more preferably 0.1% by mass or more and 2% by mass or less, 0.2% by mass or more and 1% by mass The following is particularly good.

-Crosslinking agent- In order to improve the strength and durability of the cholesteric liquid crystal layer after curing, the liquid crystal compound may contain a crosslinking agent. As the crosslinking agent, those hardened by ultraviolet rays, heat, moisture, etc. can be preferably used.

The crosslinking agent is not particularly limited, and can be appropriately selected according to the purpose. Examples include polyfunctional acrylate compounds such as trimethylolpropane tri(meth)acrylate and neopentylerythritol tri(meth)acrylate. ; Epoxy compounds such as glycidyl (meth)acrylate and ethylene glycol diglycidyl ether; 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate], 4,4-bis(ethyleneiminocarbonylamino)diphenylmethane and other aziridine compounds; hexamethylene diisocyanate, biuret-type isocyanate and other isocyanate compounds; has an azoline group in the side chain The polyoxazoline compound; vinyl trimethoxysilane, N-(2-aminoethyl) 3-aminopropyl trimethoxysilane and other alkoxysilane compounds. In addition, a known catalyst can be used depending on the reactivity of the crosslinking agent, and not only the strength and durability of the cholesteric liquid crystal layer can be improved, but also the productivity can be improved.

The above-mentioned liquid crystal composition may include one type of crosslinking agent alone, or may include two or more types of crosslinking agents.

From the viewpoint of the strength and durability of the cholesteric liquid crystal layer, relative to the total solid content of the liquid crystal composition, the content of the crosslinking agent is preferably 1% by mass or more and 20% by mass or less, and 3% by mass or more and It is more preferably 15% by mass or less.

-Multifunctional polymerizable compound- From the viewpoint of suppressing the change 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, among the above-mentioned compounds, cholesteric liquid crystal compounds having two or more ethylenically unsaturated groups and no cyclic ether groups, and cholesteric liquid crystal compounds having two or more cyclic ether groups and no cyclic ether groups can be mentioned. Saturated cholesteric liquid crystal compounds, cholesteric liquid crystal compounds having two or more ethylenically unsaturated groups and two or more cyclic ether groups, chiral reagents having two or more polymerizable groups, and the above-mentioned crosslinking agent. Among them, as the polyfunctional polymerizable compound, the selection includes a cholesteric liquid crystal compound having two or more ethylenically unsaturated groups and no cyclic ether group, and a cholesteric liquid crystal compound having two or more cyclic ether groups and no ethylenically unsaturated group. At least one compound from the group of the cholesteric liquid crystal compound and the chiral reagent having two or more polymerizable groups is preferable, and it is more preferable to include a chiral reagent having two or more polymerizable groups.

The above-mentioned liquid crystal composition may include one type of polyfunctional polymerizable compound alone, or may include two or more types of polyfunctional polymerizable compounds. From the viewpoint of suppressing the 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, preferably 1% by mass or more, with respect to the total solid content of the liquid crystal composition. It is more preferably 50% by mass or less, more preferably 1.5% by mass or more and 20% by mass or less, and particularly preferably 2% by mass or more and 10% by mass or less.

-Other additives- If necessary, the above-mentioned liquid crystal composition may contain other additives in addition to the above. As other additives, known additives can be used, and examples include surfactants, polymerization inhibitors, antioxidants, horizontal alignment agents, ultraviolet absorbers, light stabilizers, colorants, metal oxide particles, and the like.

In addition, the above-mentioned liquid crystal composition may contain a solvent. The solvent is not particularly limited, and can be appropriately selected according to the purpose, and it is preferable to use an organic solvent. The organic solvent is not particularly limited, and can be appropriately selected according to the purpose. For example, ketones such as methyl ethyl ketone and methyl isobutyl ketone, halogenated alkanes, amides, sulfenites, heterocyclic compounds, Hydrocarbons, esters, ethers, etc. These may be used individually by 1 type, and may use 2 or more types together. Among these, ketones are particularly preferable when considering the load on the environment. In addition, the above-mentioned components can function as a solvent.

The content of the solvent in the liquid crystal composition is not particularly limited, and it may be adjusted to the content of the solvent that can obtain the desired coatability. The content of the solid content relative to the total mass of the liquid crystal composition is not particularly limited, but 1% by mass to 90% by mass is preferable, 5% by mass to 80% by mass is more preferable, and 10% by mass to 80% by mass is particularly preferable. Relative to the total solid content of the liquid crystal composition, the content of the solvent of the liquid crystal composition during curing when the cholesteric liquid crystal layer is formed is preferably 5% by mass or less, more preferably 3% by mass or less, and 2% by mass The following are more preferable, and 1% by mass or less is particularly preferable. In addition, relative to the total mass of the cholesteric liquid crystal layer, the content of the solvent in the cholesteric liquid crystal layer formed by curing the liquid crystal composition is preferably 5% by mass or less, more preferably 3% by mass or less, 2 mass % Or less is more preferable, and 1 mass% or less is particularly preferable.

-Coating and curing of liquid crystal composition- Regarding the coating of the above-mentioned liquid crystal composition, it can be carried out by a suitable method such as roll coating, gravure printing, spin coating, etc., making the liquid crystal composition into a solution state with a solvent or forming a molten liquid by heating. Thing. In addition, it can be performed by various methods such as a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method. Furthermore, it is also possible to use an inkjet device to eject the above-mentioned liquid crystal composition from a nozzle to form a coating film.

After that, the cholesteric liquid crystal layer is formed by curing the liquid crystal composition. Through the curing, the alignment state of the molecules of the liquid crystal compound including the specific liquid crystal compound is maintained and fixed. Curing is preferably carried out by the polymerization reaction of polymerizable groups such as ethylenically unsaturated groups or cyclic ether groups possessed by the liquid crystal compound. In the case of using the above-mentioned solvent, it is preferable to dry the coating film by a known method after applying the above-mentioned liquid crystal composition and before the polymerization reaction for curing. For example, it can be dried by standing, or it can be dried by heating. After coating and drying the liquid crystal composition, the liquid crystal compound in the liquid crystal composition may be aligned.

-Selective reflectivity of cholesteric liquid crystal layer- The above-mentioned cholesteric liquid crystal layer preferably has selective reflectivity in a specific wavelength region. In this specification, selecting the reflection wavelength means that when the minimum value of the transmittance of the object (component) is set to Tmin (%), the half-value transmittance expressed by the following formula is displayed: T1/2 (%) The average value of 2 wavelengths. Selective reflectivity means that it has a specific wavelength region that satisfies the selective reflection wavelength. Calculate the half value transmittance formula: T1/2=100-(100-Tmin)÷2

The selective reflection wavelength in the cholesteric liquid crystal layer is not particularly limited, and can be set in any range of visible light (380 nm to 780 nm) and near-infrared light (over 780 nm and 2,000 nm or less), for example. Among them, it is preferable that the above-mentioned cholesteric liquid crystal layer has selective reflectivity in at least a part of the wavelength region of a wavelength of 380 nm to 1,200 nm.

-Layer structure of cholesteric liquid crystal layer- From the viewpoint of suppressing changes in reflectance after molding, the decorative film of the present disclosure preferably has two or more cholesteric liquid crystal layers. In addition, each cholesteric liquid crystal layer having two or more layers may be layers with the same composition or different layers. In the case where the decorative film of the present disclosure has two or more cholesteric liquid crystal layers, the decorative film of the present disclosure may have at least one layer formed by curing the liquid crystal composition. The total solid content contains 25% by mass or more of a cholesteric liquid crystal compound with one ethylenically unsaturated group or one cyclic ether group. From the viewpoint of suppressing changes in reflectance after molding, a cholesteric liquid crystal compound with two or more layers The liquid crystal layer is preferably a layer formed by hardening the liquid crystal composition, and the aforementioned liquid crystal composition contains 25% by mass or more with respect to the total solid content of the liquid crystal composition. It has one ethylenically unsaturated group or has one ring. Ether-based cholesteric liquid crystal compound.

When the decorative film of the present disclosure has two or more cholesteric liquid crystal layers, two or more cholesteric liquid crystal layers can be laminated together, and two or more cholesteric liquid crystal layers can also be laminated through other layers. In addition, the decoration (for example, a decorative molding film) that uses the decorative film of the present disclosure to form a decorative layer may be in the form of two or more cholesteric liquid crystal layers on one area of the substrate, or may be provided with two or more cholesteric liquid crystal layers on both sides of the substrate. The form of one or more cholesteric liquid crystal layers. It is also possible to attach two or more base materials for forming a decoration layer using the decoration film of the present disclosure to form a decoration having two or more cholesteric liquid crystal layers.

-Orientation layer- The decorative film of the present disclosure may have an alignment layer connected to the above-mentioned cholesteric liquid crystal layer. When forming a layer containing a liquid crystal compound, the alignment layer is used to orient the molecules of the liquid crystal compound in the composition for liquid crystal layer production. In the decorative film, an orientation layer may or may not be included.

The alignment layer can be provided by methods such as rubbing treatment of an organic compound (preferably a polymer), oblique deposition of inorganic compounds such as SiO, or formation of a layer with microgrooves. In addition, there is also known an alignment layer that generates an alignment function by application of an electric field, application of a magnetic field, or light irradiation.

According to the material of the bottom layer of the cholesteric liquid crystal layer, even if the alignment layer is not provided, it is possible to perform the function of the alignment layer by directly performing the alignment treatment (for example, rubbing treatment) on the bottom layer. Moreover, in the case where a liquid crystal layer is further laminated directly on the liquid crystal layer, there are cases where the liquid crystal layer of the bottom layer can be used as an alignment layer to be able to orient the liquid crystal compound used in the production of the upper layer. In this case, even if an alignment layer is not provided, or a special alignment treatment (for example, a rubbing treatment) is not performed, the liquid crystal compound in the upper layer can be aligned. Hereinafter, as a preferable example, the rubbing treatment alignment layer and the photo alignment layer used when rubbing the surface are described.

～Orientation layer of rubbing treatment～ The rubbing treatment orientation layer is an orientation layer imparted with orientation by rubbing treatment. Examples of polymers that can be used for the rubbing treatment of the alignment layer include, for example, methacrylate copolymers, styrene copolymers, polyolefins, polyvinyl alcohol, and modifications described in paragraph 0022 of Japanese Patent Application Laid-Open No. 8-338913 Polyvinyl alcohol, poly(N-methylol acrylamide), polyester, polyimide, vinyl ester copolymer, carboxymethyl cellulose, polycarbonate resin, etc. The silane coupling agent can be used as the polymer. As a polymer that can be used for the rubbing treatment of the alignment layer, water-soluble polymers (such as poly(N-methylol acrylamide), carboxymethyl cellulose, gelatin, polyvinyl alcohol, modified polyvinyl alcohol) are more suitable Preferably, gelatin, polyvinyl alcohol or modified polyvinyl alcohol is more preferable, and polyvinyl alcohol or modified polyvinyl alcohol is particularly preferable.

In the method of aligning the liquid crystal compound using the rubbing treatment alignment layer, for example, a composition for forming a cholesteric liquid crystal layer is applied to the rubbing treatment surface of the rubbing treatment alignment layer to align the molecules of the liquid crystal compound. After that, as needed, the cholesteric liquid crystal layer is formed by reacting the alignment layer polymer with the polyfunctional monomer contained in the cholesteric liquid crystal layer, or crosslinking the alignment layer polymer with a crosslinking agent. The film thickness of the alignment layer is preferably in the range of 0.1 μm to 10 μm.

～Friction treatment～ The surface of the alignment layer, support or other layer coated with the composition for forming a cholesteric liquid crystal layer may be rubbed as needed. The rubbing treatment can generally be performed by rubbing the surface of the polymer-based film with paper or cloth in a certain direction. The general method of rubbing treatment is described in "Liquid Crystal Handbook" (issued by Maruzen Publishing Co., Ltd., October 30, 2000), for example.

As a method of changing the friction density, the method described in "Liquid Crystal Handbook" (issued by Maruzen Publishing Co., Ltd.) can be used. The friction 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 circumference ratio, r is the radius of the roller, n is the rotation speed of the roller (rpm: revolutions per minute), and v is the moving speed of the stage ( Seconds).

In order to increase the friction density, increase the number of frictions, increase the contact length of the friction roller, increase the radius of the roller, increase the rotation speed of the roller or slow down the moving speed of the stage. On the other hand, in order to reduce the friction density, do the opposite. can. In addition, as the conditions at the time of the rubbing treatment, reference can also be made to the description in Patent No. 4052558.

～Light alignment layer～ The photo-alignment layer is an alignment layer that imparts orientation by light irradiation. As a photo-alignment material used in the photo-alignment layer, it is described in many documents and the like. For example, as the photo-alignment material, Japanese Patent Application Publication No. 2006-285197, Japanese Patent Application Publication No. 2007-076839, Japanese Patent Application Publication No. 2007-138138, Japanese Patent Application Publication No. 2007-094071, Japanese Patent Application Publication No. 2007 -121721, JP 2007-140465, JP 2007-156439, JP 2007-133184, JP 2009-109831, Patent No. 3883848, Patent No. 4151746 Azo compound described in Japanese Patent Publication No. 2002-229039, aromatic ester compound described in Japanese Patent Application Publication No. 2002-229039, Japanese Patent Application Publication No. 2002-265541, Japanese Patent Application Publication No. 2002-317013 having photo-orientation unit The maleimide and/or alkenyl-substituted naphthalene diimide compound, the photocrosslinkable silane derivative described in Patent No. 4205195 and Patent No. 4205198, Japanese Special Publication No. 2003-520878 The photocrosslinkable polyimide, polyamide, or ester described in the gazette, Japanese Patent Publication No. 2004-529220, and Patent No. 4162850 are preferred examples. Azo compounds, photocrosslinkable polyimines, polyamides or esters are particularly preferred.

For example, linearly polarized light irradiation or non-polarized light irradiation is performed on a layer formed of the above-mentioned material to produce a photo-alignment layer. In the present disclosure, "linearly polarized light irradiation" refers to an operation used to cause a photoreaction on a photo-alignment material. The wavelength of the light used varies according to the photo-alignment material used, and it is not particularly limited as long as it is a wavelength required for its photoreaction. It is preferable that the peak wavelength of light used in the light irradiation is 200 nm to 700 nm, and it is more preferable that the peak wavelength of light is ultraviolet light having a peak wavelength of 400 nm or less.

Regarding light sources used for light irradiation, commonly used light sources can include lamps such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury xenon lamps and carbon arc lamps, and various lasers (such as semiconductor lasers, helium neon lasers) Laser, argon ion laser, helium-cadmium laser, YAG laser), light-emitting diode, cathode ray tube, etc.

As a method of obtaining linearly polarized light, a method using a polarizing plate (such as an iodine polarizing plate, a two-color pigment polarizing plate, a wire grid polarizing plate), a method using a prism element (such as a Glan Thomson prism) and a Brewster angle can be used The reflective polarizer method or the method using light emitted from a polarized laser light source. In addition, it is possible to selectively irradiate only light of a desired wavelength by using a filter, a wavelength conversion element, and the like.

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

〔Resin layer〕 In order to impart transferability and adhesiveness to the transparent frame, the decorative film of the present disclosure may further have a resin layer on the cholesteric liquid crystal layer. One of the preferable forms of the decorative film of the present disclosure is a form in which a resin layer is further provided on the side opposite to the side having the pseudo support. One embodiment of the resin layer may be an adhesive layer described later.

As an embodiment of the resin layer, from the viewpoint of visibility, a transparent resin layer is preferable, and a layer composed of a transparent film is more preferable. The transparent film is not particularly limited as long as it has the required strength and scratch resistance. In the present disclosure, the "transparent" in the transparent film means that the total light transmittance is above 85%. The total light transmittance of the transparent film can be measured by the same method as the total light transmittance of the pseudo support described above.

Regarding the transparent film, a film obtained by forming a transparent resin into a film is preferred. Specifically, it includes polyethylene terephthalate (PET) resin, polyethylene naphthalate (PEN) resin, Resin film of acrylic resin, polycarbonate (PC) resin, triacetyl cellulose (TAC), cycloolefin polymer (COP) and other resins. In particular, from the viewpoint of shape followability with respect to the mold, 60% by mass or more (more preferably 80% by mass or more, and even more preferably 100% by mass) acrylic acid is contained relative to the total resin components contained in the transparent film A resin film of resin, polycarbonate resin or polyethylene terephthalate resin is preferable. In particular, a resin film containing 60% by mass or more (more preferably 80% by mass or more, and still more preferably 100% by mass) relative to the total resin components contained in the transparent film is more preferable.

In addition, when the resin layer is composed of a transparent film, the thickness of the resin layer is not particularly limited, but is preferably 20 μm to 350 μm, more preferably 50 μm to 300 μm, and more preferably 75 μm to 250 μm.

As the transparent film, commercially available products can be used. Examples of commercially available products include ACRYPLEN (registered trademark) HBS010 (acrylic resin film, manufactured by Mitsubishi Chemical Asia Pacific Pte. Ltd.), TECHNOLLOY (registered trademark) S001G (acrylic resin) Film, manufactured by Sumitomo Chemical Co., Ltd.), C000 (polycarbonate resin film, manufactured by Sumitomo Chemical Co., Ltd.), C001 (acrylic resin/polycarbonate resin laminated film, manufactured by Sumitomo Chemical Co., Ltd. )Wait.

-Formation of resin layer- The method of forming the resin layer using a transparent film is not particularly limited. For example, a method of laminating a transparent film on a cholesteric liquid crystal layer can preferably be cited. As an apparatus used when laminating transparent films, known laminators such as laminators, vacuum laminators, and automatic cutting laminators that can further improve productivity can be used. The laminator is provided with any roller that can be heated, such as a rubber roller, and one that can be pressurized and heated is preferable. By the heating of the laminator, at least one of the transparent film and the cholesteric liquid crystal layer is melted, so that the adhesion between the cholesteric liquid crystal layer and the transparent film can be further improved.

The temperature when laminating the transparent film can be determined according to the material of the transparent film and the melting temperature of the cholesteric liquid crystal layer. Regarding the temperature of the transparent film, it can be set to a temperature of 60°C to 150°C. It can be set to 65°C. The temperature of ～130℃ is more preferable, and the temperature of 70℃～100℃ is especially preferable.

In addition, when laminating a transparent film, it is better to apply a linear pressure of 60N/cm to 200N/cm between the transparent film and the cholesteric liquid crystal layer, and it is more preferable to apply a linear pressure of 70N/cm to 160N/cm, and apply 80N/cm. ~120N/cm line pressure is particularly good.

＜Adhesive layer＞ From the standpoint of the peelability of the pseudo support and the adhesion to the frame to which the decorative film is attached, the decorative film of the present disclosure preferably has an adhesive layer. The subsequent layer is a layer included as an embodiment of the resin layer.

After attaching the decorative film to the frame, the dummy support can be peeled off, so it is better to provide an adhesive layer on the side opposite to the dummy support of the cholesteric liquid crystal layer. That is, one of the preferred forms of the decorative film of the present disclosure is to have a pseudo support, a colored layer, a cholesteric liquid crystal layer, and an adhesive layer.

Also, as described later, the dummy support may be peeled off before attaching to the substrate (film base material, transparent frame, etc.), and the outermost layer on the cholesteric liquid crystal layer side of the decorative film from which the dummy support has been peeled After the adhesive layer is formed on it, it is attached to the base material.

The material of the adhesive layer is not particularly limited, and can be appropriately selected according to the purpose. For example, a layer including a well-known adhesive or adhesive can be mentioned.

The decorative film of the present disclosure is preferably laminated with a pseudo support, a colored layer, a cholesteric liquid crystal layer, and an adhesive layer in sequence. By adopting the above sequence, when the transparent frame is attached to the decorative film, the colored layer can be visually recognized from the transparent frame side through the cholesteric liquid crystal layer, and the pseudo support can be peeled off after attaching the decorative film to the transparent frame.

-Adhesive- Examples of adhesives include acrylic adhesives, rubber-based adhesives, and silicone-based adhesives. Also, examples of adhesives include acrylic adhesives described in "Release paper, release film and adhesive tape characteristics and its control technology", Information Agency, 2004, Chapter 2", and ultraviolet (UV) Hardening adhesives, silicone adhesives, etc. Furthermore, acrylic adhesives refer to adhesives containing (meth)acrylic monomer polymers ((meth)acrylic polymers). When an adhesive is included, an adhesive imparting agent may also be included.

-Adhesive- Examples of adhesives include urethane resin adhesives, polyester adhesives, acrylic resin adhesives, ethylene vinyl acetate resin adhesives, polyvinyl alcohol adhesives, polyamide adhesives, silicone adhesives, and the like. From the viewpoint of higher bonding strength, a urethane resin adhesive or a silicone adhesive is preferable.

When the decorative film of the present disclosure has an adhesive layer, the relationship between the thickness of the colored layer (T2), the thickness of the cholesteric liquid crystal layer (T3), and the thickness of the adhesive layer (T4) satisfies T4<10 (T2+T3) as Better. By satisfying the above relationship, it is possible to obtain a thin decorative film with excellent gloss and visibility when visually recognized through a transparent frame. Regarding the relationship between T2, T3, and T4, T4<8 (T2+T3) is more preferable, T4<5 (T2+T3) is more preferable, and T4<3 (T2+T3) is particularly preferable.

-Method of forming adhesive layer- The method of forming the adhesive layer is not particularly limited. As a method of forming the adhesive layer, for example, a method of laminating a protective film with an adhesive layer in such a way that the adhesive layer is in contact with the cholesteric liquid crystal layer, and laminating an adhesive layer so as to be in contact with the cholesteric liquid crystal layer alone. The method, the method of coating the composition containing the above-mentioned adhesive or adhesive on the cholesteric liquid crystal layer, etc. The laminating method or coating method preferably includes the same method as the laminating method of the transparent film or the coating method of the composition for forming a colored layer.

As the thickness of the adhesive layer in the decorative film, from the standpoint of having both adhesion and handleability, 2μm-40μm is preferred, 3μm-25μm is more preferred, 4μm-20μm is more preferred, and 4μm-15μm is particularly preferred .

[Other layers] The decorative film of the present disclosure may have other layers besides the above. As other layers, a reflective layer, a self-repairing layer, an antistatic layer, an antifouling layer, an electromagnetic wave preventing layer, a conductive layer, etc., which are well-known layers in a decorative film can be mentioned. The other layers in the decorative film of the present disclosure can be formed by known methods. For example, a method in which a composition containing components contained in the layers (layer forming composition) is applied in a layer form and dried.

-Cover film- For the purpose of preventing pollution and the like, the decorative film of the present disclosure can be used as a cover film (that is, a protective film) on the outermost side of one side having a colored layer and cholesteric liquid crystal based on a pseudo support. As the cover film, it has flexibility and is not particularly limited as long as it is a material with good releasability, and resin films such as polyethylene films can be mentioned. The method of attaching the cover film is not particularly limited, and a known attaching method may be mentioned. For example, a method of laminating the cover film on the target surface (for example, the surface of the cholesteric liquid crystal layer or the adhesive layer) may be mentioned.

(decorations) The decoration of the present disclosure is a decoration that uses the decoration film of the present disclosure to decorate an article, and the decoration obtained by the decoration method of the present disclosure described later is preferred. The decoration of the present disclosure includes a decoration molded body. That is, the decorative object of the present disclosure is a molded body that uses the decorative film of the present disclosure to decorate a substrate. The decorative molded body of the present disclosure also includes a form before peeling off the pseudo support of the decorative film of the present disclosure. The decorative formed body may be a formed body obtained by using the decorative film of the present disclosure, or may also be a formed body obtained by using the decorative formed film obtained by using the decorative film of the present disclosure.

The decoration of the present disclosure can be used to affix a transparent frame with a thickness of 0.5 mm or more on the side opposite to the side of the pseudo support having the decorative film of the present disclosure, and the transparent frame is separated from the side of the transparent body. The cholesteric liquid crystal layer visually recognizes the decorative panel of the colored layer.

As a transparent frame, what is necessary is just to have transparency which can visually recognize the colored layer through the cholesteric liquid crystal layer. As the main component of the transparent frame, a resin material, glass, etc. may be mentioned, and from the viewpoint of durability, glass is preferred. Among them, the main component of the transparent frame refers to a component that displays 50% by mass or more of the components constituting the transparent frame. Furthermore, it is preferable that the transparent frame has a three-dimensional shape. The size of the transparent frame can be appropriately determined according to the purpose. From the viewpoint of durability, a transparent frame system having a thickness of 0.5 mm or more is also preferable. The upper limit of the thickness can be appropriately determined according to the purpose, and can be set to 2 mm, for example.

(Decorative molding film) The decorative film of the present disclosure is a decorative molding film that has a substrate, a colored layer, and a cholesteric liquid crystal layer, and is used to visually recognize the colored layer through the cholesteric liquid crystal layer. The decorative forming film of the present disclosure includes a form before peeling off the pseudo support of the decorative film of the present disclosure. The colored layer and the cholesteric liquid crystal layer in the decorative forming film of the present disclosure are the same as the colored layer and the cholesteric liquid crystal layer in the decorative film of the present disclosure, and the preferred forms are also the same. In addition, the preferred form of the other layers is also the same.

The base film base material in the decorative molding film of the present disclosure is preferred. In addition, the base material in the decorative molded film of the present disclosure is preferably a base material for molding. As the base material, it is the same as the base material described later, and the preferred form is also the same. In addition, for the manufacturing method of the decorative molded film of the present disclosure, reference can be made to the method of attaching to the substrate in the decoration method of the present disclosure described later.

(Decoration method) The decoration method of the present disclosure is not particularly limited as long as it is a decoration method using the decoration film of the present disclosure, but includes the process of attaching the decoration film to the object to be decorated from the cholesteric liquid crystal layer side and peeling off the decoration film of the present disclosure The manufacturing process of the pseudo support is better. Furthermore, it is more preferable that the decorative object is a transparent frame.

-The process of attaching the decorative film to the decorative object from the side of the cholesteric liquid crystal layer- The decoration method of the present disclosure includes a process of attaching a decoration film to a decoration object from the side of the cholesteric liquid crystal layer. The method of sticking to a decorative object (for example, a transparent frame) is not particularly limited, and the method in the method of manufacturing a decorative molded body described later can be referred to.

-The process of peeling off the pseudo support- The decoration method of the present disclosure preferably includes a process of peeling the above-mentioned pseudo support from the decoration film of the present disclosure. It does not specifically limit as a peeling method, What is necessary is just to peel by a well-known method. For example, a method of holding a part of the dummy support using a base material such as fingers or pliers and peeling it off can be cited.

When using the decorative film to manufacture the decorative panel of one embodiment of the decorative object, at least have a transparent frame (preferably having a thickness of 0.5 mm or more) on the side opposite to the side of the pseudo support having the decorative film After the thickness of the transparent frame), the process of peeling off the dummy support is better. From the viewpoints of film followability and prevention of peeling over time due to residual stress, the process of laminating the transparent frame having a thickness of 0.5 mm or more is preferably a thermoforming process at 60° C. or more.

Here, an example of the layer structure of the decorative film will be described using FIG. 1. FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of the decorative film of the present disclosure. The decoration film 20 has a colored layer 24 on the pseudo support 22, an alignment layer 26 on the colored layer 24, a cholesteric liquid crystal layer 28 on the alignment layer 26, and an adhesive layer 30 on the cholesteric liquid crystal layer 28. In addition, although illustration is omitted, the above-mentioned peeling layer may be provided between the dummy support 22 and the colored layer 24.

2 is a schematic cross-sectional view showing another example of the decorative molded body (before peeling off the dummy support) of the present disclosure. The decorative molded body 50 has a colored layer 24 on the pseudo support 22, an alignment layer 26 on the colored layer 24, a cholesteric liquid crystal layer 28 on the alignment layer 26, and an adhesive layer 30 on the cholesteric liquid crystal layer 28, and A transparent frame 40 is provided on the adhesive layer 30.

3 is a schematic cross-sectional view showing an example of the decorative molded body (after peeling off the dummy support) of the present disclosure. The decorative molded body 60 has a colored layer 24, an alignment layer 26 on the colored layer 24, a cholesteric liquid crystal layer 28 on the alignment layer 26, an adhesive layer 30 on the cholesteric liquid crystal layer 28, and an adhesive layer 30 on the adhesive layer 30 Transparent frame 40.

(Method of manufacturing decorative molded body and decorative molded body) The manufacturing method of the decorative molded body of the present disclosure is not particularly limited, as long as it is a method of manufacturing a decorative molded body by using the decorative film of the present disclosure for decoration and molding. It is preferable to include a process of forming the decorative film of the present disclosure and a process of peeling off the pseudo support after forming.

The decorative forming system of the present disclosure uses the decorative film of the present disclosure or the decorative forming film of the present disclosure to obtain a decorative formed body, preferably manufactured by the manufacturing method of the decorative forming body of the present disclosure. Since the decorative film of the present disclosure is also excellent in three-dimensional formability, it can be preferably used in the manufacture of decorative molded bodies, for example, when a decorative molded body is manufactured by at least one molding selected from the group consisting of three-dimensional molding and embedded molding Especially good.

In addition, it is also possible to use the decorative film of the present disclosure as a decorative molded body by attaching the decorative film of the present disclosure to a molded body after molding. When a decorative molded body is produced, by using the decorative film of the present disclosure, it can also be applied to molds of more complicated shapes and smaller shapes, so that the application of the decorative molded body can be broadened. Hereinafter, an example of embedding molding will be given, and a method of manufacturing a decorative molded body will be described in detail.

In the embedded molding, the decorative molded body is obtained by, for example, pre-arranging a decorative molding film in a mold and injecting a molding base resin into the mold. By this embedding molding, a decorative molded body of a decorative film integrated on the surface of the resin molded body can be obtained.

Examples of resins that can be used as base resins (that is, resins constituting the resin molded body) include acrylic resins, silicone resins, polyester resins, urethane resins, and olefin resins.

In addition, when the decorative molded body is produced, an adhesive layer may be provided between the decorative molded film and the resin molded body. As an adhesive agent for forming an adhesive agent layer, a well-known adhesive agent can be selected suitably. Specifically, for example, an adhesive containing a vinyl chloride/vinyl ester copolymer and an acrylic resin can be mentioned. A commercially available product can be used as the adhesive, and examples of the commercially available product include IMB-003 of Teikoku Printing Inks Mfg. Co., Ltd. and the like.

Hereinafter, an embodiment of a method of manufacturing a decorative molded body by embedding molding will be described. The manufacturing method of the decorative molded body includes a process of arranging a decorative molded film of a certain size into a quadrangular shape in an injection molding mold and closing the mold, a process of injecting a molten resin into the mold, and a process of further curing the injected resin and then taking it out. .

The injection molding mold (ie, forming mold) used in the manufacture of decorative molded bodies has a mold with a convex shape (ie, a convex mold) and a mold with a concave shape corresponding to the convex shape (ie, a concave mold), and it becomes A decorative molding film is placed on the molding surface of the inner peripheral surface of the concave mold, and then the mold is closed.

Among them, it is also possible to shape the decorative molding film (pre-forming) by using the molding die before arranging the decorative molding film in the molding die, to give the decorative molding film a three-dimensional shape in advance, and to supply the decorative molding film to the molding die. In addition, when the decorative film is placed in the molding die, it is necessary to align the decorative molding film with the molding die in a state where the decorative molding film is inserted into the molding die.

As a method of aligning the decorative molding film with the molding die while inserting the decorative molding film into the molding die, there is a method of inserting and holding the fixing pin of the male die into the positioning hole of the female die. Among them, the alignment hole is pre-formed with the end of the decorative molded film in the concave mold (the position where the three-dimensional shape is not given after the molding).

In addition, in the punch, a fixing pin is formed in advance at a position to be fitted with the alignment hole. In addition, as a method of aligning the decorative molding film with the molding die while inserting the decorative molding film into the molding die, in addition to the method of inserting a fixing pin into the alignment hole, the following methods can be used.

For example, it is possible to exemplify a method in which an alignment mark is provided in advance to a position in a decorative molded film that is not provided with a three-dimensional shape after molding, and the decorative molded film is driven by a conveyer side to perform fine adjustment and alignment. In the case of this method, when viewed from the product part of the injection molded product (decorative molded product), it is better to recognize the alignment mark at two or more diagonal corners.

After aligning the decorative molding film and the molding die and closing the molding die, the molten resin is injected into the molding die into which the decorative molding film is inserted. At the time of injection, the molten resin is injected to the molding substrate side of the decorative molded film.

The temperature of the molten resin injected into the mold is set according to the physical properties of the resin used. For example, if the resin to be used is an acrylic resin, the temperature of the molten resin is preferably within a range of 240°C or higher and 260°C or lower.

Furthermore, in order to suppress abnormal deformation of the decorative molded film due to heat or gas generated when the molten resin is injected into the molding die, the injection port (injection port) of the punch can be set according to the shape of the molding die or the type of molten resin. Exit). After the molten resin injected into the molding die inserted with the decorative molding film is solidified, the molding die is opened, and the molding die is taken out from the molding die. The solidified molten resin, that is, the molding base material is solidified with the decorative molding film in the middle of the decorative molding. body.

The intermediate decorative molded body is integrated with the dummy part of the decorative molded body around the decorative part of the final product (decorative molded body). Wherein, the dummy part has a through hole formed by inserting the fixing pin when the above-mentioned positioning is performed. Therefore, it is possible to obtain a decorative molded body by performing a finishing process that removes the above-mentioned burrs and dummy parts from the decorative part in the intermediate decorative molded body before finishing.

The decorative molded body obtained as described above can be exposed to increase the degree of hardening of the colored layer in the decorative film. By performing this exposure, the adhesion between the colored layer and the cholesteric liquid crystal layer and between the cholesteric liquid crystal layer and the decorative molded body is further improved, and the durability against heat and the like is further improved.

In addition, as the above-mentioned molding, three-dimensional molding can also be preferably given. Three-dimensional forming can preferably include thermoforming, vacuum forming, pressure forming, and vacuum pressure forming. The method of vacuum forming is not particularly limited, but a method of three-dimensional forming in a heated state under vacuum is preferred. Vacuum refers to the state where the room is evacuated and set to a vacuum degree of 100 Pa or less. The temperature during three-dimensional molding may be appropriately set according to the molding substrate used, and a temperature range of 60°C or higher is preferred, a temperature range of 80°C or higher is more preferred, and a temperature range of 100°C or higher is even more preferred. The upper limit of the temperature during the three-dimensional molding is preferably 200°C. The temperature during three-dimensional molding refers to the temperature of the molding substrate used for three-dimensional molding, and is measured by attaching a thermocouple to the surface of the molding substrate.

The above-mentioned vacuum forming can be performed using a vacuum forming technique widely known in the forming field. For example, Formech508FS manufactured by Nihon Seizuki Kogyo Co., Ltd. can be used for vacuum forming.

＜Use＞ The use of the decorative molded body obtained as described above is not particularly limited, and the decorative molded body can be used for various articles. As the application of the decorative panel including the decorative molded body or the decorative molded body, for example, the interior/exterior decoration of electronic devices (such as wearable devices and smartphones), the interior/exterior decoration of automobiles, and the interior/exterior decoration of electrical products are particularly preferred. External decoration, packaging containers, etc. [Example]

Examples are given below to further illustrate the present disclosure in detail. The scope of the present disclosure is not limited to the specific examples shown below. In addition, unless otherwise specified, "parts" are the basis of quality.

(Example 1) ＜Preparation of pseudo support 1＞ As the pseudo support 1, a PET film with a peeling layer (Unipeel TR-6, thickness 50 μm, A4 size, manufactured by UNITIKA LTD.) was prepared.

<Preparation of black pigment dispersion> Carbon black, a dispersant, a polymer, and a solvent were mixed so as to have the following composition of the black pigment dispersion, and a three-roll mill and a bead mill were used to obtain a black pigment dispersion. Furthermore, the average particle size measured using MICROTRAC FRA (Honeywell Japan Ltd.) was 163 nm.

-The composition of the black pigment dispersion- ･Resin-coated carbon black produced in accordance with the description in paragraphs 0036 to 0042 of Patent No. 5320652: 20.0% by mass ･Dispersant 1 (the following structure): 1.0% by mass ･Polymer (random copolymer of benzyl methacrylate/methacrylic acid = 72/28 mole ratio, weight average molecular weight 30,000): 6.0% by mass ･Propylene glycol monomethyl ether acetate: 73.0% by mass

[Chemical formula 10]

<Composition of Coating Liquid 1 for Colored Layer Formation> ･Black pigment dispersion: 30 parts by mass ･Polymerizable compound 1: manufactured by Sartomer Japan Inc., urethane acrylate oligomer, CN-996NS: 25 parts by mass Binder resin 3: Urethane modified propylene polymer (containing polyol) 35% by mass ethyl acetate/ethyl methyl ketone/isopropanol solution: 25 parts by mass ･Photopolymerization initiator (Irgacure 2959, manufactured by BASF Corporation): 1.0 part by mass ･Methyl ethyl ketone: 19 parts by mass

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

<Formation of Orientation Layer 1> The coating liquid 1 for forming an alignment layer was coated on the colored layer 1 using a wire bar coater. After that, it was dried at 100° C. for 120 seconds to form an alignment layer 1 with a layer thickness of 0.5 μm.

[Composition of the coating solution for forming the alignment layer 1] ･Modified polyvinyl alcohol shown below: 28 parts by mass ･Citrate (AS3, manufactured by Sankyo Kagaku Yakuhin Co., Ltd.): 1.2 parts by mass ･Photopolymerization initiator (Irgacure 2959, manufactured by BASF Corporation): 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 numbers on the lower right of the following compounds and each structural unit indicate molar ratio. Weight average molecular weight: 12000)

[Chemical formula 11]

<Formation of cholesteric liquid crystal layer 1> With respect to the orientation layer 1 produced above, rubbing treatment was performed in the direction of 31.5° counterclockwise rotation based on the short side direction of the PET film (A4 size) (rayon cloth, pressure: 0.1kgf (0.98N)) , Rotation speed: 1,000rpm (revolutions per minute: rotation speed per minute), transmission speed: 10m/min, frequency: 1 round trip).

The components of the coating liquid 1 for forming a cholesteric liquid crystal layer as shown below were stirred and dissolved in a container kept at 25° C. to prepare a coating liquid 1 for forming a cholesteric liquid crystal layer (liquid crystal composition 1).

[Composition of coating solution 1 for forming cholesteric liquid crystal layer] Methyl ethyl ketone: 150.6 parts Liquid crystal compound 1 (rod-shaped liquid crystal compound): 92 parts Photopolymerization initiator A (IRGACURE 907, manufactured by BASF Corporation): 0.50 parts Chiral Reagent A: 4.00 copies Chiral Reagent B: 4.00 copies The following surfactant F1: 0.027 parts

Liquid crystal compound 1 (monofunctional): rod-shaped liquid crystal compound. In addition, in the case of radical polymerization, even if it has an oxetanyl group (cationically polymerizable functional group), since it has only one acryloxy group (radical polymerizable group), it is defined as monofunctional. The same is true for cationic polymerization.

[Chemical formula 12]

Chiral Reagent A (2-functional): the following compounds

[Chemical formula 13]

Chiral reagent B (0 function): the following compound. In addition, in the following compounds, Bu represents n-butyl.

[Chemical formula 14]

Surfactant F1: the following compounds

[Chemical formula 15]

Coating liquid 1 for forming a cholesteric liquid crystal layer prepared by using a wire bar coater on the surface of the rubbed alignment layer 1 was dried at 85°C for 120 seconds, and then compared to the formed build-up layer The entire surface of the cholesteric liquid crystal layer of the body was exposed to an exposure amount of 70 mJ/cm ² (i-ray) to form a cholesteric liquid crystal layer 1 with a thickness of 1.4 μm.

<Formation of Adhesive Layer 1> By coating the cholesteric liquid crystal layer 1 with an acrylic adhesive liquid (SK-Dyne SG-50Y, manufactured by Soken Chemical & Engineering Co., Ltd.) using a comma coater, and drying it at 120°C for 2 minutes, The adhesive layer 1 with a layer thickness of 10 μm was formed. Through the above, a laminate 1 (that is, a decorative film) having a dummy support 1, a colored layer 1, an alignment layer 1, a cholesteric liquid crystal layer 1, and an adhesive layer 1 in this order was produced.

＜Forming processing＞ For the laminated body 1, a transparent frame 100 (formed body base material, thickness 0.5 mm) having the cross-sectional shape shown in FIG. 4A and the upper surface shape shown in FIG. 4B is used as a mold, and is like the adhesive layer of the laminated body 1. Press molding (TOM molding) is performed as if one surface is in contact with the surface of the mold on one side having the concave portion to be molded. In the press forming process, a TOM forming machine NGF-0510-R (manufactured by Fu-se Vacuum Forming Ltd.) is used, the forming temperature is 120°C, and the elongation ratio at the highest part is 30%. After that, the dummy support was manually peeled off at a speed of 1 m/min to obtain a decorative molded body 1.

In FIGS. 4A and 4B, D represents width, L represents length, and H represents height. In this embodiment, as the transparent frame 100, a transparent frame with D=75 nm, L=150 mm, and H=0.7 mm is used.

<Measurement> The dummy support 1, the colored layer 1, the liquid crystal layer 1, and the adhesive layer 1 were subjected to the measurement of the elastic modulus at 25°C by the above-mentioned method. The measurement results are shown in Table 1. In addition, in Examples 2 to 9, 15 to 18, and Comparative Examples 1 to 3, the elastic modulus of the colored layer was measured by the method described above. In Examples 10 to 14, the coloring layer, the cholesteric liquid crystal layer, and the adhesive layer were subjected to the measurement of the elastic modulus at 25°C by the above-mentioned method. The measurement results are shown in each table describing each example and comparative example.

＜Performance evaluation＞ -Reflection characteristics- Using a spectrophotometer V-670 manufactured by JASCO Corporation, the laminated body 1 (decorative film) before forming was measured from the transparent frame side and perpendicular to the surface of the transparent frame in the wavelength range of 380nm to 1,100nm. ) Reflectivity. The reflectance represents the highest of the maximum values of the reflectance spectrum. As a result of the evaluation, A, B, or C is preferable, A or 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 reflectivity is less than 5%.

-Pseudo support peelability- The state of the peeling surface (coloring layer surface) of the pseudo support of the decorative molded body 1 was visually observed and evaluated. In addition, the evaluation was performed from a position at a distance of 50 cm in the vertical direction from the plane of the transparent frame at 90°C. As a result of the evaluation, A, B, or C is preferable, A or B is more preferable, and A is particularly preferable. ＜＜Evaluation Criteria＞＞ A: It has a uniform surface shape, and no defect or film breakage is found. B: Defects and breakage are found in an area greater than 0% and less than 1%. C: Defects and breakage are found in an area greater than 1% and less than 5%. D: Defects and breakage are found in an area of 5% or more and less than 10%. E: Defects and breakages are found in 10% or more of the area.

-Brightness- The obtained decorative molded body 1 was evaluated by visually observing the brightness when visually recognized from the transparent frame side. In addition, the evaluation was performed from a position at a distance of 50 cm in the vertical direction from the plane of the transparent frame at 90°C. As a result of the evaluation, A, B, or C is preferable, A or B is more preferable, and A is particularly preferable. ＜＜Evaluation Criteria＞＞ A: High brightness can be confirmed. B: The brightness can be confirmed, but it looks a little muddy as a whole. C: A little brilliance can be confirmed. D: It is difficult to confirm the brightness.

-Design changes (color variability according to the direction of visual recognition)- Regarding the obtained laminate 1 (decorative film), when the direction perpendicular to the surface direction of the decoration film is set to 0°, the change in hue when visually recognized from the angles of 0° and 45° (for example, at 0° It is yellow in the direction, blue in the 45° direction, etc.) for evaluation. As a result of the evaluation, A, B or C is better, A and B are even better, and A is especially better. ＜＜Evaluation Criteria＞＞ A: When visually recognized from the 0° direction and when visually recognized from the 45° direction, a change in color tone can be clearly recognized. B: When visually recognized from the 0° direction and when visually recognized from the 45° direction, a change in color tone can be confirmed. C: When visually recognized from the 0° direction and when visually recognized from the 45° direction, a slight change in color tone can be confirmed. D: When visually recognized from the 0° direction and when visually recognized from the 45° direction, the change in hue cannot be confirmed.

Table 1 summarizes the evaluation results.

(Examples 2 to 5) Except that the coating liquid 1 for forming a colored layer was used, and the layer thicknesses were changed to the film thicknesses described in Table 1 or Table 2 to form colored layers 2 to 5, the same procedure as in Example 1 was carried out. Production of laminated bodies 2-5 and decorative molded bodies 2-5. The layered bodies 2 to 5 and the decorative molded bodies 2 to 5 were evaluated in the same manner as in Example 1. The evaluation results are summarized in Table 1 or Table 2.

(Examples 6-7) Except that the coating liquid 1 for forming the colored layer was used, the layer thickness was changed to the film thickness described in Table 2 to form the colored layers 6-7, and the coating liquid 1 for the cholesteric liquid crystal layer was changed to Table 1. Except that the cholesteric liquid crystal layers 2 to 3 were formed with the layer thickness described in the above, the laminated bodies 6 to 7 and the decorative molded bodies 6 to 7 were produced in the same manner as in Example 1. The layered bodies 6 to 7 and the decorative molded bodies 2 to 5 were evaluated in the same manner as in Example 1. Table 2 summarizes the evaluation results.

(Examples 8-9) Except that by using acrylic adhesive liquid (SK-Dyne SG-50Y, manufactured by Soken Chemical & Engineering Co., Ltd.), and changing the film thickness to the layer thickness described in Table 2, the adhesive layers 2 to 3 are formed. Other than that, in the same manner as in Example 1, the laminated bodies 8 to 9 and the decorative molded bodies 8 to 9 were produced. The layered bodies 8-9 and the decorative molded bodies 8-9 were evaluated in the same manner as in Example 1. Table 2 summarizes the evaluation results.

(Example 10) The laminated body 10 and the decorative molded body 10 were produced in the same manner as in Example 1, except that the coloring layer 8 was formed using the coating liquid 2 for forming a colored layer. The layered bodies 8-9 and the decorative molded bodies 8-9 were evaluated in the same manner as in Example 1. Table 3 summarizes the evaluation results.

<The composition of the coating liquid 2 for forming a colored layer> ･Black pigment dispersion: 30 parts by mass ･Polymerizable compound 1: manufactured by Sartomer Japan Inc., urethane acrylate oligomer, CN-996NS: 50 parts by mass ･Photopolymerization initiator (Irgacure 2959, manufactured by BASF Corporation): 1.0 part by mass ･Methyl ethyl ketone: 19 parts by mass

(Example 11) The laminated body 11 and the decorative molded body 11 were produced in the same manner as in Example 1, except that the coloring layer 9 was formed using the coating liquid 3 for forming a colored layer. The laminated body 11 and the decorative molded body 11 were evaluated in the same manner as in Example 1. Table 3 summarizes the evaluation results.

<The composition of the coating liquid 3 for forming a colored layer> ･Black pigment dispersion: 30 parts by mass ･Polymerizable compound 1: manufactured by Sartomer Japan Inc., urethane acrylate oligomer, CN-996NS: 15 parts by mass ･ADHM6 (Amino ester adhesive, manufactured by JUJO CHEMICAL CO.,LTD.): 35 parts by mass ･Photopolymerization initiator (Irgacure 2959, manufactured by BASF Corporation): 1.0 part by mass ･Methyl ethyl ketone: 19 parts by mass

(Example 12) The laminated body 12 and the decorative molded body 12 were produced in the same manner as in Example 1, except that the coloring layer 8 was formed using the coating liquid 4 for forming a colored layer. The laminated body 12 and the decorative molded body 12 were evaluated in the same manner as in Example 1. Table 4 summarizes the evaluation results.

<The composition of the coating liquid 4 for forming a colored layer> ･Black pigment dispersion: 30 parts by mass ･Polymerizable compound 1: manufactured by Sartomer Japan Inc., urethane acrylate oligomer, CN-996NS: 30 parts by mass ･Polymerizable compound 2: manufactured by Sartomer Japan Inc., dipentaerythritol hexaacrylate: 20 parts by mass ･Photopolymerization initiator (Irgacure 2959, manufactured by BASF Corporation): 1.0 part by mass ･Methyl ethyl ketone: 19 parts by mass

(Example 13) The laminated body 13 and the decorative molded body 13 were produced in the same manner as in Example 1, except that the coloring layer 8 was formed using the coating liquid 5 for forming a colored layer. The laminated body 13 and the decorative molded body 13 were evaluated in the same manner as in Example 1. Table 4 summarizes the evaluation results.

<Composition of Coating Liquid 5 for Colored Layer Formation> ･Black pigment dispersion: 30 parts by mass ･Polymerizable compound 1: manufactured by Sartomer Japan Inc., urethane acrylate oligomer, CN-996NS: 5 parts by mass ･Polymerizable compound 2: manufactured by Sartomer Japan Inc., dipentaerythritol hexaacrylate: 45 parts by mass ･Photopolymerization initiator (Irgacure 2959, manufactured by BASF Corporation): 1.0 part by mass ･Methyl ethyl ketone: 19 parts by mass

(Example 14) Except that the pseudo support 1 was changed to a polyurethane elastomer film (SILKRON ES85, manufactured by Okura Industrial Co., Ltd., 100 um) as the pseudo support 2, a laminate 14 was produced in the same manner as in Example 1. The laminated body 14 was used to manufacture the decorative molded body 14. The laminated body 14 and the decorative molded body 14 were evaluated in the same manner as in Example 1. Table 4 summarizes the evaluation results.

(Example 15) In the same manner as in Example 1, except that Nax REAL537 (manufactured by NIPPONPAINT Co., Ltd., red paint) was used in place of the coating solution 1 for forming the colored layer, the laminated body 15 and the decorative molded body 15 were produced. . The laminated body 15 and the decorative molded body 15 were evaluated in the same manner as in Example 1. Table 5 summarizes the evaluation results.

(Example 16) Except for using Nax REAL609 (manufactured by NIPPONPAINT Co., Ltd., blue paint) in place of the coating liquid 1 for forming a colored layer, the laminate 16 and the decorative molded body 16 were performed in the same manner as in Example 1. Evaluation. Table 5 summarizes the evaluation results.

(Example 17) The laminated body 17 and the decorative molded body 17 were produced in the same manner as in Example 1, except that the cholesteric liquid crystal layer 4 was formed using the coating liquid 2 for forming a cholesteric liquid crystal layer. The laminated body 17 and the decorative molded body 17 were evaluated in the same manner as in Example 1. Table 5 summarizes the evaluation results.

[Composition of coating liquid 2 for forming cholesteric liquid crystal layer] Methyl ethyl ketone: 150.6 parts Liquid crystal compound 1 (rod-shaped liquid crystal compound): 92 parts Photopolymerization initiator A (IRGACURE 907, manufactured by BASF Corporation): 0.50 parts Chiral Reagent A: 3.33 copies Chiral Reagent B: 3.33 copies The following surfactant F1: 0.027 parts

(Example 18) The laminated body 18 and the decorative molded body 18 were produced in the same manner as in Example 1, except that the cholesteric liquid crystal layer coating liquid 3 was used to form the cholesteric liquid crystal layer 5. The laminated body 18 and the decorative molded body 18 were evaluated in the same manner as in Example 1. Table 5 summarizes the evaluation results.

[Composition of coating liquid 3 for cholesteric liquid crystal layer] Methyl ethyl ketone: 150.6 parts Liquid crystal compound 1 (rod-shaped liquid crystal compound): 92 parts Photopolymerization initiator A (IRGACURE 907, manufactured by BASF Corporation): 0.50 parts Chiral Reagent A: 2.57 copies Chiral Reagent B: 2.57 copies The following surfactant F1: 0.027 parts

(Comparative example 1) A decorative molded body C1 was produced in the same manner as in Example 1, except that the coloring layer 10 was formed by changing the film thickness to the film thickness described in Table 6 by using the coating liquid 1 for forming a colored layer. Table 6 summarizes the evaluation results.

(Comparative example 2) Except that the coating liquid 1 for forming a colored layer was used, the layer thickness was changed to the film thickness described in Table 6 to form the colored layer 11, and the coating liquid 1 for forming a cholesteric liquid crystal layer was changed to those described in Table 6. Except that the cholesteric liquid crystal layer 6 was formed with the thickness of the layer, the laminated body C2 and the decorative molded body C2 were produced in the same manner as in Example 1. The laminated body C2 and the decorative molded body C2 were evaluated in the same manner as in Example 1. Table 6 summarizes the evaluation results.

(Comparative example 3) In the same manner as in Example 1, except that the colored layer was formed, the laminated body C3 and the decorative molded body C3 were produced. The laminated body C3 and the decorative molded body C3 were evaluated in the same manner as in Example 1. Table 6 summarizes the evaluation results.

[Table 1] Example 1 Example 2 Example 3 Example 4 Floor Layer thickness [μm] Floor Layer thickness [μm] Floor Layer thickness [μm] Floor Layer thickness [μm] Pseudo support Pseudo support 1 50 (T1) Pseudo support 1 50 (T1) Pseudo support 1 50 (T1) Pseudo support 1 50 (T1) Colored layer Colored layer 1 4 (T2) Colored layer 2 2 (T2) Colored layer 3 1 (T2) Colored layer 4 0.5 (T2) Cholesteric liquid crystal layer Liquid crystal layer 1 1.4 (T3) Liquid crystal layer 1 1.4 (T3) Liquid crystal layer 1 1.4 (T3) Liquid crystal layer 1 1.4 (T3) Subsequent layer Then layer 1 10 (T4) Then layer 1 10 (T4) Then layer 1 10 (T4) Then layer 1 10 (T4) Color of the colored layer black black black black Liquid crystal layer reflection wavelength (color) 440nm (blue) 440nm (blue) 440nm (blue) 440nm (blue) T1/T2/T3 relationship T1＞T2＞T3 T1＞T2＞T3 T1＞T2＞0.6×T3 T1＞T2＞0.3×T3 T2/T3/T4 relationship T4＜10×（T2+T3） T4＜10×（T2+T3） T4＜10×（T2+T3） T4＜10×（T2+T3） Elastic modulus of colored layer 0.08 0.08 0.08 0.08 Reflectivity A A B C Pseudo support peelability A B B C Brightness A B C C Design changes A A A C

[Table 2] Example 1 Example 5 Example 6 Example 7 Example 8 Example 9 Floor Layer thickness [μm] Floor Layer thickness [μm] Floor Layer thickness [μm] Floor Layer thickness [μm] Floor Layer thickness [μm] Floor Layer thickness [μm] Pseudo support Pseudo support 1 50 (T1) Pseudo support 1 10 (T1) Pseudo support 1 50 (T1) Pseudo support 1 50 (T1) Pseudo support 1 50 (T1) Pseudo support 1 50 (T1) Colored layer Colored layer 1 4 (T2) Colored layer 5 8 (T2) Colored layer 6 15 (T2) Colored layer 7 25 (T2) Colored layer 1 4 (T2) Colored layer 1 4 (T2) Cholesteric liquid crystal layer Liquid crystal layer 1 1.4 (T3) Liquid crystal layer 1 1.4 (T3) Liquid crystal layer 2 5 (T3) Liquid crystal layer 3 10 (T3) Liquid crystal layer 1 1.4 (T3) Liquid crystal layer 1 1.4 (T3) Subsequent layer Then layer 1 10 (T4) Then layer 1 10 (T4) Then layer 1 10 (T4) Then layer 1 10 (T4) Then layer 2 30 (T4) Then layer 3 60 (T4) Color of the colored layer black black black black black black Liquid crystal layer reflection wavelength (color) 440nm (blue) 440nm (blue) 440nm (blue) 440nm (blue) 440nm (blue) 440nm (blue) T1/T2/T3 relationship T1＞T2＞T3 T1＞T2＞T3 T1＞T2＞T3 T1＞T2＞T3 T1＞T2＞T3 T1＞T2＞T3 T2/T3/T4 relationship T4＜10×（T2+T3） T4＜10×（T2+T3） T4＜10×（T2+T3） T4＜10×(TZ+T3) T4＜11×(T2+T3) T4＜12×（T2+T3） Elastic modulus of colored layer 0.08 0.08 0.08 0.08 0.08 0.08 Reflectivity A A A A A A Pseudo support peelability A B B B B C Brightness A A B C B C Design changes A A A C A B

[table 3] Example 1 Example 10 Example 11 Floor Layer thickness [μm] Elastic modulus [Gpa] Floor Layer thickness [μm] Elastic modulus [Gpa] Floor Layer thickness [μm] Elastic modulus [Gpa] Pseudo support Pseudo support 1 50 (T1) 4 (G1) Pseudo support 1 50 (H) 4 (G1) Pseudo support 1 50 (T1) 4 (G1) Colored layer Colored layer 1 4 (T2) 0.08 (G2) Coloring layer 8 4 (T2) 0.001 (G2) Colored layer 9 4 (T2) 0.0001 (G2) Cholesteric liquid crystal layer Liquid crystal layer 1 1.4 (T3) 0.005 (G3) Liquid crystal layer 1 1.4 (T3) 0.005 (G3) Liquid crystal layer 1 1.4 (T3) 0.005 (G3) Subsequent layer Then layer 1 10 (T4) 0.0001 (G4) Then layer 1 10 (T4) 0.0001 (G4) Then layer 1 10 (T4) 0.0001 (G4) Color of the colored layer black black black Liquid crystal layer reflection wavelength (color) 440nm (blue) 440nm (blue) 440nm (blue) T1/T2/T3 relationship T1＞T2＞T3 T1＞T2＞T3 T1＞T2＞T3 T2/T3/T4 relationship T4＜10×（T2+T3） T4＜10×（T2+T3） T4＜10×（T2+T3） G1/G2/G3 G1＞G2＞G3 G1＞G2＞G3 G1＞G3＞G2 G1/G2/G3/G4 G1＞G2＞G3＞G4 G1＞G2＞G3＞G4 G1＞G3＞G2=G4 Reflectivity A A A Pseudo support peelability A B C Brightness A A B Design changes A A A

[Table 4] Example 1 Example 12 Example 13 Example 14 Floor Layer thickness [μm] Elastic modulus [Gpa] Floor Layer thickness [μm] Elastic modulus [Gpa] Floor Layer thickness [μm] Elastic modulus [Gpa] Floor Layer thickness [μm] Elastic modulus [Gpa] Pseudo support Pseudo support 1 50 (T1) 4 (G1) Pseudo support 1 50 (T1) 4 (G1) Pseudo support 1 50 (T1) 4 (G1) Pseudo support 1 50 (T1) 0.05 (G1) Colored layer Colored layer 1 4 (T2) 0.08 (G2) Colored layer 10 4 (T2) 0.4 (G2) Colored layer 11 4 (T2) 1 (G2) Colored layer 1 4 (T2) 0.08 (G2) Cholesteric liquid crystal layer Liquid crystal layer 1 1.4 (T3) 0.005 (G3) Liquid crystal layer 1 1.4 (T3) 0.005 (G3) Liquid crystal layer 1 1.4 (T3) 0.005 (G3) Liquid crystal layer 1 1.4 (T3) 0.005 (G3) Subsequent layer Then layer 1 10 (T4) 0.0001 (G4) Then layer 1 10 (T4) 0.0001 (G4) Then layer 1 10 (T4) 0.0001 (G4) Then layer 1 10 (T4) 0.0001 (G4) Color of the colored layer black black black black Liquid crystal layer reflection wavelength (color) 440nm (blue) 440nm (blue) 440nm (blue) 440nm (blue) T1/T2/T3 relationship T1＞T2＞T3 T1＞T2＞T3 T1＞T2＞T3 T1＞T2＞T3 T2/T3/T4 relationship T4＜10×（T2+T3） T4＜10×（T2+T3） T4＜10×（T2+T3） T4＜10×（T2+T3） G1/G2/G3 G1＞G2＞G3 G1＞G2＞G4 G1＞G2＞G3 G2＞G1＞G3 G1/G2/G3/G4 G1＞G2＞G3＞G4 G1＞G2＞G3＞G4 G1＞G2＞G3＞G4 G2＞G1＞G3＞G4 Reflectivity A A A A Pseudo support peelability A B C C Brightness A A A B Design changes A C C A

[table 5] Example 1 Example 15 Example 16 Example 17 Example 18 Floor Layer thickness [μm] Floor Layer thickness [μm] Floor Layer thickness [μm] Floor Layer thickness [μm] Floor Layer thickness [μm] Pseudo support Pseudo support 1 50 (T1) Pseudo support 1 50 (T1) Pseudo support 1 50 (T1) Pseudo support 1 50 (T1) Pseudo support 1 50 (T1) Colored layer Colored layer 1 4 (T2) Colored layer 2 4 (T2) Colored layer 3 4 (T2) Coloring layer 8 4 (T2) Colored layer 9 4 (T2) Cholesteric liquid crystal layer Liquid crystal layer 1 1.4 (T3) Liquid crystal layer 1 1.4 (T3) Liquid crystal layer 1 1.4 (T3) Liquid crystal layer 4 1.4 (T3) Liquid crystal layer 5 1.4 (T3) Subsequent layer Then layer 1 10 (T4) Then layer 1 10 (T4) Then layer 1 10 (T4) Then layer 1 10 (T4) Then layer 1 10 (T4) Color of the colored layer black red blue black black Liquid crystal layer reflection wavelength (color) 440nm (blue) 440nm (blue) 440nm (blue) 550nm (green) 660nm (red) T1/T2/T3 relationship T1＞T2＞T3 T1＞T2＞T3 T1＞T2＞T3 T1＞T2＞T3 T1＞T2＞T3 T2/T3/T4 relationship T4＜10×（T2+T3） T4＜10×（T2+T3） T4＜10×（T2+T3） T4＜10×（T2+T3） T4＜10×（T2+T3） Elastic modulus of colored layer [Gpa]@25℃ 0.08 0.08 0.08 0.08 0.08 Reflectivity A A A A A Pseudo support peelability A B C B C Brightness A B C A B Design changes A A B A A

[Table 6] Example 1 Comparative example 1 Comparative example 2 Comparative example 3 Floor Layer thickness [μm] Floor Layer thickness [μm] Floor Layer thickness [μm] Floor Layer thickness [μm] Pseudo support Pseudo support 1 50 (T1) Pseudo support 1 50 (T1) Pseudo support 1 50 (T1) Pseudo support 1 50 (T1) Colored layer Colored layer 1 4 (T2) Colored layer 10 0.1 (T2) Colored layer 11 0.4 (T2) - - Cholesteric liquid crystal layer Liquid crystal layer 1 1.4 (T3) Liquid crystal layer 1 1.4 (T3) Liquid crystal layer 6 5 (T3) Liquid crystal layer 1 1.4 (T3) Subsequent layer Then layer 1 10 (T4) Then layer 1 10 (T4) Then layer 1 10 (T4) Then layer 1 10 (T4) Color of the colored layer black black black black Liquid crystal layer reflection wavelength (color) 440nm (blue) 440nm (blue) 440nm (blue) 440nm (blue) T1/T2/T3 relationship T1＞T2＞T3 T1＞0.1×T3＞T2 T1＞0.1×T3＞T2 - T2/T3/T4 relationship T4＜10×（T2+T3） T4＜10×（T2+T3） T4＜10×（T2+T3） - Elastic modulus of colored layer [Gpa]@25℃ 0.08 0.08 0.08 0.08 Reflectivity A A B C Pseudo support peelability A D C E Brightness A D D D Design changes A D D C

The details of the symbols shown in Table 1 to Table 6 are as follows. T1: The thickness of the pseudo support T2: The thickness of the colored layer T3: The thickness of the cholesteric liquid crystal layer T4: Adhesive layer thickness G1: The modulus of elasticity of the pseudo support G2: The modulus of elasticity of the colored layer G3: Elastic modulus of cholesteric liquid crystal layer G4: Elastic modulus of the adhesive layer In Tables 1 to 6, the cholesteric liquid crystal layer formed in each of the Examples and Comparative Examples is abbreviated as the liquid crystal layer. In addition to Table 1, Example 1 is also recorded in Tables 2 to 6.

From the results described in Tables 1 to 5, it is confirmed that the decorative films of Examples 1 to 17 have excellent peelability of the pseudo support, high brightness, and color variability according to the direction of visual recognition (designability). ) Excellent decorative film. On the other hand, from the results described in Table 6, it was confirmed that the decorative films of Comparative Examples 1 to 3 had poor releasability, brilliance, and color variability (design properties) according to the direction of visibility.

Regarding the disclosure of Japanese Patent Application No. 2019-132924 filed on July 18, 2019, the entirety is incorporated into this specification by reference. All documents, patent applications, and technical specifications described in this specification are incorporated into this specification by reference to the same extent that they are specific and each entered by reference.

20: Decorative film 22: pseudo support 24: Colored layer 26: Orientation layer 28: Cholesterol type liquid crystal layer 30: Next layer 40: Transparent frame 50: Decorative molding (before peeling off the pseudo support) 60: Decorative molding (after peeling off the pseudo support) 100: Transparent frame W: width L: length H: height

Fig. 1 is a schematic cross-sectional view showing an example of the decorative film of the present disclosure. 2 is a schematic cross-sectional view showing an example of the decorative molded body (before peeling off the dummy support) of the present disclosure. 3 is a schematic cross-sectional view showing an example of the decorative molded body (after peeling off the dummy support) of the present disclosure. Fig. 4A is a schematic cross-sectional view showing the transparent frame used in the embodiment. Fig. 4B is a schematic top view of the transparent frame used in the embodiment.

20: Decorative film

22: pseudo support

24: Colored layer

26: Orientation layer

28: Cholesterol type liquid crystal layer

30: Next layer

Claims (14)

A decorative film, which has: Pseudo support Colored layer; and Cholesterol type liquid crystal layer, The relationship between the thickness T1 of the pseudo support, the thickness T2 of the colored layer, and the thickness T3 of the cholesteric liquid crystal layer satisfies T1>T2>0.1×T3, and is used to visually recognize the colored layer through the cholesteric liquid crystal layer. A decorative film, which has: Pseudo support Colored layer; and Cholesterol type liquid crystal layer, The relationship between the thickness T1 of the pseudo support, the thickness T2 of the colored layer, and the thickness T3 of the cholesteric liquid crystal layer satisfies T1>T2>T3, and is used to visually recognize the colored layer through the cholesteric liquid crystal layer. The decorative film according to claim 1 or claim 2, wherein The elastic modulus at 25°C of the colored layer is 0.0001 Gpa or more and less than 0.5 Gpa. The decorative film according to claim 1 or claim 2, wherein A resin layer is also provided on the side opposite to the side having the aforementioned pseudo support. A decorative film, which has: Pseudo support Colored layer Cholesterol type liquid crystal layer; and Next layer, The relationship between the thickness T2 of the colored layer, the thickness T3 of the cholesteric liquid crystal layer, and the thickness T4 of the adhesive layer satisfies T4<10 (T2+T3), and is used to visually recognize the colored layer through the cholesteric liquid crystal layer. The decorative film according to claim 5, wherein The elastic modulus at 25°C of the colored layer is 0.0001 Gpa or more and less than 0.5 Gpa. A decorative panel in which a transparent frame with a thickness of 0.5 mm or more is attached to the side opposite to the side of the pseudo support having the decorative film described in claim 1, claim 2, or claim 5, and It is used to visually recognize the colored layer from the transparent frame side through the cholesteric liquid crystal layer. The decorative panel as described in claim 7, wherein The main component of the aforementioned transparent frame is glass. The decorative panel as described in claim 7, wherein The aforementioned transparent frame has a three-dimensional shape. A method for manufacturing a decorative panel, which has at least a surface of 0.5 mm or more attached to the side opposite to the side of the aforementioned pseudo support having the decorative film described in claim 1, claim 2, or claim 5. After the thickness of the transparent frame, the manufacturing process of peeling off the aforementioned dummy support. The method of manufacturing a decorative panel according to claim 10, wherein The process of laminating the aforementioned transparent frame with a thickness of 0.5mm or more is a heat forming process at 60°C or more. An electronic device comprising the decorative panel described in claim 7. A wearable device comprising the decorative panel described in claim 7. A smart phone comprising the decorative panel described in claim 7.

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