JP7309919B2 - LAMINATED PRODUCT AND MANUFACTURING METHOD THEREOF, MOLDED PRODUCT AND MANUFACTURING METHOD THEREOF, ELECTRONIC DEVICE CASE PANEL, AND ELECTRONIC DEVICE - Google Patents

Description

TECHNICAL FIELD The present disclosure relates to a laminate and its manufacturing method, a molded article and its manufacturing method, a housing panel of an electronic device, and an electronic device.

A laminate in which a liquid crystal layer is provided on a substrate can be used, for example, as a decorative molded film. A decorative molded film includes a base material and a liquid crystal layer that is a decorative film, and can be subjected to a molding process to obtain a decorative molded product (hereinafter sometimes referred to as a "molded product"). . Also known is a decorative molding in which a decorative film is placed on the surface of a resin molding to color the surface in a desired hue or to provide a desired pattern on the surface.
The decorative molding is obtained, for example, by placing a decorative molding film in advance in a mold and injecting a base resin into the mold, and the decorative film is integrated with the surface of the resin molding. It has a complex structure.
Injection molding of a base resin after placing a decorative molding film in advance in a mold is generally referred to as film insert molding or simply insert molding. Also, the decorated molded body may be produced by attaching a decorative film to the molded body after molding.

Further, as a conventional decorative molded film, for example, Japanese Patent Application Laid-Open No. 2001-105795 describes a hot stamp foil in which a cholesteric liquid crystalline polymer layer having a selective reflection wavelength range in visible light is laminated as a transfer layer. It is

The problem to be solved by one embodiment of the present disclosure is to provide a laminate having high designability in which patterns are formed by selective reflection of light of different wavelengths and excellent sharpness of boundaries between patterns. It is in.
A problem to be solved by another embodiment of the present disclosure is to provide a method for manufacturing the laminate.
A problem to be solved by another embodiment of the present disclosure is to provide a molded product obtained by molding the laminate.
A problem to be solved by another embodiment of the present disclosure is to provide a method for manufacturing the molded product.
A problem to be solved by another embodiment of the present disclosure is to provide a housing panel for an electronic device including the laminate.
A problem to be solved by another embodiment of the present disclosure is to provide an electronic device including the molding.

Means for solving the above problems include the following aspects.
<1> A laminate having a base material and a liquid crystal layer containing a liquid crystal compound and a photoisomerizable compound provided on the base material,
In the liquid crystal layer, a plurality of patterns with different selective reflection wavelengths are formed in the in-plane direction,
A layered product in which the width of bleeding at the boundaries of the plurality of patterns is 1 μm or more and less than 100 μm.
<2> The laminate according to <1>, which is a decorative molded film.
<3> a substrate, a liquid crystal layer containing a liquid crystal compound and a photoisomerizable compound provided on the substrate, and a plurality of substrates adjacent to at least one of the substrate and the liquid crystal layer and having different light transmittances preparing a liquid crystal material having an optical mask layer patterned in an in-plane direction;
and a step of irradiating the liquid crystal layer with light through the optical mask layer to photoisomerize the photoisomerizable compound.
<4> Production of the laminate according to <3>, in which the optical mask layer is adjacent to the substrate, and the liquid crystal layer is provided on the surface of the substrate opposite to the side where the optical mask layer is adjacent. Method.
<5> The method for manufacturing a laminate according to <3> or <4>, wherein at least some of the plurality of patterns have different light transmittances in a wavelength range of 250 nm to 400 nm.
<6> The method for producing a laminate according to any one of <3> to <5>, wherein the plurality of patterns differ in maximum value of light transmittance by 30% or more.
<7> The method for producing a laminate according to any one of <3> to <6>, wherein the plurality of patterns has an in-plane average transmittance of 50% or more in a wavelength range of 400 nm to 780 nm.
<8> The method for producing a laminate according to any one of <3> to <7>, wherein the optical mask layer is formed by a printing method.
<9> The method for producing a laminate according to any one of <3> to <8>, wherein the laminate is a decorative molding film used for decorating a housing panel of an electronic device.
<10> A molded product obtained by molding the laminate according to <1> or <2>.
<11> A method for producing a molded article, comprising a step of molding the laminate obtained by the method for producing a laminate according to any one of <3> to <9>.
<12> An electronic device housing panel comprising the laminate according to <1> or <2>.
<13> An electronic device comprising the molded article according to <10>.

According to an embodiment of the present disclosure, it is possible to provide a layered product in which patterns are formed by selective reflection of light of different wavelengths, which has high designability and excellent sharpness of boundaries between patterns.
According to another embodiment of the present disclosure, a method for manufacturing the laminate can be provided.
According to another embodiment of the present disclosure, it is possible to provide a molded product obtained by molding the laminate.
According to another embodiment of the present disclosure, it is possible to provide a method for manufacturing the molded product.
According to another embodiment of the present disclosure, it is possible to provide a housing panel for an electronic device including the laminate.
According to another embodiment of the present disclosure, it is possible to provide an electronic device including the molded product.

FIG. 1 is a schematic plan view schematically showing the pattern of the optical mask layer. FIG. 2A is a schematic plan view schematically showing an example of the shape of the glass member. FIG. 2B is a schematic cross-sectional view schematically showing a cross section cut in a direction parallel to the longitudinal direction of the glass member of FIG. 2A.

The content of the present disclosure will be described in detail below. The description of the constituent elements described below may be made based on representative embodiments of the present disclosure, but the present disclosure is not limited to such embodiments.
In addition, in the present disclosure, "to" indicating a numerical range is used to include the numerical values described before and after it as a lower limit and an upper limit.
In the numerical ranges described step by step in the present disclosure, the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step. . Moreover, in the numerical ranges described in the present disclosure, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
Furthermore, in the present disclosure, when there are multiple substances corresponding to each component in the composition, the amount of each component in the composition is the total amount of the corresponding substances present in the composition unless otherwise specified. means
In the present disclosure, the term "process" includes not only an independent process, but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.
In the present disclosure, "total solid content" refers to the total mass of components excluding the solvent from the total composition of the composition. Moreover, as described above, the “solid content” is the component excluding the solvent, and may be solid or liquid at 25° C., for example.
In the notation of groups (atomic groups) in the present disclosure, notations that do not indicate substitution or unsubstituted include not only those not having substituents but also those having substituents. For example, the term “alkyl group” includes not only alkyl groups having no substituents (unsubstituted alkyl groups) but also alkyl groups having substituents (substituted alkyl groups).
In the present disclosure, "(meth)acrylic" is a term used as a concept that includes both acrylic and methacrylic, and "(meth)acrylate" is a term that is used as a concept that includes both acrylate and methacrylate. be.
In the present disclosure, a combination of two or more preferred aspects is a more preferred aspect.
Unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure are gels using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation). It is a molecular weight converted using polystyrene as a standard substance detected by a permeation chromatography (GPC) analyzer using THF (tetrahydrofuran) as a solvent and a differential refractometer.
In the present disclosure, "light" is a concept that includes active energy rays such as γ-rays, β-rays, electron beams, ultraviolet rays, and visible rays.
The drawings referred to in the following description are exemplary and schematic, and the present disclosure is not limited to these drawings. Also, reference numerals in the drawings may be omitted.
The present disclosure will now be described in detail.

(Laminate)
A laminate according to the present disclosure includes a substrate and a liquid crystal layer containing a liquid crystal compound and a photoisomerizable compound provided on the substrate. In the liquid crystal layer, a plurality of patterns having different selective reflection wavelengths are formed in the in-plane direction, and the bleeding width at the boundary between the patterns is 1 μm or more and less than 100 μm.
In the present disclosure, the "liquid crystal layer" means a cured product of a liquid crystal composition in a laminate, and may be referred to as a "cured liquid crystal layer" or a "cured liquid crystal layer". means an uncured liquid crystal composition in the later-described liquid crystal material used in .
The “liquid crystal composition” is a composition containing components contained in the liquid crystal layer, and the “cured product of the liquid crystal composition” includes dried products and polymerized cured products of the liquid crystal composition.

As a result of intensive studies by the present inventors, it was found that by adopting the above configuration, it is possible to provide a laminate having high designability in which patterns are formed by selective reflection of different wavelengths and excellent sharpness of boundaries between patterns. rice field. Such a laminate can be suitably used, for example, as a decorative molded film used for decoration.
Although the action mechanism of the excellent effects of the above configuration is not clear, it is presumed as follows.
The length of the helical pitch of the liquid crystal phase formed by the liquid crystal compound in the liquid crystal layer is obtained by exposing the liquid crystal layer containing the liquid crystal compound and the photoisomerizable compound to light through an optical mask layer to photoisomerize the photoisomerizable compound. The thickness can be varied corresponding to the light transmittance of the optical mask layer. Thereby, the maximum wavelength of the reflected light of the liquid crystal layer can be changed, and a pattern by selective reflection of different wavelengths can be formed in the liquid crystal layer. At this time, if the optical mask layer is adjacent to the liquid crystal layer or the base material, for example, if it is laminated directly on the base material, the distance between the liquid crystal layer and the optical mask layer will be close, and the reflected wavelength at the pattern boundary will change. It is estimated that a laminate having excellent sharpness can be provided.

Each layer such as the substrate and the liquid crystal layer will be described in detail below. The liquid crystal layer need only be on the substrate, and does not have to be in direct contact with the substrate. For example, it may be on the substrate via another layer such as a colored layer to be described later.

<Liquid crystal layer>
In the liquid crystal layer, a plurality of patterns having different selective reflection wavelengths are formed in the in-plane direction. Thereby, the color of the liquid crystal layer can be changed in the in-plane direction, and a laminated body having a high designability can be obtained.

- Selective reflectivity of liquid crystal layer -
The liquid crystal layer has selective reflectivity in a specific wavelength range.
In the present disclosure, the selective reflection wavelength is the half-value transmittance expressed by the following formula, where T _min (%) is the minimum value and the minimum value of the transmittance of the target object (member): T _{1/ 2} (%) means the average value of two wavelengths, and having selective reflectivity means having a specific wavelength range that satisfies the selective reflection wavelength.
The transmittance is measured using a spectrophotometer (eg, a spectrophotometer “UV-2100” manufactured by Shimadzu Corporation, a spectrophotometer “V-670” manufactured by JASCO Corporation).
Formula for calculating half-value transmittance: T _1/2 = 100-(100-T _min )/2
The selective reflection wavelength in the liquid crystal layer is not particularly limited, and can be set, for example, in any range of visible light (380 nm to 780 nm) and near-infrared light (more than 780 nm and 2,000 nm or less). .
Above all, the liquid crystal layer preferably has selective reflectivity in at least part of the wavelength range of 380 nm to 1,200 nm.

- Reflectance of laminate -
The maximum wavelength of the reflectance of the laminate according to the present disclosure is preferably in the range of 380 nm to 780 nm from the viewpoint of designability. Moreover, it is preferable that the pattern is formed by selective reflection of different wavelengths within the range of 380 nm to 780 nm. More preferably, the difference in maximum wavelength of reflectance includes a region of 100 nm or more in the plane.

The reflectance of the laminate according to the present disclosure is obtained by bonding a black polyethylene terephthalate (PET) film (manufactured by Tomoekawa Paper Co., Ltd., trade name "Kukkiri Mieru") to the outermost layer on the opposite side of the laminate, It is obtained from a reflection spectrum measured using a spectrophotometer (for example, a spectrophotometer "V-670" manufactured by JASCO Corporation) with the surface on which the liquid crystal layer is formed as an incident surface.

In the liquid crystal layer, the width of bleeding at the boundaries between the patterns is 1 μm or more and less than 100 μm, whereby a laminate having excellent sharpness at the boundaries between patterns can be obtained.

At the boundary of the pattern, the helical pitch of the cholesteric liquid crystal changes, so the color of the reflected light changes, and a region where the helical pitch changes by 10% or more in the in-plane direction of the liquid crystal layer is recognized as bleeding. In the present disclosure, the width in the in-plane direction of the liquid crystal layer recognized as such bleeding at the boundary of the pattern is referred to as "the width of the bleeding at the boundary of the pattern."
The bleeding width at the boundary of the pattern is measured as follows.
A section of the laminate is prepared using a microtome (for example, RX-860, manufactured by ) Observation using SU3800 manufactured by Hitachi High-Tech. In the pattern boundary, the width of the region where the helical pitch changes by 10% or more in the in-plane direction of the liquid crystal layer is measured and defined as the "bleeding width of the pattern boundary".

The bleeding width at the boundary between the patterns is preferably 1 μm or more and less than 20 μm, and more preferably 2 μm or more and less than 8 μm.

-Layer structure of the liquid crystal layer-
In the laminate, only one liquid crystal layer may be formed, or two or more layers may be formed.
Further, each of the two or more liquid crystal layers may have the same composition or may have different compositions, and at least one layer may be a liquid crystal layer containing a liquid crystal compound and a photoisomerizable compound. It may have a liquid crystal layer that does not contain an isomerizing compound.

-Thickness of liquid crystal layer-
The thickness of the liquid crystal layer is preferably less than 10 μm, more preferably 5 μm or less, even more preferably 0.05 μm to 5 μm, from the viewpoint of suppressing change in reflectance after molding the laminate. Particularly preferred is 0.1 μm to 4 μm.
When the laminate has two or more liquid crystal layers, it is preferable that each liquid crystal layer independently has a thickness within the above range.

<Base material>
As the base material used in the present disclosure, conventionally known base materials used for molding such as three-dimensional molding and insert molding can be used without particular limitation. It may be appropriately selected according to suitability for molding.
Moreover, the shape and material of the substrate are not particularly limited, and may be appropriately selected as desired. The substrate is preferably a resin substrate, more preferably a resin film substrate, from the viewpoint of ease of molding (especially ease of insert molding) and resistance to chipping.

Specific examples of the base material include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), acrylic resin, urethane resin, urethane-acrylic resin, polycarbonate (PC), acrylic-polycarbonate resin, triacetyl cellulose (TAC). , polyolefin, cycloolefin polymer (COP), and acrylonitrile/butadiene/styrene copolymer resin (ABS resin).
Above all, from the viewpoint of moldability and strength, it is at least one resin film selected from the group consisting of PET, acrylic resin, urethane resin, urethane-acrylic resin, PC, acrylic-polycarbonate resin, and polypropylene. More preferably, it is at least one resin film selected from the group consisting of PET, acrylic resin, PC, and acrylic-polycarbonate resin.
Also, the substrate may be a laminated resin substrate having two or more layers. For example, an acrylic resin/polycarbonate laminated film is preferable.

The base material may contain additives, if necessary.
Additives include, for example, mineral oils, hydrocarbons, fatty acids, alcohols, fatty acid esters, fatty acid amides, metallic soaps, natural waxes, lubricants such as silicone, inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, halogen compounds, Organic flame retardants such as phosphorus, metal powder, talc, calcium carbonate, potassium titanate, glass fiber, carbon fiber, organic or inorganic fillers such as wood powder, antioxidants, UV inhibitors, lubricants, dispersants, Coupling agents, foaming agents, additives such as coloring agents, polyester resins, polyacetal resins, polyamide resins, polyphenylene ether resins, and engineering plastics other than the resins described above may be mentioned.

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

The thickness of the base material may be determined according to the intended use of the molded product to be produced, the handleability of the base material, and the like. Although the thickness is not particularly limited, it is preferably 1 µm or more, more preferably 10 µm or more, still more preferably 15 µm or more, and particularly preferably 30 µm or more from the viewpoint of handling. The upper limit is preferably 200 μm or less, more preferably 125 μm or less, even more preferably 75 μm or less, and particularly preferably 50 μm or less, from the viewpoint of obtaining high sharpness at pattern boundaries.

<Colored layer>
From the viewpoint of designability, it is preferable that the laminate according to the present disclosure (in a certain aspect, the decorative molded film) further have a colored layer. A colored layer is a layer containing a coloring agent.
The position of the colored layer is not particularly limited and can be provided at any desired position, but the following two aspects are preferred.
In one aspect, the laminate preferably further has a colored layer between the substrate and the liquid crystal layer from the viewpoint of design.
In another aspect, from the viewpoint of designability, molding processability and durability, it is preferable to further have a colored layer on the liquid crystal layer on the side opposite to the side having the substrate.

Moreover, the laminate may have only one colored layer, or may have two or more colored layers.
In the laminate, at least one of the colored layers is preferably a layer for viewing through the liquid crystal layer.
When at least one of the colored layers is viewed through the liquid crystal layer, the color changes depending on the viewing angle of the colored layer based on the anisotropy of the liquid crystal layer depending on the angle of incident light. It is inferred that designability is shown.
Further, when the laminate has two or more colored layers, at least one of the colored layers is a layer for viewing through the liquid crystal layer, and at least one of the other colored layers is positioned in the viewing direction from the liquid crystal layer. A preferred embodiment is a layer close to (hereinafter also referred to as a "color filter layer").
The colored layer (i.e., color filter layer) closer to the viewing direction than the liquid crystal layer is a layer that is highly transmissive to at least light of a specific wavelength, and the layer structure is not particularly limited, and is a monochromatic color filter layer. or a color filter layer having a color filter structure of two or more colors and, if necessary, a black matrix or the like.
By having a color filter layer, it is possible to obtain a layered product that has further designability and allows visual recognition of only a specific wavelength range.
Further, the total light transmittance of at least one of the colored layers, preferably the colored layer for viewing through the liquid crystal layer, is preferably 10% or less from the viewpoint of visibility. The total light transmittance can be measured with a spectrophotometer (eg, spectrophotometer “UV-2100” manufactured by Shimadzu Corporation).

The color of the colored layer is not limited and can be appropriately selected according to the use of the laminate. Examples of colors of the colored layer include black, gray, white, red, orange, yellow, green, blue, and purple. Also, the color of the colored layer may be a metallic color.

From the viewpoint of strength and scratch resistance, the colored layer preferably contains a resin. Examples of resins include binder resins described later. Further, the colored layer may be a layer obtained by curing a polymerizable compound, or a layer containing a polymerizable compound and a polymerization initiator.
The polymerizable compound and the polymerization initiator are not particularly limited, and known ones can be used.

-coloring agent-
Examples of coloring agents include pigments and dyes, and pigments are preferred from the viewpoint of durability. In order to give the colored layer a metallic tone, metal particles, pearl pigments and the like can be applied, and methods such as vapor deposition and plating can also be applied.

The pigment is not limited, and known inorganic pigments, organic pigments, and the like can be applied.
Examples of inorganic pigments include white pigments such as titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, and barium sulfate, carbon black, titanium black, titanium carbon, iron oxide, graphite, and the like. black pigment, iron oxide, barium yellow, cadmium red, chrome yellow and the like.
As the inorganic pigment, the inorganic pigments described in paragraphs 0015 and 0114 of JP-A-2005-7765 can also be applied.

Examples of organic pigments include phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; azo pigments such as azo red, azo yellow and azo orange; quinacridone pigments such as quinacridone red, syncash red and syncash magenta; perylene pigments such as perylene maroon; carbazole violet; anthrapyridine; flavanthrone yellow; isoindoline yellow;
Specific examples of organic pigments include C.I. I. Pigment Red 177, 179, 224, 242, 254, 255, 264; I. Pigment Yellow 138, 139, 150, 180, 185 and other yellow pigments, C.I. I. Pigment Orange 36, 38, 71 and other orange pigments, C.I. I. Pigment Green 7, 36, 58 and other green pigments, C.I. I. Pigment Blue 15:6, a blue pigment such as C.I. I. Purple pigments such as Pigment Violet 23 may be mentioned.
As the organic pigment, the organic pigment described in paragraph 0093 of JP-A-2009-256572 can also be applied.

The pigment may include a pigment having light transmittance and light reflectivity (so-called luster pigment). Luster pigments include, for example, metallic luster pigments such as aluminum, copper, zinc, iron, nickel, tin, aluminum oxide, and alloys thereof, interference mica pigments, white mica pigments, graphite pigments, glass flake pigments, and the like. are mentioned. The bright pigment may be colorless or colored.
When light exposure is performed in molding the laminate, the bright pigment is preferably used within a range that does not interfere with curing by exposure.

A coloring agent may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, when using 2 or more types of coloring agents, you may combine an inorganic pigment and an organic pigment.
The content of the coloring agent in the colored layer is preferably 1% by mass to 50% by mass, preferably 5% by mass to 50% by mass, based on the total mass of the colored layer, from the viewpoint of the desired color expression and molding processability. % is more preferable, and 10% by mass to 40% by mass is particularly preferable.

- Dispersant -
The colored layer may contain a dispersant from the viewpoint of improving the dispersibility of the colorant contained in the colored layer, particularly the pigment. By containing a dispersant, the dispersibility of the colorant in the formed colored layer is improved, and the resulting laminate can have a uniform color.

The dispersant can be appropriately selected according to the type, shape, etc. of the colorant, and is preferably a polymer dispersant.
Polymeric dispersants include, for example, silicone polymers, acrylic polymers, and polyester polymers. When it is desired to impart heat resistance to the laminate, for example, it is preferable to use a silicone polymer such as a graft-type silicone polymer as the dispersant.

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

A commercially available product may be used as the dispersant. Commercially available products include EFKA 4300 (acrylic polymer dispersant) manufactured by BASF Japan, Homogenol L-18, Homogenol L-95 and Homogenol L-100 manufactured by Kao Corporation, and manufactured by Nippon Lubrizol Co., Ltd. Solsperse 20000 and Solsperse 24000, and DISPERBYK-110, DISPERBYK-164, DISPERBYK-180 and DISPERBYK-182 manufactured by BYK-Chemie Japan Co., Ltd. can be mentioned. "Homogenol", "Solsperse" and "DISPERBYK" are all registered trademarks.

A dispersing agent may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the dispersant in the colored layer is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the colorant.

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

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

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

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

-Method of forming colored layer-
Examples of the method for forming the colored layer include a method using a colored layer-forming composition and a method of bonding a colored film. Among the above methods, a method using a composition for forming a colored layer is preferable as the method for forming the colored layer. Moreover, you may form a colored layer using commercially available paints, such as nax Real series, nax Admira series, nax multi series (made by Nippon Paint Co., Ltd.), Retan PG series (made by Kansai Paint Co., Ltd.).

Examples of the method using the colored layer-forming composition include a method of applying the colored layer-forming composition to form a colored layer, and a method of printing the colored layer-forming composition to form a colored layer. Examples of printing methods include screen printing, inkjet printing, flexographic printing, gravure printing, and offset printing.

The colored layer-forming composition contains a colorant. Moreover, the composition for forming a colored layer preferably contains an organic solvent, and may contain each of the above components that can be contained in the colored layer.
The content of each of the above components that can be contained in the composition for forming a colored layer is the amount obtained by replacing the "colored layer" with the "composition for forming a colored layer" in the description regarding the content of each of the above components in the colored layer. is preferably adjusted within the range of

The organic solvent is not limited, and known organic solvents can be applied. Examples of organic solvents include alcohol compounds, ester compounds, ether compounds, ketone compounds, aromatic hydrocarbon compounds, and the like.

An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the organic solvent in the colored layer-forming composition is preferably 5% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, based on the total mass of the colored layer-forming composition.

Examples of the method for preparing the colored layer-forming composition include a method of mixing an organic solvent and a component contained in the colored layer, such as a colorant. Further, when the composition for forming a colored layer contains a pigment as a colorant, from the viewpoint of further enhancing the uniform dispersibility and dispersion stability of the pigment, a pigment dispersion containing a pigment and a dispersant is used to form the colored layer. It is preferred to prepare a forming composition.

-Thickness of colored layer-
Although the thickness of the colored layer is not particularly limited, it is preferably 0.5 μm or more, more preferably 3 μm or more, and further preferably 3 μm to 50 μm from the viewpoint of visibility and three-dimensional moldability. It is preferably 3 μm to 20 μm, particularly preferably 3 μm to 20 μm.
When the laminate has two or more colored layers, it is preferable that each colored layer independently has a thickness within the above range.

<Orientation layer>
A laminate according to the present disclosure may have an alignment layer in contact with the liquid crystal layer. The alignment layer is used to orient the molecules of the liquid crystal compound in the liquid crystal layer when forming the liquid crystal layer.
The alignment layer is used when forming a layer such as a liquid crystal layer, and the laminate may or may not include the alignment layer.

The alignment layer can be provided by rubbing treatment of an organic compound (preferably polymer), oblique vapor deposition of an inorganic compound such as SiO, formation of a layer having microgrooves, or the like. Further, an alignment layer is known in which an alignment function is produced by application of an electric field, application of a magnetic field, or light irradiation.
Depending on the material of the lower layer such as the base material and the liquid crystal layer, the lower layer can be made to function as an orientation layer by directly subjecting the lower layer to an orientation treatment (for example, rubbing treatment) without providing an orientation layer. An example of such a base material for the lower layer is polyethylene terephthalate (PET).
In addition, when a layer is laminated directly on the liquid crystal layer, the lower liquid crystal layer may act as an alignment layer to orient the liquid crystal compound for the fabrication of the upper layer. In such a case, the liquid crystal compound in the upper layer can be aligned without providing an alignment layer or performing a special alignment treatment (for example, rubbing treatment).

Hereinafter, a rubbing-treated alignment layer and a photo-alignment layer, which are used by rubbing the surface, will be described as preferred examples.

-Rubbing treatment alignment layer-
Examples of polymers that can be used in the rubbing alignment layer include methacrylate copolymers, styrene copolymers, polyolefins, polyvinyl alcohols and modified polyvinyl alcohols described in paragraph 0022 of JP-A-8-338913; Poly(N-methylolacrylamide), polyester, polyimide, vinyl acetate copolymer, carboxymethyl cellulose, polycarbonate and the like are included. A silane coupling agent can be used as the polymer. Water-soluble polymers (e.g., poly(N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol, modified polyvinyl alcohol) are preferred, gelatin, polyvinyl alcohol or modified polyvinyl alcohol are more preferred, and polyvinyl alcohol or modified polyvinyl alcohol is particularly preferred. .

A liquid crystal composition is applied to the rubbing-treated surface of the alignment layer to orient the molecules of the liquid crystal compound. After that, the liquid crystal layer can be formed by reacting the alignment layer polymer with a polyfunctional monomer contained in the liquid crystal layer, or by cross-linking the alignment layer polymer using a cross-linking agent, if necessary.
The thickness of the alignment layer is preferably in the range of 0.01 μm to 10 μm.

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

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

In order to increase the rubbing density, it is necessary to increase the number of times of rubbing, lengthen the contact length of the rubbing roller, increase the radius of the roller, increase the rotation speed of the roller, and slow down the stage movement speed. To do this, do the opposite. In addition, the description in Japanese Patent No. 4052558 can be referred to as conditions for the rubbing treatment.

- Photo-alignment layer -
A large number of documents and the like describe photo-alignment materials used in photo-alignment layers formed by light irradiation. For example, JP-A-2006-285197, JP-A-2007-76839, JP-A-2007-138138, JP-A-2007-94071, JP-A-2007-121721, JP-A-2007-140465, Azo compounds described in JP-A-2007-156439, JP-A-2007-133184, JP-A-2009-109831, JP-A-3883848, JP-A-4151746, JP-A-2002-229039 Aromatic ester compounds of, JP-A-2002-265541, maleimide and / or alkenyl-substituted nadimide compounds having photo-orientation units described in JP-A-2002-317013, Patent No. 4205195, Patent No. 4205198 Preferred examples include the photocrosslinkable silane derivative described in JP-T-2003-520878, JP-T-2004-529220, and photocrosslinkable polyimide, polyamide or ester described in JP-A-4162850. Particularly preferred are azo compounds, photocrosslinkable polyimides, polyamides, and esters.

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

The light source used for light irradiation includes known light sources such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury xenon lamps, carbon arc lamps, and various lasers (e.g., semiconductor lasers, helium neon). lasers, argon ion lasers, helium-cadmium lasers, YAG lasers), light-emitting diodes, cathode ray tubes, and the like.

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

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

<Protective layer>
Laminates according to the present disclosure may also have a protective layer.
The protective layer may be a layer that has sufficient strength to protect the liquid crystal layer and the like and is excellent in weather resistance such as ultraviolet light (UV (Ultra Violet) light) and wet heat. In addition, from the viewpoint of visibility and black density (ability to suppress glare due to reflected light from the outside, for example, suppression of glare from a fluorescent lamp), a protective layer having antireflection properties may be used.
The protective layer may be formed by applying a protective layer-forming coating liquid containing the components described below.

From the viewpoint of strength and weather resistance, the protective layer preferably contains a resin. The group consisting of siloxane resin, fluororesin, acrylic resin, melamine resin, polyolefin resin, polyester resin, polycarbonate resin, and urethane resin. It is more preferable to contain at least one resin selected from, and it is further preferable to contain at least one resin selected from the group consisting of siloxane resins having voids, fluororesins, acrylic resins, and urethane resins. .

-Refractive index of protective layer-
The refractive index of the protective layer is preferably 1.05 to 1.6, more preferably 1.2 to 1.5, even more preferably 1.2 to 1.4, from the viewpoint of visibility and antireflection properties. .
In the present disclosure, refractive index is the refractive index for light with a wavelength of 550 nm at 25°C.
In addition, when used for the exterior of automobiles, etc., the refractive index should be set in a range close to those refractive indices, that is, in the range of 1.4 to 1.5, in order to make contamination such as wax and gasoline inconspicuous. , dirt becomes less conspicuous, which is preferable.
In addition, the refractive index of each layer in the present disclosure is obtained by measuring the transmission spectrum with a spectrophotometer for a single film of the protective layer formed on the alkali-free glass OA-10G, and the transmittance obtained by the above measurement, The thickness and refractive index of each layer are obtained by performing a fitting analysis using the transmittance calculated by the optical interference method. It can also be measured using a Carnew precision refractometer (eg, "KPR-3000" manufactured by Shimadzu Corporation).
In the case of forming a protective layer having voids, if a siloxane resin or a fluororesin is included, the refractive index of the protective layer can be made 1.5 or less, preferably 1.4 or less. A good protective layer is easily obtained. Moreover, by including low refractive index particles, the same antireflection effect can be obtained even if the refractive index of the protective layer is lowered to 1.5 or less.

-Thickness of protective layer-
Although the thickness of the protective layer is not particularly limited, it is preferably 2 μm or more, more preferably 4 μm or more, even more preferably 4 μm to 50 μm, from the viewpoint of scratch resistance and three-dimensional moldability. Particularly preferred is between 4 μm and 20 μm.

- Fluororesin -
The fluororesin is not particularly limited, but includes those described in paragraphs 0076 to 0106 of JP-A-2009-217258 and paragraphs 0083 to 0127 of JP-A-2007-229999.
Examples of fluororesins include fluoroalkyl resins obtained by substituting fluorine for hydrogen in olefins, such as polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxyalkane, perfluoro There are copolymers such as ethylene propene and ethylene tetrafluoroethylene, and fluororesin dispersions which are copolymerized with an emulsifier or a component that enhances affinity with water and dispersed in water. Specific examples of such fluororesins include Lumiflon and Obligato manufactured by Asahi Glass Co., Ltd., Zeffle and Neoflon manufactured by Daikin Industries, Ltd., Teflon (registered trademark) manufactured by DuPont, and Kynar manufactured by Arkema.
Further, for example, a compound having at least one of a polymerizable functional group and a crosslinkable functional group and containing a fluorine atom may be used, such as perfluoroalkyl (meth)acrylate, vinyl fluoride monomer, fluorine Examples include radically polymerizable monomers such as vinylidene chloride monomers and cationically polymerizable monomers such as perfluorooxetane. Specific examples of such fluorine compounds include LINC3A manufactured by Kyoeisha Chemical Co., Ltd., Optool manufactured by Daikin Industries, Ltd., Opstar manufactured by Arakawa Chemical Industries, Ltd., and tetrafluorooxetane manufactured by Daikin Industries, Ltd. .

- Low refractive index particles -
Low refractive index particles, preferably particles having a refractive index of 1.45 or less, are not particularly limited, but include those described in paragraphs 0075 to 0103 of JP-A-2009-217258.
Examples of low refractive index particles include inorganic oxide particles such as silica, hollow particles using resin particles such as acrylic resin particles, porous particles having a porous structure on the particle surface, and materials whose refractive index is low. and low fluoride particles.
Specific examples of such hollow particles include Sururia manufactured by JGC Catalysts & Chemicals Co., Ltd., Silinax manufactured by Nittetsu Mining Co., Ltd., Techpolymer MBX, SBX, NH manufactured by Sekisui Plastics Co., Ltd., multi-hollow particles, etc. However, specific examples of porous particles include Light Star manufactured by Nissan Chemical Industries, Ltd., and specific examples of fluoride particles include magnesium fluoride nanoparticles manufactured by Rare Metals Research Institute Co., Ltd. . Core-shell particles may also be used to form closed voids in a matrix comprising the resin.
Examples of the method of forming a protective layer by applying a protective layer-forming coating liquid containing hollow particles include, for example, the method described in paragraphs 0028 to 0029 of JP-A-2009-103808, or JP-A-2008-262187. paragraphs 0030 to 0031, or paragraph 0018 of JP-A-2017-500384 can be applied.

-Siloxane resin, siloxane compound-
The protective layer-forming coating liquid preferably contains a siloxane compound. A suitable siloxane resin can be obtained by subjecting the siloxane compound to hydrolytic condensation.
In particular, as the siloxane compound, at least one compound selected from the group consisting of a siloxane compound represented by the following formula 1 and a hydrolytic condensate of the siloxane compound represented by the following formula 1 (hereinafter referred to as a specific siloxane Also referred to as a compound.) is preferred.

In Formula 1, R ¹ , R ² and R ³ each independently represent an alkyl group having 1 to 6 carbon atoms or an alkenyl group, and R ⁴ is each independently an alkyl group, vinyl group, Alternatively, vinyl group, epoxy group, vinylphenyl group, (meth)acryloxy group, (meth)acrylamide group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyoxyalkyl group, carboxy group and quaternary represents an alkyl group having a group selected from the group consisting of an ammonium group, m represents an integer of 0-2, and n represents an integer of 1-20.

The hydrolytic condensate of the siloxane compound represented by Formula 1 is obtained by hydrolyzing at least a part of the siloxane compound represented by Formula 1 and the substituents on the silicon atoms in the siloxane compound represented by Formula 1. , and a compound having a silanol group are condensed.

The alkyl group or alkenyl group having 1 to 6 carbon atoms in R ¹ , R ² and R ³ in Formula 1 may be linear, branched, or have a ring structure. good too. The alkyl group or alkenyl group having 1 to 6 carbon atoms is preferably an alkyl group from the viewpoint of strength, light transmittance and haze of the protective layer.
Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, n-hexyl group and cyclohexyl group. is preferably a methyl group or an ethyl group, more preferably a methyl group.
R ⁴ in Formula 1 is preferably an alkyl group, more preferably an alkyl group having 1 to 8 carbon atoms, from the viewpoint of the strength, light transmittance and haze of the protective layer. preferable.
The number of carbon atoms in R ⁴ in Formula 1 is preferably 1-40, more preferably 1-20, and particularly preferably 1-8.
m in Formula 1 is preferably 1 or 2, more preferably 2, from the viewpoint of the strength, light transmittance and haze of the protective layer.
n in Formula 1 is preferably an integer of 2 to 20 from the viewpoint of the strength, light transmittance and haze of the protective layer.

Examples of specific siloxane compounds include Shin-Etsu Chemical Co., Ltd. KBE-04, KBE-13, KBE-22, KBE-1003, KBM-303, KBE-403, KBM-1403, KBE-503, KBM- 5103, KBE-903, KBE-9103P, KBE-585, KBE-803, KBE-846, KR-500, KR-515, KR-516, KR-517, KR-518, X-12-1135, X- Dynasylan 4150 manufactured by Evonik Japan Co., Ltd.; MKC silicate MS51, MKC silicate MS56, MKC silicate MS57, MKC silicate MS56S manufactured by Mitsubishi Chemical Corporation; Ethyl silicate manufactured by Colcoat Co., Ltd. 28, N-propyl silicate, N-butyl silicate, SS-101;
It may also contain a condensation catalyst that promotes condensation of the siloxane compound.
By including a condensation catalyst in the protective layer-forming coating liquid, a protective layer having more excellent durability can be formed.
The condensation catalyst is not particularly limited, and known condensation catalysts can be used.

-Urethane resin-
A urethane resin that can be suitably used for the protective layer can be obtained by a reaction of a polyisocyanate compound (for example, a diisocyanate compound) and a polyol, or a polymerization reaction of a urethane (meth)acrylate compound.

Examples of polyols used in synthesizing polyurethane resins include polyester polyols, polyether polyols, polycarbonate polyols, and polyacrylic polyols. Among them, polyester polyol or polyacrylic polyol is preferable from the viewpoint of impact resistance.

A polyester polyol can be obtained by a known method using an esterification reaction using a polybasic acid and a polyhydric alcohol.

A polycarboxylic acid is used as the polybasic acid component of the polyester polyol, but if necessary, a monobasic fatty acid or the like may also be used together. Examples of polycarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydroisophthalic acid, hexahydrophthalic acid, hexahydroterephthalic acid, trimellitic acid, pyromellitic acid, and other such aromatic Polycarboxylic acids, adipic acid, sebacic acid, succinic acid, azelaic acid, fumaric acid, maleic acid, itaconic acid, and other such aliphatic polycarboxylic acids and their anhydrides. These polybasic acids may be used alone, or it is possible to use a combination of two or more thereof.

Examples of polyhydric alcohol components of polyester polyols, and likewise polyhydric alcohols used in the synthesis of polyurethane resins, include glycols and trihydric or higher polyhydric alcohols. Examples of glycols are ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, hexylene glycol, 1,3-butanediol, 1,4- butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, methylpropanediol, cyclohexanedimethanol, 3,3-diethyl-1,5- Including pentanediol and the like. Examples of trihydric or higher polyhydric alcohols include glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and the like. These polyhydric alcohols can be used alone, or two or more of them can be used in combination.

Examples of dimethylol alkanoates include dimethylol propionate, dimethylol butanoate, dimethylol pentanoate, dimethylol heptanoate, dimethylol octanoate, and dimethylol nonanoate. These dimethylol alkanoates can be used alone, or a combination of two or more thereof can be used.

Various known polyacrylic polyols having a hydroxyl group capable of reacting with an isocyanate group can be used as the polyacrylic polyol. For example, (meth)acrylic acid, various (meth)acrylic acids to which a hydroxy group is added, (meth)acrylic acid alkyl esters, (meth)acrylamide and derivatives thereof, carboxylic acid esters of vinyl alcohol, unsaturated carboxylic acids, Polyacrylic polyols containing at least one or more monomers such as hydrocarbons having chain unsaturated alkyl moieties can be mentioned.

Examples of polyisocyanate compounds are 4,4′-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, p- or m-phenylene diisocyanate, xylylene diisocyanate, and m - aromatic diisocyanates such as tetramethylxylylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexylmethane diisocyanate, and cycloaliphatic diisocyanates such as hydrogenated tolylene diisocyanate, and Including aliphatic diisocyanates such as hexamethylene diisocyanate. Among these, alicyclic diisocyanates are preferred in terms of resistance to fading and the like. These diisocyanate compounds may be used alone, or it is possible to use combinations of two or more thereof.

Urethane (meth)acrylate will be explained. A method for producing urethane (meth)acrylate includes, for example, a method of subjecting a compound having a hydroxyl group and a (meth)acryloyl group to a polyisocyanate compound for a urethanization reaction.

Compounds having a hydroxy group and a (meth)acryloyl group include, for example, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxy-n-butyl (meth)acrylate, 2-hydroxypropyl (Meth) acrylate, 2-hydroxy-n-butyl (meth) acrylate, 3-hydroxy-n-butyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N-(2-hydroxyethyl) (Meth)acrylamide, glycerin mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, 2-(meth)acryloyloxyethyl- 2-hydroxyethyl phthalate, monofunctional (meth)acrylates having a hydroxyl group such as lactone-modified (meth)acrylates having a terminal hydroxyl group; trimethylolpropane di(meth)acrylate, isocyanuric acid ethylene oxide (EO)-modified diacrylate , pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate and other polyfunctional (meth)acrylates having a hydroxy group. , pentaerythritol triacrylate or dipentaerythritol pentaacrylate are preferred. These compounds having a hydroxy group and a (meth)acryloyl group can be used alone or in combination of two or more.

Examples of polyisocyanates include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, m-xylylene diisocyanate, m-phenylenebis(dimethylmethylene) diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, 1,3-bis(isocyanato Aliphatic or alicyclic diisocyanates such as methyl)cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate etc.

Urethane (meth)acrylate can be cured by irradiation with actinic rays. The actinic rays refer to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When the protective layer is cured by irradiating ultraviolet rays as actinic rays after molding, it is preferable to add a photopolymerization initiator to the protective layer to improve curability. Moreover, if necessary, a photosensitizer can be further added to improve curability.

-Surfactant-
The protective layer-forming coating liquid preferably contains a surfactant.
Examples of surfactants include nonionic surfactants, anionic surfactants that are ionic surfactants, cationic surfactants, amphoteric surfactants, and the like, all of which can be suitably used in the present disclosure.

-Other ingredients-
The protective layer-forming coating solution may contain other components in addition to the components described above, depending on the purpose.
As other components, known additives can be used, such as antistatic agents and preservatives.

- Antistatic agent -
The protective layer-forming coating liquid may contain an antistatic agent.
Antistatic agents are used for the purpose of suppressing adhesion of contaminants by imparting antistatic properties to the protective layer.
The antistatic agent for imparting antistatic properties is not particularly limited.
As the antistatic agent used in the protective layer, at least one selected from the group consisting of metal oxide particles, metal nanoparticles, conductive polymers, and ionic liquids can be preferably used. Antistatic agents may be used in combination of two or more.
Metal oxide particles need to be added in a relatively large amount in order to impart antistatic properties, but since they are inorganic particles, the inclusion of metal oxide particles further enhances the antifouling properties of the protective layer. can be done.

The metal oxide particles are not particularly limited, but include tin oxide particles, antimony-doped tin oxide particles, tin-doped indium oxide particles, zinc oxide particles, silica particles and the like.
Metal oxide particles have a large refractive index, and if the particle size is large, there is a concern that light transmission may decrease due to scattering of transmitted light. It is more preferably 30 nm or less, and particularly preferably 30 nm or less. Also, the lower limit is preferably 2 nm or more.
The shape of the particles is not particularly limited, and may be spherical, plate-like, or needle-like.
The average primary particle size of the metal oxide particles can be determined from the photograph obtained by observing the dispersed particles with a transmission electron microscope. From the photographic image, the projected area of the particles is determined, and the equivalent circle diameter is determined therefrom and taken as the average particle diameter (average primary particle diameter). The average primary particle diameter in the present disclosure is a value calculated by measuring the projected area of 300 or more particles and determining the equivalent circle diameter.
When the shape of the metal oxide particles is not spherical, other methods such as dynamic light scattering may be used.

One type of antistatic agent may be contained in the protective layer-forming coating liquid, or two or more types may be contained. When two or more kinds of metal oxide particles are contained, two or more kinds of particles different in average primary particle diameter, shape and material from each other may be used.
In the protective layer-forming coating liquid, the content of the antistatic agent is preferably 40% by mass or less, more preferably 30% by mass or less, based on the total solid content of the protective layer-forming coating liquid. 20% by mass or less is particularly preferable.
By setting the content of the antistatic agent within the above range, it is possible to effectively impart antistatic properties to the protective layer without lowering the film-forming properties of the protective layer-forming coating liquid.
When metal oxide particles are used as an antistatic agent, the content is preferably 30% by mass or less, more preferably 20% by mass or less, relative to the total mass of the coating liquid for forming a protective layer. , 10% by mass or less.
By setting the content of the metal oxide particles within the above range, the dispersibility of the metal oxide particles in the coating liquid for forming the protective layer is improved, the occurrence of aggregation is suppressed, and the necessary antistatic property is imparted to the protective layer. can do.

-Preparation of coating solution for forming protective layer-
The method for preparing the coating solution for forming a protective layer is not particularly limited. A method for producing a coating liquid for forming a protective layer by forming a shell layer on the surface of an organic solvent dispersed by hydrolytic condensation to prepare core-shell particles, and mixing an organic solvent, a surfactant, the above-described resin, and a monomer. and the like.

-Formation of protective layer-
The protective layer forming coating solution described above is applied onto the lower layer of the protective layer and dried to form the protective layer.
The method of applying the protective layer-forming coating liquid is not particularly limited, and any of known coating methods such as spray coating, brush coating, roller coating, bar coating, and dip coating can be applied.
Before applying the protective layer-forming coating liquid, the lower layer to which the protective layer-forming coating liquid is applied may be subjected to surface treatment such as corona discharge treatment, glow treatment, atmospheric pressure plasma treatment, flame treatment, and ultraviolet irradiation treatment. may be applied.

Drying of the protective layer-forming coating solution may be performed at room temperature (25° C.) or by heating. From the viewpoint of sufficiently volatilizing the organic solvent contained in the coating liquid for forming the protective layer, the light transmittance of the protective layer and the suppression of coloration, and furthermore, the decomposition temperature of the resin base material when the resin base material is used as the base material It is preferable to heat to 40° C. to 200° C. from the point of heating at the following temperature. Further, from the viewpoint of suppressing thermal deformation of the resin base material, it is more preferable to perform heating at 40°C to 120°C.
When heating is performed, the heating time is not particularly limited, but is preferably 1 minute to 30 minutes.

In addition, the method of forming the protective layer is not particularly limited. Examples include a method of laminating the protective layer to the lower layer, and a method of laminating the protective layer to the lower layer via an adhesive.

<Resin layer>
In a mode including a colored layer, the laminate according to the present disclosure may further have a resin layer between the liquid crystal layer and the colored layer in order to ensure the flatness of the liquid crystal layer.
The resin layer is preferably a layer containing a different kind of resin from the protective layer.
From the viewpoint of visibility, the resin layer is preferably a transparent resin layer, more preferably a layer made of a transparent film.
The transparent film is not particularly limited as long as it has the required strength and scratch resistance.
In the present disclosure, "transparent" in the transparent film means having a total light transmittance of 85% or more. The total light transmittance of the transparent film can be measured by the same method as the total light transmittance of the colored layer described above.

The transparent film is preferably a film obtained by forming a transparent resin, specifically polyethylene terephthalate (PET), polyethylene naphthalate (PEN), acrylic resin, polycarbonate (PC), triacetyl cellulose (TAC ) and resin films containing resins such as cycloolefin polymer (COP).
In particular, from the viewpoint of conformability to molds, acrylic resin, polycarbonate, or polyethylene terephthalate is added to 60% by mass or more (more preferably 80% by mass or more, more preferably 100% by mass) of the total resin components contained in the transparent film. % by mass) is preferred. In particular, a resin film containing 60% by mass or more (more preferably 80% by mass or more, still more preferably 100% by mass) of an acrylic resin based on the total resin components contained in the transparent film is more preferable.
The thickness of the resin layer is not particularly limited, but is preferably 50 μm to 150 μm.

As the transparent film, a commercially available product may be used. Commercially available products include, for example, Acryprene (registered trademark) HBS010 (acrylic resin film, manufactured by Mitsubishi Chemical Corporation), Technoloy (registered trademark) S001G (acrylic resin film, Sumitomo Chemical Co., Ltd.), C000 (polycarbonate resin film, Sumitomo Chemical Co., Ltd.), C001 (acrylic resin/polycarbonate resin laminated film, Sumitomo Chemical Co., Ltd.), and the like.

-Formation of resin layer-
A method for forming the resin layer is not particularly limited, but a method of laminating a transparent film on the colored layer is preferable.
As an apparatus used for laminating a transparent film, a known laminator such as a laminator, a vacuum laminator, and an autocut laminator capable of further improving productivity can be used.
Preferably, the laminator is equipped with any heatable roller, such as a rubber roller, and can be applied with pressure and heat.
At least one of the transparent film and the liquid crystal layer is partially melted by the heat from the laminator, and the adhesion between the liquid crystal layer and the transparent film can be further enhanced.

The temperature at which the transparent film is laminated may be determined according to the material of the transparent film, the melting temperature of the liquid crystal layer, etc., but it is preferable that the temperature of the transparent film can be 60°C to 150°C. , 65°C to 130°C, and particularly preferably 70°C to 100°C.

Further, when laminating the transparent film, it is preferable to apply a linear pressure of 60 N/cm to 200 N/cm, more preferably 70 N/cm to 160 N/cm, between the transparent film and the liquid crystal layer. , a linear pressure of 80 N/cm to 120 N/cm is particularly preferred.

<Adhesive layer>
The laminate according to the present disclosure may have an adhesive layer from the viewpoint of facilitating attachment to other members (preferably other molding members) and enhancing adhesion between layers.
The material of the adhesive layer is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include known adhesives or adhesive layers containing adhesives. From the viewpoint of light resistance, the adhesive layer preferably contains an ultraviolet absorber. Examples of the ultraviolet absorber include those described below for the ultraviolet absorbing layer.

-Adhesive-
Examples of adhesives include acrylic adhesives, rubber adhesives, and silicone adhesives. Also, as examples of adhesives, acrylic adhesives and ultraviolet (UV) curable adhesives described in Chapter 2 of "Release Paper/Release Film and Adhesive Tape Characteristic Evaluation and Control Technology", Information Organization, 2004 agents, silicone adhesives, and the like. The acrylic pressure-sensitive adhesive refers to a pressure-sensitive adhesive containing a polymer of (meth)acrylic monomers ((meth)acrylic polymer).
When a pressure-sensitive adhesive is included, a tackifier may also be included.

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

-Method of forming adhesive layer-
The method of forming the adhesive layer is not particularly limited, and a protective film having an adhesive layer formed thereon is laminated so that the adhesive layer and the adherend (e.g., liquid crystal layer, substrate, colored layer, etc.) are in contact with each other. , a method of laminating an adhesive layer alone so as to be in contact with an adherend, a method of applying a pressure-sensitive adhesive or a composition containing an adhesive onto an adherend, and the like. As the lamination method or application method, the same methods as the above-described transparent film lamination method or the application method of the colored layer forming composition are preferably used.

The thickness of the adhesive layer in the laminate is preferably 5 μm to 100 μm from the viewpoint of both adhesive strength and handling properties.

<Ultraviolet absorption layer>
The laminate according to the present disclosure preferably has an ultraviolet (UV) absorption layer from the viewpoint of light resistance, and has an ultraviolet absorption layer at a position where the liquid crystal layer cured through the ultraviolet absorption layer is visible. is more preferred.
The ultraviolet absorption layer is preferably a layer containing an ultraviolet absorber, more preferably a layer containing an ultraviolet absorber and a binder polymer.
As the ultraviolet absorber, any known ultraviolet absorber can be used without particular limitation, and it may be an organic compound or an inorganic compound.
Examples of ultraviolet absorbers include triazine compounds, benzotriazole compounds, benzophenone compounds, salicylic acid compounds, and metal oxide particles. Further, the ultraviolet absorber may be a polymer containing an ultraviolet absorbing structure, and the polymer containing an ultraviolet absorbing structure includes at least part of the structure of a triazine compound, a benzotriazole compound, a benzophenone compound, a salicylic acid compound, or the like. Examples thereof include acrylic resins containing monomer units derived from acrylic acid ester compounds.
Examples of metal oxide particles include titanium oxide particles, zinc oxide particles, and cerium oxide particles.
Examples of binder polymers include polyolefins, acrylic resins, polyesters, fluororesins, siloxane resins and polyurethanes.
The UV-absorbing layer is formed by coating each component contained in the UV-absorbing layer and a UV-absorbing layer-forming coating solution containing a solvent, if necessary, onto the surface base material, and drying if necessary. .

The thickness of the ultraviolet absorption layer is not particularly limited, but from the viewpoint of light resistance and three-dimensional moldability, it is preferably 0.01 μm to 100 μm, more preferably 0.1 μm to 50 μm, and 0.5 μm. ~20 μm is particularly preferred.

<Optical mask layer>
A laminate according to the present disclosure may include an optical mask layer, described below, for patterning the liquid crystal layer during its manufacturing process. For example, in the laminate according to the present disclosure, between the substrate and the liquid crystal layer, the surface of the liquid crystal layer opposite to the side having the substrate, the surface of the substrate opposite to the side having the liquid crystal layer, etc. An optical mask layer may be provided.

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

<Cover film>
The laminate according to the present disclosure may have a cover film as the outermost layer for the purpose of preventing contamination and the like.
As the cover film, any material having flexibility and good releasability can be used without any particular limitation, and examples thereof include resin films such as polyethylene films.
The method of attaching the cover film is not particularly limited, and includes known attaching methods, such as a method of laminating the cover film on the protective layer.

<Preferred Layer Structure of Laminate>
The layer structure of the laminate according to the present disclosure is not particularly limited except that it has a substrate and a cured liquid crystal layer. It is preferably mentioned. In addition, in each layer structure described below, it is preferable that the outermost layer is viewed from the side of the layer described on the right side.
Layer structure 1: Base material/optical mask layer/cured liquid crystal layer Layer structure 2: Optical mask layer/base material/cured liquid crystal layer Layer structure 3: Colored layer/optical mask layer/hardened liquid crystal layer/base layer Layer structure 4: Coloring Layer/optical mask layer/substrate/cured liquid crystal layer Among these, in the exemplary embodiment described above, the layer configuration 4 is most preferable from the viewpoint of patterning properties and suppressing visibility of the optical mask layer.
Furthermore, in the above-described exemplary embodiment, from the viewpoint of adhesion to other members, the laminate includes the layers described on the right side as the outermost layer in each layer configuration (that is, layer configuration 1, layer configuration 2, and layer configuration It is preferable to further have an adhesive layer on the side of the liquid crystal layer in 4 and on the side of the substrate in layer structure 3).
Furthermore, from the viewpoint of light resistance, the laminate according to the present disclosure preferably contains an ultraviolet absorber in the adhesive layer or further has an ultraviolet absorbing layer. The position of the ultraviolet absorbing layer is preferably a position where the cured liquid crystal layer can be visually recognized through the ultraviolet absorbing layer.

The laminate according to the present disclosure (in one aspect, the decorative molded film) is not particularly limited in application and can be used in various applications, for example, interior and exterior of housing panels of electronic devices, electronic devices, automobiles interior and exterior (for example, automobile exterior panels), interior and exterior of electrical appliances, packaging containers, housings of electrical appliances, covers for smartphones and tablets, and the like. Among them, it may be preferably used for housing panels of electronic devices, particularly exteriors of housing panels of electronic devices, and interior and exterior applications of electric products.

(Molded products, housing panels for electronic devices)
A molded product according to the present disclosure is a molded product obtained by molding a laminate (in one aspect, a decorative molded film) according to the present disclosure.
Further, the molded product according to the present disclosure is preferably a molded product obtained by molding a laminate manufactured by the method for manufacturing a laminate according to the present disclosure.
Furthermore, although the method for producing the molded product according to the present disclosure is not particularly limited, it is preferably a molded product manufactured by the molding method according to the present disclosure, which will be described later.
The molded product according to the present disclosure is not particularly limited in use, and can be used for, for example, the same uses as those described above for the laminate according to the present disclosure.

The shape of the molded product according to the present disclosure is not particularly limited as long as it has a desired shape.
In addition, even if the molded product according to the present disclosure is obtained by molding only the shape of the laminate according to the present disclosure, as described later, the laminate is insert-molded and the laminate is integrally formed on the surface of the resin molded product. It may also be a molded article that has been made into.
The housing panel of the electronic device according to the present disclosure may have known members used for the housing panel of the electronic device, in addition to the molding according to the present disclosure.

(Laminate manufacturing method)
The manufacturing method of the laminate according to the present disclosure is not particularly limited, but it can be preferably manufactured by the method for manufacturing the laminate according to the present disclosure, which will be described below.
A method for manufacturing a laminate according to the present disclosure includes:
A substrate, a liquid crystal layer containing a liquid crystal compound and a photoisomerizable compound provided on the substrate, and a plurality of patterns adjacent to at least one of the liquid crystal layer and the substrate and having different light transmittances are formed on the surface. an optical mask layer formed inward (hereinafter sometimes referred to as a "liquid crystal material preparation step");
a step of irradiating the liquid crystal layer with light through the optical mask layer to photoisomerize the photoisomerizable compound (hereinafter sometimes referred to as a “photoisomerization step”).

Hereinafter, a method for manufacturing a laminate according to the present disclosure will be described in detail.

<Liquid crystal material preparation process>
The liquid crystal material preparation step comprises: a substrate; a liquid crystal layer containing a liquid crystal compound and a photoisomerizable compound provided on the substrate; and an optical mask layer in which a plurality of different patterns are formed in an in-plane direction.

-Base material-
As the base material, those described above for the laminate can be used.

- Optical mask layer -
The optical mask layer is adjacent to at least one of the liquid crystal layer and the substrate, and has a plurality of patterns with different light transmittances formed in the in-plane direction. In the photoisomerization step, which will be described later in detail, the liquid crystal is irradiated with light through an optical mask layer to photoisomerize the photoisomerizable compound in the liquid crystal layer, thereby forming a plurality of patterns with mutually different selective reflection wavelengths. It can be formed in the in-plane direction of the liquid crystal layer.
The optical mask layer has a region having a material for adjusting light transmittance and a region having no material for adjusting light transmittance, so that a plurality of patterns having different light transmittances are formed in the in-plane direction. It can be anything. For example, the optical mask layer may have a region printed with an ink containing a light-absorbing or reflective component and a non-printed region, as will be described later.

The optical mask layer may be adjacent to the substrate. For example, a liquid crystal layer may be provided on the side of the substrate opposite to the side adjacent to the optical mask layer.
Also, the optical mask layer may be adjacent to the liquid crystal layer. For example, an optical mask layer may be provided on the side of the liquid crystal layer opposite to the side having the substrate.
Also, the optical mask layer may be adjacent to both the substrate and the liquid crystal layer. For example, an optical mask layer may be provided between the substrate and the liquid crystal layer.

The optical mask layer is preferably patterned with a difference in light transmittance in the wavelength range of 250 nm to 400 nm. That is, at least some of the plurality of patterns of the optical mask layer preferably have different light transmittances in the wavelength range of 250 nm to 400 nm. When the photoisomerization of the photoisomerizable compound in the liquid crystal layer occurs in the wavelength range of 250 to 400 nm, the optical mask layer formed with a plurality of patterns having different light transmittances in the wavelength range of 250 to 400 nm allows the optical mask layer to have a light transmittance of 250 to 400 nm. The transmittance in the wavelength range of 400 nm varies in the in-plane direction. The photoisomerization rate of the photoisomerizable compound in the liquid crystal layer can be controlled in the in-plane direction according to the change in the transmittance in the in-plane direction. You can draw in layers. The plurality of patterns of the optical mask layer preferably have different light transmittances in the wavelength range of 280 nm to 380 nm, more preferably 300 nm to 350 nm.
In a plurality of patterns of the optical mask layer, the difference in maximum transmittance is preferably 30% or more, more preferably 50% or more, and even more preferably 75% or more. That is, the maximum values of the light transmittance of the plurality of patterns of the optical mask preferably differ by 30% or more, more preferably by 50% or more, and even more preferably by 75% or more. The greater the difference in transmittance, the better the patterning properties, and the more varied the color tone of the selective reflection pattern can be formed.
As long as the light transmittance in the wavelength range of 250 nm to 400 nm is different from each other in at least part of the plurality of patterns of the optical mask layer, the light transmittance in other wavelength regions is not particularly limited. The laminate according to the present disclosure preferably has a form in which the base color layer is visually recognized through the liquid crystal layer. It is preferable that the average transmittance of the inside is 50% or more. The average transmittance is more preferably 65% or higher, still more preferably 80% or higher.

The light transmittance of the pattern of the optical mask layer can be measured with a spectrophotometer (for example, a spectrophotometer "UV-2100" manufactured by Shimadzu Corporation).

The pattern of the optical mask layer preferably contains at least a component that absorbs or reflects light in the wavelength range of 250 nm to 400 nm and a binder. Colorants such as pigments and dyes, ultraviolet absorbers, and the like are preferably used as components that absorb light in the wavelength range of 250 nm to 400 nm.
From the viewpoint of durability, it is preferable to use a pigment or an ultraviolet absorber.

The pigment that can be contained in the pattern of the optical mask layer is not limited, and known inorganic pigments, organic pigments, and the like can be applied.
Examples of inorganic pigments include white pigments such as titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, and barium sulfate, carbon black, titanium black, titanium carbon, iron oxide, graphite, and the like. black pigment, iron oxide, barium yellow, cadmium red, chrome yellow and the like.
As the inorganic pigment, the inorganic pigments described in paragraphs 0015 and 0114 of JP-A-2005-7765 can also be applied.

Examples of organic pigments include phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; azo pigments such as azo red, azo yellow and azo orange; quinacridone pigments such as quinacridone red, syncash red and syncash magenta; perylene pigments such as perylene maroon; carbazole violet; anthrapyridine; flavanthrone yellow; isoindoline yellow;
Specific examples of organic pigments include C.I. I. Pigment Red 177, 179, 224, 242, 254, 255, 264; I. Pigment Yellow 138, 139, 150, 180, 185 and other yellow pigments, C.I. I. Pigment Orange 36, 38, 71 and other orange pigments, C.I. I. Pigment Green 7, 36, 58 and other green pigments, C.I. I. Pigment Blue 15:6, a blue pigment such as C.I. I. and purple pigments such as Pigment Violet 23.
As the organic pigment, the organic pigment described in paragraph 0093 of JP-A-2009-256572 can also be applied.

The pigment may include a pigment having light transmittance and light reflectivity (so-called luster pigment). Luster pigments include, for example, metallic luster pigments such as aluminum, copper, zinc, iron, nickel, tin, aluminum oxide, and alloys thereof, interference mica pigments, white mica pigments, graphite pigments, glass flake pigments, and the like. are mentioned. The bright pigment may be colorless or colored.
When light exposure is performed in molding the laminate, the bright pigment is preferably used within a range that does not interfere with curing by exposure.

Colorants that can be contained in the pattern of the optical mask layer may be used singly or in combination of two or more. Moreover, when using 2 or more types of coloring agents, you may combine an inorganic pigment and an organic pigment.
The content of the colorant in the pattern of the optical mask layer is preferably 1% by mass to 50% by mass with respect to the total mass of the pattern of the optical mask layer, from the viewpoint of expression of the desired color and suitability for molding. 5% to 50% by mass is more preferable, and 10% to 40% by mass is particularly preferable.

As the ultraviolet absorber that can be contained in the pattern of the optical mask layer, any known ultraviolet absorber can be used without particular limitation, and it may be an organic compound or an inorganic compound.
Examples of ultraviolet absorbers include triazine compounds, benzotriazole compounds, benzophenone compounds, salicylic acid compounds, and metal oxide particles. Further, the ultraviolet absorber may be a polymer containing an ultraviolet absorbing structure, and the polymer containing an ultraviolet absorbing structure includes at least part of the structure of a triazine compound, a benzotriazole compound, a benzophenone compound, a salicylic acid compound, or the like. Examples thereof include acrylic resins containing monomer units derived from acrylic acid ester compounds. Particularly preferred are triazine compounds.
Examples of metal oxide particles include titanium oxide particles, zinc oxide particles, and cerium oxide particles.

Binder polymers that can be contained in the pattern of the optical mask layer include polyolefins, acrylic resins, polyesters, fluororesins, siloxane resins and polyurethanes.

-Other additives-
The optical mask layer may contain additives other than those mentioned above, if necessary.
As other additives, known additives can be used, including surfactants, polymerization inhibitors, antioxidants, horizontal alignment agents, light stabilizers, and the like.

The distance between the optical mask layer and the liquid crystal layer is preferably short from the viewpoint of improving the sharpness of the pattern boundary by reducing the width of bleeding at the pattern boundary. The distance is preferably 150 μm or less, more preferably 100 μm or less, still more preferably 75 μm or less, and particularly preferably 50 μm or less. In order to shorten the distance between the optical mask layer and the liquid crystal layer, means such as reducing the thickness of the base material, which will be described later, can be considered.

-Formation of optical mask layer-
The optical mask layer forming step is not particularly limited, and may be a step of applying (for example, applying) a composition containing the above components to the substrate or liquid crystal layer.
The pattern of the optical mask layer is preferably formed by a printing method. Examples of the printing method include direct gravure printing, reverse gravure coating printing, screen printing, flexographic printing, offset printing, inkjet printing, and the like. A direct gravure printing method, a reverse gravure coating printing method, and a screen printing method are preferred, and a direct gravure printing method is more preferred.

The optical mask layer is formed by, for example, printing a printing ink containing a component that absorbs light in the wavelength range of 250 nm to 400 nm, a binder, and a solvent by the above printing method, and drying if necessary. you can The solvent is not particularly limited, and examples thereof include those described later in the liquid crystal composition.

The optical mask layer has a portion patterned with an ink containing component 1 having light absorption or reflection in the wavelength range of 250 nm to 400 nm, and light absorption in the wavelength range of 250 nm to 400 nm from this component, or It is also preferred to include both portions patterned with inks containing low reflectance components.

In particular, in a portion where a pattern is not formed with ink containing a component having light absorption or reflection, or where the printed film thickness is small, light absorption or reflectance in the wavelength range of 250 nm to 400 nm is higher than that of this component. By forming a pattern with an ink containing a component with a low molecular weight, the film thickness of the pattern of the optical mask layer becomes uniform, and the winding and handling properties of the substrate are improved. It is also preferred to provide an overcoat layer over the patterned portion of the ink containing a component that absorbs or reflects light in the wavelength range of 250 nm to 400 nm.

-Liquid crystal layer-
A liquid crystal layer containing a liquid crystal compound and a photoisomerizable compound is provided on the substrate.
In the liquid crystal layer, by changing at least one selected from the group consisting of the pitch of the helical structure in the liquid crystal layer, the refractive index, and the thickness, the color changes depending on the angle viewed and the color itself viewed. can be adjusted. The pitch of the helical structure can be easily adjusted by changing the amount of chiral agent added. Specifically, Fuji Film Research Report No. 50 (2005) p. 60-63 for a detailed description. The pitch of the helical structure can also be adjusted by adjusting the conditions such as the temperature, illuminance, and irradiation time for fixing the cholesteric alignment state.

In addition, the liquid crystal layer cured after the curing step described below preferably has a cholesteric liquid crystal compound fixed in a cholesteric alignment state. The cholesteric alignment state may include an alignment state that reflects right-handed circularly polarized light, an alignment state that reflects left-handed circularly polarized light, or both. The cholesteric liquid crystal compound is not particularly limited, and various known compounds can be used.

- Cholesteric Liquid Crystal Compounds -
The liquid crystal layer preferably contains a cholesteric liquid crystal compound.
Cholesteric liquid crystal compounds include a rod-like type and a disk-like type depending on their shape. Furthermore, low-molecular-weight and high-molecular-weight types are mentioned, respectively. In the present disclosure, the term "polymer" in cholesteric liquid crystal compounds refers to those having a degree of polymerization of 100 or more (Polymer Physics, Phase Transition Dynamics, Masao Doi, p.2, Iwanami Shoten, 1992).
Although any cholesteric liquid crystal compound can be used in the present disclosure, it is preferred to use a rod-like cholesteric liquid crystal compound.
In the present disclosure, when a layer formed from a liquid crystal composition containing a cholesteric liquid crystal compound (that is, a cured liquid crystal layer) is described, even if the formed liquid crystal layer does not contain a compound having liquid crystallinity, good. For example, the low-molecular-weight cholesteric liquid crystal compound has a group that reacts with heat, light, etc., and as a result, it is polymerized or crosslinked by the reaction with heat, light, etc., and has a high molecular weight and loses liquid crystallinity. It can be layers.
As the cholesteric liquid crystal compound, two or more rod-shaped cholesteric liquid crystal compounds, two or more discotic liquid crystal compounds, or a mixture of a rod-shaped cholesteric liquid crystal compound and a discotic liquid crystal compound may be used. It is more preferable to use a rod-shaped cholesteric liquid crystal compound or a disk-shaped cholesteric liquid crystal compound having a reactive group because it can reduce temperature change and humidity change, and at least one liquid crystal molecule has two or more reactive groups. It is even more preferable to have In the case of a mixture of two or more cholesteric liquid crystal compounds, at least one preferably has two or more reactive groups.

Moreover, it is preferable to use a cholesteric liquid crystal compound having two or more reactive groups with different crosslinking mechanisms. When the above compound is used, an optically anisotropic layer containing a polymer having an unreacted reactive group is prepared by selecting conditions and polymerizing only a part of two or more reactive groups. is preferred.
The crosslinking mechanism is not particularly limited, such as condensation reaction, hydrogen bonding, and polymerization, but the crosslinking mechanism of at least one of the above two or more reactive groups is preferably polymerization, and it is more preferable to use two or more different polymerizations. preferable. In the cross-linking reaction in the above cross-linking, not only vinyl groups, (meth)acryl groups, epoxy groups, oxetanyl groups and vinyl ether groups used for polymerization but also hydroxyl groups, carboxy groups and amino groups can be used.

A compound having two or more reactive groups with different cross-linking mechanisms in the present disclosure is a compound that can be cross-linked using stepwise different cross-linking reaction steps. The corresponding reactive groups react as functional groups. Further, for example, in the case of a polymer such as polyvinyl alcohol having a hydroxy group in a side chain, after performing a polymerization reaction to polymerize the polymer, when the hydroxy group in the side chain is crosslinked with an aldehyde or the like, two or more different In the present disclosure, a compound having two or more different reactive groups means that two or more different reactive groups are used in the liquid crystal layer at the time of forming the liquid crystal layer on the substrate or the like. Compounds with different reactive groups, which can then be crosslinked stepwise, are preferred.
Further, the reactive group is preferably a polymerizable group. Polymerizable groups include radically polymerizable groups and cationically polymerizable groups.
Among them, it is particularly preferable to use a cholesteric liquid crystal compound having two or more polymerizable groups.
As reaction conditions for stepwise cross-linking, any of a difference in temperature, a difference in wavelength of light (irradiation), and a difference in polymerization mechanism may be used. It is more preferable to control by the kind of polymerization initiator to be used.
As a combination of polymerizable groups, a combination of a radically polymerizable group and a cationic polymerizable group is preferable. Among them, a combination in which the radically polymerizable group is a vinyl group or a (meth)acrylic group and the cationic polymerizable group is an epoxy group, an oxetanyl group, or a vinyl ether group is particularly preferable because the reactivity can be easily controlled.
Among them, the cholesteric liquid crystal compound preferably has a radically polymerizable group from the viewpoint of reactivity and ease of fixation of the pitch of the helical structure.
Examples of reactive groups are shown below. Et represents an ethyl group, and n-Pr represents an n-propyl group.

Rod-shaped cholesteric liquid crystal compounds include azomethine compounds, azoxy compounds, cyanobiphenyl compounds, cyanophenyl ester compounds, benzoate ester compounds, cyclohexanecarboxylic acid phenyl ester compounds, cyanophenylcyclohexane compounds, cyano-substituted phenylpyrimidine compounds, and alkoxy-substituted phenylpyrimidine compounds. , phenyldioxane compounds, tolan compounds and alkenylcyclohexylbenzonitrile compounds. Not only low-molecular-weight cholesteric liquid crystal compounds as described above, but also high-molecular-weight cholesteric liquid-crystal compounds can be used. The polymer cholesteric liquid crystal compound is a polymer compound obtained by polymerizing a rod-like cholesteric liquid crystal compound having a low molecular weight reactive group. Examples of rod-shaped cholesteric liquid crystal compounds include those described in JP-A-2008-281989, JP-A-11-513019 (International Publication No. 97/00600) or JP-A-2006-526165.

Specific examples of the rod-shaped cholesteric liquid crystal compound are shown below, but are not limited thereto. The compounds shown below can be synthesized by the method described in Japanese Patent Publication No. 11-513019 (International Publication No. 97/00600).

Discotic cholesteric liquid crystal compounds include low-molecular-weight discotic cholesteric liquid crystal compounds such as monomers, and polymerizable discotic cholesteric liquid crystal compounds.
Examples of discotic cholesteric liquid crystal compounds include C.I. Destrade et al., Mol. Cryst. 71, 111 (1981), benzene derivatives, C.I. Destrade et al., Mol. Cryst. 122, 141 (1985); Physicslett, A, 78, 82 (1990); Kohne et al., Angew. Chem. 96, 70 (1984) and the cyclohexane derivative described in J. Am. M. In the report of Lehn et al., J. Am. Chem. Commun. , 1794 (1985); In the report of Zhang et al., J. Am. Am. Chem. Soc. 116, 2655 (1994), azacrown-based or phenylacetylene-based macrocycles.
The discotic cholesteric liquid crystal compound has a structure in which the various structures described above are used as a discotic core at the center of the molecule, and groups (L) such as straight-chain alkyl groups, alkoxy groups, and substituted benzoyloxy groups are radially substituted. They are liquid crystalline and include what is generally called discotic liquid crystals. However, when such a molecular assembly is uniformly oriented, it exhibits negative uniaxiality, but is not limited to this description. Examples of discotic cholesteric liquid crystal compounds include those described in paragraphs 0061 to 0075 of JP-A-2008-281989.
When a disk-shaped cholesteric liquid crystal compound having a reactive group is used as the cholesteric liquid crystal compound, it is fixed in any alignment state of horizontal alignment, vertical alignment, tilt alignment, and twist alignment in the cured liquid crystal layer described later. may

In a liquid crystal layer containing a cholesteric liquid crystal compound, a polymerizable monomer may be added to promote cross-linking of the cholesteric liquid crystal compound.
For example, a monomer or oligomer that has two or more ethylenically unsaturated bonds and undergoes addition polymerization upon irradiation with light can be used.
Such monomers and oligomers can include compounds having at least one addition polymerizable ethylenically unsaturated group in the molecule. Examples include monofunctional acrylates or monofunctional methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate and phenoxyethyl (meth)acrylate; polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate; ) acrylate, trimethylolethane triacrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane diacrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, di Pentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl) isocyanurate, tri(acryloyloxyethyl) ) cyanurate, glycerin tri(meth)acrylate; polyfunctional acrylates or polyfunctional methacrylates obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as trimethylolpropane and glycerin and then (meth)acrylated them. .

Furthermore, urethane acrylate compounds described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-B-48-64183, JP-B-49-43191 and polyester acrylate compounds described in JP-B-52-30490; and polyfunctional acrylates or methacrylates such as epoxy acrylate compounds which are reaction products of epoxy resins and (meth)acrylic acid.
Among these, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol penta(meth)acrylate are preferred.
In addition, the "polymerizable compound B" described in JP-A-11-133600 can also be mentioned as a suitable compound.
These monomers or oligomers may be used alone or in combination of two or more.

Cationic polymerizable monomers can also be used. For example, JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, JP-A-2001-55507, JP-A-2001-310938, JP-A-2001-310937, JP-A-2001-220526 and epoxy compounds, vinyl ether compounds, and oxetane compounds exemplified in each publication.
Epoxy compounds include the following aromatic epoxides, alicyclic epoxides and aliphatic epoxides.
Examples of aromatic epoxides include di- or polyglycidyl ethers of bisphenol A or its alkylene oxide adducts, di- or polyglycidyl ethers of hydrogenated bisphenol A or its alkylene oxide adducts, and novolac type epoxy resins. . Examples of the alkylene oxide include ethylene oxide and propylene oxide.
Cyclohexene oxide obtained by epoxidizing a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene ring with an appropriate oxidizing agent such as hydrogen peroxide or peracid as the alicyclic epoxide. or a cyclopentene oxide-containing compound.
Preferred aliphatic epoxides include di- or polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts. Representative examples thereof include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, Diglycidyl ether of alkylene glycol such as diglycidyl ether of 1,6-hexanediol, polyglycidyl ether of polyhydric alcohol such as di- or triglycidyl ether of glycerin or alkylene oxide adduct thereof, polyethylene glycol or alkylene oxide adduct thereof and diglycidyl ether of polyalkylene glycol such as diglycidyl ether of polypropylene glycol or its alkylene oxide adduct. Examples of the alkylene oxide include ethylene oxide and propylene oxide.

Monofunctional or bifunctional oxetane monomers can also be used as cationic polymerizable monomers. For example, 3-ethyl-3-hydroxymethyloxetane (trade name OXT101, manufactured by Toagosei Co., Ltd.), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene (trade name OXT121, etc.), 3 - Ethyl-3-(phenoxymethyl) oxetane (OXT211 etc.), di(1-ethyl-3-oxetanyl) methyl ether (OXT221 etc.), 3-ethyl-3-(2-ethylhexyloxymethyl) oxetane ( OXT212, etc.) can be preferably used, and in particular, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(phenoxymethyl)oxetane, di(1-ethyl-3-oxetanyl)methyl ether, etc. Any known monofunctional or polyfunctional oxetane compounds described in JP-A-2001-220526 and JP-A-2001-310937 can be used.

When two or more optically anisotropic layers made of a liquid crystal composition containing a cholesteric liquid crystal compound are laminated, the combination of the liquid crystal compounds is not particularly limited, and lamination of layers in which all of the cholesteric liquid crystal compounds are rod-shaped cholesteric liquid crystal compounds. As the cholesteric liquid crystal compound, either a laminate of a layer containing a discotic cholesteric liquid crystal compound and a layer containing a rod-like cholesteric liquid crystal compound, or a laminate of layers in which all of the cholesteric liquid crystal compounds are discotic cholesteric liquid crystal compounds. may be Also, the combination of the alignment states of the layers is not particularly limited, and cured liquid crystal layers having the same alignment state may be stacked, or cured liquid crystal layers having different alignment states may be stacked.

The liquid crystal layer may contain one type of cholesteric liquid crystal compound alone, or may contain two or more types thereof.
From the viewpoint of designability, the content of the cholesteric liquid crystal compound is preferably 30% by mass or more and 99% by mass or less, more preferably 40% by mass or more and 99% by mass or less, relative to the total mass of the liquid crystal layer. , more preferably 60% by mass or more and 99% by mass or less, and particularly preferably 70% by mass or more and 98% by mass or less.

-Crosslinking density in the cured liquid crystal layer of the laminate-
When a cholesteric liquid crystal compound having a radically polymerizable group is used in the liquid crystal layer, the cross-linking density by the radically polymerizable group in the cured liquid crystal layer in the laminate according to the present disclosure is effective for fixation of liquid crystal alignment, three-dimensional moldability, and molding. From the viewpoint of suppressing reflectance change later, it is preferably 0.05 mol/L or more and 1 mol/L or less, more preferably 0.1 mol/L or more and 0.5 mol/L or less, and 0.15 mol/L. 0.45 mol/L or less is more preferable, and 0.2 mol/L or more and 0.4 mol/L or less is particularly preferable.
The cross-linking density is measured as follows using "FT/IR-4000" manufactured by JASCO Corporation.
A liquid crystal layer is formed on a silicon wafer SiD-4 manufactured by Canosys.
The reaction consumption rate of the C=C double bond (ethylenically unsaturated bond) is estimated by the following formula, and the equivalent amount (mol/L) of the C=C double bond contained in the liquid crystal layer is calculated from the amount added in the prescription. and multiplied by the reaction consumption rate, the crosslink density by the radically polymerizable groups in the cured liquid crystal layer is obtained.
Reaction consumption rate = (Peak intensity derived from C=C double bond before curing-Peak intensity derived from C=C double bond after curing)/Peak intensity derived from C=C double bond before curing

-Photoisomerizable compound-
The liquid crystal layer contains a photoisomerizable compound.
The photoisomerizable compound may be a compound that can be photoisomerized, but from the viewpoint of suppressing change in reflectance after molding and maintaining the isomerized structure, it is preferable that the compound changes its steric structure upon exposure to light. preferable.
In the photoisomerization step, the photoisomerization structure of the photoisomerization compound to be photoisomerized is not particularly limited. From the viewpoint, it is preferably a structure whose steric structure changes by exposure, more preferably has a disubstituted or more ethylenically unsaturated bond whose EZ configuration is isomerized by exposure, and 2 whose EZ configuration is isomerized by exposure. It is particularly preferred to have a substituted ethylenically unsaturated bond.
Isomerization of the EZ configuration in this disclosure also includes cis-trans isomerization.
Moreover, the disubstituted ethylenically unsaturated bond is preferably an ethylenically unsaturated bond in which an aromatic group and an ester bond are substituted.
In addition, the photoisomerizable compound may have only one photoisomerizable structure or may have two or more photoisomerizable structures. From the viewpoint of maintaining the structure, it is preferable to have two or more, more preferably two to four, and particularly preferably two.

Even when a photoisomerizable compound having a disubstituted or more ethylenically unsaturated bond is used as the photoisomerizable structure, in the liquid crystal layer, the photoisomerized portion of the photoisomerizable compound and the photoisomerizable compound The portion where is not photoisomerized can be confirmed by the presence or absence of the photoisomerizable compound that is not polymerized.

The photoisomerizable compound is preferably a photoisomerizable compound that also acts as a chiral agent, which will be described later.
The photoisomerizable compound that also acts as a chiral agent is preferably a chiral agent having a molar extinction coefficient of 30,000 or more at a wavelength of 313 nm.
Moreover, as a photoisomerizable compound that also acts as a chiral agent, a compound represented by the following formula (CH1) is preferably exemplified.
The compound represented by the following formula (CH1) can change the alignment structure such as the helical pitch (twisting force, helical twist angle) of the cholesteric liquid crystal phase depending on the amount of light irradiated.
In addition, the compound represented by the following formula (CH1) is a compound in which the EZ configuration of two ethylenically unsaturated bonds can be isomerized by exposure.

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

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

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

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

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

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

As the photoisomerizable compound, the compounds described below are preferably exemplified. Bu represents an n-butyl group.
In these compounds below, the steric configuration of each ethylenically unsaturated bond is E-form (trans-form), but changes to Z-form (cis-form) by exposure.

The liquid crystal layer may contain one type of photoisomerizable compound alone, or two or more types thereof.
The content of the photoisomerizable compound is not particularly limited, but from the viewpoint of suppressing change in reflectance after molding, it is preferably 1% by mass or more and 20% by mass or less with respect to the total mass of the liquid crystal layer, and 2% by mass. % or more and 10 mass % or less, more preferably 3 mass % or more and 9 mass % or less, and particularly preferably 4 mass % or more and 8 mass % or less.

- Chiral agent (optically active compound) -
The liquid crystal layer preferably contains a chiral agent (optically active compound) from the viewpoints of easiness of forming the liquid crystal layer and easiness of adjusting the pitch of the helical structure.
A chiral agent has a function of inducing a helical structure in a liquid crystal layer.
A chiral agent has a function of inducing a helical structure of a cholesteric liquid crystal phase. The chiral compound may be selected depending on the purpose, since the induced helical sense or helical pitch differs depending on the compound.
A known compound can be used as the chiral agent, but it preferably has a cinnamoyl group. Examples of chiral agents include Liquid Crystal Device Handbook (Chapter 3, Section 4-3, Chiral Agents for TN and STN, p. 199, Japan Society for the Promotion of Science, 142nd Committee, 1989).
, as well as Japanese Patent Application Laid-Open No. 2003-287623, Japanese Patent Application Laid-Open No. 2002-302487,
JP 2002-80478, JP 2002-80851, JP 2010-1
Compounds described in JP-A-81852 and JP-A-2014-034581 are exemplified.

The chiral agent preferably contains an asymmetric carbon atom, but an axially chiral compound or planar chiral compound that does not contain an asymmetric carbon atom can also be used as the chiral agent. Examples of axially or planarly chiral compounds include binaphthyl, helicene, paracyclophane and derivatives thereof.
Moreover, the chiral agent may have a polymerizable group.
When both the chiral agent and the cholesteric liquid crystal compound have a polymerizable group, the chiral agent having a polymerizable group (polymerizable chiral agent) and the cholesteric liquid crystal compound having a polymerizable group (polymerizable cholesteric liquid crystal compound) A polymer having a structural unit derived from a polymerizable cholesteric liquid crystal compound and a structural unit derived from a chiral agent can be formed by a polymerization reaction.
In this aspect, the polymerizable group possessed by the polymerizable chiral agent is preferably the same type of group as the polymerizable group possessed by the polymerizable cholesteric liquid crystal compound.
The polymerizable group of the chiral agent is preferably an ethylenically unsaturated group, an epoxy group or an aziridinyl group, more preferably an ethylenically unsaturated group, and particularly preferably an ethylenically unsaturated polymerizable group. .
Also, the chiral agent may be a cholestech liquid crystal compound.
Among them, the liquid crystal layer is composed of a photoisomerizable compound that also acts as a chiral agent as a chiral agent from the viewpoints of easiness of forming the liquid crystal layer, easiness of adjusting the pitch of the helical structure, and suppression of change in reflectance after molding. and more preferably at least one compound represented by the above formula (CH1).

As chiral agents, isosorbide derivatives, isomannide derivatives, binaphthyl derivatives and the like can be preferably used. As the isosorbide derivative, a commercially available product such as LC-756 manufactured by BASF may be used.

The liquid crystal layer may contain chiral agents singly or in combination of two or more.
The content of the chiral agent can be appropriately selected according to the structure of the cholesteric liquid crystal compound to be used and the desired pitch of the helical structure. From the viewpoint of suppressing reflectance change later, it is preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 10% by mass or less, and 3% by mass of the total mass of the liquid crystal layer. It is more preferably 9 mass % or more, and particularly preferably 4 mass % or more and 8 mass % or less.
In addition, the content of the chiral agent having a polymerizable group is preferably 0.2% by mass or more and 15% by mass or less with respect to the total mass of the liquid crystal layer from the viewpoint of suppressing change in reflectance after molding. 5% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 8% by mass or less, and particularly preferably 1.5% by mass or more and 5% by mass or less.
Furthermore, when a chiral agent having no polymerizable group is contained, the content of the chiral agent having no polymerizable group is 0.2% with respect to the total mass of the liquid crystal layer, from the viewpoint of suppressing change in reflectance after molding. It is preferably from 0.5% to 10% by mass, and particularly preferably from 2% to 8% by mass.
In addition, the pitch of the helical structure of the cholesteric liquid crystal in the liquid crystal layer, and the selective reflection wavelength and its range described later can be easily adjusted not only by the type of cholesteric liquid crystal compound used but also by adjusting the content of the chiral agent. can be changed. Although it cannot be generalized, if the content of the chiral agent in the liquid crystal layer is doubled, the pitch may be halved and the central value of the selective reflection wavelength may also be halved.

-Polymerization initiator-
The liquid crystal layer preferably contains a polymerization initiator, more preferably a photopolymerization initiator.
A known polymerization initiator can be used as the polymerization initiator.
Moreover, the polymerization initiator is preferably a photopolymerization initiator capable of initiating a polymerization reaction by ultraviolet irradiation.
Examples of photopolymerization initiators include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether compounds (described in US Pat. No. 2,448,828), α-hydrocarbon substituted Aromatic acyloin compounds (described in US Pat. No. 2,722,512), polynuclear quinone compounds (described in US Pat. Japanese Patent No. 3549367), acridine compounds and phenazine compounds (Japanese Patent Laid-Open No. 60-105667, US Pat. No. 4,239,850), oxadiazole compounds (US Pat. No. 4,212,970), etc. mentioned.

Moreover, a well-known thing can be used as a photoradical polymerization initiator.
Examples of photoradical polymerization initiators include α-hydroxyalkylphenone compounds, α-aminoalkylphenone compounds, acylphosphine oxide compounds, thioxanthone compounds (for example, "Kayacure DETX" (2,4-diethyl thioxanthone)), oxime ester compounds, and the like.
Further, as the photocationic polymerization initiator, a known one can be used.
As the photocationic polymerization initiator, iodonium salt compounds, sulfonium salt compounds and the like are preferably used.

The liquid crystal layer may contain one polymerization initiator alone, or may contain two or more polymerization initiators.
The content of the polymerization initiator can be appropriately selected according to the structure of the cholesteric liquid crystal compound to be used and the desired pitch of the helical structure. From the viewpoint of strength of the layer, it is preferably 0.05% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less, based on the total mass of the liquid crystal layer. It is more preferably 1% by mass or more and 4% by mass or less, and particularly preferably 0.2% by mass or more and 3% by mass or less.

-Crosslinking agent-
The liquid crystal layer may contain a cross-linking agent in order to improve the strength and durability of the liquid crystal layer after curing. As the cross-linking agent, one that is cured by ultraviolet rays, heat, humidity, or the like can be preferably used.
The cross-linking agent is not particularly limited and can be appropriately selected depending on the intended purpose. For example, polyfunctional acrylate compounds such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate; Epoxy compounds such as ethylene glycol diglycidyl ether, 3′,4′-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate; 2-ethylhexyloxetane, oxetane compounds such as xylylene bisoxetane; 2,2-bishydroxymethyl aziridine compounds such as butanol-tris[3-(1-aziridinyl)propionate] and 4,4-bis(ethyleneiminocarbonylamino)diphenylmethane; isocyanate compounds such as hexamethylene diisocyanate and biuret type isocyanate; having an oxazoline group in the side chain polyoxazoline compounds; alkoxysilane compounds such as vinyltrimethoxysilane and N-(2-aminoethyl)3-aminopropyltrimethoxysilane; Further, a known catalyst can be used depending on the reactivity of the cross-linking agent, and productivity can be improved in addition to improving the strength and durability of the liquid crystal layer.

The liquid crystal layer may contain one type of cross-linking agent alone, or two or more types thereof.
From the viewpoint of the strength and durability of the liquid crystal layer, the content of the cross-linking agent is preferably 1% by mass or more and 20% by mass or less, and 3% by mass or more and 15% by mass or less with respect to the total mass of the liquid crystal layer. is more preferable.

- Polyfunctional polymerizable compound -
The liquid crystal layer preferably contains a polyfunctional polymerizable compound from the viewpoint of suppression of change in reflectance after molding.
Examples of polyfunctional polymerizable compounds include 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 ethylene a cholesteric liquid crystal compound having no polyunsaturated groups, a cholesteric liquid crystal compound having two or more ethylenically unsaturated groups and two or more cyclic ether groups, a chiral agent having two or more polymerizable groups, and the cross-linking agents.
As the ethylenically unsaturated group, a (meth)acryl group is preferred, and a (meth)acryloxy group is more preferred.
As the cyclic ether group, an epoxy group and an oxetanyl group are preferred, and an oxetanyl group is more preferred.
Among them, as the polyfunctional polymerizable compound, a cholesteric liquid crystal compound having two or more ethylenically unsaturated groups and no cyclic ether group, a cholesteric liquid crystal compound having two or more cyclic ether groups and ethylenically unsaturated It preferably contains at least one compound selected from the group consisting of a group-free cholesteric liquid crystal compound and a chiral agent having two or more polymerizable groups, and a chiral agent having two or more polymerizable groups. It is more preferable to include

From the viewpoint of suppressing change in reflectance after molding, the content of the polyfunctional polymerizable compound is preferably 0.5% by mass or more and 70% by mass or less, and 1% by mass or more and 50% by mass of the total mass of the liquid crystal layer. It is 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-
The liquid crystal layer may contain additives other than those mentioned above, if necessary.
Other additives that can be used include known additives such as surfactants, polymerization inhibitors, antioxidants, horizontal alignment agents, UV absorbers, light stabilizers, colorants, and metal oxide particles. can be mentioned.

The liquid crystal layer forming step is not particularly limited, and is, for example, a step of applying (for example, coating) a liquid crystal composition containing a liquid crystal compound and a photoisomerizable compound to a substrate to form a film (liquid crystal layer). is preferred.

The details of the components contained in the liquid crystal composition are the same as those described above for the liquid crystal layer. shall be read as

In addition, from the viewpoint of facilitating application, the liquid crystal composition may contain a solvent. The solvent is not particularly limited and can be appropriately selected depending on the intended purpose, but an organic solvent is preferably used.
The organic solvent is not particularly limited and can be appropriately selected depending on the purpose. Examples include ketone compounds such as methyl ethyl ketone and methyl isobutyl ketone, alkyl halide compounds, amide compounds, sulfoxide compounds, heterocyclic compounds, and hydrocarbon compounds. , ester compounds, ether compounds, and alcohol compounds. These may be used individually by 1 type, and may use 2 or more types together. Among these, ketone compounds are particularly preferred in consideration of the load on the environment. Moreover, the above-mentioned component may function as a solvent.

When the liquid crystal composition contains a solvent, the content of the solvent is preferably 40% by mass to 90% by mass, more preferably 50% by mass to 80% by mass, relative to the total amount of the liquid crystal composition. preferable.

When a liquid crystal layer is formed using a liquid crystal composition containing a solvent, the solvent derived from the liquid crystal composition may remain in the liquid crystal layer after curing, and the liquid crystal layer after curing contains the solvent. You can stay.
The content of the solvent in the liquid crystal layer after curing is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 2% by mass or less, relative to the total mass of the liquid crystal layer. It is preferably 1% by mass or less, and particularly preferably 1% by mass or less.

The method of preparing the liquid crystal composition is not particularly limited, and for example, the liquid crystal composition may be prepared by a method of mixing each component such as a liquid crystal compound.

-Formation of liquid crystal layer-
The formation of the liquid crystal layer is carried out by turning the liquid crystal composition containing the above components into a solution state with a solvent, or by heating the liquid crystal composition into a liquid such as a melt, and applying the roll coating method, gravure printing method, or spin coating. It can be performed by a method of developing in an appropriate method such as a method. Furthermore, various methods such as wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating and die coating can be used. A coating film can also be formed by discharging the liquid crystal composition from a nozzle using an inkjet device.
When the above solvent is used, it is preferable to dry by a known method after applying the liquid crystal composition. For example, it may be dried by standing or may be dried by heating.
The amount of the liquid crystal composition to be applied may be appropriately set in consideration of the liquid crystal layer after drying.
In the liquid crystal layer after application and drying of the liquid crystal composition, it is preferable that the liquid crystal compound in the liquid crystal layer is oriented.

<Photoisomerization step>
The photoisomerization step is a step of irradiating the liquid crystal layer with light through the optical mask layer to photoisomerize the photoisomerizable compound contained in the liquid crystal layer. Thereby, a plurality of patterns having different selective reflection wavelengths can be formed in the in-plane direction of the liquid crystal layer.
In the photoisomerization step, it is preferable to isomerize part of the liquid crystal layer from the viewpoint of suppressing change in reflectance after molding, and it is more preferable to isomerize part of the liquid crystal layer depending on the shape to be molded. preferable.
Moreover, in the photoisomerization step, the isomerization ratio of the photoisomerization compound may be changed according to the shape to be molded. For example, the liquid crystal layer may have a portion where the isomerization ratio is 0% and a portion where the isomerization ratio is 100%, or a portion where the isomerization ratio changes from 0% to 100% may be formed in the liquid crystal layer. Alternatively, the liquid crystal layer may have a portion where the isomerization ratio is 0% and a portion where the isomerization ratio changes from 50% to 100%.
In particular, according to the shape to be molded, it is preferable that the isomerization ratio is higher in the portion where the stretch ratio of the laminate is increased during molding.

In the photoisomerization step, it is preferable to isomerize the photoisomerizable compound by exposing only a part of the liquid crystal layer. Also, the isomerization ratio can be controlled according to the exposure intensity.
The wavelength of light for photoisomerization in the photoisomerization step is not particularly limited, and may be appropriately selected according to the photoisomerizable compound.
The light to be exposed in the photoisomerization step may be light containing a photoisomerizable wavelength, but it is preferable to photoisomerize using at least light in the wavelength range of 400 nm or less, and in the wavelength range of 360 nm or less. It is more preferable to use light, and it is particularly preferable to perform photoisomerization using at least light in the wavelength range of 310 nm or more and 360 nm or less.
Known means and known methods can be used to adjust the exposure wavelength in the photoisomerization step. Examples thereof include a method using an optical filter, a method using two or more types of optical filters, and a method using a light source with a specific wavelength.
In the photoisomerization step, the exposure is preferably performed with light in a wavelength range in which the photopolymerization initiator in the liquid crystal layer does not generate polymerization initiation species. For example, an optical mask layer that transmits light in a wavelength range that causes photoisomerization of a photoisomeric compound and blocks light in a wavelength range that generates polymerization initiation species from the photopolymerization initiator can be preferably used.

Specific examples of the light source in the photoisomerization step include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and the like. Moreover, as a light source, a light-emitting diode or the like that can irradiate light with a narrow wavelength band can be used. In that case, a mask other than the optical mask layer may or may not be used as required.
The amount ^of exposure in the photoisomerization step ^is not particularly limited, ^and may be set as appropriate ^. It is more preferable to have Further, the exposure amount may be changed in each part of the liquid crystal layer according to the desired isomerization ratio.
Moreover, it is preferable to heat during the isomerization by exposure. The heating temperature is not particularly limited, and may be selected depending on the photoisomerizable compound used, and is, for example, 60°C to 120°C.
Further, the exposure method is not particularly limited as long as photoisomerization is possible. can be done.

From the viewpoint of improving the sharpness of the pattern boundary by reducing the width of bleeding at the pattern boundary, it is preferable to reduce the distance between the light source and the optical mask layer. The distance is preferably 2 mm or less, more preferably 1 mm or less, even more preferably 0.5 mm or less, and particularly preferably 0.1 mm or less.

<Curing process>
The method for producing a laminate according to the present disclosure preferably includes a step of curing the liquid crystal layer after the photoisomerization step (hereinafter also referred to as a “curing step”). The above-mentioned curing makes it easy to maintain and fix the alignment state of the molecules of the liquid crystal compound.
The curing is preferably carried out by a polymerization reaction of a polymerizable group such as an ethylenically unsaturated group or a cyclic ether group possessed by a compound contained in the liquid crystal layer.
Further, the curing may be performed by exposure or by heat.

The curing is preferably performed by exposure. When curing is performed by exposure, the liquid crystal layer preferably contains a photopolymerization initiator.
The light source for exposure can be appropriately selected and used according to the photopolymerization initiator. For example, a light source capable of irradiating light in a wavelength range (eg, 365 nm, 405 nm) is preferably used, and specific examples include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and the like.
^The amount of ^{exposure is} not particularly limited and may be set as appropriate ^. .
In addition, in order to facilitate alignment of the liquid crystal compound during curing by exposure, it is preferable to heat. The heating temperature is not particularly limited, and may be selected according to the composition of the liquid crystal layer to be cured.
Moreover, not only the liquid crystal layer is formed by the above-mentioned exposure, but also other layers such as a colored layer may be cured by exposure, if necessary.
Further, as the exposure method, for example, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can also be suitably used in the present disclosure.

The time between the photoisomerization step and the curing step is preferably 0.01 seconds or more and 10 minutes or less. It is more preferably 0.1 seconds or more and 5 minutes or less, still more preferably 0.2 seconds or more and 1 minute or less, and particularly preferably 0.5 seconds or more and 30 seconds or less. When the time between the photoisomerization step and the curing step is within the above range, the reorientation of the liquid crystal compound occurs in response to the photoisomerization at 0.01 seconds or more, and a pattern in which the reflected light is patterned is formed. It can be easily formed, and in 10 minutes or less, the thermal diffusion of the photoisomerized compound in the film can be easily suppressed, and the sharpness of the boundary of the pattern can be easily maintained.

Moreover, when the liquid crystal layer is cured by heat, the heating temperature and the heating time are not particularly limited, and may be appropriately selected according to the thermal polymerization initiator and the like to be used. For example, the heating temperature is preferably 60° C. or higher and 200° C. or lower, and the heating time is preferably 1 minute to 2 hours. The heating means is not particularly limited, and known heating means can be used. Examples thereof include heaters, ovens, hot plates, infrared lamps, infrared lasers, and the like.

Moreover, the oxygen concentration in the curing step is not limited, and may be carried out in an oxygen atmosphere, in the air, or in a low-oxygen atmosphere (preferably, oxygen concentration of 1,000 ppm or less). Furthermore, in order to accelerate curing, the curing step is preferably performed in a low-oxygen atmosphere, more preferably under heating and in a low-oxygen atmosphere.

<Other processes>
The method for manufacturing a laminate according to the present disclosure may optionally include other steps than the steps described above.
Other steps include, for example, a step of forming each layer described above, specifically a step of forming a colored layer, a step of forming a protective layer, a step of forming an adhesive layer, and the like.
Formation of each of the layers such as the colored layer can be performed using the above-described method or a known method.

(Manufacturing method of molding)
A method for manufacturing a molded article according to the present disclosure includes a step of molding a laminate according to the present disclosure or a laminate manufactured by a method for manufacturing a laminate according to the present disclosure.

<Molding process>
The laminate according to the present disclosure (in one aspect, the film for decorative molding) is excellent in moldability, and thus can be suitably used in the production of molded products. It is particularly suitable when producing a molding by molding at least one selected from
Hereinafter, a method for producing a molded product (molding method) will be described in detail, taking insert molding as an example.

In insert molding, a molded product is obtained, for example, by placing a laminate in advance in a mold and injection-molding a base resin in the mold. By this insert molding, a molded product in which the laminate is integrated with the surface of the resin molded product is obtained.

An embodiment of a method for producing a molded article by insert molding will be described below.
The method of manufacturing a molded product consists of the steps of placing the laminate in the mold for injection molding and closing the mold, then injecting the molten resin into the mold, and taking out the injected resin when it solidifies. Including process.

The mold for injection molding (i.e., molding mold) used to manufacture the decorative molded product includes a mold having a convex shape (i.e., male mold) and a mold having a concave shape corresponding to the convex shape (i.e., A female mold) is provided, and the mold is closed after the laminate is arranged on the molding surface, which is the inner peripheral surface of the female mold.

Here, before arranging the laminate in the molding die, the laminate is given a three-dimensional shape in advance by molding (preforming) the laminate using the molding die. It is also possible to place it and supply it to the molding die.
Further, when placing the laminate in the mold, it is necessary to align the laminate and the mold while the laminate is inserted into the mold.

As a method of aligning the laminate and the molding die while the laminate is inserted into the molding die, a method of inserting and holding fixing pins of the male die into the alignment holes of the female die. There is
Here, the positioning holes are formed in advance in the female die at the end of the laminate (the position where the three-dimensional shape is not given after molding).

In addition, the fixing pin is formed in advance at a position to be fitted in the positioning hole in the male mold.
In addition, as a method of aligning the laminate and the molding die while the laminate is inserted into the molding die, the following method can be used in addition to the method of inserting the fixing pin into the alignment hole. is possible.

For example, there is a method of finely adjusting and aligning the laminated body by driving the conveying device of the laminated body to a position alignment mark previously attached to a position where the three-dimensional shape is not imparted after molding. In this method, it is preferable to recognize the alignment mark at two or more diagonal points when viewed from the product portion of the injection molded product (decorative molded product).

After the laminate and the molding die are aligned and the molding die is closed, molten resin is injected into the molding die into which the laminate is inserted. At the time of injection, the molten resin is injected onto the resin substrate side of the laminate.

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

In addition, the position of the injection port (injection port) of the male mold was changed to prevent abnormal deformation of the laminate due to the heat and gas generated when the molten resin was injected into the mold. You may set according to the shape of a metal mold|die or the kind of molten resin.
After the molten resin injected into the molding die into which the laminate was inserted solidified, the molding die was opened, and the laminate was fixed from the molding die to the solidified molten resin forming base material. An intermediate decorative molding is taken out.

In the intermediate molding, the burr and the dummy portion of the molded product are integrated around the decorative portion that will be the final product (molded product). Here, the dummy portion has an insertion hole formed by inserting a fixing pin in the alignment described above.
For this reason, a molded product can be obtained by subjecting an intermediate molded product before finishing processing to finishing processing for removing the burrs and the dummy portion.

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

The above-mentioned vacuum molding can be performed using a vacuum molding technique widely known in the molding field.

<Other processes>
The method for manufacturing a molded product according to the present disclosure includes steps other than those described above, such as the step of attaching the laminate to the molding member, the step of removing burrs from the molded product as described above, and the step of removing the dummy from the molded product. Any other steps may be included as desired, such as removing portions.
Other steps are not particularly limited and can be performed using known means and methods.

EXAMPLES The present disclosure will be described in detail below with reference to Examples, but the present disclosure is not limited to these. In the present examples, "%" and "parts" mean "% by mass" and "parts by mass", respectively, unless otherwise specified.

(Example 1)
<Preparation of base material>
As a substrate, PET with an easy-adhesion layer (thickness: 38 μm, Cosmoshine (registered trademark) A4300, manufactured by Toyobo Co., Ltd.) was prepared.

<Production of optical mask layer>
Mask printing ink 1 was prepared having the composition described below.
-Composition of mask printing ink 1-
・Urethane-modified acrylic binder (8UA-301, solid content 30%): 35.00 parts by mass ・Cyclohexanone: 30.00 parts by mass ・Methyl ethyl ketone: 34.99 parts by mass ・Tinuvin479 (manufactured by BASF, UV absorber): 1 .00 parts by mass F553 (surfactant manufactured by DIC): 0.01 parts by mass

A pattern shown in FIG. 1 was printed on A4300 using mask printing ink 1 with a gravure printing machine (K printing proofer, manufactured by RK Print Coat Instruments). In FIG. 1, the area shown in black is the ink-printed portion, and the ink-printed portion and other portions have different light transmittances.
After printing, the film was dried at 80°C for 2 minutes to prepare a mask.
The thickest portion of the printed film thickness was 3.0 μm.
The in-plane average transmittance of the printed portion of the manufactured mask at 400 nm to 780 nm exceeded 90%. Moreover, the difference between the portion with the highest transmittance at a wavelength of 330 nm and the portion with the lowest transmittance in the optical mask layer exceeded 90%.

<Formation of liquid crystal alignment layer>
A liquid crystal alignment layer coating liquid 1 having the composition described below was prepared.
-Composition of coating liquid 1 for forming liquid crystal alignment layer-
・Modified polyvinyl alcohol (compound 1) having the structure shown below: 10.00 parts by mass ・Water: 55.00 parts by mass ・Methanol: 35.00 parts by mass

- Modified polyvinyl alcohol (compound 1): the following compound. The lower right number of each structural unit represents the molar ratio.

On the surface opposite to the surface of A4300 on which the optical mask layer was formed, the liquid crystal alignment layer forming coating liquid 1 was applied with a wire bar (count #10) and dried at 100 ° C. for 2 minutes to form a liquid crystal alignment layer. A laminate was obtained.
Next, the prepared liquid crystal alignment layer is rubbed in a direction rotated 3° counterclockwise with respect to the short side direction (rayon cloth, pressure 0.1 kgf, number of rotations 1,000 rpm, conveying speed 10 m / min, number of times 1 time) was applied.

<Formation of liquid crystal layer>
A coating liquid 1 for forming a liquid crystal layer having the composition described below was prepared.
-Composition of Liquid Crystal Layer Forming Coating Liquid 1-
Liquid crystal compound 1 (compound 2): 2.42 parts by mass Liquid crystal compound 2 (compound 5): 0.30 parts by mass Liquid crystal compound 3 (compound 6): 0.30 parts by mass Chiral agent 1 (LC756, 2 Chiral agent having two acryloxy groups and a liquid crystal structure, manufactured by BASF): 0.204 parts by mass Chiral agent 2 (compound 3): 0.023 parts by mass Photopolymerization initiator (Kayacure DETX, 2,4-diethylthioxanthone , Nippon Kayaku Co., Ltd.): 0.091 parts by mass Surfactant (Compound 4, methyl ethyl ketone (MEK) 1% diluted solution): 0.97 parts by mass Methyl ethyl ketone (solvent): 4.37 parts by mass Cyclohexanone (solvent): 1.33 parts by mass

Liquid crystal compound 1 (compound 2): the following compound

Chiral agent 2 (compound 3): the following compound. In the compounds below, Bu represents an n-butyl group.

Surfactant (compound 4): the following compound

Liquid crystal compound 2 (compound 5): the following compound

Liquid crystal compound 3 (compound 6): the following compound

After coating the liquid crystal layer forming coating liquid 1 on the liquid crystal alignment layer prepared above using a wire bar (count #10), drying treatment was performed at 85 ° C. for 2 minutes to form a liquid crystal layer with a thickness of 3 μm. .
Next, from the side on which the optical mask layer is formed, light from a metal halide lamp (MAL625NAL, manufactured by GS Yuasa Co., Ltd.) with an exposure amount of 50 mJ/cm ² is irradiated to the portion of the liquid crystal layer to be isomerized to perform isomerization treatment. gone.
Furthermore, on a hot plate at 85 ° C., light is irradiated from a metal halide lamp (MAL625NAL manufactured by GS Yuasa Co., Ltd.) with an exposure amount of 30 mJ / cm ² in a low oxygen atmosphere (oxygen concentration 1,000 ppm or less). By doing so, the liquid crystal layer was cured to obtain a laminate (decorative film for molding) each having an isomerized portion and a non-isomerized portion.

<Evaluation of laminate (decorative molded film)>
-Crosslinking density-
The crosslink density was evaluated using FT/IR-4000 manufactured by JASCO Corporation.
A liquid crystal alignment layer and a liquid crystal layer were formed by the above procedure on a silicon wafer SiD-4 manufactured by Canosys.
The reaction consumption rate of the C=C double bond (ethylenically unsaturated bond) is estimated by the following formula, and the equivalent amount of the C=C double bond (mol/L ) and multiplied by the reaction consumption rate, the cross-linking density of the ethylenically unsaturated bond of the liquid crystal layer was obtained.
Reaction consumption rate = (Peak intensity derived from C=C double bond before curing-Peak intensity derived from C=C double bond after curing)/Peak intensity derived from C=C double bond before curing

- Evaluation of reflection characteristics -
Reflection characteristics were evaluated using a spectrophotometer V-670 manufactured by JASCO Corporation.
Black PET (manufactured by Tomoegawa Paper Works Co., Ltd., trade name “Kukkiri Mieru”) was attached to the surface of the laminate with a liquid crystal layer produced on Technolloy C003 by the above procedure on which the liquid crystal layer was not formed, and the liquid crystal layer was formed. The reflection spectrum was measured using the formed surface as an incident surface, and the reflection wavelengths of the portions with the most different tints were measured.

<Formation of colored layer>
On the optical mask layer of the laminate, nax real super black paint manufactured by Nippon Paint Co., Ltd. was applied using a wire bar (#20) and dried at 100 ° C. for 2 minutes to give a 10 μm thick coloring. A layered laminate was obtained.

<Formation of adhesive layer>
On the surface on which the liquid crystal layer of the laminate with a colored layer is formed, an adhesive sheet having protective films on both sides (G25, thickness 25 μm, manufactured by Nichiei Kako Co., Ltd.) After peeling off the protective film on one side, the temporary support A decorative molding film was obtained by laminating an adhesive sheet (temperature: 30°C, linear pressure: 100 N/cm, transport speed: 0.1 m/min) on the surface from which the was peeled off. The protective film on one side was not peeled off. As described above, a decorative molding film having a protective film, an adhesive layer, a liquid crystal layer, a liquid crystal alignment layer, a substrate, an optical mask layer, and a colored layer in this order was obtained.

<Formation of molding>
Assuming a smartphone housing panel, the glass member 10 shown in FIGS. 2A and 2B was made to have three-dimensional formability. The member 10 has a major surface 12 shown in FIG. 2A and a cross-section 22 parallel to the longitudinal direction of the member 10 as shown in FIG. 2B.
After peeling off the protective sheet of the pressure-sensitive adhesive sheet prepared by the above procedure, vacuum molding was performed using a TOM molding machine NGF0406 manufactured by Fuse Vacuum Co., Ltd. at a heating temperature of 170° C. to form a molding.

-Pattern evaluation-
The obtained molding was visually evaluated from a distance of 50 cm. A and B are preferred, and A is particularly preferred.
<Criteria>
A: A clear reflection color pattern is visually recognized.
B: If you look closely, you can see the pattern of the reflected color.
C: No pattern of reflected color is visible.

-Sharpness of Pattern Boundaries-
The bleeding width at the boundary of the pattern was measured as follows.
A slice of the laminate is prepared using a microtome (RX-860, manufactured by Daiwa Koki Kogyo Co., Ltd.), and the boundary of the pattern is examined with a scanning electron microscope (for example, Hitachi Co., Ltd.) for the cross section of the liquid crystal layer of the slice. Observation was made using SU3800 manufactured by Hitech. In the pattern boundary, the width of the region where the helical pitch changes by 10% or more in the in-plane direction of the liquid crystal layer was measured and defined as the "bleeding width of the pattern boundary". A and B were determined to be acceptable. A is particularly preferred.
<Criteria>
A: The bleeding width at the pattern boundary is 1 μm or more and less than 20 μm.
B: The bleeding width at the pattern boundary is 20 μm or more and less than 100 μm.
E: The bleeding width at the pattern boundary is 100 μm or more.

(Example 2)
A decorative panel was produced in the same manner as in Example 1, except that naxreal 320 white paint manufactured by Nippon Paint Co., Ltd. was used as the colored layer.

(Example 3)
A decorative panel was produced in the same manner as in Example 1, except that naxreal 537 thread red paint manufactured by Nippon Paint Co., Ltd. was used as the colored layer.

(Example 4)
Light from a metal halide lamp (“MAL625NAL” manufactured by GS Yuasa Co., Ltd.) with an exposure amount of 100 mJ/cm ² is applied to the part of the liquid crystal layer to be isomerized from the side of the laminate with the liquid crystal layer on which the optical mask layer is formed. A decorative panel was produced in the same manner as in Example 1, except that the isomerization treatment was performed by irradiation.

(Example 5)
Light from a metal halide lamp (“MAL625NAL” manufactured by GS Yuasa Co., Ltd.) with an exposure amount of 200 mJ/cm ² is applied to the isomerized portion of the liquid crystal layer from the side of the laminate with the liquid crystal layer formed with the optical mask layer. A decorative panel was produced in the same manner as in Example 1, except that the isomerization treatment was performed by irradiation.

(Example 6)
A decorative panel was produced in the same manner as in Example 1, except that naxreal 320 white paint (mask printing ink 2) manufactured by Nippon Paint Co., Ltd. was used as the optical mask layer forming ink.
The in-plane average transmittance of the printed portion of the manufactured mask at 400 nm to 780 nm was 45%. In the optical mask layer, the highest transmittance at a wavelength of 330 nm had a transmittance of 91% or more, and the lowest part had an absorptance of 1% or less.

(Example 7)
A decorative panel was produced in the same manner as in Example 1, except that Mask Printing Ink 3 having the composition described below was used as the optical mask layer forming ink.
-Composition of mask printing ink 3-
・Urethane-modified acrylic binder (8UA-301, solid content 30%): 35.00 parts by mass ・Cyclohexanone: 30.00 parts by mass ・Methyl ethyl ketone: 34.99 parts by mass ・Tinuvin479 (manufactured by BASF, UV absorber): 0 .20 parts by mass F553 (surfactant manufactured by DIC): 0.01 parts by mass

The thickest portion of the printed film thickness was 0.5 μm.
The in-plane average transmittance of the printed portion of the manufactured mask at 400 nm to 780 nm exceeded 90%. The difference between the portion with the highest transmittance at a wavelength of 330 nm and the portion with the lowest transmittance in the optical mask layer was 40%.

(Example 8)
A decorative panel was produced in the same manner as in Example 1, except that Technolloy C000 (polycarbonate, 250 μm) was used as the base material.

(Comparative example 1)
A decorative panel was produced in the same manner as in Example 1, except that no optical mask layer was formed.

(Comparative example 2)
An optical mask layer was printed in the same manner as in Example 1 on A4300. Also, a liquid crystal alignment layer and a liquid crystal layer were formed in the same manner as in Example 1 on another A4300 on which the optical mask layer was not printed. After that, the surface of A4300 having the optical mask layer formed thereon, which is opposite to the side having the optical mask layer, is superimposed on the surface of A4300 having the liquid crystal alignment layer and the liquid crystal layer formed thereon, which is opposite to the side having the liquid crystal layer. The isomerization treatment was performed through the mask layer. A decorative panel was produced in the same manner as in Example 1 except for the above.

Table 1 shows the results of evaluating the designability of Examples 1 to 8 and Comparative Examples 1 and 2.

The disclosure of Japanese Patent Application No. 2019-235082 filed on December 25, 2019 is incorporated herein by reference in its entirety. All publications, patent applications and technical standards mentioned herein are to the same extent as if each individual publication, patent application and technical standard were specifically and individually indicated to be incorporated by reference. incorporated herein by reference.

Claims (12)

a liquid crystal layer containing a liquid crystal compound and a photoisomerizable compound;
a substrate;
an optical mask layer in which a plurality of patterns with different light transmittances are formed in an in-plane direction;
A laminate having, in this order, a colored layer,
The liquid crystal layer has a plurality of patterns with different selective reflection wavelengths formed in an in-plane direction,
The layered product, wherein the width of bleeding at the boundaries of the plurality of patterns is 1 μm or more and less than 100 μm. The laminate according to claim 1, which is a decorative molded film. A liquid crystal material having, in this order, a liquid crystal layer containing a liquid crystal compound and a photoisomerizable compound, a substrate, an optical mask layer having a plurality of patterns with different light transmittance formed in an in-plane direction, and a colored layer. a step of preparing
and a step of irradiating the liquid crystal layer with light through the optical mask layer to photoisomerize the photoisomerizable compound. 4. The laminate according to claim 3, wherein the optical mask layer is adjacent to the substrate, and the liquid crystal layer is provided on the surface of the substrate opposite to the side on which the optical mask layer is adjacent. manufacturing method. 5. The method for producing a laminate according to claim 3, wherein at least some of the plurality of patterns have different light transmittances in a wavelength range of 250 nm to 400 nm. The method for producing a laminate according to any one of claims 3 to 5, wherein the plurality of patterns have an in-plane average transmittance of 50% or more in a wavelength range of 400 nm to 780 nm. The method for producing a laminate according to any one of claims 3 to 6, wherein the optical mask layer is formed by a printing method. The method for producing a laminate according to any one of claims 3 to 7, wherein the laminate is a decorative molded film used for decorating a housing panel of an electronic device. A molding obtained by molding the laminate according to claim 1 or 2. A method for producing a molded article, comprising a step of molding a laminate obtained by the method for producing a laminate according to any one of claims 3 to 8. An electronic device housing panel comprising the laminate according to claim 1 or 2. An electronic device comprising the molding according to claim 9 .