WO2022059292A1

WO2022059292A1 - Decorative film, method for manufacturing decorative film, molded object, electronic device, and automobile exterior plate

Info

Publication number: WO2022059292A1
Application number: PCT/JP2021/024823
Authority: WO
Inventors: 陽大石井; 佑一早田
Original assignee: 富士フイルム株式会社
Priority date: 2020-09-18
Filing date: 2021-06-30
Publication date: 2022-03-24
Also published as: JPWO2022059292A1

Abstract

Provided are a decorative film and an application thereof, the decorative film comprising at least: a first resin layer having a cholesteric regularity and in which two or more regions having different wavelengths of maximum reflectance are provided in the same plane and a wavelength of maximum reflectance in at least one region exists in the ranges of 380 nm or less or 800 nm or more; a second resin layer having a cholesteric regularity different from that of the first resin layer; and a coloring layer.

Description

Decorative film, manufacturing method of decorative film, molded products, electronic devices and automobile exterior panels

This disclosure relates to a decorative film, a method for manufacturing a decorative film, a molded product, an electronic device, and an automobile exterior plate.

Conventionally, for the purpose of improving designability, a decorative film having a metallic luster has been applied to, for example, the surface of molded products such as home appliances, office equipment, and automobile parts. A resin film containing metal particles is used as the decorative film, but it is an alternative from the viewpoint of environmental load due to the use of heavy metals and the risk of causing radio interference when applied to electronic devices and the like. The development of decorative films that can be used as products is desired.

In recent years, it has been studied to use a decorative film containing a resin layer having a cholesteric regularity, which has high reflection luminance and spectral characteristics and can give a beautiful appearance.

The resin layer having cholesteric regularity has a cholesteric liquid crystal phase having a spiral structure in the layer that selectively reflects circularly polarized light having a reflection center wavelength that correlates with the spiral pitch.
Then, by providing a region having a spiral structure having a different spiral pitch in the plane of the resin layer, the visually recognized color can be changed, for example, a gradation tone that changes in the order of blue, green, and red. Since the color change can be displayed, a high degree of design can be imparted to the molded product.
However, the color change that can be displayed by the conventional decorative film including one resin layer having the above-mentioned cholesteric regularity is the color change from the short wavelength to the long wavelength side (blue to green to red). It is difficult to display complex color changes, and there is a demand for a decorative film with a wider variety.

Further, Japanese Patent Application Laid-Open No. 2010-11104, Japanese Patent Application Laid-Open No. 2017-205988, International Publication No. 2020/122245 and International Publication No. 2018/79606 include a decorative film containing two or more resin layers having cholesteric regularity. Is disclosed.
Japanese Unexamined Patent Publication No. 2010-111104 includes a laminate containing a resin layer having a first cholesteric regularity and a resin layer having a second cholesteric regularity, and has the above-mentioned first cholesteric regularity. The resin layer is a layer that transmits the first circularly polarized light and reflects the second circularly polarized light that is different from the first circularly polarized light, and the second cholesteric resin layer is the first cholesteric. Decorative films are disclosed that are arranged to reflect at least a portion of the first circularly polarized light that has passed through a regular resin layer.
Japanese Patent Application Laid-Open No. 2017-20598 describes a first patterned cholesteric liquid crystal reflective layer that reflects a first circularly polarized light having a characteristic reflection peak wavelength of 400 nm or more and 700 nm or less, and a characteristic reflection peak wavelength. A decorative film including a second patterned cholesteric liquid crystal reflective layer that reflects a second circularly polarized light having a peak wavelength of 400 nm or more and 700 nm or less and having a characteristic reflection peak wavelength different from that of the first circularly polarized light is disclosed. Has been done.
International Publication No. 2020/122245 discloses a decorative film containing one or more liquid crystal layers including regions having different maximum reflectance wavelengths.
International Publication No. 2018/79606 discloses a decorative film containing two or more liquid crystal layers including regions having different maximum reflectance wavelengths.

The decorative film containing two or more resin layers disclosed in JP-A-2010-111104 is intended to impart a metallic luster to a molded product, does not display a color, and is a design. The sex was not enough.
Further, although the cholesteric liquid crystal reflective layer contained in the decorative film disclosed in JP-A-2017-205988 has a different color, there is no change in the color in the plane of the cholesteric liquid crystal reflective layer. , There was room for improvement in the design.
Further, the decorative films disclosed in International Publication No. 2020/122245 and International Publication No. 2018/79606 are the same as the decorative films disclosed in JP-A-2010-111104 and JP-A-2017-205988. In addition, there was room for further improvement in the variation of color change. In addition, there is room for improvement in the color tones displayed by the decorative films disclosed in International Publication No. 2020/122245 and International Publication No. 2018/79606 from the viewpoint of visibility.
As described above, the conventional decorative films disclosed in JP-A-2010-111104, JP-A-2017-205988, International Publication No. 2020/122245, International Publication No. 2018/79606, etc. have a design property. We have now found that there is room for further improvement.

The problem to be solved by one embodiment of the present disclosure is that a decorative film, a molded product, or a decorative film having high visibility, being able to display a wide variety of color changes, and having excellent designability. The purpose is to provide manufacturing methods, automobile exterior panels and electronic devices.

<1> Cholesteric having two or more regions having different wavelengths having the maximum reflectance in the same plane, and having a wavelength having the maximum reflectance in the range of 380 nm or less or 800 nm or more in at least one region. The first resin layer with regularity and
A second resin layer having a cholesteric regularity different from that of the first resin layer,
Colored layer and
Includes at least a decorative film.

<2> The second resin layer has two or more regions having different wavelengths for maximum reflectance in the same plane, and the wavelength for maximum reflectance in at least one region is 380 nm or less or 800 nm. The decorative film according to <1>, which exists in the above range.

<3> A region in which the wavelength of the maximum reflectance of the first resin layer is in the range of 380 nm or less or 800 nm or more.
The decorative film according to <2>, which is provided at a position where at least a part of a region having a wavelength of 380 nm or less or 800 nm or more, which is the maximum reflectance of the second resin layer, overlaps.

<4> A region in which the wavelength having the maximum reflectance is more than 380 nm and less than 800 nm as at least one of two or more regions having different wavelengths having the maximum reflectance. The decorative film according to any one of <1> to <3>.

<5> The decorative film according to any one of <1> to <4>, which has an in-plane average reflectance of 20% or more.

<6> The decorative film according to any one of <1> to <5>, wherein the first resin layer and the second resin layer are laminated adjacent to each other.

<7> The decorative film according to any one of <1> to <6>, wherein the first resin layer and the second resin layer reflect circularly polarized light in the same direction.

<8> A process of preparing a liquid crystal material including a base material and a liquid crystal layer, and
The liquid crystal layer is subjected to photoisomerization treatment, and the liquid crystal layer contains at least one region having a wavelength having a maximum reflectance in the range of 380 nm or less or 800 nm or more, and the wavelength having a maximum reflectance is different. A step of curing the liquid crystal layer to form a first resin layer having cholesteric regularity after making the state having one or more regions.
A step of forming a second resin layer having a cholesteric regularity different from that of the first resin layer on the first resin layer, and a step of forming the second resin layer.
A method for manufacturing a decorative film, including.

<9> A step of preparing a liquid crystal material containing a base material and a second resin layer having cholesteric regularity, and
A liquid crystal layer is formed on the second resin layer, the liquid crystal layer is subjected to photoisomerization treatment, and the liquid crystal layer has a wavelength having a maximum reflectance in the range of 380 nm or less or 800 nm or more. A first having a cholesteric regularity different from that of the second resin layer by curing the liquid crystal layer after making the state having two or more regions having different wavelengths having the maximum reflectances containing at least one of the above. The process of forming the resin layer and
A method for manufacturing a decorative film, including.

<10> The method for producing a decorative film according to <8> or <9>, wherein the liquid crystal layer is formed of a liquid crystal composition containing a monofunctional liquid crystal compound.

<11> The method for producing a decorative film according to <10>, wherein the liquid crystal composition contains at least one of a polyfunctional liquid crystal compound and a polyfunctional non-liquid crystalline polymerizable monomer.

<12> The ratio of the sum of the content of the monofunctional liquid crystal compound to the content of the polyfunctional liquid crystal compound and the polyfunctional non-liquid crystal polymerizable monomer in the liquid crystal composition is based on the mass. The method for producing a decorative film according to <11>, which is 85:15 to 40:60.

<13> A molded product obtained by molding the decorative film according to any one of <1> to <7>.

<14> An electronic device including the decorative film according to any one of <1> to <7>.

<15> An automobile exterior plate having the molded product according to <13>.

According to the present disclosure, a decorative film, a molded product, a method for manufacturing a decorative film, an electronic device, and an automobile exterior, which are highly visible, can display a wide variety of color changes, and have excellent designability. A board can be provided.

FIG. 1 is a schematic cross-sectional view showing an example of the first resin layer. FIG. 2 is a schematic cross-sectional view showing another example of the first resin layer. FIG. 3 is a schematic cross-sectional view showing another example of the first resin layer. FIG. 4 is a schematic cross-sectional view showing another example of the first resin layer. FIG. 5 is a schematic cross-sectional view showing an example of a decorative film. FIG. 6 is a schematic cross-sectional view showing another example of the decorative film. FIG. 7 is a schematic cross-sectional view showing another example of the decorative film. FIG. 8 is a schematic cross-sectional view showing another example of the decorative film. FIG. 9 is a schematic plan view showing the patterning mask 1 used in the embodiment. FIG. 10 is a schematic plan view showing the patterning mask 2 used in the embodiment. FIG. 11 is a schematic plan view showing the patterning mask 3 used in the embodiment. FIG. 12 is a schematic plan view showing the patterning mask 4 used in the examples. FIG. 13 is a schematic cross-sectional view showing the decorative film produced in the examples. FIG. 14 is a schematic cross-sectional view showing the decorative film produced in the examples. FIG. 15 is a schematic cross-sectional view showing the decorative film produced in the examples. FIG. 16 is a schematic cross-sectional view showing the decorative film produced in the examples. FIG. 17 is a schematic cross-sectional view showing the decorative film produced in the examples. FIG. 18 is a schematic cross-sectional view showing the decorative film produced in the examples. FIG. 19 is a schematic cross-sectional view showing the decorative film produced in the examples. FIG. 20 is a schematic cross-sectional view showing the decorative film produced in the examples. FIG. 21 is a schematic cross-sectional view showing the decorative film produced in the examples. FIG. 22 is a schematic cross-sectional view showing the decorative film produced in the examples.

The contents of this disclosure will be described in detail below. The description of the constituents described below may be based on the representative embodiments of the present disclosure, but the present disclosure is not limited to such embodiments.

In the present disclosure, the numerical range indicated by using "-" includes the numerical values before and after "-" as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in another stepwise description. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, each component may contain a plurality of applicable substances. When a plurality of substances corresponding to each component are present in the composition, the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified. Means quantity.
In the notation of a group (atomic group) in the present disclosure, the notation that does not describe substitution or non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present disclosure, "(meth) acrylic" is a term used in a concept that includes both acrylic and methacrylic, and "(meth) acryloyl" is a term that is used as a concept that includes both acryloyl and methacrylic. be.
In the present disclosure, the term "layer" includes not only the case where the layer is formed in the entire region when observing the region where the layer is present, but also the case where the layer is formed only in a part of the region. Is done.
In the present disclosure, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
In the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
In the present disclosure, the "total solid content" means the total mass of the components excluding the solvent from the total composition of the composition. Further, the "solid content" is a component excluding the solvent as described above, and may be, for example, a solid or a liquid at 25 ° C.
In the drawings, the components substantially the same as the components are designated by the same reference numerals, and the description thereof will be omitted.
Hereinafter, the present disclosure will be described in detail.

(Decorative film)
The decorative film according to the present disclosure has two or more regions having different wavelengths having the maximum reflectance in the same plane, and the wavelength having the maximum reflectance in at least one region is 380 nm or less or 800 nm or more. A first resin layer having cholesteric regularity (hereinafter, also simply referred to as “first resin layer”) existing in the range and a second resin having cholesteric regularity different from the first resin layer. A decorative film including at least a layer (hereinafter, also simply referred to as a “second resin layer”) and a colored layer.
The positional relationship between the first resin layer and the second resin layer is not particularly limited, and any layer may be on top.
The colored layer may be provided on the first resin layer or may be provided on the second resin layer. Further, it may be provided on or below the first resin layer or the second resin layer via another resin layer or the like described below.

According to the embodiment of the present disclosure, it is possible to obtain a decorative film having high visibility, being able to display a wide variety of color change, and having excellent design.

The reason why the decorative film according to the present disclosure has high visibility, can display a wide variety of color changes, and has excellent designability is presumed as follows, but is limited to this. It's not something.
The first resin layer included in the decorative film according to the present disclosure has two or more regions having different wavelengths having the maximum reflectance in the same plane, and the wavelength having the maximum reflectance in at least one region is It exists in the range of 380 nm or less or 800 nm or more.
That is, since the first resin layer has a region that does not cause color mixing and additive color mixing indicated by the second resin layer and the colored layer when laminated with the second resin layer and the colored layer, Japanese Patent Application Laid-Open No. 2010. -It becomes possible to display a complicated color change that cannot be displayed by the decorative film disclosed in Japanese Patent Publication No. 111104, and the designability is improved.
Further, since the decorative film contains a colored layer, the color displayed by the decorative film including the colored layer is visually recognized as compared with the color displayed by the decorative film disclosed in International Publication No. 2018/79606 and the like. The sex has been improved.

The decorative film according to the present disclosure is also referred to as another resin layer having cholesteric regularity (hereinafter, simply referred to as “other resin layer”), which is different from the cholesteric regularity of the first resin layer and the second resin layer. ) Can be further included. The decorative film according to the present disclosure may contain one layer of other resin layers, or may contain two or more layers. Further, the other resin layer may be provided on the first resin layer or may be provided on the second resin layer, and may be provided between the first resin layer and the second resin layer. It may be provided in.

It is preferable that the first resin layer and the second resin layer are laminated adjacent to each other. By laminating the first resin layer and the second resin layer adjacent to each other instead of laminating them via an adhesive or the like, the thickness of the decorative film can be suppressed and the decorative film can be easily molded. It is possible to improve the sex. When the decorative film has another resin layer, it is preferable that the other resin layer is laminated adjacent to at least one of the first resin layer and the second resin layer.

The total thickness of the first resin layer and the second resin layer (including the thickness of the other resin layer if provided) is preferably less than 25 μm, more preferably less than 20 μm, and 10 μm. It is more preferably less than. By setting the total thickness within the above numerical range, the ease of molding the decorative film can be improved. Further, from the viewpoint of improving the reflectance of each resin layer, the total thickness is preferably 1 μm or more, more preferably 2 μm or more, and further preferably 3 μm or more.
Further, when the resin layers are bonded together using an adhesive or the like, the thickness of the layer formed by the adhesive or the like is also included in the total thickness.

In the first resin layer or the like, it was selected from the group consisting of the spiral pitch (twisting force and helix angle) of the spiral structure formed by the liquid crystal compound described below, the refractive index of the resin layer, and the thickness of the resin layer. By changing at least one condition, it is possible to adjust the color tones that change according to the viewing angle and the color tones that are visually recognized.
The spiral pitch of the spiral structure can be easily adjusted by changing, for example, the type of chiral compound or the amount of the chiral compound added. Regarding the adjustment of the spiral pitch, see Fujifilm Research Report No. 50 (2005) p. There is a detailed description in 60-63. Further, the spiral pitch of the spiral structure can be adjusted by conditions such as temperature, illuminance or irradiation time when fixing the cholesteric orientation state.

The selective reflectivity of the first resin layer, the second resin layer, and the other resin layer may be for either left circular polarization or right circular polarization, but circular polarization in the same direction is selectively used. It is preferable that it reflects on. The first resin layer, the second resin layer, and the other resin layer selectively reflect circularly polarized light in the same direction, whereby the occurrence of interference fringes in the decorative film can be prevented.

The decorative film may have a base material. Further, the decorative film may have an alignment layer.

From the viewpoint of brilliance, the in-plane average reflectance of the decorative film is preferably 20% or more, more preferably 30% or more, further preferably 40% or more, and 45% or more. It is particularly preferable to have.
In the present disclosure, the in-plane average reflectance of the decorative film is measured as follows.
A spectrophotometer (Nippon Spectroscopy Co., Ltd., V-670) equipped with a large integrating sphere device (Nippon Spectroscopy Co., Ltd., ILV-471) was used for the outermost resin layer of the decorative film. Light having a wavelength of 300 nm to 1500 nm is incident from a vertical direction (an angle of 90 ° with respect to the surface of the resin layer), and the peak wavelength is read from the obtained spectral spectrum to obtain the reflectance of the peak wavelength. The reflectance of the peak wavelength is measured on the entire surface of the outermost resin layer, and the average of the measured values is taken as the in-plane average reflectance.

<First resin layer>
The first resin layer has two or more regions having different wavelengths having the maximum reflectance in the same plane. Further, as a region included in the two or more regions, there is at least one region (hereinafter, also referred to as a specific region A) in which the wavelength having the maximum reflectance is in the range of 380 nm or less or 800 nm or more.

Further, since the reflection band is narrow and the transparency can be easily adjusted, the wavelength having the maximum reflectance in the specific region A is preferably 380 nm or less.

The two or more regions of the first resin layer selectively reflect light in a specific wavelength range (hereinafter, also referred to as selective reflectivity).
In the present disclosure, "having selective reflectivity" means that a spectrophotometer equipped with a large integrating sphere device (manufactured by Nippon Spectroscopy Co., Ltd., ILV-471) (manufactured by Nippon Spectroscopy Co., Ltd., V-670) is used. When light having a wavelength of 300 nm to 1500 nm is incident on the above region and the integrated reflectance is measured, a spectral waveform having at least one mountain shape (peak) with the wavelength as the horizontal axis can be obtained.
Further, the wavelengths of the two or more regions, which have the maximum reflectance, are different from each other.
In the present disclosure, the wavelength having the maximum reflectance means the wavelength having the maximum reflectance at the peak of the spectral waveform obtained as described above.
When there are a plurality of peaks, the peak including the reflectance that becomes the maximum value is adopted.

The area of the specific area A is not particularly limited, and it is preferable to appropriately adjust the area according to the color required for the decorative film according to the present disclosure.

The first resin layer may have one specific region A or two or more specific regions A in the same plane. When the first resin layer has two or more specific regions A, the wavelength at which the reflectance of each region is maximized may be the same or different. When the first resin layer has two or more specific regions A, the areas of the respective regions may be the same or different.
When the first resin layer has one specific region A in the same plane, the position where the specific region A is provided is not particularly limited, and as shown in FIG. 1, one end of the first resin layer 10 is provided. The specific area A11 may be provided, and as shown in FIG. 2, the specific area A11 may be provided at a position other than the end portion such as the central portion.
Further, when the first resin layer has two or more specific regions A in the same plane, the position where the specific regions A are provided is not particularly limited. When the first resin layer has two specific regions A in the same plane, for example, as shown in FIG. 3, it may be provided at both ends of the first resin layer 10, and as shown in FIG. It may be provided at a position other than the end portion.

In the present disclosure, the reflectance of light having a wavelength of more than 380 nm and less than 800 nm is measured by a spectrophotometer (manufactured by JASCO Corporation, ILV-471) equipped with a large integrating sphere device (manufactured by JASCO Corporation, ILV-471) as described above. , V-670) can be used for measurement.

The first resin layer is a region having a wavelength of more than 380 nm and less than 800 nm having a maximum reflectance as at least one of the two or more regions (hereinafter, also referred to as “other region A”). ) May have.
Since the first resin layer has the other region A, the region where additive color mixing occurs with the second resin layer and the colored layer in the laminated state with the second resin layer and the colored layer, and the additive color mixing are Areas that do not occur are mixed, and it becomes possible to display more complicated color change in the decorative film, and the designability is further improved.

The area of the other area A is not particularly limited, and it is preferable to appropriately adjust the area according to the color required for the decorative film according to the present disclosure.

The first resin layer may have one other region A or two or more regions A. When the first resin layer has two or more other regions A, the wavelength at which the reflectance of each region is maximized may be the same or different. Further, when the first resin layer has two or more other regions A, the areas of the respective regions may be the same or different.
When the first resin layer has one other region A in the same plane, the position where the other region A is provided is not particularly limited, and as shown in FIG. 1, of the first resin layer 10. The other region A12 may be provided at one end, or as shown in FIG. 3, the other region A12 may be provided at a position other than the end portion such as the central portion.
When the first resin layer has two or more other regions A in the same plane, the position where the other regions A12 are provided is not particularly limited. When the first resin layer has two other regions A in the same plane, for example, as shown in FIG. 2, it may be provided at both ends of the first resin layer 10, and other than the end portions. It may be provided at a position (not shown).

Further, in the other region A of the first resin layer, the wavelength having the maximum reflectance may be continuously changed in the plane. For example, by adopting a configuration in which the wavelength having the maximum reflectance continuously changes from 381 nm to 450 nm, it is possible to provide another region A in which the color tone changes in a gradation from purple to blue, and the decorative film can be formed. The design of the product can be further improved.
Further, a specific region A having a configuration in which the wavelength having the maximum reflectance continuously changes from 350 nm to 380 nm, and another region A having a configuration in which the wavelength having the maximum reflectance continuously changes from 381 nm to 450 nm. By providing the above in the order of the surfaces, it is possible to display the color change in a gradation tone in the order of transparency, purple and blue.

The maximum reflectance of the other region A in the wavelength range of more than 380 nm and less than 800 nm is preferably 20% or more, more preferably 30% or more, still more preferably 40% or more. , 45% or more is particularly preferable. When the maximum reflectance is 20% or more, the visibility of the decorative film can be further improved.

In the specific region A of the first resin layer, when the wavelength having the maximum reflectance is 380 nm or less, the thickness of the first resin layer is preferably 1 μm to 5 μm, preferably 1 μm to 4 μm. Is more preferable, and 1 μm to 3 μm is even more preferable.
In the specific region A of the first resin layer, when the wavelength having the maximum reflectance is 800 nm or more, the thickness of the first resin layer is preferably 1 μm to 6 μm, preferably 2 μm to 6 μm. Is more preferable, and 3 μm to 6 μm is even more preferable.

<Second resin layer>
The configuration of the second resin layer is not particularly limited as long as it has a cholesteric regularity different from that of the first resin layer, but two or more regions having different wavelengths having the maximum reflectance are in the same plane. It is preferable to have it in.
Further, as a region included in the two or more regions, it is possible to have at least one region (hereinafter, also referred to as a specific region B) in which the wavelength having the maximum reflectance is in the range of 380 nm or less or 800 nm or more. preferable. By having the above-mentioned region in the second resin layer, it becomes possible to display a more complicated color change in the decorative film, and the designability is further improved.
It is preferable that the specific region B is provided at a position where at least a part of the specific region A overlaps with the specific region A of the first resin layer. With the above configuration, the tint of the colored layer contained in the decorative film of the present disclosure can be visually recognized, and the design of the decorative film can be further improved (see FIG. 5). Further, the specific area B may be provided at a position completely overlapping with the specific area A.

The area of the specific area B is not particularly limited, and it is preferable to appropriately adjust the area according to the color required for the decorative film according to the present disclosure.

The second resin layer may have one specific region B or two or more specific regions B in the same plane. When the second resin layer has two or more specific regions B, the wavelength at which the reflectance of each region is maximized may be the same or different. Further, when the second resin layer has two or more specific regions B, the areas of the respective regions may be the same or different.
In the second resin layer, the position where the specific region B is provided can be the same as the position where the specific region A is provided in the first resin layer, such as the end portion or the central portion.

Further, in the specific region B of the second resin layer, the wavelength having the maximum reflectance may be continuously changed in the plane as in the specific region A.
Further, since the preferable numerical range of the reflectance of light having a wavelength of more than 380 nm and less than 800 nm in the specific region B is the same as that of the specific region A, the description thereof is omitted here.

The second resin layer is a region included in the two or more regions and has a wavelength having a maximum reflectance of more than 380 nm and less than 800 nm (hereinafter, also referred to as “other region B”). ) May have. Since the second resin layer has the other region B, it is possible to display a more complicated color change in the decorative film, and the designability is further improved.
Here, as shown in FIG. 5, the first resin layer 10 has the specific region A11 and the other region A12, the second resin layer 20 has the specific region B21 and the other region B22, and is specified. The color of the decorative film 1 having a structure in which a part of the region A11 and the specific region B21 overlap each other will be described.
In the region where the specific region A11 and the specific region B21 overlap, the incident light is reflected by the colored layer 30, so that only the tint of the colored layer 30 (monochromatic region) can be visually recognized in the above region (Fig.). Dashed line of 5 (1)).
In the region where the specific region A11 and the other region B22 overlap, for example, the blue right circular polarization is reflected by the second resin layer 20, and the other light is reflected by the colored layer 30. In the region, the tint of the other region B22 of the second resin layer 20 and the tint of the colored layer 30 can be visually recognized (the broken line (2) in FIG. 5). ). When the color of the colored layer 30 is black, the light transmitted through the first resin layer 10 is not reflected by the colored layer 30, and only the color of the other region B22 of the second resin layer 20 is present. Observed (not shown).
In the region where the other regions A12 and the other regions B22 overlap, the incident light is, for example, the red right circular polarization reflected in the first resin layer 10 and the blue right circular polarization in the second resin layer 20. Since it is reflected and other light is reflected by the colored layer 20, in the above region, the color of the other region A12 of the first resin layer 10 and the other region B22 of the second resin layer 20 are present. The tint of the above and the tint of the colored layer 30 can be visually recognized (broken line (3) in FIG. 5). When the color of the colored layer 30 is black, the light transmitted through the first resin layer 10 is not reflected by the colored layer 30, and the color of the other region A12 of the first resin layer 10 and the color of the other region A12. The tint of the other region B22 of the second resin layer 20 and the tint of the additive color can be visually recognized (not shown).

The area of the other area B is not particularly limited, and it is preferable to appropriately adjust the area according to the color required for the decorative film according to the present disclosure.

The second resin layer may have one other region B, or may have two or more regions B. When the second resin layer has two or more other regions B, the wavelength at which the reflectance of each region is maximized may be the same or different. When the second resin layer has two or more other regions B, the areas of the regions may be the same or different.

The position where the other region B is provided in the second resin layer can be the same as the position where the other region A is provided in the first resin layer, such as the end portion or the central portion.

Further, in the other region B of the second resin layer, the wavelength that becomes the maximum reflectance may be continuously changed in the plane as in the other region A.

The maximum reflectance of the other region B in the wavelength range of more than 380 nm and less than 800 nm is preferably 20% or more, more preferably 30% or more. When the maximum reflectance is 20% or more, the visibility of the decorative film can be further improved.

Further, since the preferable thickness of the second resin layer is the same as that of the first resin layer, the description thereof is omitted here.

<Other resin layers>
The decorative film according to the present disclosure may include a resin layer other than the first resin layer and the second resin layer, such as a third resin layer, a fourth resin layer, and a fifth resin layer. By including the other resin layer in the decorative film according to the present disclosure, it becomes possible to display a more complicated color change in the decorative film, and the designability is further improved.
The composition of the other resin layers has a cholesteric regularity different from that of the first resin layer and the second resin layer, and when the decorative film contains a plurality of other resin layers, other resin layers are used. As long as the resin layers have different cholesteric regularities, there is no particular limitation, but the two or more regions having different wavelengths having the maximum reflectance are contained in the same plane and are included in the two or more regions. It is preferable to have at least one region (hereinafter, also referred to as a specific region C) in which the wavelength having the maximum reflectance is in the range of 380 nm or less or 800 nm or more. When the other resin layer has the above-mentioned region, it becomes possible to display a more complicated color change in the decorative film, and the designability is further improved.
The specific region C is preferably provided at a position where at least a part of the specific region A overlaps with the specific region A of the first resin layer. When the second resin layer has the specific region B, it is preferable that the second resin layer is provided at a position where at least a part of the specific region A, the specific region B, and the specific region C overlap. As a result, the tint of the colored layer contained in the decorative film of the present disclosure can be visually recognized, and the design of the decorative film can be further improved. Further, the specific area C may be provided at a position completely overlapping the specific area A or the specific area B.

The area of the specific area C is not particularly limited, and it is preferable to appropriately adjust the area according to the color required for the decorative film according to the present disclosure.

The other resin layer may have one specific region C or two or more specific regions C in the same plane. When the other resin layer has two or more specific regions C, the wavelength at which the reflectance of each region is maximized may be the same or different. Further, when the other resin layer has two or more specific regions C, the areas of the respective regions may be the same or different.
In the other resin layer, the position where the specific region C is provided can be the same as the position where the specific region A is provided in the first resin layer, such as the central portion or the end portion.

Since the preferable numerical range of the reflectance of light having a wavelength of more than 380 nm and less than 800 nm in the specific region C is the same as that of the specific region A, the description thereof is omitted here.

The other resin layer is a region included in the two or more regions, in which the wavelength having the maximum reflectance is more than 380 nm and less than 800 nm (hereinafter, also referred to as “other region C”). May have. Since the other resin layer has the other region C, it becomes possible to display a more complicated color change in the decorative flum, and the designability is further improved.

The area of the other area C is not particularly limited, and it is preferable to appropriately adjust the area according to the color required for the decorative film according to the present disclosure.

The other resin layer may have one other region C or two or more regions C. When the other resin layer has two or more other regions C, the wavelength at which the reflectance of each region is maximized may be the same or different. Further, when the other resin layer has two or more other regions C, the areas of the respective regions may be the same or different.
In the other resin layer, the position where the other region C is provided can be the same as the position where the other region A is provided in the first resin layer, such as the central portion or the end portion.

Further, in the other region C of the other resin layer, the wavelength that becomes the maximum reflectance may be continuously changed in the plane as in the other region A.

The maximum reflectance of the other region C in the wavelength range of more than 380 nm and less than 800 nm is preferably 20% or more, more preferably 30% or more. When the maximum reflectance is 20% or more, the visibility of the decorative film can be further improved.

Further, since the preferable thickness of the other resin layers is the same as that of the first resin layer, the description thereof is omitted here.

The following is an example of specific embodiments of the decorative film, but the present disclosure is not limited thereto.

The decorative film 1 shown in FIG. 6 includes a first resin layer 10, a second resin layer 20, and a colored layer 30.
The specific region A11 of the first resin layer 10 is transparent from one end (left end in FIG. 6) to the boundary with the other region A12, and the other region A12 is from the boundary to the other end (the other end). In the in-plane direction up to the right end portion in FIG. 6, for example, the hue changes in a gradation tone from purple to blue.
Further, the specific region B21 of the second resin layer 20 is transparent from the other end to the boundary with the other region B22, and the other region B22 is in the plane from the boundary to the one end. In the direction, for example, the tint changes in a gradation tone from magenta to red.
In the decorative film 1 on which the first resin layer 10 and the second resin layer 20 are laminated, gradation-like colors are displayed in the order of blue, magenta, and red from one end to the other end.

The decorative film 1 shown in FIG. 7 includes a first resin layer 10, a second resin layer 20, and a colored layer 30.
Further, as shown in FIG. 7, the specific region A11 of the first resin layer 10 and the specific region B21 of the second resin layer 20 are provided at overlapping positions, and the color of the colored layer 30 is provided in the region. You can see the taste.

The decorative film 1 shown in FIG. 8 includes a first resin layer 10, a second resin layer 20, and a colored layer 30.
Further, as shown in FIG. 8, the specific region A11 of the first resin layer 10 is transparent from one end (left end in FIG. 8) to the boundary with the other region A12, and is the other region A12. Displays a constant color, for example, a red color from the boundary to the other end (right end in FIG. 8). Further, the other region B22 of the second resin layer 20 extends from one end to the other end, and a certain color, for example, a blue color is displayed.
The decorative film 1 on which the first resin layer 10 and the second resin layer 20 are laminated has a blue tint from one end to the boundary and a purple tint from the boundary to the other end.

<Colored layer>
The decorative film according to the present disclosure includes a colored layer. By including the colored layer in the decorative film, it is possible to display a more complicated color change and improve the visibility of the color.
The colored layer may be provided on the first resin layer, may be provided on the second resin layer, and may be provided between the first resin layer and the second resin layer. You may. Further, the colored layer may be provided on the entire surface of the first resin layer or the like, or may be provided on a part thereof.

When the decorative film includes the following base material, the colored layer is provided between the first resin layer, the second resin layer or another resin layer and the base material from the viewpoint of designability. Is preferable.
Further, from the viewpoint of ease of molding and durability, it is preferable that the colored layer is provided on the resin layer on the side opposite to the side on which the base material is provided.
The position where the colored layer is provided is not limited to the above example, and can be appropriately changed depending on the use of the decorative film.

The decorative film according to the present disclosure may have only one colored layer or may have two or more layers.
In the decorative film according to the present disclosure, from the viewpoint of designability, it is preferable that at least one of the colored layers is a layer for visually recognizing through the resin layer.
By visually recognizing the colored layer through the resin layer, a color change occurs according to the angle at which the colored layer is visually recognized based on the anisotropy according to the angle of the incident light in the resin layer. It is presumed that the decorative film according to the disclosure has a special design property.
Further, when the specific region A and the specific region B and the like overlap in the first resin layer and the second resin layer included in the resin layer, the color of the colored layer can be confirmed, and the addition according to the present disclosure. It is presumed that the decorative film displays more complicated color changes and has more design.
Further, the total light transmittance of the colored layer for visual recognition through at least one layer of the colored layer, preferably the resin layer, is preferably 10% or less from the viewpoint of visibility.
In the present disclosure, the measurement of the total light transmittance is based on the Japanese Industrial Standards (JIS) K 7375 issued in 2008 using a spectrophotometer (for example, spectrophotometer UV-2100 manufactured by Shimadzu Corporation). Can be measured.

When the decorative film according to the present disclosure has two or more colored layers, at least one of the colored layers is a layer for visually recognizing via the resin layer, and at least one of the other colored layers. A mode in which the layer is a layer closer to the viewing direction than the resin layer (also referred to as a “color filter layer”) is preferably mentioned. In addition, "close to the viewing direction" means that the decorative film is provided at a position close to the viewer when the decorative film is visually recognized.
The colored layer (color filter layer) that is closer to the viewing direction than the resin layer is a layer having high transparency to light of at least a specific wavelength, and the layer structure is not particularly limited, and is a single color color filter layer. It may be 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 the color filter layer, the decorative film according to the present disclosure can be further designed, and a decorative film in which only a specific wavelength range can be visually recognized can be obtained.

The color of the colored layer is not particularly limited and can be appropriately selected depending on the intended use. Examples of the color of the colored layer include black, gray, white, red, orange, yellow, green, blue and purple. Further, the color of the colored layer may be a metallic color.
By setting the color of the colored layer to black, as described above, only the color of the other region A of the first resin layer or the color of the other region B of the second resin layer can be visually recognized. A region can be provided, and the design of the decorative film can be further improved. Further, by setting the color of the colored layer to black, the visibility of the displayed tint can be further improved.
Further, by setting the color of the colored layer to white, the color of the other region A of the first resin layer or the color of the other region B of the second resin layer can be complemented and displayed. The range of colors can be widened, and the design of the decorative film can be further improved.

The colored layer preferably contains a resin from the viewpoint of strength and scratch resistance. Examples of the resin include the following binder resins.
Further, the colored layer may be a layer obtained by curing the following polymerizable compound, or may be a layer containing the polymerizable compound and the polymerization initiator. The polymerizable compound and the polymerization initiator are not particularly limited, and known polymerizable compounds and known polymerization initiators can be used.
The colored layer may be a thin-film deposition film layer or a plating layer.

The colored layer can contain a colorant, and examples thereof include pigments and dyes. From the viewpoint of durability, pigments are preferable.

The type of pigment is not particularly limited, and known inorganic pigments and organic pigments can be used.
Examples of the inorganic pigment 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 and graphite. Examples thereof include black pigments, pearl pigments in which the surface of a mica or a piece of glass is coated with a metal oxide such as titanium oxide, iron oxide, barium yellow, cadmium red, and chrome yellow.
As the inorganic pigment, the inorganic pigment described in JP-A-2005-7765 can also be used.

Examples of the organic pigment 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, cinacridone red and cinacridone magenta, perylene red and Examples thereof include perylene pigments such as perylene maroon, carbazole violet, anthrapyridine, flavanthron yellow, isoindrin yellow, induthron blue, dibrom anzasron red, anthraquinone red, and diketopyrrolopyrrole.

As the pigment, a pigment having light transmission or light reflection (so-called brilliant pigment) may be used. Examples of the glitter pigment include metal glitter pigments such as aluminum, copper, zinc, iron, nickel, tin, aluminum oxide, and alloys thereof, interfering mica pigments, white mica pigments, graphite pigments, and glass flake pigments. And so on. The bright pigment may be uncolored or colored.
When the bright pigment is exposed in the molding of the decorative film, it is preferable that the bright pigment is used within a range that does not interfere with the curing due to the exposure.

The colorant may be used alone or in combination of two or more. Further, when two or more kinds of colorants are used, an inorganic pigment and an organic pigment may be combined.
The content of the colorant 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 development of the desired color and the suitability for molding. % Is more preferable, and 10% by mass to 40% by mass is particularly preferable.

The colored layer can contain a dispersant. When the colored layer contains a dispersant, the dispersibility of the colorant, particularly the pigment in the colored layer is improved, and the color can be made uniform in the decorative film.

The type of dispersant is preferably appropriately selected according to the type and shape of the colorant, and is preferably a polymer dispersant.
Examples of the polymer dispersant include silicone polymers, (meth) acrylic polymers and polyester polymers. When it is desired to impart heat resistance to the decorative film, for example, it is preferable to use a silicone polymer such as a graft type silicone polymer as a dispersant.
A commercially available dispersant may be used.

The weight average molecular weight of the dispersant is preferably 1,000 to 5,000,000, more preferably 2,000 to 3,000,000, from the viewpoint of dispersibility of the colorant. , 500 to 3,000,000 is particularly preferable.
In the present disclosure, the "weight average molecular weight" is determined by a gel permeation chromatography (GPC) analyzer using a column of TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (all of which are trade names manufactured by Toso Co., Ltd.). Tetrahydrofuran), which is the molecular weight detected by a differential refractometer and converted using polystyrene as a standard substance.

The dispersant may be used alone or in combination of two or more. The content of the dispersant in the colored layer is preferably 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the colorant.

The colored layer preferably contains a binder resin from the viewpoint of ease of molding.
The type of binder resin is not particularly limited, and known resins can be used. The binder resin is preferably a transparent resin from the viewpoint of making the colored layer a desired color, and specifically, a resin having a total light transmittance of 80% or more is preferable.

Examples of the binder resin include (meth) acrylic resin, silicone resin, polyester resin, urethane resin, polyolefin resin and the like. The binder resin may be a homopolymer of a specific monomer or a copolymer of a specific monomer and another monomer.

The binder resin may be used alone or in combination of two or more.
The content of the binder resin in the colored layer is preferably 5% by mass to 70% by mass and 10% by mass to 60% by mass with respect to the total mass of the colored layer from the viewpoint of ease of molding. Is more preferable, and 20% by mass to 60% by mass is particularly preferable.

The colored layer may contain additives in addition to the above components, if necessary.
The type of additive is not particularly limited, and known additives can be used. Examples of the additive include a surfactant described in Japanese Patent No. 4502784 and Japanese Patent Application Laid-Open No. 2009-237362, and a thermal polymerization inhibitor (also referred to as a polymerization inhibitor, preferably phenothiazine) described in Japanese Patent No. 4502784. ), And the additives described in JP-A-2000-310706.

The thickness of the colored layer is not particularly limited, but is preferably 0.5 μm or more, more preferably 3 μm or more, and 3 μm to 50 μm from the viewpoint of visibility and three-dimensional moldability. It is more preferably 3 μm to 20 μm, and particularly preferably 3 μm to 20 μm.
When the decorative film has two or more colored layers, it is preferable that each colored layer is independently in the above-mentioned thickness range.

<Orientation layer>
The decorative film according to the present disclosure may have an alignment layer. The position of the alignment layer is not particularly limited, but it is preferably provided adjacent to the first resin layer, the second resin layer, or other resin layer. The alignment layer is used to orient the molecules of the liquid crystal compound contained in the liquid crystal composition used when forming the resin layer.
The alignment layer may be present when forming the first resin layer or the like, and the produced decorative film does not have to have the alignment layer.

The oriented layer can be formed by using means such as rubbing treatment of a layer containing an organic compound (preferably a polymer), oblique vapor deposition of an inorganic compound such as SiO, or formation of a layer having microgrooves.
Further, the alignment layer can be formed by applying an electric field, applying a magnetic field, or irradiating light to the layer to generate an alignment function (hereinafter, the alignment layer in which the alignment function is generated by light irradiation is lighted. Also called an oriented layer).
Depending on the material contained in the base material or another resin layer provided as the lower layer of the formed resin layer, the lower layer is directly subjected to an alignment treatment (for example, a rubbing treatment) to function as an alignment layer. It is also possible, and it is not necessary to separately provide an alignment layer (hereinafter, the alignment layer in which the alignment function is generated by performing the rubbing treatment is referred to as a rubbing treatment alignment layer). As an example of the material contained in the above-mentioned lower layer, polyethylene terephthalate (PET) and the like can be mentioned.
Further, when another resin layer or the like is directly formed on the first resin layer or the second resin layer, the lower first resin layer or the like functions as an orientation layer, and the other resin layer which is the upper layer. In some cases, the liquid crystal compound contained in the liquid crystal composition used for forming the above can be oriented, and it is not necessary to provide an alignment layer or perform an orientation treatment. Liquid crystal compound

The thickness of the alignment layer is preferably 0.01 μm to 10 μm.

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

-Rubbing treatment alignment layer-
The rubbing treatment alignment layer may contain a polymer. Examples of the polymer include, for example, the methacrylate-based copolymer, the styrene-based copolymer, the polyolefin, the polyvinyl alcohol, the modified polyvinyl alcohol, the poly (N-methylolacrylamide), and the polyethylene terephthalate described in JP-A-8-338913. Examples thereof include polyester resins such as PET), polyimide resins, vinyl acetate copolymers, carboxymethyl cellulose and polycarbonate resins.
Further, the silane coupling agent can be contained in the rubbing alignment layer as a polymer.
The polymer contained in the rubbing treatment alignment layer is preferably a water-soluble polymer, specifically, poly (N-methylolacrylamide), carboxymethyl cellulose, gelatin, polyvinyl alcohol, modified polyvinyl alcohol and the like, and gelatin, polyvinyl alcohol or modified Polyvinyl alcohol is more preferable, and polyvinyl alcohol or modified polyvinyl alcohol is further preferable.

The liquid crystal composition is applied to the rubbing-treated surface of the alignment layer to orient the molecules of the liquid crystal compound. Then, if necessary, the polymer contained in the alignment layer is reacted with the polyfunctional monomer contained in the first resin layer, or the polymer contained in the alignment layer is crosslinked using a crosslinking agent. By allowing the resin layer to be formed, the first resin layer can be formed.

-Light alignment layer-
The photo-alignment layer can contain a photo-alignment material. Examples of the photo-alignment material include JP-A-2006-285197, JP-A-2007-76839, JP-A-2007-138138, JP-A-2007-94071, JP-A-2007-121721, and JP-A. Azo compounds and azo compounds described in JP-A-2007-140465, JP-A-2007-156439, JP-A-2007-133184, JP-A-2009-109831, Patent No. 3883848, Patent No. 4151746, etc. Aromatic ester compounds described in JP-A-2002-229039, maleimide and / or alkenyl-substituted nadiimide compounds having photo-orientation units described in JP-A-2002-265541 and JP-A-2002-317013, Patent No. Photocrossable silane derivatives described in 4205195 and Japanese Patent No. 4205198, photocrossable polyimides and polyamides described in JP-A-2003-520878, JP-A-2004-522220, and Japanese Patent No. 4162850. Esters are also preferred examples. Particularly preferred are azo compounds, photocrosslinkable polyimides, polyamides or esters.

<Base material>
The decorative film according to the present disclosure may contain a base material. The shape and material of the base material are not particularly limited and can be appropriately selected depending on the intended use.
From the viewpoint of ease of insert molding and chipping resistance, the base material is preferably a resin base material, and more preferably a resin film base material.

Examples of the base material include PET resin, polyethylene naphthalate (PEN) resin, polyolefin resin (preferably polypropylene), (meth) acrylic resin, urethane resin, urethane-modified (meth) acrylic resin, polycarbonate (PC) resin, and the like. Examples thereof include resin films containing resins such as (meth) acrylic modified polycarbonate resin, triacetyl cellulose (TAC), cycloolefin polymer (COP), and (meth) acrylonitrile / butadiene / styrene copolymer resin (ABS resin).
Among the above, from the viewpoint of ease of molding and strength, the group consists of PET resin, (meth) acrylic resin, urethane resin, urethane-modified (meth) acrylic resin, PC resin, (meth) acrylic-modified polycarbonate resin, and polypropylene resin. A resin film containing at least one selected resin is preferable, and a resin film containing at least one resin selected from the group consisting of (meth) acrylic resin, PC resin and (meth) acrylic-modified polycarbonate resin. Is more preferable.
Further, the base material may be a laminated resin base material having two or more layers. A laminate of a (meth) acrylic resin film and a polycarbonate resin film is a preferable example.

The base material may contain additives, if necessary.
Examples of the additive include mineral oils, hydrocarbons, fatty acids, alcohols, fatty acid esters, fatty acid amides, metal soaps, lubricants such as natural waxes and silicones, inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, and halogen-based organics. Organic flame retardants such as flame retardants and phosphorus-based organic flame retardants, organic fillers such as metal powder, talc, calcium carbonate, potassium titanate, glass fiber, carbon fiber and wood powder, inorganic fillers, antioxidants, UV protection Agents, lubricants, dispersants, coupling agents, foaming agents, colorants, and engineering plastics such as polyolefin resins, polyester resins, polyacetal resins, polyamide resins or polyphenylene ether resins other than the above-mentioned resins.

The thickness of the base material is not particularly limited and is preferably selected as appropriate depending on the intended use of the decorative film, but the thickness of the base material is preferably 1 μm or more, more preferably 10 μm or more, and further preferably 20 μm or more. It is preferable, and 50 μm or more is particularly preferable. The thickness of the base material is preferably 500 μm or less, more preferably 450 μm or less, still more preferably 200 μm or less.

The base material is preferably surface-treated from the viewpoint of adhesion to adjacent layers. Examples of the surface treatment include corona discharge treatment, plasma treatment, ozone treatment, frame treatment and the like.
Further, the base material may be made of a material having high peelability, and may be used in the production of a decorative film and may be peeled off from the produced decorative film.

(Other layers)
The decorative film of the present disclosure may optionally include other layers in addition to the layers described above. For example, a protective layer, an antistatic layer, an antireflection layer, a color correction layer, an ultraviolet absorbing layer, a gas barrier layer, a peeling layer, an adhesive layer, an adhesive layer and the like can be mentioned.

(Method for manufacturing a decorative film according to the first aspect)
The method for manufacturing a decorative film according to the present disclosure is as follows.
The process of preparing a liquid crystal material including a base material and a liquid crystal layer, and
The liquid crystal layer is subjected to photoisomerization treatment, and the liquid crystal layer contains at least one region having a wavelength having a maximum reflectance in the range of 380 nm or less or 800 nm or more, and the wavelength having a maximum reflectance is different. A step of curing the liquid crystal layer to form a first resin layer having cholesteric regularity after making the state having one or more regions.
A step of forming a second resin layer having a cholesteric regularity different from that of the first resin layer on the first resin layer, and a step of forming the second resin layer.
including.

Further, the method for producing a decorative film of the present disclosure can include a step of forming another resin layer.

<Process of preparing liquid crystal material>
The liquid crystal material includes a base material and a liquid crystal layer. The liquid crystal layer can be formed by applying a liquid crystal composition on a substrate and heating the liquid crystal layer. Further, a commercially available liquid crystal material may be used.

As the base material, those manufactured by a conventionally known method using the above-mentioned materials may be used, or commercially available ones may be used. Examples of commercially available products include Technoloy (registered trademark) series (acrylic resin film or laminate of acrylic resin film and polycarbonate resin film, manufactured by Sumitomo Chemical Co., Ltd.) and the like.
The base material may be peeled off after the decorative film is manufactured.

The method for applying the liquid crystal composition onto the substrate is not particularly limited, and is a wire bar coating method, a curtain coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a die coating method, and a spin coating method. , Dip coating method, spray coating method, slide coating method and the like. Moreover, as the above-mentioned application method, a method of transferring a liquid crystal composition separately coated on a support can be mentioned. Further, as the above-mentioned application method, a method of dropping a liquid crystal composition can be mentioned. As the dotting method, an inkjet method can be used.
The liquid crystal compound can be oriented by heating the applied liquid crystal composition. The heating temperature is preferably 200 ° C. or lower, more preferably 130 ° C. or lower. The heat treatment forms a liquid crystal layer having a structure in which the liquid crystal compound is twisted and oriented so as to have a spiral axis in a direction substantially perpendicular to the formation surface.
When the liquid crystal composition contains the above solvent, it is preferably dried by a known method. For example, it may be dried by leaving it or air-drying, or it may be dried by heating.
The amount of the liquid crystal composition to be applied may be appropriately adjusted in consideration of the thickness of the first resin layer after drying. The first resin layer may be formed on the base material, and the base material may be formed. It may be formed on the colored layer or other resin layer provided above. Further, since the materials that can be contained in the liquid crystal composition have been described above, the description thereof will be omitted here.

-Liquid crystal compositions and liquid crystal compounds-
The liquid crystal composition can contain a liquid crystal compound. The liquid crystal composition can contain a non-liquid crystal polymerizable monomer. The liquid crystal composition can contain a chiral compound. The liquid crystal composition can contain a cross-linking agent. The liquid crystal composition can contain other additives. The liquid crystal composition can contain a solvent.

Examples of the liquid crystal compound include a rod-shaped compound (hereinafter, also referred to as a rod-shaped liquid crystal compound) and a disk-shaped compound (hereinafter, also referred to as a disk-shaped liquid crystal compound), and from the viewpoint of easiness of forming a spiral structure, the liquid crystal compound includes. It is preferably a rod-shaped liquid crystal compound.
Further, the liquid crystal composition may contain two or more kinds of rod-shaped liquid crystal compounds, two or more kinds of disc-shaped liquid crystal compounds, or a mixture of a rod-shaped liquid crystal compound and a disc-shaped liquid crystal compound.
The formed resin layer does not have to contain a liquid crystal compound. For example, in the first resin layer, a low molecular weight liquid crystal compound having a group that reacts with heat, light, or the like reacts with heat, light, or the like, crosslinks, and becomes high molecular weight, resulting in liquid crystallinity. It may be a layer containing a compound that has lost the above.

Further, the combination of the liquid crystal compounds used for forming the resin layer is not particularly limited.
All of the liquid crystal compounds used for forming the resin layer may be rod-shaped liquid crystal compounds, all may be disc-shaped liquid crystal compounds, and all may be rod-shaped liquid crystal compounds and disc-shaped liquid crystal compounds. It may be a mixture. The mixing ratio of the rod-shaped liquid crystal compound and the disk-shaped liquid crystal compound in the above mixture may be different for each layer or may be the same. Further, a layer in which all are formed of a rod-shaped liquid crystal compound and a layer in which all of which are formed of a disk-shaped liquid crystal compound may be laminated.

Further, the liquid crystal compound may be a low molecular weight compound or a high molecular weight compound. In the present disclosure, the term "polymer compound" refers to a compound having a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, Masao Doi, p. 2, Iwanami Shoten, 1992). It was

Since the influence of temperature and humidity on the formation of the spiral structure can be reduced, the liquid crystal compound preferably has a reactive group in one molecule, and preferably has two or more reactive groups in one molecule. More preferred. Hereinafter, a liquid crystal compound having one reactive group in one molecule is also referred to as a “monofunctional liquid crystal compound”, and a liquid crystal compound having two or more reactive groups in one molecule is referred to as a “polyfunctional liquid crystal compound”. Also called.
The liquid crystal composition preferably contains a monofunctional liquid crystal compound. By containing the monofunctional liquid crystal compound in the liquid crystal composition, the ease of molding the decorative film can be improved.

When a resin layer is further formed on the formed resin layer, for example, when a second resin layer is formed on the first resin layer, the liquid crystal composition used for forming the first resin layer is a liquid crystal composition. It preferably contains at least one of a polyfunctional liquid crystal compound and a polyfunctional non-liquid crystal polymerizable monomer. When the liquid crystal composition contains at least one of a polyfunctional liquid crystal compound and a polyfunctional non-liquid crystal polymerizable monomer, the liquid crystal composition for forming the second resin layer is placed on the first resin layer. At the time of application, it is possible to prevent the liquid crystal composition for forming the second resin layer from being mixed with the components in the first resin layer.
The content of the polyfunctional liquid crystal compound and the polyfunctional non-liquid crystal polymerized monomer in the liquid crystal composition is preferably 10% by mass or more, more preferably 15% by mass or more, and 20% by mass. % Or more is more preferable. The content of the polyfunctional liquid crystal compound and the polyfunctional non-liquid crystal polymerized monomer in the liquid crystal composition is preferably 50% by mass or less.
Further, from the viewpoint of moldability of the decorative film, the liquid crystal composition preferably contains a monofunctional liquid crystal compound in addition to at least one of the polyfunctional liquid crystal compound and the polyfunctional non-liquid crystal polymerized monomer.
When the liquid crystal composition contains a monofunctional liquid crystal compound, a polyfunctional liquid crystal compound and a polyfunctional non-liquid crystal polymerized monomer, the content of the monofunctional liquid crystal compound in the liquid crystal composition and the polyfunctional liquid crystal property. The ratio to the content of the compound and the polyfunctional non-liquid crystal polymerizable monomer (content of the monofunctional liquid crystal compound: the sum of the contents of the polyfunctional liquid crystal compound and the polyfunctional non-liquid crystal polymerizable monomer) is On a mass basis, it is preferably 95: 5 to 1:99, more preferably 85:15 to 10:90, even more preferably 85:15 to 20:80, and 85:15 to 40. : 60 is particularly preferable.

The liquid crystal composition for forming the resin layer provided on the outermost surface (hereinafter, also referred to as the outermost surface resin layer) is larger than the liquid crystal composition for forming the resin layer provided below the outermost surface resin layer. It is preferable that the content of the functional liquid crystal compound and the polyfunctional non-liquid crystal polymerized monomer is small from the viewpoint of moldability of the decorative film. In the present disclosure, the outermost surface resin layer may be a first resin layer, a second resin layer, or another resin layer.

Further, the polyfunctional liquid crystal compound preferably has two or more kinds of reactive groups having different cross-linking mechanisms. By using the above liquid crystal compound and selecting the reaction conditions, a part of the reactive groups of the liquid crystal compound can be polymerized, and the layer contains a compound having an unreacted reactive group. Can be done.
Examples of the cross-linking mechanism include a condensation polymerization reaction, a hydrogen bond reaction, and an addition polymerization reaction. The phrase "having two or more reactive groups having different cross-linking mechanisms" also includes the case of having two or more reactive groups having different polymerization reactions as the cross-linking mechanism.
When the polyfunctional liquid crystal compound has two or more kinds of reactive groups having different cross-linking mechanisms, it is preferable that the cross-linking mechanism of at least one reactive group is a polymerization reaction, and the cross-linking mechanism of two or more kinds of reactive groups is preferable. It is more preferable that the polymerization reactions are different.

A liquid crystal compound having two or more kinds of reactive groups having different cross-linking mechanisms is a compound that can be cross-linked stepwise by using different cross-linking reaction steps, and in each step of the cross-linking reaction step, it depends on each cross-linking mechanism. The reactive group reacts as a functional group.
Further, for example, when a polymerization reaction for polymerizing a polymer such as polyvinyl alcohol having a hydroxy group in the side chain is performed and then the hydroxy group in the side chain is crosslinked with an aldehyde or the like, two or more different cross-linking mechanisms are used. I was there.
In the present disclosure, a liquid crystal compound having two or more different reactive groups has two or more different reactive groups at the time of forming the resin layer, and the reactive groups are crosslinked stepwise after formation. It is preferably a compound that can be made to react.

The reactive group is preferably a polymerizable group. Examples of the polymerizable group include a radically polymerizable group and a cationically polymerizable group. The liquid crystal compound is preferably a polyfunctional liquid crystal compound having two or more kinds of polymerizable groups.
The difference in reaction conditions for stepwise cross-linking may be any of a difference in temperature, a difference in wavelength of light (irradiation line), and a difference in polymerization mechanism, but the difference in polymerization mechanism is used because the reaction can be easily separated. It is preferable, and it is more preferable to control it depending on the type of the polymerization initiator used.

Examples of the polymerizable group include a vinyl group, a (meth) acrylic group, an epoxy group, an oxetanyl group, a vinyl ether group, a hydroxy group, a carboxy group and an amino group.
As the combination of the polymerizable group, a combination of a radically polymerizable group and a cationically polymerizable group is preferable. Among them, the combination in which the radically polymerizable group is a vinyl group or a (meth) acrylic group and the cationically polymerizable group is an epoxy group, an oxetanyl group or a vinyl ether group is easy to control the reactivity. preferable.
Above all, the liquid crystal compound preferably has a radically polymerizable group from the viewpoint of reactivity and ease of fixing the spiral pitch of the helical structure.
Examples of reactive groups are shown below, but the reactive groups are not limited thereto. In addition, Et represents an ethyl group, and n-Pr represents an n-propyl group.

Examples of the rod-shaped liquid liquid compound include azomethine-based compounds, azoxy-based compounds, cyanobiphenyl-based compounds, cyanophenyl ester-based compounds, benzoic acid ester-based compounds, cyclohexanecarboxylic acid phenyl ester-based compounds, cyanophenylcyclohexane-based compounds, and cyano-substituted phenylpyrimidine. Preferred examples thereof include system compounds, alkoxy-substituted phenylpyrimidine-based compounds, phenyldioxane-based compounds, trans-based compounds and alkenylcyclohexylbenzonitrile-based compounds.
Not only the small molecule liquid crystal compound but also the high molecular weight liquid crystal compound can be used. The polymer liquid crystal compound is a polymer compound obtained by polymerizing a low-molecular-weight rod-shaped liquid crystal compound having a reactive group.
Examples of the rod-shaped liquid crystal compound include the compounds described in JP-A-2008-281989, JP-A No. 11-513019, JP-A-2006-526165, and the like.

Specific examples of the rod-shaped liquid crystal compound are shown below, but the present invention is not limited thereto. The compounds shown below can be synthesized by the method described in JP-A No. 11-513019.

I-20

I-21

I-22

I-23

I-24

Examples of the disc-shaped liquid crystal compound include a low molecular weight disc-shaped liquid crystal compound such as a monomer and a polymerizable disc-shaped liquid crystal compound.
Examples of disc-shaped liquid crystal compounds include C.I. Research report by Destrade et al., Mol. Cryst. Benzene Derivatives, C.I., p. 71, p. 111 (1981). Research report by Destrade et al., Mol. Cryst. Volume 122, p. 141 (1985), Physicslett, A, 78, p. 82 (1990). Research report by Kohne et al., Angew. Chem. Cyclohexane derivatives described in Vol. 96, p. 70 (1984), as well as J. Mol. M. Research report by Lehn et al., J. Mol. Chem. Commun. , 1794 (1985) and J. Mol. Research report by Zhang et al., J. Mol. Am. Chem. Soc. Examples thereof include the aza-crown macrocycle and the phenylacetylene macrocycle described in Vol. 116, p. 2655 (1994).
In the disk-shaped liquid crystal compound, the above-mentioned various structures are used as a disk-shaped mother nucleus at the center of the molecule, and a group (L) such as a linear alkyl group, an alkoxy group, or a substituted benzoyloxy group is used as a side chain of the mother nucleus for radiation. A compound having a shape-like structure and exhibiting liquidity is included. The above compound is generally called a disc-shaped liquid crystal display.
When the aggregate of the above compounds is uniformly oriented, it exhibits negative uniaxiality, but the disk-shaped liquid crystal compound is not limited to this description. When a disk-shaped liquid crystal compound having a reactive group is used as the liquid liquid compound, it may be fixed in any of the horizontal orientation, the vertical orientation, the tilt orientation, and the twist orientation in the cured resin layer.

The liquid crystal composition may contain one kind of liquid crystal compound or two or more kinds of liquid crystal compounds.
The content of the liquid crystal compound in the liquid crystal composition is preferably 30% by mass to 99% by mass, preferably 40% by mass, based on the total solid content in the liquid crystal composition from the viewpoint of the design of the decorative film. It is more preferably% to 99% by mass, further preferably 60% by mass to 99% by mass, and particularly preferably 70% by mass to 98% by mass.

-Non-liquid crystal polymerizable monomer-
The liquid crystal composition may contain a non-liquid crystal polymerizable monomer. By containing the non-liquid crystal polymerizable monomer in the liquid crystal composition, the cross-linking reaction of the liquid crystal compound at the time of forming the first resin layer is promoted.
As the non-liquidity polymerizable monomer, for example, a monomer or oligomer having two or more ethylenically unsaturated bonds and addition-polymerizing by irradiation with light can be used as the non-liquidity polymerizable monomer.
In the present disclosure, the oligomer is a polymer of a monomer and means a compound having a degree of polymerization of 2 or more and 15 or less.
Further, the non-liquid crystal polymerization monomer may be monofunctional or polyfunctional.

Examples of the monomer and oligomer include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule.
Examples of the monomers and oligomers include monofunctional (meth) acrylates 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, trimethylol ethanetriacrylate, trimethylolpropanetri (meth) acrylate, trimethylolpropanediacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) Acrylate, Dipentaerythritol Hexa (meth) Acrylate, Dipentaerythritol Penta (meth) Acrylate, Hexadiol Di (Meta) Acrylate, Trimethylol Propanetri (Acryloyloxypropyl) Ether, Tri (Acryloyloxyethyl) Isocyanurate, Tri ( Acryloyloxyethyl) cyanurate and glycerin tri (meth) acrylate; polyfunctional (meth) acrylates such as compounds obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as trimethylolpropane and glycerin and then (meth) acrylated. be able to.

Further, examples of the above-mentioned monomers and oligomers include urethane acrylate compounds described in JP-A-48-41708, JP-A-50-6034, JP-A-51-37193, and the like; JP-A-48. -The polyester acrylate compound described in Japanese Patent Publication No. -64183, Japanese Patent Publication No. 49-43191, Japanese Patent Publication No. 52-30490, etc .; and the epoxy acrylate compound which is a reaction product of the epoxy resin and (meth) acrylic acid. Such as polyfunctional (meth) acrylic relay can be mentioned.
Among the above-mentioned compounds, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate or dipentaerythritol penta (meth) acrylate are preferable.
In addition, the "polymerizable compound B" described in JP-A-11-133600 can also be mentioned as an example of the above-mentioned non-liquid crystal polymerizable monomer.
The above-mentioned monomer or oligomer may be used alone or in combination of two or more.

Further, as the non-liquid crystal polymerizable monomer, a cationically polymerizable monomer 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 and JP-A-2001-220526 Examples thereof include epoxy compounds, vinyl ether compounds, oxetane compounds and the like exemplified in each publication.

Further, as the cationically polymerizable monomer, a monofunctional or bifunctional oxetane monomer can also be used.
As a monofunctional or bifunctional oxetane monomer, for example, 3-ethyl-3-hydroxymethyloxetane (manufactured by Toa Synthetic Co., Ltd., trade name OXT101, etc.), 1,4-bis [(3-ethyl-3-oxetanyl)). Methoxymethyl] benzene (manufactured by Toa Synthetic Co., Ltd., trade name OXT121, etc.), 3-ethyl-3- (phenoxymethyl) oxetane (manufactured by Toa Synthetic Co., Ltd., trade name OXT211 etc.), di (1-ethyl-3) -Oxetanyl) methyl ether (manufactured by Toa Synthetic Co., Ltd., trade name OXT221, etc.) or 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (manufactured by Toa Synthetic Co., Ltd., trade name OXT212, etc.) is preferable. It can be used, and in particular, a compound such as 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane or di (1-ethyl-3-oxetanyl) methyl ether, or JP-A-2001- Any known monofunctional or polyfunctional oxetane compound such as the compounds described in JP-A-220526 or JP-A-2001-310937 can be used.

-Chiral compound-
The liquid crystal composition preferably contains a chiral compound from the viewpoint of easy formation of the resin layer and easy adjustment of the spiral pitch of the spiral structure. The chiral compound has a function of inducing a helical structure for a cholesteric liquid crystal compound.
The chiral compound may be selected according to the purpose because the twisting direction or the spiral pitch of the induced spiral differs depending on the liquid crystal compound. The chiral compound is not particularly limited, and a known compound (for example, "Liquid Crystal Device Handbook", Chapter 3, Section 4-3, TN (twisted nematic), STN (Super-twisted nematic) chiral agent, p. 199, Japanese Science Compounds described in 1989, edited by the 142nd Committee of the Promotion Association), isosorbide, and isomannide derivatives can be used. The chiral compound generally contains an asymmetric carbon atom, but an axial asymmetric compound or a planar asymmetric compound that does not contain an asymmetric carbon atom can also be used as the chiral compound. Examples of the axial asymmetric compound or the planar asymmetric compound preferably include binaphthyl compounds, helicene compounds, and paracyclophane compounds.
Examples of the chiral compound include a photoisomerized chiral compound and a polymerizable chiral compound.

As the chiral compound, one kind may be used alone, or two or more kinds may be used in combination.

When the liquid crystal composition contains a chiral compound, the content of the chiral compound is 1% by mass to 20% by mass with respect to the total solid content of the liquid crystal composition from the viewpoint of more easily obtaining the target reflection wavelength. It is preferably 1% by mass to 15% by mass, more preferably 1% by mass to 10% by mass.

－－Photoisomerized chiral compound －－
The liquid crystal composition preferably contains a photoisomerized chiral compound as the chiral compound from the viewpoint of more easily adjusting the selective reflection wavelength. The photoisomerized chiral compound means a compound having a photoisomerized structure and chirality in one molecule.

The photoisomerized chiral compound is preferably a compound whose three-dimensional structure changes with exposure from the viewpoint of ease of photoisomerization and maintenance of the isomerized structure, and the EZ (Zussammen, Ethgen) arrangement is isomerized by exposure. It is more preferable to have an ethylenically unsaturated bond having two or more substitutions, and it is particularly preferable to have an ethylenically unsaturated bond having three substitutions whose EZ arrangement is isomerized by exposure.

When the photoisomerized chiral compound is isomerized by exposure, it changes the orientation structure such as the spiral pitch (twisting force, spiral twist angle) of the spiral structure in the liquid crystal phase.
Further, the photoisomerization ratio of the photoisomerized chiral compound can be adjusted by the exposure amount at the time of exposure. Depending on the photoisomerization ratio of the photoisomerized chiral compound, the length of the spiral pitch of the spiral structure in the liquid crystal phase can be changed, and the selective reflection wavelength can be changed. The photoisomerization ratio means the ratio of the number of molecules of the photoisomerized chiral compound to the total number of molecules of the photoisomerized chiral compound.

The isomerization of the EZ arrangement in the present disclosure also includes cis-trans isomerization. Further, the compound having an ethylenically unsaturated bond having two substitutions is preferably a compound having an ethylenically unsaturated bond substituted with an aromatic group and an ester bond.

Further, the photoisomerized chiral compound may have only one photoisomerized structure and may have two or more photoisomerized chiral compounds. From the viewpoint of ease of photoisomerization and maintenance of the isomerized structure, the photoisomerized compound preferably has two or more photoisomerized structures, and preferably has two to four. It is more preferable to have two, and it is particularly preferable to have two.

Specifically, the photoisomerized chiral compound is preferably a compound represented by the following formula (CH1).

The compound represented by the following formula (CH1) can change the orientation structure such as the spiral pitch (twisting force, helix angle) of the cholesteric liquid crystal phase according to the exposure amount at the time of exposure.

Further, the compound represented by the following formula (CH1) is a compound in which the EZ arrangement in the two ethylenically unsaturated bonds can be isomerized by exposure.

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

It is preferable that Ar ^CH1 and Ar ^CH2 in the formula (CH1) are independently aryl groups.

The aryl group in Ar ^CH1 and Ar ^CH2 of the formula (CH1) may have a substituent, preferably has a total carbon number of 6 to 40, and more preferably has a total carbon number of 6 to 30. The substituent is a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a hydroxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carboxy group, a cyano group, or a heterocyclic group. A halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an acyloxy group, an alkoxycarbonyl group, or an aryloxycarbonyl group is more preferable.

It is preferable that R ^CH1 and R ^CH2 in the formula (CH1) are independently cyano groups.

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

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

R ^CH3 and R ^CH4 in the formula (CH2) and the formula (CH3) are independently hydrogen atom, halogen atom, alkyl group, alkoxy group, aryl group, alkoxy group, hydroxy group, alkoxycarbonyl group, aryloxycarbonyl group, respectively. Alternatively, it is preferably an acyloxy group, more preferably an alkoxy group, a hydroxy group, or an acyloxy group, and particularly preferably an alkoxy group.

It is preferable that L ^CH1 and L ^CH2 in the formula (CH2) and the formula (CH3) are independently alkoxy groups having 1 to 10 carbon atoms or hydroxy groups, respectively.

NCH1 in the formula (CH2) is preferably 0 or 1, more preferably 0.

NCH2 in the formula (CH3) is preferably 0 or 1, more preferably 0.

The complex aromatic ring group in Ar ^CH1 and Ar ^CH2 of the formula (CH1) may have a substituent, preferably has a total carbon number of 4 to 40, and more preferably has a total carbon number of 4 to 30. preferable. As the substituent, for example, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, a hydroxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, or a cyano group is preferable. A halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an acyloxy group is more preferable.

The heteroaromatic ring group is preferably a pyridyl group, a pyrimidinyl group, a frill group, or a benzofuranyl group, and more preferably a pyridyl group or a pyrimidinyl group.

The following compounds are preferably mentioned as the compound represented by the formula (CH1). The following compounds are compounds in which the molecular configuration of each ethylenically unsaturated bond changes with exposure.

As the photoisomerized chiral compound, one type may be used alone, or two or more types may be used in combination.

When the liquid crystal composition contains a photoisomerized chiral compound, the content of the photoisomerized chiral compound is 0 with respect to the total solid content of the liquid crystal composition from the viewpoint of more easily obtaining the desired reflection wavelength. It is preferably 5.5% by mass to 15% by mass, more preferably 1% by mass to 10% by mass, and even more preferably 2% by mass to 9% by mass.

--Polymerizable chiral compound ---
The liquid crystal composition preferably contains a polymerizable chiral compound as the chiral compound from the viewpoint of more easily fixing the helical structure of the liquid crystal compound. The polymerizable chiral compound means a chiral compound having a polymerizable group. The polymerizable chiral compound referred to here does not have a photoisomerized structure and is distinguished from the photoisomerized chiral compound.

Examples of the polymerizable group of the polymerizable chiral compound include a radical polymerizable group and a cationically polymerizable group. The polymerizable group is preferably an ethylenically unsaturated group, an epoxy group or an aziridinyl group, and more preferably an ethylenically unsaturated group.

The polymerizable chiral compound is preferably a compound containing an asymmetric carbon atom, but may be an axial asymmetric compound or a planar asymmetric compound that does not contain an asymmetric carbon atom. Examples of axial or asymmetric compounds include binaphthyl, helicene, paracyclophane and derivatives thereof.

When the liquid crystal composition contains a liquid crystal compound having a polymerizable group, the polymerizable chiral compound preferably contains a polymerizable group of the same type as the polymerizable group of the liquid crystal compound. For example, when the liquid crystal compound has a radically polymerizable group, it is preferable that the polymerizable chiral compound also contains a radically polymerizable group. As a result, a polymer obtained by polymerizing a liquid crystal compound having a polymerizable group and a polymerizable chiral compound is formed, and the helical structure of the liquid crystal compound can be more easily fixed.

The polymerizable chiral compound is preferably an isosorbide derivative, an isomannide derivative, or a binaphthyl derivative. Examples of commercially available isosorbide derivatives include "Pario Color LC756" manufactured by BASF.

As the polymerizable chiral compound, one type may be used alone, or two or more types may be used in combination.

When the liquid crystal composition contains a polymerizable chiral compound, the content of the polymerizable chiral compound is 0.5 with respect to the total solid content of the liquid crystal composition from the viewpoint of more easily obtaining the desired reflection wavelength. It is preferably from mass% to 8% by mass, more preferably from 1% by mass to 10% by mass, and even more preferably from 1% by mass to 5% by mass.

-Polymer initiator-
The liquid crystal composition may contain a polymerization initiator. As the polymerization initiator, known ones can be selected and used, but a photopolymerization initiator is preferable, and a photopolymerization initiator that initiates the polymerization reaction by irradiation with ultraviolet rays is more preferable. Further, the photopolymerization initiator may be a photoradical polymerization initiator or a photocationic polymerization initiator.
Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. No. 2,376,661 and US Pat. No. 2,376,670, etc.), acidoin ether compounds (described in US Pat. No. 2,448,828, etc.), α. -Hydroxide-substituted aromatic acidoine compounds (described in US Pat. No. 2,225,512, etc.), polynuclear quinone compounds (described in US Pat. No. 3,46127 and US Pat. No. 2,951,758, etc.), triarylimidazole dimer and p-. Combination with aminophenyl ketone (described in US Pat. No. 3,549,67, etc.), aclysine compound and phenazine compound (described in JP-A-60-105667 and US Pat. No. 4,239,850, etc.), and oxadiazole compound (described in JP-A-60-105667, etc.), and oxadiazole compound (described in JP-A-60-105667, etc.). US Pat. No. 4,212,970 (described in the specification, etc.)) and the like.

Further, as the photoradical polymerization initiator, a known photoradical polymerization initiator can be used. Preferred examples of the photoradical polymerization initiator include α-hydroxyalkylphenone compounds, α-aminoalkylphenone compounds, acylphosphine oxide compounds, thioxanthone compounds and oxime ester compounds.
Further, as the photocationic polymerization initiator, a known photocationic polymerization initiator can be used. Preferred examples of the photocationic polymerization initiator include iodonium salt compounds and sulfonium salt compounds.

The liquid crystal composition may contain one kind of polymerization initiator, or may contain two or more kinds of polymerization initiators.
The content of the polymerization initiator in the liquid crystal composition is preferably appropriately selected according to the structure of the liquid crystal compound to be used and the desired spiral pitch of the spiral structure to be formed, but the spiral pitch of the spiral structure can be easily adjusted. From the viewpoint of properties, polymerization rate and strength of the resin layer after curing, it is preferably 0.05% by mass to 10% by mass, preferably 0.05% by mass or more, based on the total solid content in the liquid crystal composition. It is more preferably 5% by mass, further preferably 0.1% by mass to 4% by mass, and particularly preferably 0.2% by mass to 3% by mass.

-Crosslinking agent-
The liquid crystal composition preferably contains a cross-linking agent from the viewpoint of the strength and durability of the resin layer after curing. As the cross-linking agent, one that causes a cross-linking curing reaction by ultraviolet rays, heat or humidity can be preferably used.
The type of the cross-linking agent is not particularly limited, and is, for example, a polyfunctional acrylate compound such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate; glycidyl (meth) acrylate, ethylene glycol diglycidyl ether and 3'. , 4'-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate and other epoxy compounds; 2-ethylhexyloxetane and xylylenebisoxetane and other oxetane compounds; 2,2-bishydroxymethylbutanol-tris [3- (1- (1-) Azilidinyl) propionate] and aziridine compounds such as 4,4-bis (ethyleneiminocarbonylamino) diphenylmethane; isocyanate compounds such as hexamethylenediisocyanate and biuret-type isocyanate; polyoxazoline compounds having an oxazolin group in the side chain; vinyltrimethoxysilane and Examples thereof include alkoxysilane compounds such as N- (2-aminoethyl) 3-aminopropyltrimethoxysilane.
Further, a known catalyst can be contained in the liquid crystal composition depending on the reactivity of the cross-linking agent, and the productivity can be improved in addition to the improvement of the strength and durability of the resin layer.

The liquid crystal composition may contain one kind of cross-linking agent or two or more kinds.
From the viewpoint of the strength and durability of the first resin layer, the content of the cross-linking agent in the liquid crystal composition is preferably 1% by mass to 20% by mass with respect to the total solid content in the liquid crystal composition. It is more preferably 3% by mass to 15% by mass.

-Polyfunctional polymerizable compound-
The liquid crystal composition preferably contains a polyfunctional polymerizable compound from the viewpoint of suppressing a change in reflectance after molding. The polyfunctional polymerizable compound is a cholesteric liquid crystal compound having two or more ethylenically unsaturated groups and no cyclic ether group in the above-mentioned compounds, and having two or more cyclic ether groups. A cholesteric liquid crystal compound having no ethylenically unsaturated group, a cholesteric liquid crystal compound having two or more ethylenically unsaturated groups and two or more cyclic ether groups, and a chiral compound having two or more polymerizable groups. , The above-mentioned cross-linking agent. The ethylenically unsaturated group is preferably a (meth) acrylic group or a (meth) acryloyl group, and more preferably a (meth) acryloyl group.
The cyclic ether group is preferably an epoxy group or an oxetanyl group, and more preferably an oxetanyl group. Among the above-mentioned polyfunctional polymerizable compounds, a liquid crystal compound having two or more ethylenically unsaturated groups and not having a cyclic ether group, and having two or more cyclic ether groups and having an ethylenically unsaturated group. A liquid crystal compound having no group or a chiral compound having two or more polymerizable groups is preferable, and a chiral compound having two or more polymerizable groups is more preferable.

From the viewpoint of suppressing the change in reflectance after molding, the content of the polyfunctional polymerizable compound in the liquid crystal composition is 0.5% by mass to 70% by mass with respect to the total solid content in the liquid crystal composition. Is more preferable, 1% by mass to 50% by mass is more preferable, and 1.5% by mass to 20% by mass is further preferable.

-Other additives-
The liquid crystal composition may contain other additives, if necessary.
As other additives, known additives can be used, such as surfactants, polymerization inhibitors, antioxidants, horizontal alignment agents, ultraviolet absorbers, light stabilizers, colorants and metal oxide particles. Can be mentioned.

-solvent-
The liquid crystal composition may contain a solvent. The solvent is not particularly limited and may be appropriately selected depending on the intended purpose, but an organic solvent is preferably used.
Examples of the organic solvent include ketone compounds such as methyl ethyl ketone and methyl isobutyl ketone, alkyl halide compounds, amide compounds, sulfoxide compounds, heterocyclic compounds, hydrocarbon compounds, ester compounds, ether compounds and alcohol compounds. Examples include compounds. Among the above-mentioned organic solvents, a ketone compound is particularly preferable from the viewpoint of environmental load. Moreover, the above-mentioned component may function as a solvent.

The liquid crystal composition may contain one kind of solvent, or may contain two or more kinds of solvents.
The content of the solvent in the cured resin layer is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 2% by mass or less, based on the total mass of the resin layer. It is preferably 1% by mass or less, and particularly preferably 1% by mass or less.

<Step of forming the first resin layer>
In the step of forming the first resin layer, the liquid crystal layer on the base material is subjected to photoisomerization treatment, and the liquid crystal layer has a wavelength having a maximum reflectance in the range of 380 nm or less or 800 nm or more. A first resin layer is formed by curing the liquid crystal layer after making it into a state having two or more regions having different wavelengths having maximum reflectances, including at least one region (specific region A). ..
Further, in the photoisomerization treatment, the liquid crystal layer has a region (other region A) in which a wavelength having a maximum reflectance exists in a range of more than 380 nm and less than 800 nm in addition to the specific region A. Is preferable.

The photoisomerization treatment step is a step of photoisomerizing the photoisomerization compound contained in the liquid crystal layer. In the photoisomerization treatment step, since two or more regions having different wavelengths having the maximum reflectance are formed, photoisomerization may be performed so that a difference in the photoisomerization ratio for each region occurs in the liquid crystal layer surface. preferable. Further, a part of the liquid crystal layer may be photoisomerized.
The photoisomerization ratio of the photoisomerization compound is not particularly limited, and is preferably changed as appropriate according to the color required for the decorative film. Further, the progress of photoisomerization can be known by measuring the wavelength which is the maximum reflectance in the photoisomerization portion.
The photoisomerization ratio represents the ratio of the number of photoisomerized photoisomerized compound molecules to the total number of molecules of the target photoisomerized compound, and can be obtained by measuring the maximum reflectance in the photoisomerized portion. can.

In the photoisomerization treatment step, the exposure intensity to the liquid crystal layer can be changed depending on the region. For example, photoisomerization may be performed by exposing the liquid crystal layer with a plurality of steps or a stepless continuous difference in exposure intensity, or by exposing only a part of the liquid crystal layer. , May be photoisomerized. The photoisomerization ratio can also be controlled according to the exposure intensity.

In order to adjust the photoisomerization ratio for each region, a mask may be used to perform a photoisomerization treatment step. Further, the mask may be used alone or in combination of two or more.
The mask is not particularly limited, and a known light-shielding means such as a mask can be used. For example, a mask in which the amount of transmitted light is different between the photoisomerizable portion and the non-photoisomerizable portion of the liquid crystal layer may be used, or the amount of transmitted light is not constant and changes depending on the portion. (For example, the patterning mask shown in FIGS. 9 to 12 and the like) may be used.
Further, the patterning of the mask can be performed by using a method such as gravure printing, screen printing, a laser printer or an inkjet printer.

The wavelength of the light used for the exposure in the photoisomerization treatment step is not particularly limited, and may be appropriately selected depending on the type of the photoisomerization compound and the color required for the decorative film.
The wavelength of the light to be exposed in the photoisomerization step is, for example, preferably 400 nm or less, more preferably 380 nm or less, and further preferably 300 nm to 380 nm.
A known means and a known method can be used for adjusting the exposure wavelength in the photoisomerization step. For example, a method using an optical filter, a method using two or more types of optical filters, a method using a light source having a specific wavelength, and the like can be mentioned.
When a liquid crystal composition containing a photopolymerization initiator is used for forming the resin layer, in the photoisomerization step, the above exposure may be performed with light in a wavelength range in which the polymerization initiator does not generate a polymerization initiator. preferable.
For example, a mask that transmits light in the wavelength range in which photoisomerization of the photoisomer compound occurs and shields light in the wavelength range in which the polymerization initiator is generated from the photopolymerization initiator can be preferably used.

Specific examples of the light source include an ultra-high pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp. Further, as the light source, a light emitting diode or the like capable of irradiating light having a narrow wavelength range can also be used.
The exposure amount in the photoisomerization step is not particularly limited and may be appropriately set according to the color required for the decorative film. Further, the exposure amount may be changed in each part of the liquid crystal layer according to the desired photoisomerization ratio.
Further, it is preferable to heat the light isomerization by the above exposure. The heating temperature is not particularly limited and may be selected depending on the photoisomerization compound to be used and the like, and examples thereof include 30 ° C. to 120 ° C.
The exposure method is not particularly limited as long as photoisomerization is possible, but for example, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 are preferably used in the present disclosure. Can be done.

The step of forming the first resin layer includes a step of curing the liquid crystal layer subjected to the photoisomerization treatment.
By the curing, the cholesteric liquid crystal phase is fixed in a state where the orientation of the molecules of the liquid crystal compound is maintained.
The curing of the liquid crystal layer is preferably carried out by the polymerization reaction of a compound having a polymerizable group such as an ethylenically unsaturated group or a cyclic ether group contained in the liquid crystal composition.
The curing of the liquid crystal layer may be performed by exposure or by heating, but it is preferably performed by exposure.

The light source for exposure is not particularly limited, and can be appropriately selected and used according to the type of photopolymerization initiator or the like to be used. For example, a light source capable of irradiating light in a wavelength range of 285 nm, 365 nm or 405 nm is preferable, and specific examples thereof include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp and a UV-LED light source.
The exposure amount is not particularly limited and may be appropriately set, preferably 5 mJ / cm ² to 2,000 mJ / cm ² , and more preferably 10 mJ / cm ² to 1,000 mJ / cm ² .
In addition, it is preferable to heat in order to improve the oriented state formed during the curing by the above exposure and to maintain the formed oriented state. The heating temperature is not particularly limited and may be selected depending on the composition of the liquid crystal layer to be cured, and examples thereof include 30 ° C. to 120 ° C.
Further, not only the liquid crystal layer may be cured by the above exposure, but also other layers such as a colored layer may be cured by the exposure as needed.
Further, as the exposure method, for example, the method described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be suitably used in the present disclosure.

Further, when the liquid crystal layer is cured by heating, the heating temperature and the heating time are not particularly limited and may be appropriately selected depending on the thermal polymerization initiator and the like to be used. For example, the heating temperature is preferably 60 ° C. to 200 ° C., 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, and examples thereof include a heater, an oven, a hot plate, an infrared lamp, and an infrared laser.

Further, the oxygen concentration in the environment where the curing step is performed is not limited, and whether it is performed in an oxygen atmosphere or an atmosphere, it is performed in a low oxygen atmosphere (preferably, the oxygen concentration is 1,000 ppm (parts per million)). In the following, that is, an atmosphere that does not contain oxygen or contains oxygen of more than 0 ppm and 1,000 ppm or less) may be used. From the viewpoint of the curing rate, the curing step is preferably performed in a low oxygen atmosphere, more preferably under heating and in a low oxygen atmosphere.

<Step of forming an alignment layer>
The step of forming the first resin layer can include a step of forming an alignment layer before the step of forming a liquid crystal layer.
The alignment layer may be formed by subjecting a base material, a second resin layer, or another resin layer arranged under the first resin layer to a rubbing treatment or the like, and rubbing on the base material. It may be performed by forming an alignment layer, or by forming a photoalignment layer on a substrate.

The rubbing treatment can generally be carried out by rubbing the surface of a film containing a polymer as a main component with paper or cloth in a certain direction. A general method of rubbing processing is described in, for example, "LCD Handbook" (published by Maruzensha, October 30, 2000).

As a method for changing the rubbing density, the method described in "LCD Handbook" (published by Maruzensha) can be used. The rubbing density (L) is quantified by the following formula (A).
Equation (A) L = Nl (1 + 2πrn / 60v)
In the formula (A), N is the number of rubbing, l is the contact length of the rubbing roller, r is the radius of the roller, n is the rotation speed of the roller (rpm: rotations per minute), and v is the stage moving speed (speed per second).

In order to increase the rubbing density, it is sufficient to increase the number of rubbing, increase 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, while decreasing the rubbing density. To do this, do the opposite. Further, as the conditions for the rubbing process, the description of Japanese Patent No. 4052558 can also be referred to.

The photo-alignment layer can be formed by irradiating a layer containing a material such as the above-mentioned ester formed on a substrate with linearly polarized light or non-polarized light.
By irradiating with linearly polarized light, a photoreaction can be caused in the photo-aligned material. The wavelength of the light used varies depending on the photoalignment material used, and is not particularly limited as long as it is a wavelength required for the photoreaction. The light used for light irradiation is preferably light having a peak wavelength of 200 nm to 700 nm, and more preferably ultraviolet light having a peak wavelength of 400 nm or less.

The light source used for light irradiation is a known light source, for example, a tungsten lamp, a halogen lamp, a xenon lamp, a xenon flash lamp, a mercury lamp, a mercury xenon lamp, a lamp such as a carbon arc lamp, and various lasers (for example, a semiconductor laser and a helium). Examples thereof include a neon laser, an argon ion laser, a helium cadmium laser, a YAG (itrium aluminum garnet) laser, etc.), a light emitting diode, and a cathode wire tube.

As a means for obtaining linear polarization, a method using a polarizing plate (for example, iodine polarizing plate, two-color dye polarizing plate, wire grid polarizing plate, etc.), a prism-based element (for example, Gran Thomson prism, etc.) or a Brewster angle is used. Examples thereof include a method using a polarized reflecting type polarizing element and a method using light emitted from a laser light source having polarization. Further, only light having a required wavelength may be selectively irradiated by using a filter, a wavelength conversion element, or the like.

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

<Step of forming the second resin layer>
The step of forming the second resin layer includes a step of applying a liquid crystal composition on the first resin layer and heating it to form a liquid crystal layer, and a step of curing the liquid crystal layer. Can be done.
The liquid crystal composition used for forming the second resin layer can contain the above-mentioned materials that can be contained in the liquid crystal composition used for forming the first resin layer.
Further, in the step of forming the second resin layer, the liquid crystal layer is subjected to photoisomerization treatment before being cured, and the liquid crystal layer has a wavelength having a maximum reflectance in the range of 380 nm or less or 800 nm or more. It is possible to include a step of including at least one region (specific region B) and having two or more regions having different wavelengths having the maximum reflectance. Further, in the above step, the liquid crystal layer may be in a state of having a region (other region B) in which a wavelength having a maximum reflectance exists in a range of more than 380 nm and less than 800 nm in addition to the specific region B. preferable.
Since the details and preferred embodiments of each step are the same as those of the step of forming the first resin layer, the description thereof is omitted here.

<Step of forming other resin layers>
The other steps of forming the resin layer include a step of applying a liquid crystal composition on a base material, a first resin layer or a second resin layer and heating to form a liquid crystal layer, and a step of forming the liquid crystal layer. It can include a step of curing.
The liquid crystal composition used for forming the other resin layer can include the above-mentioned materials that can be contained in the liquid crystal composition used for forming the first resin layer.
Further, in the step of forming the other resin layer, the liquid crystal layer is subjected to photoisomerization treatment before being cured, and the wavelength having the maximum reflectance is in the range of 380 nm or less or 800 nm or more (specific region). A step of forming two or more regions having different wavelengths having a maximum reflectance, including at least one C), can be included. Further, in the above step, the liquid crystal layer may be in a state of having a region (other region B) in which a wavelength having a maximum reflectance exists in a range of more than 380 nm and less than 800 nm in addition to the specific region C. preferable.
Further, when the other resin layer is provided under the first resin layer, the step of forming the other resin layer may include a step of forming the alignment layer.
Since the details and preferred embodiments of each step are the same as those of the step of forming the first resin layer, the description thereof is omitted here.

<Step of forming a colored layer>
The method for producing a decorative film of the present disclosure can include a step of forming a colored layer. The colored layer can be formed by applying the above-mentioned material to, for example, the surface of the base material opposite to the side on which the first resin layer or the like is provided and drying.

(Method for manufacturing a decorative film according to the second aspect)
The method for manufacturing a decorative film according to the present disclosure is as follows.
A step of preparing a liquid crystal material containing a base material and a second resin layer having cholesteric regularity, and
A liquid crystal layer is formed on the second resin layer, the liquid crystal layer is subjected to photoisomerization treatment, and the liquid crystal layer has a wavelength having a maximum reflectance in the range of 380 nm or less or 800 nm or more. A first having a cholesteric regularity different from that of the second resin layer by curing the liquid crystal layer after making the state having two or more regions having different wavelengths having the maximum reflectances containing at least one of the above. The process of forming the resin layer and
including.

Further, the method for producing a decorative film of the present disclosure can include a step of forming another resin layer.
Further, the method for producing a decorative film of the present disclosure can include a step of forming a colored layer.
In the method for producing a decorative film according to the second aspect, the decoration according to the first aspect is provided except that the step of forming the second resin layer can include a step of forming an alignment layer. Since it is the same as the film manufacturing method, the description is omitted here.

(Molded product)
The molded product according to the present disclosure is a molded product obtained by molding the decorative film according to the present disclosure. Further, the shape of the molded product according to the present disclosure is not particularly limited and can be appropriately selected depending on the intended use.
Further, the molded product according to the present disclosure is preferably a molded product obtained by molding a decorative film produced by the method for producing a decorative film according to the present disclosure.
The molding method is not particularly limited, and examples thereof include vacuum forming, vacuum pressure forming, plug assisted vacuum forming, in-molding, insert molding, cold molding, press molding and drawing molding.

The use of the molded product according to the present disclosure is not particularly limited, and can be used for various articles. For example, the interior / exterior of an automobile, the interior / exterior of an electronic device, a packaging container, and the like are particularly preferably mentioned. Among the above, it is preferable to apply it for decorating the interior and exterior of an automobile, and it is more preferable to apply it to the exterior of an automobile.

(Electronic device)
The electronic device according to the present disclosure includes a decorative film according to the present disclosure.
The type of electronic device according to the present disclosure is not particularly limited, and examples thereof include smartphones, mobile phones, tablets, and the like. It is preferable that a decorative film is applied for the decoration of the electronic device described above.
Further, the electronic device according to the present disclosure may have a known member used for the electronic device such as an element, in addition to the decorative film according to the present disclosure.

(Car exterior plate)
The automobile exterior plate according to the present disclosure has a molded product according to the present disclosure. The shape of the automobile exterior plate according to the present disclosure is not particularly limited and may be any desired shape.
The automobile exterior plate according to the present disclosure may have a known member used for the automobile exterior plate in addition to the molded product according to the present disclosure.

Hereinafter, the present disclosure will be described in more detail with reference to Examples, but the present disclosure is not limited to the following Examples as long as the gist of the present disclosure is not exceeded. Unless otherwise specified, "%" is based on mass.

<Preparation of liquid crystal composition 1>
A liquid crystal composition 1 having the composition described below was prepared.
-Liquid compound 1 11.98 parts by mass-Liquid compound 2 5.99 parts by mass-Liquid compound 3 5.99 parts by mass-Mix of liquid compound 1 (mass ratio 83:15: 2)
5.99 parts by mass, polymerizable chiral compound (BASF, Pariocolor LC756)
0.75 parts by mass, photoisomerized chiral compound 1 2.40 parts by mass, photoinitiator (manufactured by IGM Resins, Omnirad 127)
0.30 parts by mass, surfactant 1 0.10 parts by mass, surfactant 2 0.01 parts by mass, methyl ethyl ketone 46.55 parts by mass, cyclohexanone 19.95 parts by mass

The structure of the liquid crystal compound 1 is shown below.

The structure of the liquid crystal compound 2 is shown below.

The structure of the liquid crystal compound 3 is shown below.

The structure of each liquid crystal compound contained in the mixture 1 of the liquid crystal compounds is shown below. The numbers described are the contents (% by mass) in the mixture 1.

The structure of the photoisomerized chiral compound 1 is shown below.

The structure of the surfactant 1 is shown below.

The structure of the surfactant 2 is shown below.

<Preparation of liquid crystal composition 2>
A liquid crystal composition 2 having the composition described below was prepared.
・ Liquid crystal compound 1 17.97 parts by mass ・ Liquid crystal compound 2 5.99 parts by mass ・ Liquid crystal compound 3 5.99 parts by mass ・ Polymerizable chiral compound (BASF, Palio Color LC756)
0.75 parts by mass, photoisomerized chiral compound 1 2.40 parts by mass, photoinitiator (manufactured by IGM Resins, Omnirad 127)
0.30 parts by mass, surfactant 1 0.10 parts by mass, surfactant 2 0.01 parts by mass, methyl ethyl ketone 46.55 parts by mass, cyclohexanone 19.95 parts by mass

<Preparation of liquid crystal composition 3>
A liquid crystal composition 3 having the composition described below was prepared.
-Liquid compound 1 12.37 parts by mass-Liquid compound 2 6.18 parts by mass-Liquid compound 3 6.18 parts by mass-Mix of liquid crystal compound 1 (mass ratio 83: 15: 2) 6.18 mass Part ・ Polymerizable chiral compound (BASF, Paliocolor LC756)
2.16 parts by mass, photopolymerization initiator (manufactured by IGM Regins, Omnirad127)
0.31 part by mass ・ Surfactant 1 0.10 part by mass ・ Surfactant 2 0.01 part by mass ・ Methyl ethyl ketone 46.55 part by mass ・ Cyclohexanone 19.95 part by mass

<Preparation of liquid crystal composition 4>
A liquid crystal composition 4 having the composition described below was prepared.
・ Liquid crystal compound 1 18.64 parts by mass ・ Liquid crystal compound 2 6.21 parts by mass ・ Liquid crystal compound 3 6.21 parts by mass ・ Polymerizable chiral compound (BASF, Palio Color LC756)
0.78 part by mass, photoisomerized chiral compound 1 1.24 parts by mass, photoinitiator (manufactured by IGM Regins, Omnirad127)
0.31 part by mass ・ Surfactant 1 0.10 part by mass ・ Surfactant 2 0.01 part by mass ・ Methyl ethyl ketone 46.55 part by mass ・ Cyclohexanone 19.95 part by mass

<Preparation of liquid crystal composition 5>
A liquid crystal composition 5 having the composition described below was prepared.
・ Liquid crystal compound 1 18.55 parts by mass ・ Liquid crystal compound 2 6.18 parts by mass ・ Liquid crystal compound 3 6.18 parts by mass ・ Polymerizable chiral compound (BASF, Palio Color LC756)
0.77 parts by mass, photoisomerized chiral compound 1 1.39 parts by mass, photoinitiator (manufactured by IGM Regins, Omnirad 127)
0.31 part by mass ・ Surfactant 1 0.10 part by mass ・ Surfactant 2 0.01 part by mass ・ Methyl ethyl ketone 46.55 part by mass ・ Cyclohexanone 19.95 part by mass

<Preparation of liquid crystal composition 6>
A liquid crystal composition 6 having the composition described below was prepared.
・ Liquid crystal compound 1 19.02 parts by mass ・ Liquid crystal compound 2 6.34 parts by mass ・ Liquid crystal compound 3 6.34 parts by mass ・ Photoisomerized chiral compound 2 1.36 parts by mass ・ Photopolymerization initiator (IGM resin) Manufactured by Omnirad127)
0.32 parts by mass, surfactant 1 0.10 parts by mass, surfactant 2 0.01 parts by mass, methyl ethyl ketone 46.55 parts by mass, cyclohexanone 19.95 parts by mass

The structure of the photoisomerized chiral compound 2 is shown below.

<Preparation of liquid crystal composition 7>
A liquid crystal composition 7 having the composition described below was prepared.
-Liquid compound 1 12.31 parts by mass-Liquid compound 2 6.15 parts by mass-Liquid compound 3 6.15 parts by mass-Mix of liquid crystal compound 1 (mass ratio 83: 15: 2) 6.15 mass Part ・ Polymerizable chiral compound (BASF, Paliocolor LC756)
0.77 parts by mass, photoisomerized chiral compound 1 1.54 parts by mass, photoinitiator (manufactured by IGM Resins, Omnirad 127)
0.31 part by mass ・ Surfactant 1 0.10 part by mass ・ Surfactant 2 0.01 part by mass ・ Methyl ethyl ketone 46.55 part by mass ・ Cyclohexanone 19.95 part by mass

<Liquid crystal composition 8>
A liquid crystal composition 8 having the composition described below was prepared.
・ Mixture 1 of liquid crystalline compound (mass ratio 83: 15: 2) 30.92 parts by mass ・ Polymerizable chiral compound (BASF, Paliocolor LC756)
2.16 parts by mass, photopolymerization initiator (manufactured by IGM Regins, Omnirad127)
0.31 part by mass ・ Surfactant 1 0.10 part by mass ・ Surfactant 2 0.01 part by mass ・ Methyl ethyl ketone 46.55 part by mass ・ Cyclohexanone 19.95 part by mass

<Liquid crystal composition 9>
A liquid crystal composition 9 having the composition described below was prepared.
・ Mixture 1 of liquid crystal compound (mass ratio 83: 15: 2) 31.20 parts by mass ・ Polymerizable chiral compound (BASF, Paliocolor LC756)
1.87 parts by mass, photopolymerization initiator (manufactured by IGM Regins, Omnirad127)
0.31 part by mass ・ Surfactant 1 0.10 part by mass ・ Surfactant 2 0.01 part by mass ・ Methyl ethyl ketone 46.55 part by mass ・ Cyclohexanone 19.95 part by mass

<Preparation of liquid crystal composition 10>
A liquid crystal composition 10 having the composition described below was prepared.
・ Liquid crystal compound 1 18.13 parts by mass ・ Liquid crystal compound 2 6.04 parts by mass ・ Liquid crystal compound 3 6.04 parts by mass ・ Polymerizable chiral compound (BASF, Palio Color LC756)
0.76 parts by mass, photoisomerized chiral compound 2.12 parts by mass, photoinitiator (manufactured by IGM Regins, Omnirad127)
0.30 parts by mass, surfactant 1 0.10 parts by mass, surfactant 2 0.01 parts by mass, methyl ethyl ketone 46.55 parts by mass, cyclohexanone 19.95 parts by mass

<Preparation of liquid crystal composition 11>
A liquid crystal composition 11 having the composition described below was prepared.
・ Mixture of liquid crystal compound 1 (mass ratio 83: 15: 2) 30.79 parts by mass ・ Polymerizable photoisomerized chiral compound 1.45 parts by mass ・ Photopolymerization initiator 1.23 parts by mass (diethylthioxanthone, Fujifilm) Wako Pure Chemical Industries, Ltd.)
・ Surfactant 1 0.02 parts by mass ・ Surfactant 2 0.02 parts by mass ・ Methyl ethyl ketone 46.55 parts by mass ・ Cyclohexanone 19.95 parts by mass

The structure of the polymerizable photoisomerized chiral compound is shown below.

<Preparation of liquid crystal composition 12>
A liquid crystal composition 12 having the composition described below was prepared.
・ Mixture of liquid crystal compound 1 (mass ratio 83: 15: 2) 29.10 parts by mass ・ Photoisomerized chiral compound 3 3.20 parts by mass ・ Photopolymerization initiator 1.16 parts by mass (diethylthioxanthone, Fujifilm sum) Kojunyaku Co., Ltd.)
-Surfactant 1 0.01 parts by mass-Surfactant 2 0.02 parts by mass-Methylethylketone 46.55 parts by mass-Cyclohexanone 19.95 parts by mass

The structure of the isomerized chiral compound 3 is shown below.

<Preparation of mask for patterning>
The patterning masks 1 to 4 shown in FIGS. 9 to 12 were prepared.
The patterning mask 1 shown in FIG. 9 is a mask in which the light transmittance in the vicinity of the central portion is 100% and the light transmittance continuously changes to 0% toward both ends.
The patterning mask 2 shown in FIG. 10 is a mask in which the light transmittance at both ends is 100% and the light transmittance continuously changes to 0% toward the vicinity of the central portion.
The patterning mask 3 shown in FIG. 11 is a mask in which the light transmittance at one end is 100% and the light transmittance continuously changes to 0% toward the other end.
The patterning mask 4 shown in FIG. 12 is a mask having a light transmittance of 0% on one side and a light transmittance of 100% on the other side with the center as a boundary.

In the following Examples and Comparative Examples, the "wavelength having the maximum reflectance" was measured as follows.
For the first resin layer or the like, a spectrophotometer (V-670 manufactured by Nippon Spectral Co., Ltd.) equipped with a large integrating sphere device (manufactured by Nippon Spectral Co., Ltd., ILV-471) is used, and the wavelength is 300 nm. Light of about 1500 nm is incident on the above region, the integrated reflectance is measured, and a spectral waveform is obtained.
The wavelength at which the reflectance is maximum at the peak of the spectral waveform is defined as the “wavelength at which the reflectance is maximum”. When there are a plurality of peaks, the peak including the reflectance that becomes the maximum value is adopted.

<< Example 1 >>
As the base material 40, a laminate of a methacrylic resin film and a polycarbonate resin film (Technoloy (registered trademark) C000 manufactured by Sumika Acrylic Sales Co., Ltd., thickness 100 μm) was prepared to have a size of 21 cm × 30 cm. The surface of the base material on the methacrylic resin film side was subjected to a corona discharge treatment under the condition of 75 W · min / m ² .

The alignment layer forming composition having the following composition is applied to the corona discharge-treated surface of the base material 40 using a wire bar (count # 10), and then dried at a temperature of 100 ° C. for 2 minutes to form the alignment layer. Formed.
-Composition of composition for forming an oriented layer-
・ Modified polyvinyl alcohol 10.00 parts by mass ・ Water 55.00 parts by mass ・ Methanol 35.00 parts by mass

The structure of the modified polyvinyl alcohol is shown below. The number at the bottom right of each building block represents the molar ratio.

Next, the formed alignment layer was subjected to a rubbing treatment (rayon cloth, pressure 0.98 N, rotation speed 1,000 rpm, transfer speed 10 m / min, number of times) in a direction rotated 3 ° counterclockwise with respect to the short side direction. Once) was given.

The liquid crystal composition 1 prepared above was applied onto the rubbing treatment alignment layer using a wire bar (count # 5) and heated at a temperature of 85 ° C. for 2 minutes to form a liquid crystal layer.

The patterning mask 1 was brought into close contact with the side of the base material opposite to the side on which the liquid crystal layer was formed. Next, from the mask side, light was irradiated from the mask side using a metal halide lamp (MAL625NAL manufactured by GS Yuasa Co., Ltd., irradiation wavelength 200 nm to 500 nm) so as to have an exposure amount of 30 mJ / cm ² , and in the non-mask region. The liquid crystal layer was photoisomerized.

Next, the mask was removed, and the substrate on which the liquid crystal layer was formed was placed on the hot plate at 85 ° C. so that the surface of the substrate opposite to the surface on which the liquid crystal layer was formed was in contact with the hot plate. Under an oxygen concentration of 1,000 ppm or less), the above metal halide lamp is used to irradiate light so that the exposure amount is 100 mJ / cm ² , and the liquid crystal layer is cured to cure the first resin layer 10a having a thickness of 3 μm. Formed.
As shown in FIG. 13, in the first resin layer 10a, a region having a maximum reflectance in the range of 350 nm to 380 nm (specific region A11a) and a wavelength having a maximum reflectance in the range of 381 nm to 450 nm. The region existing in (the other region A12a) was confirmed.
Further, when the first resin layer was visually observed, the specific region A11a was transparent from one end of the first resin layer 10a (the left end in FIG. 13) to the boundary with the other regions A12a. From the boundary to the boundary with the other specific area A11a (hereinafter, also referred to as other boundary), the other area A12a displays a color that changes in a gradation from purple to blue, and is the first from the other boundary. The other specific region A11a was transparent up to the other end of the resin layer 10a (the right end in FIG. 13).

The liquid crystal composition 4 was applied onto the formed first resin layer using a wire bar (count # 7) and heated at a temperature of 85 ° C. for 2 minutes to form a liquid crystal layer.

The patterning mask 2 was brought into close contact with the liquid crystal layer. Next, from the mask side, using the metal halide lamp, light was irradiated so as to have an exposure amount of 60 mJ / cm ² , and the liquid crystal layer was photoisomerized in the non-mask region.

Next, the mask was removed, and the substrate on which the liquid crystal layer was formed was placed on the hot plate at 85 ° C. so that the surface of the substrate opposite to the surface on which the liquid crystal layer was formed was in contact with the hot plate. Under an oxygen concentration of 1,000 ppm or less), the above metal halide lamp is used to irradiate light so that the exposure amount is 100 mJ / cm ² , and the liquid crystal layer is cured to cure the second resin layer 20a having a thickness of 4 μm. Formed.
In the second resin layer 20a, as shown in FIG. 13, a region having a maximum reflectance in the range of 800 nm to 850 nm (specific region B21a) and a wavelength having a maximum reflectance in the range of 650 nm to 799 nm. The region existing in (the other region B22a) was confirmed.
Further, when the second resin layer was visually observed, the specific region B21a was transparent from one end portion (left end portion in FIG. 13) of the second resin layer 20a to the boundary with the other region B22a. From the boundary to the boundary with the other specific area B21a (hereinafter, also referred to as other boundary), the other area B22a displays a color that changes in a gradation from red to magenta, and is the second from the other boundary. The other specific region B21 was transparent up to the other end of the resin layer 20a (the right end in FIG. 13).

A black paint (REAL Mirror Black manufactured by Nippon Paint Co., Ltd.) was applied to the side opposite to the side on which the first resin layer of the base material was formed, using a wire bar (count # 24). The mixture was dried at a temperature of 80 ° C. for 2 minutes to form a colored layer 30 having a thickness of 10 μm, and a decorative film 1a was obtained.
When the decorative film 1a was visually observed, black color, which is the color of the colored layer, was confirmed at both ends. In addition, the central portion of the decorative film 1a displays a tint that changes in a gradation tone in the order of blue, magenta, and red.
The first resin layer 10a and the second resin layer 20a included in the decorative film 1a both reflect circular polarization in the right direction.

The total light transmittance of the colored layer 30 formed as described above was measured using a spectrophotometer (Spectrophotometer UV-2100, manufactured by Shimadzu Corporation) in accordance with JIS K7375 issued in 2008. When measured, it was 0.06%.

<< Example 2 >>
The first resin layer 10b was formed in the same manner as in Example 1 except that the patterning mask 1 was changed to the patterning mask 3 and the exposure amount in the photoisomerization treatment was changed to 45 mJ / cm ² .
In the first resin layer 10b, as shown in FIG. 14, a region having a maximum reflectance in the range of 350 nm to 380 nm (specific region A11b) and a wavelength having a maximum reflectance in the range of 381 nm to 550 nm. The region existing in (the other region A12b) was confirmed.
Further, when the first resin layer 10b was visually observed, the specific region A11b was transparent from one end of the first resin layer 10b (the left end in FIG. 14) to the boundary with the other regions A12b. From the boundary to the other end of the first resin layer 10b (the right end in FIG. 14), the other regions A12b displayed a color that changed in a gradation from purple to green.

In the formation of the second resin layer 20b, the patterning mask 3 was used instead of the patterning mask 2, and the photoisomerization treatment was performed so that the exposure amount was 90 mJ / cm ² . In the same manner as in 1, the formation of the second resin layer 20b was formed to produce the decorative film 1b. The patterning mask 3 was used in the direction opposite to the direction of the change in transmittance used for forming the first resin layer 10b.
In the second resin layer 20b, as shown in FIG. 14, a region having a maximum reflectance in the range of 800 nm to 950 nm (specific region B21b) and a wavelength having a maximum reflectance in the range of 650 nm to 799 nm. The region existing in (the other region B22b) was confirmed.
Further, when the second resin layer 20b was visually observed, the specific region B21b was transparent from one end of the second resin layer 20b (the left end in FIG. 14) to the boundary with the other regions B22b. From the boundary to the other end of the second resin layer 20b (the right end in FIG. 14), the other region B22b displayed a color that changed in a gradation from red to magenta.
The first resin layer 10b and the second resin layer 20b included in the decorative film 1b both reflect circular polarization in the right direction.

When the decorative film 1b was visually observed, black color, which is the color of the colored layer, was confirmed at one end thereof. Further, the decorative film 1b displayed a tint that changes in a gradation tone in the order of blue, blue-green, and yellow, following the visible region of the colored layer.

<< Example 3 >>
A decorative film 1c was produced in the same manner as in Example 1 except that the liquid crystal composition 6 was used instead of the liquid crystal composition 4 in the formation of the second resin layer.
In the second resin layer 20c, as shown in FIG. 15, a region having a maximum reflectance in the range of 800 nm to 850 nm (specific region B21c) and a wavelength having a maximum reflectance in the range of 650 nm to 799 nm. The region existing in (the other region B22c) was confirmed.
Further, when the second resin layer 20c was visually observed, the specific region B21c was transparent from one end portion (left end portion in FIG. 15) of the second resin layer 20c to the boundary with the other region B22c. From the above boundary to the boundary with the other specific area B21c (hereinafter, also referred to as another boundary), the other area B22c displays a color that changes in a gradation from red to magenta, and from the other boundary to the first. The other specific region B21c was transparent up to the other end of the resin layer 20c of No. 2 (the right end in FIG. 15).
When the decorative film 1c was visually observed, black color, which is the color of the colored layer, was confirmed at both ends. In addition, the central portion of the decorative film 1c displayed a tint that changes in a gradation tone in the order of blue, magenta, and red.
The first resin layer 10a included in the decorative film 1c reflects the circular polarization in the right direction, and the second resin layer 20c reflects the circular polarization in the left direction.

<< Example 4 >>
The first resin layer 10d was formed on the base material 40 in the same manner as in Example 1 except that the liquid crystal composition 2 was used instead of the liquid crystal composition 1.
In the first resin layer 10d, as shown in FIG. 16, a region having a maximum reflectance in the range of 350 nm to 380 nm (specific region A11d) and a wavelength having a maximum reflectance in the range of 381 nm to 450 nm. The region existing in (the other region A12d) was confirmed.
Further, when the first resin layer 10d was visually observed, the specific region A11d was transparent from one end of the first resin layer 10d (the left end in FIG. 16) to the boundary with the other regions A12d. From the above boundary to the boundary with the other specific area A11d (hereinafter, also referred to as other boundary), the other area A12d displays a color that changes in a gradation from purple to blue, and is the first from the other boundary. The other specific region A11d was transparent up to the other end of the resin layer 10d (the right end in FIG. 16).

The base material used in Example 1 (hereinafter referred to as another base material) was separately prepared, and a rubbing treatment alignment layer was formed on one surface as in Example 1. The base material was not subjected to corona discharge treatment.

A second resin layer 20a was formed on the rubbing-treated alignment layer formed as described above in the same manner as in Example 1. One side of the OCA (Optical Clear Adaptive) film 60 (manufactured by Nikko Shinka Co., Ltd., G25) having a thickness of 25 μm is bonded onto the second resin layer 20a, and then the other side of the OCA film is bonded. The first resin layer 10d formed on the substrate as described above was bonded to the substrate. After the above bonding, the other base materials were peeled off.

A colored layer 30 was formed on the side of the base material 40 opposite to the side on which the first resin layer 10d and the like were formed in the same manner as in Example 1 to obtain a decorative film 1d.
When the decorative film 1d was visually observed, black color, which is the color of the colored layer, was confirmed at both ends. In addition, the central portion of the decorative film 1d displayed a tint that changes in a gradation tone in the order of blue, magenta, and red.
Both the first resin layer and the second resin layer included in the decorative film 1d reflect the circular polarization in the right direction.

<< Example 5 >>
Examples except that the wire bar used for forming the first resin layer was changed to the one having a count # 3.5 and the wire bar used for forming the second resin layer was changed to the one having a count # 4. A decorative film was produced in the same manner as in 1. The thickness of the first resin layer was 2 μm, and the thickness of the second resin layer was 2.5 μm.

<< Example 6 >>
In the formation of the second resin layer, the patterning mask 3 is used in the same direction as the direction of the transmittance change used for forming the first resin layer, and the light is applied so that the exposure amount is 30 mJ / cm ² . The decorative film 1e was produced in the same manner as in Example 2 except that the isomerization treatment was performed.
In the second resin layer 20e, as shown in FIG. 17, a region (other region B22e) in which the wavelength having the maximum reflectance is in the range of 600 nm to 700 nm was confirmed.
Further, when the second resin layer 20e was visually observed, a gradation from orange to red from one end (left end in FIG. 17) to the other end (right end in FIG. 17) of the second resin layer 20e was observed. The color that changes to the tone is displayed.
The first resin layer 10b and the second resin layer 20e included in the decorative film 1e both reflect circular polarization in the right direction.
Further, when the decorative film 1e was visually observed, the colors changing in a gradation tone were displayed in the order of orange and magenta.

<< Example 7 >>
In the same manner as in Example 1, a rubbing treatment alignment layer was formed on the corona treated surface of the base material 40.
Next, the liquid crystal composition 3 was applied onto the rubbing treatment alignment layer using a wire bar (count # 5) and heated at a temperature of 85 ° C. for 2 minutes to form a liquid crystal layer.

Next, the base material on which the liquid crystal layer was formed was placed on a hot plate at 85 ° C. so that the surface of the base material opposite to the surface on which the liquid crystal layer was formed was in contact with the hot plate, and a low oxygen atmosphere (oxygen concentration 1,000 ppm) was placed. Below), using the metal halide lamp, light was irradiated so as to have an exposure amount of 100 mJ / cm ² , the liquid crystal layer was cured, and the second resin layer 20f shown in FIG. 18 was formed.
In the second resin layer 20f, a region (other region B22f) in which the wavelength having the maximum reflectance exists at 450 nm was confirmed.
Moreover, when the second resin layer 20f was visually observed, a blue tint was displayed.

The liquid crystal composition 4 was applied onto the second resin layer 20f using a wire bar (count # 7) and heated at a temperature of 85 ° C. for 2 minutes to form a liquid crystal layer.

The patterning mask 4 was brought into close contact with the liquid crystal layer. Next, from the mask side, using the metal halide lamp, light was irradiated so as to have an exposure amount of 60 mJ / cm ² , and the liquid crystal layer was photoisomerized in the non-mask region.

Next, the mask was removed, and the base material on which the liquid crystal layer was formed was placed on a hot plate at 85 ° C. so that the surface of the base material opposite to the surface on which the liquid crystal layer was formed was in contact with the hot plate. Under an oxygen concentration of 1,000 ppm or less), the above metal halide lamp was used to irradiate light so as to have an exposure amount of 100 mJ / cm ² , and the liquid crystal layer was cured to form the first resin layer 10f.
In the first resin layer 10f, as shown in FIG. 18, a region having a maximum reflectance wavelength of 850 nm (specific region A11f) and a region having a maximum reflectance wavelength of 650 nm (other regions). A12f) was confirmed.
Further, when the first resin layer was visually observed, the specific region A11f had a transparent color from one end of the first resin layer 10f (the left end in FIG. 18) to the boundary with the other regions A12f. The display was performed, and the red tint was displayed from the boundary to the other end of the first resin layer 10f (the right end in FIG. 18).
Both the first resin layer 10f and the second resin layer 20f reflect the circular polarization in the right direction.

Similar to Example 1, a colored layer 30 was formed on the side of the base material 40 opposite to the side on which the second resin layer 20f and the like were formed to obtain a decorative film 1f.
When the decorative film 1f was visually observed, a region displaying blue and a region displaying magenta were observed with the center as a boundary.

<< Example 8 >>
In the formation of the first resin layer and the second resin layer, 1 g of the decorative film shown in FIG. 19 was produced in the same manner as in Example 1 except that the patterning mask 3 was used. In the formation of the second resin layer 20 g, the patterning mask 3 was used in the direction opposite to the direction of the change in transmittance used for forming the first resin layer 10 g.
When 1 g of the decorative film was visually observed, black color, which is the color of the colored layer 30, was confirmed at one end thereof. In addition, 1 g of the decorative film displayed a tint that changed in a gradation tone in the order of purple and magenta, following the visible region of the colored layer 30.

<< Example 9 >>
The first 2.5 μm thick wire bar was placed on the rubbing-treated oriented layer in the same manner as in Example 1 except that the wire bar used for forming the first resin layer was changed to that of count # 4.5. The resin layer 10a of the above was formed.

The wire bar used to form the second resin layer was changed to that of count # 6, the liquid crystal composition 4 was changed to the liquid crystal composition 7, and the exposure amount in the photoisomerization treatment was 120 mJ / cm ² . A second resin layer 20h having a thickness of 3.5 μm was formed on the first resin layer 10a in the same manner as in Example 1.
In the second resin layer 20h, as shown in FIG. 20, a region having a maximum reflectance in the range of 800 nm to 950 nm (specific region B21h) and a wavelength having a maximum reflectance in the range of 550 nm to 799 nm. The region existing in (the other region B22h) was confirmed.
Further, when the second resin layer 20h was visually observed, the specific region B21h was transparent from one end portion (left end portion in FIG. 20) of the second resin layer 20h to the boundary with the other region B22h. From the above boundary to the boundary with the other specific area B21h (hereinafter, also referred to as another boundary), the other area B22h displays a color that changes in a gradation from green to magenta, and from the other boundary to the first. The other specific region B21h was transparent up to the other end of the resin layer 20h of No. 2 (the right end in FIG. 20).

The liquid crystal composition 7 was applied onto the formed second resin layer 20h using a wire bar (count # 6) and heated at a temperature of 85 ° C. for 2 minutes to form a liquid crystal layer.

Next, the mask was removed, and the substrate on which the liquid crystal layer was formed was placed on the hot plate at 85 ° C. so that the surface of the substrate opposite to the surface on which the liquid crystal layer was formed was in contact with the hot plate. Under an oxygen concentration of 1,000 ppm or less), the above metal halide lamp is used to irradiate the liquid crystal layer with light so as to have an exposure amount of 100 mJ / cm ² , and the liquid crystal layer is cured to obtain a third resin having a thickness of 3.5 μm. The layer 50a was formed.
In the third resin layer 50a, as shown in FIG. 20, a region having a maximum reflectance in the range of 800 nm to 850 nm (specific region C51a) and a wavelength having a maximum reflectance in the range of 650 nm to 799 nm. The region existing in (the other region C52a) was confirmed.
Further, when the third resin layer 50a was visually observed, the specific region C51a was transparent from one end portion (left end portion in FIG. 20) of the third resin layer 50a to the boundary with the other region C52a. From the above boundary to the boundary with the other specific area C51a (hereinafter, also referred to as another boundary), the other area C52a displays a color that changes in a gradation from red to magenta, and from the other boundary to the first. The other specific region C51a was transparent up to the other end of the resin layer 50a of No. 3 (the right end in FIG. 20).
The first resin layer 10a, the second resin layer 20h, and the third resin layer 50a all reflect the circular polarization in the right direction.

A colored layer 30 was formed on the side of the base material 40 opposite to the side on which the first resin layer 10a and the like were formed in the same manner as in Example 1 to obtain a decorative film 1h.
When the decorative film 1h was visually observed, black color, which is the color of the colored layer, was confirmed at both ends. Further, in the central part of the decorative film 1h, magenta, white, and red were displayed in this order, and the colors changing in a gradation tone were displayed.

<< Example 10 >>
In the same manner as in Example 1, a rubbing treatment alignment layer was formed on the corona treated surface of the base material 40.
Next, the liquid crystal composition 12 was applied onto the rubbing treatment alignment layer using a wire bar (count # 5) and heated at a temperature of 85 ° C. for 2 minutes to form a liquid crystal layer.

Next, the base material on which the liquid crystal layer was formed was placed on a hot plate at 85 ° C. so that the surface of the base material opposite to the surface on which the liquid crystal layer was formed was in contact with the hot plate, and a low oxygen atmosphere (oxygen concentration 1,000 ppm) was placed. Below), using the metal halide lamp, light was irradiated so as to have an exposure amount of 800 mJ / cm ² , the liquid crystal layer was cured, and the second resin layer 20i shown in FIG. 21 was formed.
In the second resin layer 20i, a region (other region B22i) in which the wavelength having the maximum reflectance exists at 450 nm was confirmed. Moreover, when the second resin layer 20i was visually observed, a blue tint was displayed.

The liquid crystal composition 11 was applied onto the second resin layer 20i using a wire bar (count # 7) and heated at a temperature of 85 ° C. for 2 minutes to form a liquid crystal layer.

The patterning mask 4 was brought into close contact with the liquid crystal layer. Next, from the mask side, using the metal halide lamp, light was irradiated so as to have an exposure amount of 25 mJ / cm ² , and the liquid crystal layer was photoisomerized in the non-masked region.

Next, the mask was removed, and the base material on which the liquid crystal layer was formed was placed on a hot plate at 85 ° C. so that the surface of the base material opposite to the surface on which the liquid crystal layer was formed was in contact with the hot plate. Under an oxygen concentration of 1,000 ppm or less), the above metal halide lamp was used to irradiate light so as to have an exposure amount of 800 mJ / cm ² , and the liquid crystal layer was cured to form the first resin layer 10i.
In the first resin layer 10i, as shown in FIG. 21, a region having a maximum reflectance wavelength of 850 nm (specific region A11i) and a region having a maximum reflectance wavelength of 650 nm (other regions). A12i) was confirmed.
Further, when the first resin layer was visually observed, the specific region A11i had a transparent color from one end of the first resin layer 10i (the left end in FIG. 21) to the boundary with the other regions A12i. The display was performed, and the red tint was displayed from the boundary to the other end of the first resin layer 10i (the right end in FIG. 21).
The first resin layer 10i reflects the circular polarization in the right direction, and the second resin layer 20i reflects the circular polarization in the left direction.

Similar to Example 1, a colored layer 30 was formed on the side of the base material 40 opposite to the side on which the second resin layer 20i and the like were formed to obtain a decorative film 1i.
When the decorative film 1i was visually observed, a region displaying blue and a region displaying magenta were observed with the center as a boundary.

<< Example 11 >>
The first resin layer 10j was formed on the base material 40 in the same manner as in Example 10.
In the first resin layer 10ij, as shown in FIG. 22, a region having a maximum reflectance wavelength of 850 nm (specific region A11j) and a region having a maximum reflectance wavelength of 650 nm (other regions). A12j) was confirmed.
Further, when the first resin layer was visually observed, the specific region A11j had a transparent color from one end of the first resin layer 10j (the left end in FIG. 22) to the boundary with the other regions A12j. The display was performed, and the red tint was displayed from the boundary to the other end of the first resin layer 10j (the right end in FIG. 22).

A second resin layer 20j was formed on the rubbing-treated alignment layer formed as described above in the same manner as in Example 10. One surface of an OCA (Optical Clear Adhesive) film 60 (manufactured by Nikko Shinka Co., Ltd., G25) having a thickness of 25 μm is bonded onto the second resin layer 20j, and then the other surface of the OCA film is bonded. The first resin layer 10j formed on the substrate as described above was bonded to the substrate. After the above bonding, the other base materials were peeled off.
In the second resin layer 20j, a region (other region B22j) in which the wavelength having the maximum reflectance exists at 450 nm was confirmed. Moreover, when the second resin layer 20j was visually observed, a blue tint was displayed.

A colored layer 30 was formed on the side of the base material 40 opposite to the side on which the first resin layer 10j and the like were formed in the same manner as in Example 1 to obtain a decorative film 1j.
When the decorative film 1j was visually observed, a region displaying blue and a region displaying magenta were observed with the center as a boundary.

<< Comparative Example 1 >>
In the same manner as in Example 1, a rubbing-treated alignment layer was formed on the corona-treated surface of the base material.
Next, the liquid crystal composition 8 was applied onto the rubbing treatment alignment layer using a wire bar (count # 2.5) and heated at a temperature of 85 ° C. for 2 minutes to form a liquid crystal layer.
Next, the base material on which the liquid crystal layer was formed was placed on a hot plate at 85 ° C. so that the surface of the base material opposite to the surface on which the liquid crystal layer was formed was in contact with the hot plate, and a low oxygen atmosphere (oxygen concentration 1,000 ppm) was placed. Below), using the metal halide lamp, light was irradiated so as to have an exposure amount of 100 mJ / cm ² , the liquid crystal layer was cured, and a first resin layer having a thickness of 1.5 μm was formed.
In the first resin layer, a region (other region B22) in which the wavelength having the maximum reflectance exists at 450 nm was confirmed.
Moreover, when the first resin layer was visually observed, a blue tint was displayed.

The liquid crystal composition 9 is applied onto the rubbing-treated alignment layer formed as described above using a wire bar (count # 3.5) and heated at a temperature of 85 ° C. for 2 minutes to form a liquid crystal layer. did.
Next, the base material on which the liquid crystal layer was formed was placed on a hot plate at 85 ° C. so that the surface of the base material opposite to the surface on which the liquid crystal layer was formed was in contact with the hot plate, and a low oxygen atmosphere (oxygen concentration 1,000 ppm) was placed. Below), using the metal halide lamp, light was irradiated so as to have an exposure amount of 100 mJ / cm ² , the liquid crystal layer was cured, and a second resin layer having a thickness of 2 μm was formed.
In the second resin layer, a region where the wavelength having the maximum reflectance exists at 550 nm was confirmed.
Moreover, when the second resin layer was visually observed, a green tint was displayed.
Both the first resin layer and the second resin layer included in the decorative film reflect the circular polarization in the right direction.

One surface of the OCA film was bonded onto the second resin layer, and then the first resin layer formed on the substrate as described above was bonded to the other surface of the OCA film. .. After the above bonding, the other base materials were peeled off to obtain a decorative film.
When the decorative film was visually observed, a single cyan color was displayed.

<< Comparative Example 2 >>
In the same manner as in Example 1, a rubbing-treated alignment layer was formed on the corona-treated surface of the base material.
Next, the liquid crystal composition 10 was applied onto the rubbing treatment alignment layer using a wire bar (count # 3.5) and heated at a temperature of 85 ° C. for 2 minutes to form a liquid crystal layer.

The patterning mask 3 was brought into close contact with the liquid crystal layer. Next, from the mask side, using the metal halide lamp, light was irradiated so as to have an exposure amount of 100 mJ / cm ² , and the liquid crystal layer was photoisomerized in the non-mask region.

Next, the base material on which the liquid crystal layer was formed was placed on a hot plate at 85 ° C. so that the surface of the base material opposite to the surface on which the liquid crystal layer was formed was in contact with the hot plate, and a low oxygen atmosphere (oxygen concentration 1,000 ppm) was placed. Below), using the above metal halide lamp, light is irradiated so as to have an exposure amount of 100 mJ / cm ² , the liquid crystal layer is cured, and a first resin layer having a thickness of 2 μm is formed and decorated. It was made into a film.
In the first resin layer, a region in which the wavelength having the maximum reflectance is in the range of 400 nm to 700 nm was confirmed.
Further, when the decorative film was visually observed, the colors that changed in a gradation tone were displayed in the order of blue, green, and red from one end to the other end.

<< Comparative Example 3 >>
A decorative film was produced in the same manner as in Example 1 except that the colored layer 30 was not formed.
When the decorative film was visually observed, both ends were transparent from the end to the center, and the central part displayed a color that changed in a gradation tone in the order of blue, magenta, and red.

[Design evaluation]
The decorative films produced in Examples and Comparative Examples were visually observed, and the designability was evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 2.
(Evaluation criteria)
A: Two or more colors were confirmed, and the existence of a visible region of the colored layer was confirmed, and excellent designability was confirmed.
B: The existence of the visible region of the colored layer was not confirmed, but two or more colors were confirmed, and high designability was confirmed.
C: Only the tint of one color was confirmed.

[Visibility evaluation]
The decorative films produced in Examples and Comparative Examples were visually observed, and the visibility was evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 2.
(Evaluation criteria)
A: The color of the displayed color was good, and excellent visibility was confirmed.
B: There was room for improvement in visibility.
C: The color development of the displayed color was not good, and the visibility was poor.

[Evaluation of brilliance]
The in-plane average reflectance of the decorative films produced in Examples and Comparative Examples was measured, and the brilliance was evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 2.
The in-plane average reflectance was measured as follows.
A spectrophotometer equipped with a large integrating sphere device (ILV-471, manufactured by Nippon Spectroscopy Co., Ltd.) for the outermost resin layer (for example, the second resin layer in Example 1) included in the decorative film. Using (V-670 manufactured by Nippon Spectroscopy Co., Ltd.), light having a wavelength of 300 nm to 1500 nm is incident from a vertical direction (an angle of 90 ° with respect to the surface of the resin layer), and the peak wavelength is obtained from the obtained spectral spectrum. Was read to obtain the reflectance at the peak wavelength.
The reflectance at the peak wavelength was measured on the entire surface of the outermost resin layer, and this average was taken as the in-plane average reflectance.
(Evaluation criteria)
A: The in-plane average reflectance was 30% or more.
B: The in-plane average reflectance was 20% or more and less than 30%.
C: The average in-plane reflectance was less than 20%.

[Evaluation of total thickness of resin layer]
The total thickness of the resin layer contained in the decorative films produced in Examples and Comparative Examples was determined and evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 2. If the OCA film is present between the resin layers, this thickness is also added to the total thickness.
(Evaluation criteria)
A: The total thickness was less than 10 μm.
B: The total thickness was 10 μm or more and less than 25 μm.
C: The total thickness was 25 μm or more.

[Evaluation of interference fringe generation suppression]
The decorative films produced in Examples and Comparative Examples were visually observed, and the ability to suppress the generation of interference fringes was evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 2.
(Evaluation criteria)
A: No interference fringes were confirmed.
B: The occurrence of interference fringes was confirmed.

From the results of the above examples, it was found that the decorative film according to the present disclosure has high visibility, can display a wide variety of color change, and has excellent designability.

The disclosure of Japanese Patent Application No. 2020-157926 filed on September 18, 2020 is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are to the same extent as specifically and individually stated that the individual documents, patent applications, and technical standards are incorporated by reference. Incorporated herein by reference.

Claims

Cholesteric regularity in which two or more regions having different wavelengths having the maximum reflectance exist in the same plane, and the wavelength having the maximum reflectance in at least one region exists in the range of 380 nm or less or 800 nm or more. The first resin layer to have and
A second resin layer having a cholesteric regularity different from that of the first resin layer,
With the colored layer,
Includes at least a decorative film.
The second resin layer has two or more regions having different wavelengths for maximum reflectance in the same plane, and the wavelength for maximum reflectance in at least one region is in the range of 380 nm or less or 800 nm or more. The decorative film according to claim 1, which is present in the above.
A region in which the wavelength of the maximum reflectance of the first resin layer is in the range of 380 nm or less or 800 nm or more, and
The decorative film according to claim 2, wherein the decorative film according to claim 2 is provided at a position where at least a part of a region having a wavelength of 380 nm or less or 800 nm or more, which is the maximum reflectance of the second resin layer, overlaps.
The first resin layer has a region in which the wavelength having the maximum reflectance is more than 380 nm and is less than 800 nm as at least one of two or more regions having different wavelengths having the maximum reflectance. The decorative film according to any one of claims 1 to 3.
The decorative film according to any one of claims 1 to 4, wherein the in-plane average reflectance is 20% or more.
The decorative film according to any one of claims 1 to 5, wherein the first resin layer and the second resin layer are laminated adjacent to each other.
The decorative film according to any one of claims 1 to 6, wherein the first resin layer and the second resin layer reflect circularly polarized light in the same direction.
The process of preparing a liquid crystal material including a base material and a liquid crystal layer, and
The liquid crystal layer is subjected to photoisomerization treatment, and the liquid crystal layer contains at least one region having a wavelength having a maximum reflectance in a range of 380 nm or less or 800 nm or more, and the wavelength having a maximum reflectance is different. A step of curing the liquid crystal layer to form a first resin layer having cholesteric regularity after making the state having one or more regions.
A step of forming a second resin layer having a cholesteric regularity different from that of the first resin layer on the first resin layer.
A method for manufacturing a decorative film, including.
A step of preparing a liquid crystal material containing a base material and a second resin layer having cholesteric regularity, and
A liquid crystal layer is formed on the second resin layer, the liquid crystal layer is subjected to photoisomerization treatment, and the liquid crystal layer has a wavelength having a maximum reflectance in the range of 380 nm or less or 800 nm or more. After having two or more regions having different wavelengths having the maximum reflectance, which contains at least one of the above, the liquid crystal layer is cured to have a cholesteric regularity different from that of the second resin layer. The process of forming the resin layer and
A method for manufacturing a decorative film, including.
The method for producing a decorative film according to claim 8 or 9, wherein the liquid crystal layer is formed of a liquid crystal composition containing a monofunctional liquid crystal compound.
The method for producing a decorative film according to claim 10, wherein the liquid crystal composition contains at least one of a polyfunctional liquid crystal compound and a polyfunctional non-liquid crystalline polymerizable monomer.
The ratio of the content of the monofunctional liquid crystal compound to the content of the polyfunctional liquid crystal compound and the content of the polyfunctional non-liquid crystal polymerizable monomer in the liquid crystal composition is 85 on a mass basis. : The method for producing a decorative film according to claim 11, which is 15 to 40:60.
A molded product obtained by molding the decorative film according to any one of claims 1 to 7.
An electronic device having the decorative film according to any one of claims 1 to 7.
An automobile exterior plate having the molded product according to claim 13.