JP2018180122A - Laminate, screen, transparent screen, and screen for bright room, and method for manufacturing laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate having excellent transparency and diffusion reflectivity, a screen, a transparent screen and a screen for a bright room using the laminate, and a method for manufacturing the laminate.SOLUTION: The laminate includes a substrate and a plurality of reflection layers stacked and supported by the substrate, in which the reflection layer is formed by fixing a cholesteric liquid crystal phase; in a cross section of the laminate, a bright part and a dark part derived from the cholesteric liquid crystal phase give a wavy structure; and the reflection layer closest to the substrate has a selective reflection center wavelength in a wavelength region of 400 nm or shorter or a wavelength region of 700 nm or longer.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate in which a reflective layer is laminated, various screens using the laminate, and a method of manufacturing the laminate.

  A layer formed by fixing a cholesteric liquid crystal phase is known as a layer having a property of selectively reflecting either right circularly polarized light or left circularly polarized light in a specific wavelength range. Therefore, it has been developed into various applications, and various applications as screens for projection have been proposed as an example.

For example, in Patent Document 1, as a reflective projection screen, a polarization selective reflection layer that diffuses and reflects a specific polarization component is provided, and the polarization selective reflection layer has at least two or more partial selective reflection layers stacked one another. Of the partial selective reflection layers, the first partial selective reflection layer, which diffuses and reflects light having a wavelength range showing the color most likely to be absorbed by the polarization selective reflection layer, is disposed on the outermost surface on the viewing side Is described.
In the projection screen described in Patent Document 1, the partial selective reflection layer has a cholesteric liquid crystal structure (a layer formed by fixing a cholesteric liquid crystal phase), and due to the structural nonuniformity (defect) of the cholesteric liquid crystal structure, Diffusely reflects light of a specific polarization component.

JP, 2005-107508, A

A projection image display member such as a projection screen using a layer formed by fixing a cholesteric liquid crystal phase is required to have a wide viewing angle.
More specifically, usually, when light is incident from the normal direction of the surface of the layer formed by fixing the cholesteric liquid crystal phase, one of right circularly polarized light and left circularly polarized light is selectively reflected. . At that time, if the reflection is performed not only in the normal direction but also in the oblique direction, it leads to the improvement of the visibility from the oblique direction. That is, when used as an application such as a screen having a layer formed by fixing a cholesteric liquid crystal phase as a reflective layer, the reflective layer is excellent in the property of reflecting incident light in various directions (so-called diffuse reflectivity). Is required.
In addition, when the layer formed by fixing the cholesteric liquid crystal phase is applied to a transparent screen or the like, high transparency is also required.

  However, in the case of the projection screen described in, for example, Patent Document 1, diffuse reflection and transparency do not meet recent requirements because diffuse reflection is obtained by introducing defects in the cholesteric liquid crystal structure. For example, a transparent screen using a layer formed by fixing a conventional cholesteric liquid crystal phase is required to further improve diffuse reflection and transparency.

  The object of the present invention is to solve such problems of the prior art, and it is a laminate from which a transparent screen or the like having good diffuse reflectivity and excellent transparency can be obtained. A screen, a transparent screen and a screen for light room to be used, and a method for producing the laminate.

In order to achieve such an object, the present invention provides the following laminate, screen, transparent screen and screen for a bright room, and a method of manufacturing the laminate.
[1] It has a substrate and a plurality of laminated reflective layers supported on the substrate,
The reflective layer is formed by immobilizing a cholesteric liquid crystal phase, and in the cross section of the reflective layer, the bright part and the dark part derived from the cholesteric liquid crystal phase have a wavelike structure,
A laminated body characterized in that the reflective layer closest to the substrate has a selective reflection center wavelength in a wavelength range of 400 nm or less or a wavelength range of 700 nm or more.
[2] The laminate according to [1], wherein the reflective layer closest to the substrate has a selective reflection center wavelength in a wavelength range of 700 nm or more.
[3] The laminate according to [1] or [2], wherein the selective reflection center wavelength of the reflective layer is different in all the reflective layers.
[4] The laminate according to any one of [1] to [3], in which the direction of the circularly polarized light reflected by the reflective layer is the same in all the reflective layers.
[5] The laminate according to any one of [1] to [4], wherein the selective reflection center wavelength of the reflective layer gradually becomes short in a direction away from the substrate.
[6] The laminate according to any one of [1] to [5], wherein the number of reflective layers is four or less.
[7] The laminate according to any one of [1] to [6], wherein the substrate does not have a tint and the total light transmittance is 70% or more.
[8] The selective reflection center wavelength of the reflective layer closest to the substrate is 700 to 1000 nm,
The laminated body in any one of [1]-[7] which has a reflective layer whose selective reflection center wavelength is 600 nm or more and less than 700 nm, and a reflective layer whose selective reflection center wavelength of at least one layer is 420 nm or more and less than 600 nm.
[9] The laminate according to any one of [1] to [8], in which the film thickness of the reflective layer closest to the substrate is the largest among the plurality of reflective layers.
[10] The laminate according to any one of [1] to [9], wherein the surface on which the reflective layer of the substrate is formed is a flat surface.
[11] A screen having the laminate according to any one of [1] to [10].
[12] A transparent screen having the laminate according to any one of [1] to [10].
[13] A light room screen having the laminate according to any one of [1] to [10].
[14] A layer formed by immobilizing a cholesteric liquid crystal phase, wherein in a cross section the light and dark portions derived from the cholesteric liquid crystal phase have a wavelike structure and the selective reflection center wavelength is 400 nm or less or 700 nm or more Forming a visible light reflective layer, and
Applying an upper layer composition containing a liquid crystal compound and a chiral agent to align the liquid crystal compound to form a cholesteric liquid crystal phase, thereby forming an upper reflective layer;
After the step of forming the non-visible light reflection layer, the step of forming the upper reflection layer on the non-visible light reflection layer is performed, or further, the upper reflection layer is formed on the formed upper reflection layer. The manufacturing method of the laminated body which performs a process one or more times.
[15] The step of forming the non-visible light reflecting layer comprises applying a non-visible light reflecting layer composition containing a liquid crystal compound and a chiral agent on a substrate and heating the applied non-visible light reflecting layer composition A manufacturing method of a layered product given in [14] which performs processing which orientates a liquid crystal compound and makes it a state of a cholesteric liquid crystal phase, and then performs processing which cools or heats a non-visible light reflection layer composition.
[16] In the step of forming the upper reflective layer, the upper layer composition is applied in forming at least one upper reflective layer, and then the upper layer composition is heated to orient the liquid crystal compound to form a cholesteric liquid crystal phase. The method for producing a laminate according to [14] or [15], wherein the upper layer composition is subjected to a treatment of cooling or heating.

  According to the present invention, a laminate from which a transparent screen or the like having high diffuse reflectance and transparency is obtained, a screen using the laminate, a transparent screen and a screen for a bright room, and a manufacturing method capable of producing the laminate Can be provided.

It is a figure which shows the cross section of the laminated body of this invention notionally. It is a conceptual diagram for demonstrating the light reflection by a cholesteric liquid crystal phase. It is a conceptual diagram for demonstrating the light reflection by a cholesteric liquid crystal phase. It is a scanning electron micrograph of the cross section of the laminated body in the Example of this invention. It is a conceptual diagram for demonstrating evaluation of the diffuse reflectivity in an Example.

Hereinafter, the present invention will be described in detail. In addition, the numerical range represented using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.
Further, in the present specification, “(meth) acrylate” is a notation representing both acrylate and methacrylate, and “(meth) acryloyl group” is a notation representing both acryloyl group and methacryloyl group, "(Meth) acrylic" is a notation representing both acrylic and methacrylic.
In the present specification, visible light is light of wavelengths visible to human eyes among electromagnetic waves, and indicates light in a wavelength range of more than 400 nm and less than 700 nm. Nonvisible light is light in a wavelength range of 400 nm or less or a wavelength range of 700 nm or more. Further, although not limited thereto, in the visible light, light in the wavelength range of 420 nm to less than 500 nm is blue light (B light), and light in the wavelength range of 500 nm to less than 600 nm is green light (G light). The light in the wavelength range of 600 nm or more and less than 700 nm is red light (R light). Further, although not limited thereto, in the invisible light, the light in the wavelength range of 200 to 400 nm is ultraviolet light, and the light in the wavelength range of 700 to 1000 nm is infrared light.

In FIG. 1, the cross section of the laminated body of this invention is shown notionally. FIG. 1 is a view conceptually showing, for example, a state in which the cross section of the laminate of the present invention is observed by a scanning electron microscope (SEM: Scanning electron microscope) (the same applies to FIG. 2 and FIG. 3 described later).
The laminate 10 shown in FIG. 1 includes a substrate 12, an infrared light reflection layer 14 formed on one surface of the substrate 12, and a red light reflection layer 16 stacked on the surface of the infrared light reflection layer 14. And the green light reflection layer 18 laminated on the surface of the red light reflection layer 16 and the blue light reflection layer 20 laminated on the surface of the green light reflection layer 18. In the following description, the substrate 12 side of the laminated body 10 is also referred to as “down”, and the blue light reflection layer 20 side is also referred to as “up”.

The infrared light reflection layer 14, the red light reflection layer 16, the green light reflection layer 18, and the blue light reflection layer 20 are all layers formed by fixing a cholesteric liquid crystal phase.
In the following description, if it is not necessary to distinguish between the infrared light reflection layer 14, the red light reflection layer 16, the green light reflection layer 18 and the blue light reflection layer 20, the total reflection layers are collectively referred to as “reflection layer”. say.
As is well known, the layer formed by fixing the cholesteric liquid crystal has wavelength selectivity for reflection, reflects only the right polarized light in the predetermined wavelength range or only the left polarized light, and transmits the other light. .
The infrared light reflection layer 14 has a selective reflection center wavelength in the region of infrared light (for example, 750 nm or 850 nm). The red light reflection layer 16 has a selective reflection center wavelength in the red light region (for example, 650 nm). The green light reflection layer 18 has a selective reflection center wavelength in a region (for example, 550 nm) of green light. Furthermore, the blue light reflection layer 20 has a selective reflection center wavelength in the blue light region (for example, 450 nm).

Further, as described above, the infrared light reflection layer 14, the red light reflection layer 16, the green light reflection layer 18, and the blue light reflection layer 20 are layers formed by fixing the cholesteric liquid crystal phase.
Therefore, in the cross section of the reflective layer (laminate 10), each reflective layer has a stripe pattern in which light portions and dark portions are alternately stacked in the thickness direction (vertical direction in FIG. 1) derived from the cholesteric liquid crystal phase. It is observed.
That is, in the cross section of the infrared light reflection layer 14, a stripe pattern in which light portions 24 and dark portions 26 are alternately stacked in the thickness direction is observed, which is derived from the cholesteric liquid crystal phase. In the cross section of the red light reflection layer 16, a stripe pattern in which light portions 28 and dark portions 30 are alternately stacked in the thickness direction is observed, which is derived from the cholesteric liquid crystal phase. In the cross section of the green light reflecting layer 18, a stripe pattern in which light portions 32 and dark portions 34 are alternately stacked in the thickness direction is observed, which is derived from the cholesteric liquid crystal phase. Furthermore, in the cross section of the blue light reflection layer 20, a stripe pattern in which light portions 36 and dark portions 38 are alternately stacked in the thickness direction is observed, which is derived from the cholesteric liquid crystal phase.

Here, in the laminate 10 of the present invention, the surface of the substrate 12 on which the reflective layer is formed is a flat surface having no unevenness or wave shape, but the infrared light reflective layer 14 formed on the substrate 12, red light The bright and dark portions in the cross section of the reflective layer 16, the green light reflective layer 18 and the blue light reflective layer 20 (the reflective layer to be stacked) have a periodic wave-like structure.
That is, in the present invention, the reflective layer is a layer having a cholesteric liquid crystal structure and having a structure in which the angle between the helical axis and the surface of the reflective layer periodically changes. In other words, the reflection layer has a cholesteric liquid crystal structure, and the cholesteric liquid crystal structure gives a stripe pattern of light and dark portions in the cross-sectional view of the reflection layer observed with a scanning electron microscope, It is a reflective layer in which the angle between the line and the surface of the reflective layer periodically changes.

FIG. 2 conceptually shows a cross section of a layer formed by fixing a general cholesteric liquid crystal phase.
As described above, as shown in FIG. 2, normally, a stripe pattern of the bright portion B and the dark portion D is observed in the cross section of the layer 42 fixed to the cholesteric liquid crystal phase disposed on the substrate 12. That is, in the cross section of the layer 42 in which the cholesteric liquid crystal phase is fixed, a layered structure in which the bright portions B and the dark portions D are alternately stacked is observed.
One bright part B in FIG. 2 and two dark parts D arranged above and below the one bright part B correspond to one spiral of the cholesteric liquid crystal phase.
Generally, the stripe pattern (layered structure) of the bright portion B and the dark portion D is formed to be parallel to the surface of the substrate 12 which is a flat surface as shown in FIG. In such an embodiment, the layer 42 in which the cholesteric liquid crystal phase is fixed exhibits specular reflectivity. That is, when light is incident from the normal direction of the layer 42 to which the cholesteric liquid crystal phase is fixed, the light is reflected in the normal direction, but light is hardly reflected in the oblique direction and is inferior in diffuse reflectivity (see FIG. See arrows in 2).

On the other hand, like the layer 46 whose cross section is conceptually shown in FIG. 3, the cholesteric liquid crystal phase is fixed with the formation surface (substrate 12) of the layer 46 formed by fixing the cholesteric liquid crystal phase as a flat surface. When the bright part B and the dark part D of the layer 46 have a wavelike structure (undulation structure), light is incident on the layer 46 having a wavelike structure (concave and convex structure) from the normal direction of the layer 46 Since there is a region where the helical axis of the liquid crystal compound is inclined as shown in FIG. 3, a part of incident light is reflected in an oblique direction (see the arrow in FIG. 3).
That is, in the reflective layer formed by fixing the cholesteric liquid crystal phase, the reflective portion having high diffuse reflectivity can be realized by the light portion B and the dark portion D having a wavelike structure. Also, the diffuse reflectivity becomes better as the unevenness of the wavelike structure of the light part B and the dark part D becomes larger.

As described above, each reflection layer of the laminate 10 of the present invention is a layer formed by fixing the cholesteric liquid crystal phase, and the light portion 28 and the dark portion 30 of the red light reflection layer 16 (striped patterns of the light portion 28 and the dark portion 30) ), Bright portions 32 and dark portions 34 of the green light reflection layer 18 (striped patterns of the bright portions 32 and the dark portions 34), and bright portions 36 and dark portions 38 of the blue light reflective layer 20 (striped patterns of the light portions 36 and dark portions 38). Each has a periodic wavelike structure.
Therefore, according to the laminate 10 of the present invention, visible light of red, green and blue can be suitably diffused and reflected by the red light reflection layer 16, the green light reflection layer 18 and the blue light reflection layer 20. As a result, when the laminate 10 of the present invention is used, for example, as a projection screen, it is possible to display an image at a wide viewing angle.

Here, in the laminate 10 according to the present invention, the light portion 24 and the dark portion 26 (striped pattern of the light portion 24 and the dark portion 26) of the infrared light reflection layer 14 formed on the surface of the substrate 12 also have a periodic wavy structure. Have. However, as described above, the infrared light reflection layer 14 has the selective reflection center wavelength in the region of infrared light. Therefore, the infrared light reflection layer 14 does not directly contribute to the diffuse reflection of visible light.
However, the laminate 10 of the present invention has the infrared light reflection layer 14 on the surface of the substrate 12 (as a reflection layer closest to the substrate), thereby enhancing the transparency of the laminate 10 and a red light reflection layer. 16. The wavy structure of the bright part and the dark part of the green light reflecting layer 18 and the blue light reflecting layer 20 can be made to be a wavy structure having asperities of sufficient size.
In the following description, the “wave-like structure of light and dark parts” of the reflective layer is also simply referred to as “wave-like structure”.

As will be described later, as an example, a reflective layer having a wavelike structure applies a composition containing a liquid crystal compound and a chiral agent to a formation surface, and heats the composition to align the liquid crystal compound in a cholesteric liquid crystal phase; Thereafter, the composition is cooled to form a cholesteric liquid crystal phase by ultraviolet irradiation or the like.
The diffuse reflectivity of the reflective layer is higher as the unevenness of the wavelike structure of the reflective layer is larger.
However, in order to make the wavelike structure of the reflective layer into a wavelike structure having a large enough unevenness for obtaining high diffuse reflectance, it is necessary to make the reflective layer to a certain thickness or more.
When the reflective layer is thickened, the light transmittance naturally decreases, and the transparency of the laminate decreases. That is, the height of the light diffusivity by the size of the unevenness of the wavelike structure of the reflective layer and the transparency of the reflective layer are in a trade-off relationship.

Here, according to the study of the present inventors, when the reflective layer (layer formed by fixing the cholesteric liquid crystal phase) is formed on the reflective layer (layer formed by fixing the cholesteric liquid crystal phase) having the wavelike structure. Following the wavelike structure of the lower reflection layer (following the wavelike structure of the reflection layer), the upper reflection layer also has a similar wavelike structure.
Furthermore, as the unevenness of the wavelike structure of the lower reflection layer is larger, the unevenness of the wavelike structure of the upper reflection layer is also larger. In addition, that the unevenness | corrugation of the wavelike structure of a reflection layer is large shows that the height of a wave is high, and the pitch of a wave is short.

The present invention has been made to obtain this finding, and has an infrared light reflection layer 14 having a selective reflection center wavelength in the infrared light region on a substrate 12, and red light reflection thereon. It has a layer 16, a green light reflecting layer 18 and a blue light reflecting layer 20.
The infrared light reflection layer 14 reflects only infrared light and transmits all visible light. That is, even if the infrared light reflection layer 14 is thickened, the transparency of the laminate 10 does not decrease. Therefore, the infrared light reflection layer 14 is formed on the substrate 12 in such a thickness that a sufficiently large corrugated structure can be obtained, and the red light reflection layer 16, the green light reflection layer 18 and the blue light reflection are formed thereon. By forming the layer 20, even if the red light reflection layer 16, the green light reflection layer 18, and the blue light reflection layer 20 are thin, the unevenness of the wave-like structure can be made sufficiently large.
Therefore, the laminate 10 of the present invention can be obtained while achieving both high transparency and good diffuse reflectivity. For example, by using it for a transparent screen, the transparency is good and the viewing angle There is a wide transparent screen.

In the laminate 10, the reflection layer formed on the surface of the substrate 12 (closest to the substrate 12) is the infrared light reflection layer 14. The infrared light reflection layer 14 is a reflection layer having a selective reflection center wavelength of 700 nm or more (a layer formed by fixing a cholesteric liquid crystal phase). If the selective reflection center wavelength of the infrared light reflective layer 14 is less than 700 nm, the transparency of the infrared light reflective layer 14 is reduced, and the laminate 10 having sufficient transparency can not be obtained.
The selective reflection central wavelength of the infrared light reflective layer 14 is preferably 700 to 1000 nm, more preferably 750 nm or more, and still more preferably 800 nm or more, in terms of good transparency.

The thickness of the infrared light reflective layer 14 is not particularly limited. The thickness of the infrared light reflection layer 14 is preferably 1 to 20 μm, more preferably 2 to 15 μm, and still more preferably 3 to 10 μm in that the unevenness of the wave-like structure of the light portion 24 and the dark portion 26 can be increased.
Further, although there is no particular limitation, it is preferable that the infrared light reflection layer 14 is the thickest among the reflection layers in that the unevenness of the wavelike structure can be made large and the transparency can be made favorable. In this case, a reflective layer having the same thickness as the infrared light reflective layer 14 may be additionally provided.

In the laminate 10, the red light reflection layer 16, the green light reflection layer 18, and the blue light reflection layer 20, which are layers obtained by fixing the cholesteric liquid crystal phase, are provided on the infrared light reflection layer 14.
As described above, when the underlying reflective layer has a corrugated structure, the corrugated structure of the upper reflective layer basically follows the corrugated structure of the underlying reflective layer.
Therefore, the wavelike structure of the red light reflecting layer 16 follows the wavelike structure of the infrared light reflecting layer 14, the wavelike structure of the green light reflecting layer 18 follows the wavelike structure of the red light reflecting layer 16, and the blue light is reflected The wavelike structure of layer 20 follows the wavelike structure of green light reflecting layer 18. Therefore, in the adjacent reflective layers, the unevenness of the wave-like structure is often the same.

The thicknesses of the red light reflection layer 16, the green light reflection layer 18, and the blue light reflection layer 20, that is, the thicknesses of the reflection layers other than the reflection layer closest to the substrate 12 are not particularly limited.
From the viewpoint of transparency, the thickness of the red light reflection layer 16, the green light reflection layer 18, and the blue light reflection layer 20 is preferably 0.1 to 10 μm, more preferably 0.2 to 8 μm, and 0.5 to 6 μm. Is more preferred.

In the laminate 10 of the present invention, the wavelike structure in the cross section of each reflective layer has a substantially uniform pitch, but the wave height may vary.
For example, the height of the wave may be highest at the central region in the thickness direction of the reflective layer and gradually lower toward the upper side (surface side) in the thickness direction and the substrate 12 side. That is, the amplitude of the wavelike structure of the cross section of the reflection layer may be the largest at the central region in the thickness direction, and may gradually decrease as it goes to the surface side and the substrate 12 side.
Alternatively, as in the wavelike structure of the layer 46 shown in FIG. 3, the structure may have a wave with uniform height throughout the thickness direction.

In the laminate 10 of the illustrated example, the surface of each reflective layer (the upper reflective layer or the interface with air) may be planar or have a concavo-convex structure.
In the case where the upper surface of the reflective layer has a concavo-convex structure, this concavo-convex structure is generally periodic (substantially periodic), and the phase of the concavities and convexities is opposite to the wavy structure of the light and dark portions of the cross section. become.
Such a reflective layer having a concavo-convex structure on the upper surface performs at least one of selection of a chiral agent and / or an orientation control agent and selection of heat treatment or cooling treatment conditions in the production method of the present invention described later. Can be formed by

In the reflective layer having irregularities on the surface, the wave height of the wavelike structure in the cross section of the reflective layer is larger than that of the reflective layer having a flat surface.
Therefore, the reflective layer having unevenness on the surface can achieve higher diffuse reflectivity.

In the laminate 10 of the present invention, the wavelike structure (wavelike structure of the light part and the dark part) in the cross section of the reflection layer is the same not only in the lateral direction of FIG. Wave-like structure is formed. That is, the wavelike structure of the reflective layer is formed two-dimensionally in the plane direction of the reflective layer, and the wavelike structure is recognized in the cross section of the reflective layer in all directions.
However, the present invention is not limited to this, and the reflective layer may have a wavelike structure in which a continuous wave travels in only one direction in the cross section. However, in terms of diffuse reflectivity, it is preferable that the reflective layer has a wavy structure in the cross section in all directions as described above.
In this regard, the same applies to the irregularities on the upper surface of the reflective layer.

In the laminate 10 of the present invention, there is no particular limitation on the pitch (the distance between the top of the wave and the top of the wave) of the wavelike structure of the light part and the dark part of the cross section of the reflective layer. 0.5-5 micrometers is preferable and, as for the pitch of the wavelike structure of a reflection layer, 1-4 micrometers is more preferable.
In order for the reflective layer to exhibit suitable diffuse reflectivity, it is preferable to reduce the pitch (period and frequency) of the wavelike structure and to increase the height of the wave (the height or amplitude of the unevenness). However, the pitch of the wavelike structure and the height of the asperities are usually in a trade-off relationship. On the other hand, by setting the pitch of the wavelike structure of the reflective layer in the above range, it is possible to form a wavelike structure having a suitable balance of pitch and height, and to form the laminate 10 having high diffuse reflectivity.

As described above, the infrared light reflection layer 14 has the selective reflection center wavelength in the region of infrared light. The red light reflection layer 16 has a selective reflection center wavelength in the area of red light. The green light reflection layer 18 has a selective reflection center wavelength in the region of green light. Furthermore, the blue light reflection layer 20 has a selective reflection center wavelength in the area of blue light.
In the laminate of the present invention, the number of reflective layers excluding the infrared light reflective layer 14 formed on the surface of the substrate 12 may be one, but is preferably two or more, and two or more. More preferably, three layers. That is, the total number of reflective layers is preferably four or less.
In addition, it is preferable that all the reflection layers except the infrared light reflection layer 14 formed on the surface of the substrate 12 have a selective reflection center wavelength in the visible light region. In addition, in any case, the laminate 10 of the present invention preferably has different selective reflection center wavelengths in all reflection layers. Thus, for example, when the laminate of the present invention is used as a projection screen or the like, a projected image can be displayed corresponding to images of various colors.

When the number of reflection layers excluding the infrared light reflection layer 14 is three, as in the illustrated example, the laminate 10 includes the red light reflection layer 16, the green light reflection layer 18, and the blue light reflection layer. It is preferred to have twenty. That is, when the number of reflection layers excluding the infrared light reflection layer 14 is three, the reflection layer of one layer preferably has a selective reflection center wavelength of 600 nm or more and less than 700 nm, and the reflection layer of one layer is The selective reflection center wavelength is preferably 500 nm or more and less than 600 nm, and the single reflection layer preferably has a selective reflection center wavelength of 420 nm or more and less than 500 nm. The same applies to the case where the number of reflective layers excluding the infrared light reflective layer 14 is four or more.
Further, when the number of reflection layers excluding the infrared light reflection layer 14 is two, the laminate of the present invention is changed to the green light reflection layer 18 and the blue light reflection layer 20, and green light-blue light It is preferred to have a reflective layer. In other words, when the reflective layer excluding the infrared light reflective layer 14 is a double layer, the laminate of the present invention preferably includes the red light reflective layer 16 and the green light-blue light reflective layer. That is, when the number of reflection layers excluding the infrared light reflection layer 14 is two, the reflection layer of one layer preferably has a selective reflection center wavelength of 600 nm or more and less than 700 nm, and another reflection layer Preferably, the selective reflection center wavelength is 420 nm or more and less than 600 nm (eg, 470 nm).
Thus, for example, when the laminate of the present invention is used as a projection screen or the like, it is possible to display a full-color projected image.

The selective reflection central wavelength (central wavelength λ of selective reflection) of the reflective layer formed by fixing the cholesteric liquid crystal layer depends on the pitch P of the helical structure in the cholesteric liquid crystal phase (= helical period), and the reflective layer (cholesteric liquid crystalline phase According to the relationship between the average refractive index n) and λ = n × P.
Here, the central wavelength λ of selective reflection of the reflective layer means a wavelength at the center of gravity of the reflection peak of the circularly polarized light reflection spectrum measured from the normal direction of the reflective layer. As understood from the above equation, the central wavelength of selective reflection can be adjusted by adjusting the pitch of the helical structure. That is, in order to adjust n value and P value, for example, to selectively reflect either right circularly polarized light or left circularly polarized light with respect to blue light, the central wavelength λ is adjusted, and apparent selection is made. The central wavelength of reflection can be in the wavelength range of 420 nm or more and less than 500 nm. The apparent central wavelength of selective reflection means the wavelength at the center of gravity of the reflection peak of the circularly polarized light reflection spectrum of the reflection layer measured from the observation direction in practical use (when used as a projection image display member). Do. The pitch of the cholesteric liquid crystal phase depends on the type of chiral agent used with the liquid crystal compound, or the concentration thereof, so that the desired pitch can be obtained by adjusting these.

The reflected light of the reflection layer formed by fixing the cholesteric liquid crystal phase is circularly polarized light. That is, the laminate 10 of the present invention reflects circularly polarized light. Whether the reflected light is right circularly polarized light or left circularly polarized light depends on the twisting direction of the helix of the cholesteric liquid crystal phase. The selective reflection of circularly polarized light by the cholesteric liquid crystal phase reflects right circularly polarized light when the helical twist direction of the cholesteric liquid crystal phase is right, and reflects left circularly polarized light when the helical twist direction is left.
The direction of swirling of the cholesteric liquid crystal phase can be adjusted by the type of liquid crystal compound forming the reflective layer or the type of chiral agent to be added.

  For the method of measuring the twist direction (sense) or pitch of the helix, see “Introduction to Liquid Crystal Chemistry Experiment” edited by The Liquid Crystal Society of Japan, published by Sigma Press 2007, p. 46, and “Liquid Crystal Handbook”, Liquid Crystal Handbook Editorial Committee Maruzen described on page 196. Methods can be used.

In the laminate 10 of the present invention, the circularly polarized light reflected by the reflective layer is not particularly limited, and may be right circularly polarized light or left circularly polarized light. However, it is preferable that the laminated body 10 of this invention reflects the circularly polarized light of the same direction (swing direction) by all the reflection layers.
Thus, for example, when the laminate of the present invention is used as a screen for projection image display, it is preferable in that the difference in reflection performance due to color does not easily occur when the light source of the projector is circularly polarized light or elliptically polarized light.

  In the present invention, other than this, for example, two red light reflecting layers having the same selective reflection center wavelength are provided, one right reflecting layer reflects red right circularly polarized light, and the other reflecting layer. It may be configured to reflect red left circularly polarized light.

As a preferred embodiment, the laminate 10 of the illustrated example has the infrared light reflection layer 14 on the surface of the substrate 12, the red light reflection layer 16 on it, and the green light reflection layer 18 on it. , And has a blue light reflection layer 20 thereon.
That is, as a preferred embodiment of the laminate 10, the reflection layer constituting the laminate 10 has the selective reflection center wavelength gradually shorter toward the upper side (the direction away from the substrate 12).
By having such a configuration, that is, by reducing the difference in selective reflection center wavelengths of adjacent reflection layers, a large difference in structure and characteristics between adjacent reflection layers, such as the pitch of the helical structure in the adjacent reflection layers It is preferable from the point of being able to form a reflective layer with less defects (a layer formed by fixing the cholesteric liquid crystal phase) and the like.

The laminate 10 shown in FIG. 1 has an infrared light reflection layer 14 having a selective reflection center wavelength in the region of infrared light as a reflection layer on the surface of the substrate 12 (reflection layer closest to the substrate 12).
The layered product of the present invention is not limited to this, and a selective reflection center in a wavelength region of 400 nm or less, preferably a wavelength region of ultraviolet light, as a reflective layer on the surface of the substrate 12 (reflection layer closest to the substrate 12). A reflective layer having a wavelength may be provided.

By setting the selective reflection central wavelength of the reflective layer formed on the surface of the substrate 12 to 400 nm or less, even if the reflective layer is thinner than the reflective layer having a selective reflection central wavelength of 700 nm or more, It is possible to form a reflective layer having a large unevenness of the wavy structure in the dark part.
On the other hand, by setting the selective reflection center wavelength of the reflection layer on the surface of the substrate 12 to 700 nm or more as in the laminate 10 shown in FIG. 1, a high quality reflection layer with few defects can be formed. By thickening the reflective layer, it is possible to obtain a wavelike structure having larger irregularities.
Therefore, when it is necessary to make the laminate thin and to obtain a large diffuse reflectance, it is preferable to set the selective reflection center wavelength of the reflective layer on the surface of the substrate 12 to 400 nm or less. If it is not necessary to do so, it is preferable to set the selective reflection center wavelength of the reflective layer on the surface of the substrate 12 to 700 nm or more. Further, in consideration of diffuse reflectance and transparency as a whole, it is preferable to set the selective reflection center wavelength of the reflective layer on the surface of the substrate 12 to 700 nm or more.

In the laminate, when the selective reflection central wavelength of the reflective layer on the surface of the substrate 12 is 400 nm or less, adjacent laminates have the selective reflection central wavelength for the same reason as the laminate 10 shown in FIG. It is preferable to reduce the difference. That is, when the selective reflection central wavelength of the reflective layer on the surface of the substrate 12 is 400 nm or less, it is preferable that the selective reflection central wavelength of the reflective layer gradually becomes longer toward the top from the substrate 12.
Therefore, when the red light reflection layer 16, the green light reflection layer 18, and the blue light reflection layer 20 are provided as in the laminate 10 shown in FIG. 1, the reflection of the selective reflection center wavelength of the surface of the substrate 12 is 400 nm or less Preferably, the blue light reflection layer 20 is formed on the layer, the green light reflection layer 18 is formed on the blue light reflection layer 20, and the red light reflection layer 16 is formed on the green light reflection layer 18.

As described above, the laminate 10 is obtained by forming the infrared light reflection layer 14, the red light reflection layer 16, the green light reflection layer 18, and the blue light reflection layer 20 on the substrate 12.
In the laminate 10, the substrate 12 is a plate for supporting a reflective layer (a composition forming the reflective layer).
The substrate 12 preferably has no color (i.e., achromatic color), and preferably has a total light transmittance of 70% or more. That is, the substrate 12 is preferably colorless and transparent. Further, the total light transmittance of the substrate 12 is more preferably 80% or more, and still more preferably 90% or more.
In the present invention, the total light transmittance may be measured according to JIS K 7361 using a commercially available measuring device such as NDH5000 or SH-7000 manufactured by Nippon Denshoku Kogyo.

The material which comprises the board | substrate 12 in particular is not restrict | limited, For example, a cellulose type polymer, a polycarbonate type polymer, a polyester type polymer, a (meth) acrylic type polymer, a styrene type polymer, a polyolefin type polymer, a vinyl chloride type polymer, an amide type polymer, Various resin materials such as imide polymers, sulfone polymers, polyethersulfone polymers, and polyetheretherketone polymers can be mentioned.
The substrate 12 may contain various additives such as a UV (ultraviolet) absorber, matting agent particles, a plasticizer, an antidegradant, and a release agent. Furthermore, the substrate 12 may have a layer such as an alignment layer on the surface.
The substrate preferably has low birefringence in the visible light range. For example, 50 nm or less is preferable and, as for the phase difference in wavelength 550 nm of a board | substrate, 20 nm or less is more preferable.

The thickness of the substrate 12 is not particularly limited, but is preferably 10 to 200 μm, and more preferably 20 to 100 μm from the viewpoint of thinning and handling.
The above thickness is intended to be the average thickness, which is the thickness of any five points of the substrate measured and the arithmetic average of them.
As described above, in the laminate 10 of the present invention, the reflective layer has a wave-like structure, but the surface on which the reflective layer of the substrate 12 is formed does not have a concavo-convex structure or a wave-like structure, and is a flat surface.

As described above, the infrared light reflection layer 14, the red light reflection layer 16, the green light reflection layer 18, and the blue light reflection layer 20 (reflection layer) are provided on the substrate 12.
Each reflective layer is a layer formed by fixing a cholesteric liquid crystal phase. Such a reflective layer is prepared, for example, by preparing a composition containing a liquid crystal compound and a chiral agent (invisible light reflective layer composition and upper layer composition), applying and drying this composition, as necessary. It can be formed by curing the composition to fix the cholesteric liquid crystal phase.

(Liquid crystal compound)
The type of liquid crystal compound is not particularly limited.
Generally, liquid crystal compounds can be classified into rod-like types (rod-like liquid crystal compounds) and disk-like types (discotic liquid crystal compounds, disk-like liquid crystal compounds) according to their shapes. Furthermore, there are a low molecular weight type and a high molecular weight type in the rod-like type and the disk-like type, respectively. In general, a polymer refers to one having a degree of polymerization of 100 or more (Polymer physics / phase transition dynamics, Masao Doi, page 2, Iwanami Shoten, 1992). Any liquid crystal compound can also be used in the present invention. In addition, two or more kinds of liquid crystal compounds may be used in combination.

  The liquid crystal compound may have a polymerizable group. The type of the polymerizable group is not particularly limited, and is preferably a functional group capable of addition polymerization reaction, and more preferably a polymerizable ethylenically unsaturated group or a ring polymerizable group. More specifically, as the polymerizable group, a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, an epoxy group, or an oxetane group is preferable, and a (meth) acryloyl group is more preferable.

As a liquid crystal compound, the liquid crystal compound represented by the following formula (I) is preferable at the point which the diffuse reflectivity of a reflection layer is more excellent.
Among them, the number obtained by dividing the number of trans-1,4-cyclohexylene groups which may have a substituent represented by A by m from the viewpoint of more excellent diffuse reflectance of the reflective layer is defined as mc. In some cases, a liquid crystal compound satisfying mc> 0.1 is preferable, and a liquid crystal compound satisfying 0.4 ≦ mc ≦ 0.8 is more preferable.
In addition, said mc is a number represented by the following formula.
mc = (number of trans-1,4-cyclohexylene groups optionally having substituents represented by A) ÷ m

During the ceremony
A represents a phenylene group which may have a substituent or a trans-1,4-cyclohexylene group which may have a substituent, and at least one of A has a substituent Also exhibit good trans-1,4-cyclohexylene groups,
L represents a single bond, _{or, -CH 2 O -, - OCH} 2 -, - (CH 2) 2 OC (= O) -, - C (= O) O (CH 2) 2 -, - C (= O) O-, -OC (= O)-, -OC (= O) O-, -CH = N-N = CH-, -CH = CH-, -C≡C-, -NHC (= O) -, -C (= O) NH-, -CH = N-, -N = CH-, -CH = CH-C (= O) O-, and -OC (= O) -CH = CH- A linking group selected from the group consisting of
m is an integer of 3 to 12,
Sp ¹ and Sp ² each independently represent a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, and 1 or 2 in the linear or branched alkylene group having 1 to 20 carbon atoms One or more -CH ₂ -is -O-, -S-, -NH-, -N (CH ₃ )-, -C (= O)-, -OC (= O)-, or -C (= O A) a linking group selected from the group consisting of groups substituted with O—;
Q ¹ and Q ² each independently represent a hydrogen atom or a polymerizable group selected from the group consisting of groups represented by the following formulas (Q-1) to (Q-5), provided that Any ^one of Q ¹ and Q ² represents a polymerizable group;

A is a phenylene group which may have a substituent or a trans-1,4-cyclohexylene group which may have a substituent. In the present specification, when a phenylene group is referred to, it is preferable to be a 1,4-phenylene group.
In addition, at least one of A is a trans-1,4-cyclohexylene group which may have a substituent.
The m A's may be the same or different.

  m represents an integer of 3 to 12, preferably 3 to 9, more preferably 3 to 7, and still more preferably 3 to 5.

The substituent which may be possessed by the phenylene group and the trans-1,4-cyclohexylene group in the formula (I) is not particularly limited, and, for example, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether Examples thereof include a substituent selected from the group consisting of a group, an amido group, an amino group, and a halogen atom, and a group configured by combining two or more of the above-described substituents. Further, examples of the substituent include the substituents represented by ^{-C (= O) -X 3 -Sp} 3 -Q 3 below. The phenylene group and the trans-1,4-cyclohexylene group may have 1 to 4 substituents. When two or more substituents are present, the two or more substituents may be the same as or different from each other.

  In the present specification, the alkyl group may be linear or branched. 1-30 are preferable, as for carbon number of an alkyl group, 1-10 are more preferable, and 1-6 are more preferable. As the alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group, n-hexyl group, isohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group. The description of the alkyl group in the alkoxy group is also the same as the description of the alkyl group above. In the present specification, specific examples of the alkylene group when it is referred to as an alkylene group include, in each of the examples of the alkyl group described above, a divalent group obtained by removing one arbitrary hydrogen atom. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

  In the present specification, the carbon number of the cycloalkyl group is preferably 3 or more, more preferably 5 or more, and preferably 20 or less, more preferably 10 or less, still more preferably 8 or less, and particularly preferably 6 or less. Examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group.

The substituent which the phenylene group and the trans-1,4-cyclohexylene group may have includes an alkyl group, an alkoxy group, and a group consisting of -C (= O) -X ³ -Sp ³ -Q ³ Preferred is a substituent selected from Here, X ³ represents a single bond, -O-, -S-, or -N (Sp ⁴ -Q ⁴ )-or a nitrogen atom forming a ring structure with Q ³ and Sp ³ Show. Sp ³ and Sp ⁴ each independently represent a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, and 1 or 2 in the linear or branched alkylene group having 1 to 20 carbon atoms One or more -CH ₂ -is -O-, -S-, -NH-, -N (CH ₃ )-, -C (= O)-, -OC (= O)-, or -C (= O And b) a linking group selected from the group consisting of groups substituted with O-.
Each of Q ³ and Q ⁴ independently represents a hydrogen atom, a cycloalkyl group, or one or more -CH _2- in a cycloalkyl group is -O-, -S-, -NH-, -N (CH ₃ A group substituted by-), -C (= O)-, -OC (= O)-, or -C (= O) O-, or a table represented by formula (Q-1) to formula (Q-5) And any polymerizable group selected from the group consisting of

In the cycloalkyl group, one or more of -CH ₂ -is -O-, -S-, -NH-, -N (CH ₃ )-, -C (= O)-, -OC (= O) Specific examples of the group substituted with-or -C (= O) O- include tetrahydrofuranyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, piperidyl, piperazinyl, morpholinyl and the like. . Among these, tetrahydrofuranyl is preferable, and 2-tetrahydrofuranyl is more preferable.

In the formula (I), L is a single bond, or -CH ₂ O-, -OCH ₂ -,-(CH ₂ ) ₂ OC (= O)-, -C (= O) O (CH ₂ ) ₂ -, -C (= O) O-, -OC (= O)-, -OC (= O) O-, -CH = CH-C (= O) O-, and -OC (= O)- A linking group selected from the group consisting of CH = CH- is shown. L is preferably -C (= O) O- or -OC (= O)-. The m L's may be the same or different.

Sp ¹ and Sp ² each independently represent a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, and 1 or 2 in the linear or branched alkylene group having 1 to 20 carbon atoms One or more -CH ₂ -is -O-, -S-, -NH-, -N (CH ₃ )-, -C (= O)-, -OC (= O)-, or -C (= O) a linking group selected from the group consisting of groups substituted with O-; Sp ¹ and Sp ² each independently represent the number of carbon atoms to which a linking group selected from the group consisting of -O-, -OC (= O)-, and -C (= O) O- is attached at both ends respectively Selected from the group consisting of linear alkylene groups of 1 to 10, -OC (= O)-, -C (= O) O-, -O-, and linear alkylene groups having 1 to 10 carbon atoms The linking group is preferably a combination of one or two or more groups, and more preferably a linear alkylene group having 1 to 10 carbon atoms in which -O- is bonded to both ends.

Each of Q ¹ and Q ² independently represents a hydrogen atom or a polymerizable group selected from the group consisting of groups represented by Formula (Q-1) to Formula (Q-5) below. However, ^one of Q ¹ and Q ² represents a polymerizable group.

  As the polymerizable group, acryloyl group (formula (Q-1)) or methacryloyl group (formula (Q-2)) is preferable.

  Specific examples of the liquid crystal compound include a liquid crystal compound represented by the following formula (I-11), a liquid crystal compound represented by the formula (I-21), and a liquid crystal compound represented by the formula (I-31) It can be mentioned. In addition to the above, a compound represented by the formula (I) of JP 2013-112631 A, a compound represented by the formula (I) of JP 2010-70543 A, a formula of JP 2008-291218 A Compound Represented by (I), Compound Represented by Formula (I) of Patent No. 4725516, Compound Represented by General Formula (II) of JP-A-2013-087109, JP-A-2007-176927 Compound described in paragraph [0043], a compound represented by the formula (1-1) of JP 2009-286885 A, a compound represented by the general formula (I) of WO 2014/10325, JP A 2016-81035 Known compounds described in the compound represented by the formula (1) in the gazette, and the compounds represented by the formula (2-1) and the formula (2-2) in JP-A-2016-121339, etc. It is below.

Liquid Crystal Compound Represented by Formula (I-11)

In the formula, R ¹¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or -Z ¹² -Sp ¹² -Q ¹² ;
L ¹¹ represents a single bond, —C (= O) O— or —O (C = O) —;
L ¹² represents —C (= O) O—, —OC (= O) — or —CONR ² —;
R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
The Z ¹¹ and Z ¹² are each independently a single bond, -O -, - NH -, - N (CH 3) -, - S -, - C (= O) O -, - OC (= O) -, -OC (= O) O- or -C (= O) NR ¹² -is shown,
R ¹² represents a hydrogen atom or -Sp ¹² -Q ¹² ;
Sp ¹¹ and Sp ¹² are each independently a single bond, a linear or branched alkylene group having from carbon atoms 1 be replaced by Q ¹¹ 12 or carbon atoms which may be substituted with Q ^11, 1 To 12 linear or branched alkylene groups, any one or more of —CH ₂ — may be —O—, —S—, —NH—, —N (Q ¹¹ ) — or —C (= O) Shows a linking group obtained by replacing with-),
Q ¹¹ is a hydrogen atom, a cycloalkyl group or a cycloalkyl group in which one or more of —CH ₂ — is —O—, —S—, —NH—, —N (CH ₃ ) —, —C (= A group consisting of a group substituted with O)-, -OC (= O)-, or -C (= O) O-, or a group represented by formula (Q-1) to formula (Q-5) And a polymerizable group selected from
Q ¹² represents a hydrogen atom or a polymerizable group selected from the group consisting of groups represented by Formula (Q-1) to Formula (Q-5),
l ¹¹ represents an integer of 0 to 2;
m ¹¹ represents an integer of 1 or 2;
n ¹¹ represents an integer of 1 to 3;
The plurality of R ¹¹ , the plurality of L ¹¹ , the plurality of L ¹² , the plurality of l ¹¹ , the plurality of Z ¹¹ , the plurality of Sp ¹¹ , and the plurality of Q ¹¹ may be the same as or different from each other.
The liquid crystal compound represented by formula (I-11) as R ^11, polymerizable where Q ¹² is selected from the group consisting of groups represented by the formula (Q-1) ~ formula (Q-5) comprising at least one -Z ¹² -Sp ¹² -Q ¹² is a group.
In the liquid crystal compound represented by the formula (I-11), Z ¹¹ is —C (= O) O— or —C (= O) NR ¹² —, and Q ¹¹ is a group represented by formula (Q-1) to preferably a -Z ¹¹ -Sp ¹¹ -Q ¹¹ is a polymerizable group selected from the group consisting of groups represented by the formula (Q-5). In the liquid crystal compound represented by the formula (I-11), as R ¹¹ , Z ¹² is —C (= O) O— or —C (= O) NR ¹² —, and Q ¹² is a formula (Q) -1) to formula (Q-5) preferably a -Z ¹² -Sp ¹² -Q ¹² is a polymerizable group selected from the group consisting of groups represented by.

The 1,4-cyclohexylene group contained in the liquid crystal compound represented by formula (I-11) is a trans-1,4-cyclohexene group.
Expression as a preferred embodiment of the liquid crystal compounds represented by (I-11), L ¹¹ is a single bond, l ¹¹ 1 (dicyclohexyl group), and, Q ¹¹ has the formula (Q-1) ~ formula (Q-5 The compound which is a polymeric group selected from the group which consists of group represented by) is mentioned.
In another preferred embodiment of the liquid crystal compound represented by the formula (I-11), m ¹¹ is 2, I ¹¹ is 0, and two R ¹¹ 's each represent -Z ^12- Sp ^12- Q ¹² And compounds wherein Q ¹² is a polymerizable group selected from the group consisting of groups represented by Formula (Q-1) to Formula (Q-5).

Liquid Crystal Compound Represented by Formula (I-21)

In the formula, each of Z ²¹ and Z ²² independently represents a trans-1,4-cyclohexylene group which may have a substituent, or a phenylene group which may have a substituent,
Each either independently above ^{substituents, -CO-X 21 -Sp 23 -Q} 23, an alkyl group, and 1 to 4 substituents selected from the group consisting of alkoxy groups,
m21 represents an integer of 1 or 2; n21 represents an integer of 0 or 1;
When m21 is 2, n21 is 0,
When m21 represents 2, two Z ²¹ may be the same or different,
At least one of Z ²¹ and Z ²² is a phenylene group which may have a substituent,
L ²¹ , L ²² , L ²³ and L ²⁴ are each independently a single bond, or -CH ₂ O-, -OCH ₂ -,-(CH ₂ ) ₂ OC (= O)-, -C (= O) ) O (CH ₂ ) ₂ —, —C (= O) O—, —OC (= O) —, —OC (= O) O—, —CH = CH—C (= O) O—, and — A linking group selected from the group consisting of OC (= O) -CH = CH-;
X ²¹ represents —O—, —S—, or —N (Sp ²⁵ -Q ²⁵ ) — or a nitrogen atom forming a ring structure with Q ²³ and Sp ²³ ,
r ²¹ represents an integer of 1 to 4;
Sp ²¹ , Sp ²² , Sp ²³ and Sp ²⁵ are each independently a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, and a linear or branched alkylene having 1 to 20 carbon atoms is -O - - 1, two or more -CH ₂ in the group, - S -, - NH - , - N (CH 3) -, - C (= O) -, - OC (= O) -, Or a linking group selected from the group consisting of -C (= O) O- substituted groups,
Q ²¹ and Q ²² each independently represent any polymerizable group selected from the group consisting of groups represented by Formula (Q-1) to Formula (Q-5),
Q ²³ is a hydrogen atom, a cycloalkyl group or a cycloalkyl group, in which one or more of —CH ₂ — is —O—, —S—, —NH—, —N (CH ₃ ) — or —C (= O)-, -OC (= O)-, or a group substituted with -C (= O) O-, selected from the group consisting of groups represented by Formula (Q-1) to Formula (Q-5) And R ²¹ represents a single bond in the case where X ²¹ is a nitrogen atom forming a ring structure with Q ²³ and Sp ²³ ;
Q ²⁵ is a hydrogen atom, a cycloalkyl group or a cycloalkyl group in which one or more of —CH ₂ — is —O—, —S—, —NH—, —N (CH ₃ ) — or —C ( A group substituted by OO) —, —OC (= O) —, or —C (= O) O— or a group represented by Formula (Q-1) to Formula (Q-5) It shows any polymerizable group selected from the group, and when Sp ²⁵ is a single bond, Q ²⁵ is not a hydrogen atom.

The liquid crystal compound represented by the formula (I-21) is also preferably a structure in which a 1,4-phenylene group and a trans-1,4-cyclohexylene group alternately exist, and for example, m21 is 2; n ²¹ is 0, and Z ²¹ is a trans-1, 4-cyclohexylene group which may have a substituent from the Q ²¹ side, or an arylene group which may have a substituent, or, m21 is 1, n21 is 1, Z ²¹ is an arylene group optionally having a substituent, and, Z ²² is an arylene group optionally having a substituent structure Is preferred.

A liquid crystal compound represented by the formula (I-31);

In the formula, R ³¹ and R ³² are each independently a group selected from the group consisting of an alkyl group, an alkoxy group, and —C (= O) —X ³¹ —Sp ³³ —Q ³³ ,
n31 and n32 each independently represent an integer of 0 to 4;
X ³¹ represents a single bond, -O-, -S-, or -N (Sp ³⁴ -Q ³⁴ )-or a nitrogen atom forming a ring structure with Q ³³ and Sp ³³ ,
Z ³¹ represents a phenylene group which may have a substituent,
Z ³² represents a trans-1,4-cyclohexylene group which may have a substituent or a phenylene group which may have a substituent,
Each either independently the above substituents, alkyl group, alkoxy group, and a ^{-C (= O) -X 31 -Sp} 33 1 to 4 substituents selected from the group consisting of -Q ^33,
m31 represents an integer of 1 or 2; m32 represents an integer of 0 to 2;
When m31 and m32 represent 2, two Z ³¹ and Z ³² may be the same or different,
L ³¹ and L ³² each independently represent a single bond, or —CH ₂ O—, —OCH ₂ —, — (CH ₂ ) ₂ OC (= O) —, —C (= O) O (CH ₂ ) _2- , -C (= O) O-, -OC (= O)-, -OC (= O) O-, -CH = CH-C (= O) O-, and -OC (= O)- Representing a linking group selected from the group consisting of CH = CH-;
Sp ³¹ , Sp ³² , Sp ³³ and Sp ³⁴ are each independently a single bond, or a linear or branched alkylene group having 1 to 20 carbon atoms, and a linear or branched alkylene group having 1 to 20 carbon atoms In which one or more of -CH ₂ -is -O-, -S-, -NH-, -N (CH ₃ )-, -C (= O)-, -OC (= O)-, or -Represents a linking group selected from the group consisting of -C (= O) O- substituted groups,
Q ³¹ and Q ³² each independently represent any polymerizable group selected from the group consisting of groups represented by Formula (Q-1) to Formula (Q-5),
Each of Q ³³ and Q ³⁴ independently represents a hydrogen atom, a cycloalkyl group, or one or more -CH _2- in a cycloalkyl group is -O-, -S-, -NH-, -N (CH ₃ A group substituted with-), -C (= O)-, -OC (= O)-, or -C (= O) O-, or a group represented by formula (Q-1) to formula (Q-5) Q ³³ represents any polymerizable group selected from the group consisting of the groups represented, and Q ³³ may represent a single bond when X ³¹ and Sp ³³ form a ring structure, and Sp ³⁴ is When it is a single bond, Q ³⁴ is not a hydrogen atom.
Particularly preferable compounds as the liquid crystal compound represented by the formula (I-31) include a compound in which Z ³² is a phenylene group and a compound in which m 32 is 0.

The compound represented by the formula (I) also preferably has a partial structure represented by the following formula (II).
In the formula (II), the black circles indicate the bonding position with the other part of the formula (I). The partial structure represented by the formula (II) may be included as part of the partial structure represented by the following formula (III) in the formula (I).

In the formula, R ¹ and R ² are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, and a group represented by —C (= O) —X ³ —Sp ³ —Q ³ Group. Here, X ³ represents a single bond, -O-, -S-, or -N (Sp ⁴ -Q ⁴ )-or a nitrogen atom forming a ring structure with Q ³ and Sp ³ Show. X ³ is preferably a single bond or -O-. R ¹ and R ² is preferably a ^{-C (= O) -X 3 -Sp} 3 -Q 3. Preferably, R ¹ and R ² are identical to each other. The bonding position of each of R ¹ and R ² to the phenylene group is not particularly limited.

Sp ³ and Sp ⁴ are each independently a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, and one or two in the linear or branched alkylene group having 1 to 20 carbon atoms The above -CH ₂ -is -O-, -S-, -NH-, -N (CH ₃ )-, -C (= O)-, -OC (= O)-, or -C (= O) Fig. 6 shows a linking group selected from the group consisting of O-substituted groups. As Sp ³ and Sp ⁴ , each independently, a linear or branched alkylene group having 1 to 10 carbon atoms is preferable, a linear alkylene group having 1 to 5 carbon atoms is more preferable, and a straight chain having 1 to 3 carbon atoms is preferable More preferred is a chain alkylene group.
Each of Q ³ and Q ⁴ independently represents a hydrogen atom, a cycloalkyl group, or one or more -CH _2- in a cycloalkyl group is -O-, -S-, -NH-, -N (CH ₃ A group substituted by-), -C (= O)-, -OC (= O)-or -C (= O) O-, or a group represented by formula (Q-1) to formula (Q-5) And any polymerizable group selected from the group consisting of

  The compound represented by the formula (I) preferably has, for example, a structure represented by the following formula (II-2).

In the formula, each of A ¹ and A ² independently represents a phenylene group which may have a substituent or a trans-1,4-cyclohexene group which may have a substituent; All are each independently 1 to 4 substituents selected from the group consisting of an alkyl group, an alkoxy group, and -C (= O) -X ³ -Sp ³ -Q ³ ,
L ¹ , L ² and L ³ are a single bond, or —CH ₂ O—, —OCH ₂ —, — (CH ₂ ) ₂ OC (= O) —, —C (OO) O (CH ₂ ) ₂ -, -C (= O) O-, -OC (= O)-, -OC (= O) O-, -CH = CH-C (= O) O-, and -OC (= O)- Representing a linking group selected from the group consisting of CH = CH-;
n1 and n2 each independently represent an integer of 0 to 9, and n1 + n2 is 9 or less.
The definitions of Q ¹ , Q ² , Sp ¹ and Sp ² are the same as the definitions of the respective groups in the above-mentioned formula (I). The definitions of X ³ , Sp ³ , Q ³ , R ¹ and R ² are the same as the definitions of the respective groups in the above-mentioned formula (II).

  Examples of the liquid crystal compound represented by the formula (I) and satisfying 0.4 ≦ mc ≦ 0.8 include, for example, those described in paragraphs [0051] to [0054] of WO 2016/047648. The compounds which have been mentioned are exemplified.

The liquid crystal compounds may be used in combination of two or more. For example, two or more kinds of liquid crystal compounds represented by formula (I) may be used in combination.
Among them, a liquid crystal compound represented by the above formula (I), which is a liquid crystal compound represented by the formula (I) together with a liquid crystal compound satisfying 0.4 ≦ mc ≦ 0.8, 0.1 It is preferable to use a liquid crystal compound satisfying <mc <0.3.

  Examples of the liquid crystal compound represented by the formula (I) and satisfying 0.1 <mc <0.3 include, for example, those described in paragraphs [0055] to [0058] of WO 2016/047648. The compounds which have been mentioned are exemplified.

  As a liquid crystal compound used in the present invention, a compound represented by the following formula (IV) described in JP-A-2014-198814, in particular, one (meth) acrylate group represented by the formula (IV) A polymerizable liquid crystal compound having the formula is also suitably used.

Formula (IV)
Wherein (IV), A ¹ represents an alkylene group having 2 to 18 carbon atoms, two or more CH ₂ that is not one of the CH ₂ or adjacent in the alkylene group is substituted by -O- Also good;
Z ¹ represents -C (= O)-, -O-C (= O)-or a single bond;
Z ² represents -C (= O)-or -C (= O) -CH = CH-;
R ¹ represents a hydrogen atom or a methyl group;
R ² represents a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, a phenyl group which may have a substituent, a vinyl group, a formyl group, a nitro group, a cyano group , Acetyl group, acetoxy group, N-acetylamide group, acryloylamino group, N, N-dimethylamino group or maleimide group, methacryloylamino group, allyloxy group, allyloxycarbamoyl group, alkyl group having 1 to 4 carbon atoms A structure represented by N-alkyloxycarbamoyl group, N- (2-methacryloyloxyethyl) carbamoyloxy group, N- (2-acryloyloxyethyl) carbamoyloxy group or the following formula (IV-2);
L ¹ , L ² , L ³ and L ⁴ are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, 2 to 4 carbon atoms Or an acyl group, a halogen atom or a hydrogen atom, and at least one of L ¹ , L ² , L ³ and L ⁴ represents a group other than a hydrogen atom.

-Z ⁵ -T-Sp-P type (IV-2)
In formula (IV-2), P represents an acryl group, a methacryl group or a hydrogen atom, and Z ⁵ represents a single bond, -C (= O) O-, -OC (= O)-, -C (= O) NR ^1- (R ¹ represents a hydrogen atom or a methyl group), -NR ¹ C (= O)-, -C (= O) S-or -SC (= O)-, T represents 1 , Sp represents a substituted or unsubstituted divalent aliphatic group having 1 to 12 carbon atoms, and one CH ₂ in the aliphatic group or _two or more non-adjacent groups in the aliphatic group. CH ₂ may be substituted with —O—, —S—, —OC (= O) —, —C (= O) O— or —OCOO—. Represents.

The compound represented by the above formula (IV) is preferably a compound represented by the following formula (V).
Formula (V)
In formula (V), n1 represents an integer of 3 to 6;
R ¹¹ represents a hydrogen atom or a methyl group;
Z ¹² represents -C (= O)-or -C (= O) -CH = CH-;
R ¹² is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group, an allyloxy group, or the following formula (IV-3) Represents the structure.
-Z ⁵¹ -T-Sp-P type (IV-3)
In formula (IV-3), P represents an acryl group or a methacryl group;
Z ⁵¹ represents -C (= O) O- or -OC (= O)-; T represents 1,4-phenylene;
Sp represents a C2-C6 divalent aliphatic group which may have a substituent. One CH ₂ or non-adjacent two or more CH ₂ in the aliphatic groups, -O -, - OC (= O) -, - C (= O) O- or -OC (= O) O -May be substituted.

The above n1 represents an integer of 3 to 6 and is preferably 3 or 4.
The Z ¹² are, -C (= O) - or -C (= O) represents -CH = CH-, -C (= O) - preferably represents a.
R ¹² represents a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group, an allyloxy group, or the above formula (IV-3) Is more preferably a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group, or a group represented by the above formula (IV-3). More preferably, it represents a structure represented by a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group, or the above formula (IV-3).

  Examples of the compound represented by the formula (IV) include the compounds described in paragraphs [0020] to [0036] of JP-A-2014-198814.

  As a liquid crystal compound used in the present invention, a compound represented by the following formula (VI), which is also described in JP-A-2014-198814, in particular, a (meth) acrylate represented by the following formula (VI) Liquid crystal compounds having no group are also suitably used.

Formula (VI)
In formula (VI), Z ³ represents -C (= O)-or -CH = CH-C (= O)-;
Z ⁴ represents -C (= O)-or -C (= O) -CH = CH-;
R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, an aromatic ring which may have a substituent, a cyclohexyl group, Vinyl, formyl, nitro, cyano, acetyl, acetoxy, acryloylamino, N, N-dimethylamino, maleimide, methacryloylamino, allyloxy, allyloxycarbamoyl, alkyl carbon number Is an N-alkyloxycarbamoyl group, an N- (2-methacryloyloxyethyl) carbamoyloxy group, an N- (2-acryloyloxyethyl) carbamoyloxy group, or a group represented by the following formula (VI-2): Represent the structure
L ⁵ , L ⁶ , L ⁷ and L ⁸ are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, 2 to 4 carbon atoms And at least one of L ⁵ , L ⁶ , L ⁷ and L ⁸ represents a group other than a hydrogen atom.

-Z ⁵ -T-Sp-P type (VI-2)
In Formula (VI-2), P represents an acryl group, a methacryl group or a hydrogen atom, and Z ⁵ represents -C (= O) O-, -OC (= O)-, -C (= O) NR ^1- (R ¹ represents a hydrogen atom or a methyl group), —NR ¹ C (= O) —, —C (= O) S—, or —SC (= O) —, and T is 1,4-phenylene And Sp represents a divalent aliphatic group having 1 to 12 carbon atoms which may have a substituent. However, one CH ₂ in the aliphatic group or _two or more non-adjacent CH _{2 s} are —O—, —S—, —OC (= O) —, —C (= O) O— or — It may be substituted by OC (= O) O-.

The compound represented by the above formula (VI) is preferably a compound represented by the following formula (VII).
Formula (VII)
In formula (VII), Z ¹³ represents -C (= O)-or -C (= O) -CH = CH-;
Z ¹⁴ represents -C (= O)-or -CH = CH-C (= O)-;
R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group, an allyloxy group, or the above formula (IV -3) represents a structure represented by -3).

The Z ¹³ are, -C (= O) - or -C (= O) represents -CH = CH-, -C (= O) - preferably represents a.
R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group, an allyloxy group or the above formula (IV- 3) represents a structure represented by a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group, or a structure represented by the above formula (IV-3) It is preferable to represent, and it is more preferable to represent a structure represented by a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group or the above formula (IV-3).

  Examples of the compound represented by the formula (VI) include the compounds described in paragraphs [0042] to [0049] of JP-A-2014-198814.

  As the liquid crystal compound used in the present invention, a compound represented by the following formula (VIII), which is also described in JP-A-2014-198814, in particular, two compounds represented by the following formula (VIII) A polymerizable liquid crystal compound having a meth) acrylate group is also suitably used.

Formula (VIII)
In formula (VIII), each of A ² and A ³ independently represents an alkylene group having 2 to 18 carbon atoms, and one CH ₂ in the alkylene group or _two or more non-adjacent CH _{2 s} are — Optionally substituted with O-;
Z ⁵ represents -C (= O)-, -OC (= O)-or a single bond;
Z ⁶ represents —C (= O) —, —C (= O) O— or a single bond;
Each of R ⁵ and R ⁶ independently represents a hydrogen atom or a methyl group;
L ⁹ , L ¹⁰ , L ¹¹ and L ¹² are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, 2 to 4 carbon atoms And at least one of L ⁹ , L ¹⁰ , L ¹¹ and L ¹² represents a group other than a hydrogen atom.

The compound represented by the above formula (VIII) is preferably a compound represented by the following formula (IX).
Formula (IX)
In formula (IX), n2 and n3 each independently represent an integer of 3 to 6;
R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a methyl group.

In formula (IX), n2 and n3 each independently represent an integer of 3 to 6, and it is preferable that the above n2 and n3 be 4.
Wherein (IX), R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a methyl group, the R ¹⁵ and R ¹⁶ preferably represents a hydrogen atom.

  Examples of the compound represented by the formula (VIII) include the compounds described in paragraphs [0056] and [0057] of JP-A-2014-198814.

  These liquid crystal compounds can be produced by known methods.

(Chiral agent (chiral compound))
The composition comprises a chiral agent.
The type of chiral agent is not particularly limited. The chiral agent may be liquid crystalline or non-liquid crystalline. Chiral agents are known various chiral agents (for example, Liquid Crystal Device Handbook, Chapter 3 Section 4-3, TN (Twisted Nematic), chiral agents for STN (Super Twisted Nematic), page 199, Japan Society for the Promotion of Science) (Composition Committee, described in 1989). Chiral agents generally contain an asymmetric carbon atom. However, an axial asymmetric compound or a planar asymmetric compound not containing an asymmetric carbon atom can also be used as a chiral agent. Examples of axial asymmetric compounds or planar asymmetric compounds include binaphthyl, helicene, paracyclophane and derivatives thereof. The chiral agent may have a polymerizable group.

The content of the chiral agent in the composition is preferably 0.5 to 30% by mass with respect to the total mass of the liquid crystal compound. The amount of chiral agent used is preferred as less will tend to not affect liquid crystallinity. Therefore, as the chiral agent, a compound having a strong twisting power is preferable so that the desired helical pitch twist orientation can be achieved even in a small amount.
Examples of chiral agents exhibiting such a strong twisting power include, for example, JP-A-2002-302487, JP-A-2002-80478, JP-A-2002-80851, JP-A-2002-179668, and JP-A-2002. JP-A-179670, JP-A-2002-338575, JP-A-2002-180051, JP-A-62-81354, WO 2002/006195, JP-A-2011-241215, JP-A-2003-287623 Chiral agents described in JP-A-2002-302487, JP-A-2002-80478, JP-A-2002-80851, and JP-A-2014-034581, and LC-756 manufactured by BASF, etc. Can be mentioned.

(Any ingredient)
The composition may contain other components other than the liquid crystal compound and the chiral agent.

(Polymerization initiator)
The composition may contain a polymerization initiator. In particular, when the liquid crystal compound has a polymerizable group, the composition preferably contains a polymerization initiator.
The polymerization initiator is preferably a photopolymerization initiator capable of initiating a polymerization reaction by ultraviolet irradiation. As a photopolymerization initiator, α-carbonyl compounds (described in each specification of US Pat. Nos. 2,367,661 and 2367670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatic acyloin Compound (described in U.S. Pat. No. 2,272,512), Polynuclear quinone compound (described in U.S. Pat. Nos. 3,046,127 and 2,951,758), Combination of triarylimidazole dimer and p-aminophenyl ketone (US Pat. No. 3,549,367 No. 4), acridine and phenazine compounds (described in JP 60-105667, US Pat. No. 4,239,850), and oxadiazole compounds (described in US Pat. No. 4,212,970).
The content of the polymerization initiator in the composition is not particularly limited, but is preferably 0.1 to 20% by mass, and more preferably 1 to 8% by mass with respect to the total mass of the liquid crystal compound.

(Alignment control agent (alignment agent))
The composition may contain an orientation control agent. The inclusion of an orientation control agent in the composition enables stable or rapid formation of a cholesteric liquid crystal phase.
As an orientation control agent, for example, a fluorine-containing (meth) acrylate polymer, compounds represented by General Formulas (X1) to (X3) described in WO2011 / 162291, paragraph [0007] of JP-A-2012-211306 Compounds described in paragraphs [0020] to [0031] in JP 2013-47204 A, compounds described in paragraphs [0165] to [0170] in WO 2016/009648, WO 2016 Paragraphs [0077] to [0081] of the / 092844 and the general formulas (Cy201) to (Cy211) described in Japanese Patent No. 4592225 and the like can be mentioned. You may contain 2 or more types selected from these. These compounds can reduce or substantially horizontally align the tilt angles of the molecules of the liquid crystal compound at the air interface of the layer. In the present specification, “horizontal alignment” means that the major axis of the liquid crystal molecule is parallel to the film surface, but it does not require that it be strictly parallel, and in the present specification it is not It means that the inclination angle to make is an orientation less than 20 degrees.
The alignment control agent may be used alone or in combination of two or more.
The content of the alignment control agent in the composition is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total mass of the liquid crystal compound. 1% by mass is more preferable.

(solvent)
The composition may contain a solvent.
The solvent includes water or an organic solvent. Examples of the organic solvent include amides such as N, N-dimethylformamide; sulfoxides such as dimethyl sulfoxide; heterocyclic compounds such as pyridine; hydrocarbons such as benzene and hexane; alkyl halides such as chloroform and dichloromethane; Esters such as methyl, butyl acetate and propylene glycol monoethyl ether acetate; Ketones such as acetone, methyl ethyl ketone, cyclohexanone and cyclopentanone; Ethers such as tetrahydrofuran and 1,2-dimethoxyethane; 1,4-butanediol di Acetate; and the like. These may be used singly or in combination of two or more.

(Other additives)
The composition comprises one or more antioxidants, UV absorbers, sensitizers, stabilizers, plasticizers, chain transfer agents, polymerization inhibitors, antifoaming agents, leveling agents, thickeners. Other additives such as flame retardants, surfactants, dispersants, and colorants such as dyes and pigments may be included.

  Such a laminate 10 of the present invention first forms the infrared light reflection layer 14 in which the light portion 24 and the dark portion 26 have a wavelike structure in cross section on the substrate 12, and on the infrared light reflection layer 14. The red light reflection layer 16, the green light reflection layer 18, and the blue light reflection layer 20 are sequentially formed by a coating method using a composition (upper layer composition) containing the liquid crystal compound and the chiral agent as described above. It can manufacture by doing.

In the formation of the infrared light reflective layer 14, first, a composition (a non-visible light reflective layer composition) including the liquid crystal compound and the chiral agent as described above is prepared, and the prepared composition is applied to the substrate 12.
The coating method is not particularly limited, and examples thereof include a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method.
In addition, you may implement the process which dries the non-visible light reflection layer composition apply | coated to the board | substrate 12 after application | coating as needed. By carrying out the drying process, the solvent can be removed from the applied composition.

Next, the non-visible light reflection layer composition (composition layer (coating film)) coated on the substrate 12 is heated to align the liquid crystal compound in the composition to a cholesteric liquid crystal phase.
The liquid crystal phase transition temperature of the non-visible light reflective layer composition is preferably in the range of 10 to 250 ° C., and more preferably in the range of 10 to 150 ° C. from the viewpoint of production suitability.
As preferred heating conditions, it is preferable to heat the composition at 40 to 100 ° C. (preferably 60 to 100 ° C.) for 0.5 to 5 minutes (preferably 0.5 to 2 minutes).

When the non-visible light reflection layer composition is heated to bring the liquid crystal compound into the cholesteric liquid crystal phase, the composition is cooled or enhanced so as to improve the helical induction power of the chiral agent contained in the non-visible light reflection layer composition. By heating, the infrared light reflection layer 14 is formed. That is, the coating layer is such that the helical inducing power (HTP: Helical Twisting Power) of the chiral agent contained in the non-visible light reflection layer composition constituting the coating layer (composition layer) formed on the substrate 12 is increased. Subject to cooling treatment or heat treatment.
By subjecting the coated layer to a cooling treatment and a heating treatment, the helical induction force of the chiral agent is increased, the twist of the liquid crystal compound is increased, and as a result, the alignment of the cholesteric liquid crystal phase (tilt of the helical axis) is changed. Thereby, the bright part 24 and the dark part 26 parallel to the substrate 12 are changed, and the infrared light reflection layer having the bright part 24 and the dark part 26 of the wavelike structure (concave and convex structure) as shown in FIG. 14 (layer of the composition in the cholesteric liquid crystal phase state) is formed.

When cooling the non-visible light reflection layer composition, it is preferable to cool the composition so that the temperature of the composition is lowered by 30 ° C. or more in that the diffuse reflection of the infrared light reflection layer 14 is more excellent . Among them, it is preferable to cool the composition so as to lower by 40 ° C. or more, and it is more preferable to cool the composition so as to decrease 50 ° C. or more, in terms of more excellent effects. The upper limit of the reduction temperature range of the cooling treatment is not particularly limited, but is usually about 70 ° C.
In addition, the said cooling process intends cooling a composition so that it may become T-30 degrees C or less, when the temperature of the composition of the state of the cholesteric liquid crystal phase before cooling is set to T degreeC.
The method of cooling is not particularly limited, and may be a method of leaving the substrate on which the composition is disposed in an atmosphere of a predetermined temperature.

There is no limitation on the cooling rate in the cooling process, but in order to suitably form the wavelike structure of the light portion 24 and the dark portion 26 of the cholesteric liquid crystal phase or the surface unevenness of the reflective layer described later. It is preferable to have a certain speed.
Specifically, it is preferable that the maximum value of the cooling rate in the cooling process is 1 ° C. or more, and more preferably 2 ° C. or more per second.

When the liquid crystal compound has a polymerizable group, after the cooling treatment or the heating treatment, the non-visible light reflecting layer composition on the substrate 12 may be cured to fix the cholesteric liquid crystal phase. This curing treatment may be performed simultaneously with the cooling treatment or the heat treatment, or may be performed after the cooling treatment or the heat treatment.
The state in which the cholesteric liquid crystal phase is “fixed” is the most typical and preferred aspect in which the alignment of the liquid crystal compound in the cholesteric liquid crystal phase is maintained. The layer is not particularly limited, and specifically, the layer has no fluidity in a temperature range of usually 0 to 50 ° C. and more severe conditions of -30 to 70 ° C., and is in an oriented form by external field or external force. It means a state in which the immobilized orientation form can be kept stable without causing a change. In the present invention, as described later, it is preferable to fix the alignment state of the cholesteric liquid crystal phase by a curing reaction that proceeds by ultraviolet irradiation.
In the layer formed by fixing the cholesteric liquid crystal phase, it is sufficient if the optical properties of the cholesteric liquid crystal phase are maintained in the layer, and it is finally necessary that the composition in the layer exhibits liquid crystallinity. Absent.

The method of curing treatment is not particularly limited, and examples thereof include light curing treatment and heat curing treatment. Among them, light irradiation treatment is preferable, and ultraviolet ray irradiation treatment is more preferable.
A light source such as an ultraviolet lamp is used for ultraviolet irradiation.
The irradiation energy amount of the ultraviolet light is not particularly limited, but generally, about 0.1 to 0.8 J / cm ² is preferable. Further, the irradiation time of the ultraviolet light is not particularly limited, but may be appropriately determined in view of both the sufficient strength and productivity of the obtained layer.

Thus, when the infrared light reflection layer 14 having the wavelike structure is formed, the red light reflection layer 16, the green light reflection layer 18 and the blue light reflection layer 20 are coated on the infrared light reflection layer 14 by a coating method. Are formed sequentially.
Thereby, the red light reflecting layer 16 having the wavelike structure (wavelike structure of the light part and the dark part) in the cross section following the wavelike structure of the cross section of the infrared light reflecting layer 14, the green light reflecting layer 18 and the blue light reflecting layer 20 can be formed.

In the formation of the red light reflection layer 16, first, similarly to the non-visible light reflection layer composition, an upper layer composition for forming the red light reflection layer 16 including the liquid crystal compound as described above and a chiral agent is prepared. .
Next, the upper layer composition is applied onto (the surface of) the infrared light reflective layer 14. As the application method, the same method as the non-visible light reflection layer composition is used.
Then, after drying the upper layer composition as necessary, the liquid crystal compound in the composition layer formed on the infrared light reflective layer 14 is oriented to form the red light reflective layer 16 as a cholesteric liquid crystal phase. Form. When the liquid crystal compound has a polymerizable group, the curing treatment of the composition may be performed as in the case of the infrared light reflective layer 14.

In the present invention, preferably, the red light reflection layer 16 is also formed in the same manner as the infrared light reflection layer 14. That is, orientation of the liquid crystal compound in the composition layer formed on the infrared light reflective layer 14 is performed by heating the upper layer composition to align the liquid crystal compound, and then the cooling treatment or heat treatment of the upper layer composition is performed. I do.
Thereby, the unevenness | corrugation of the wavelike structure of the red light reflection layer 16 can be enlarged, and the red light reflection layer 16 which is excellent in diffuse reflectivity can be formed.

  As described above, when the lower reflection layer has a wavelike structure in the cross section, the upper reflection layer also follows the wavelike structure of the lower reflection layer, so that the bright and dark parts in the cross section have a wavelike structure. Accordingly, the red light reflecting layer 16 formed on the infrared light reflecting layer 14 by the application method also has a wavy structure in the light portion 28 and the dark portion 30 in the cross section.

Then, the upper layer composition for forming the green light reflecting layer 18 containing the similar liquid crystal compound and the chiral agent is prepared, and the green light reflecting layer 18 is formed in the same manner. Furthermore, the upper layer composition for forming the blue light reflection layer 20 containing the same liquid crystal compound and a chiral agent is prepared, and the blue light reflection layer 20 is formed by the same method, whereby the laminate 10 is produced. Similar to the red light reflection layer 16, these reflection layers also follow the wavelike structure of the lower reflection layer, and the light parts and dark parts in the cross section become wavelike structures.
In the case of forming more reflective layers, the same film formation may be repeated depending on the number of reflective layers to be formed.

Such a laminate 10 of the present invention can be used as a screen and a half mirror for projection image display. Moreover, it can also be utilized as a filter (for example, refer Unexamined-Japanese-Patent No. 2003-294948) which improves the color purity of the display light of a color filter or a display by controlling a reflection zone.
In addition, the laminate 10 can be used for various applications such as a polarization element, a reflection film, an antireflective film, a viewing angle compensation film, holography, and an alignment film, which are components of an optical element.

The laminate 10 of the present invention is particularly suitably used as a projected image display member such as a screen for projection image display. Specifically, it is suitably used as a transparent screen and a light room screen.
That is, by the function of the reflection layer as described above, it is possible to form a projection image by reflecting circularly polarized light of one of senses at a wavelength of the projection light which shows selective reflection. The projection video may be displayed on the surface of the projection display member surface and may be viewed as such, or may be a virtual image that appears to be floated on the tip of the projection display member as viewed from the observer.

  A clear projection image can be displayed using light efficiently by adjusting the central wavelength of the selective reflection of each reflection layer according to the emission wavelength range of the light source used for projection and the use mode of the projection image display member Can. In particular, by adjusting the central wavelength of the selective reflection of the reflective layer according to the emission wavelength range of the light source used for projection, it is possible to display a clear color projection image with good light utilization efficiency.

  Also, for example, by making the projection image display member transparent to light in the visible light region, it can be a half mirror usable as a combiner for a head-up display. The projection-image display half mirror can visibly display the image projected from the projector, and when the projection-image display half mirror is observed from the same side on which the image is displayed, the opposite side is displayed. You can simultaneously observe the information or landscape on the side.

  Hereinafter, the features of the present invention will be more specifically described by way of examples and comparative examples. The materials, amounts used, proportions, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention should not be construed as limited by the specific examples shown below.

[Preparation of Liquid Crystal Compositions 1 to 6]
Liquid crystal compositions 1 to 6 were prepared by mixing the components shown in Table 1 below. The amount of each component is all parts by mass.

Rod-like liquid crystal compound 101

Rod-like liquid crystal compound 102

Rod-like liquid crystal compound 201

Rod-like liquid crystal compound 202

Chiral agent

Orientation control agent (In the following formulas, "33" and "67" represent the content (mol%) of each repeating unit to all repeating units)

Example 1
A rubbing-treated PET film (manufactured by Fujifilm Corporation) was prepared as the substrate 12.
The liquid crystal composition 1 was applied to the rubbing-treated surface of the substrate 12 as a non-visible light reflective layer composition at room temperature using a wire bar. The coated layer of the liquid crystal composition 1 was dried at room temperature for 10 seconds, and then heated for 1 minute in an atmosphere of 95 ° C. to align the liquid crystal compound.
Thereafter, UV light (ultraviolet light) is applied to the coated layer at 80% for 8 seconds using a Fusion D bulb (lamp 90 mW / cm ² ) at 30 ° C. 14 was formed. In the above procedure, after orienting the liquid crystal compound at 95 ° C., the liquid crystal composition was cooled to 30 ° C.
A part of the formed infrared light reflection layer 14 is peeled off, and the film thickness of the infrared light reflection layer 14 is measured using a 10 × objective lens with a shape measurement laser microscope VK-X200 (manufactured by Keyence Corporation) did. As a result, the film thickness of the infrared light reflection layer 14 was 4 μm.

Subsequently, the liquid crystal composition 3 was applied on the infrared light reflective layer 14 as an upper layer composition. The application of the liquid crystal composition 3 was performed in the same manner as the invisible light reflective layer composition. Thereafter, drying, heating (alignment), cooling and curing of the liquid crystal composition 3 were performed in the same manner as in the infrared light reflective layer 14 to form the red light reflective layer 16 on the infrared light reflective layer 14. When the film thickness was similarly measured, the film thickness of the red light reflective layer 16 was 2 μm.
Similarly, the green light reflection layer 18 is formed on the red light reflection layer 16 using the liquid crystal composition 4, and the blue light reflection layer 20 is formed on the green light reflection layer 18 using the liquid crystal composition 5. It formed and the laminated body 10 was produced. The film thickness of the green light reflection layer 18 was 1 μm, and the film thickness of the blue light reflection layer 20 was 1 μm.
The reflection wavelength of the laminate was measured using a spectrophotometer (UV-3100PC, manufactured by Shimadzu Corporation). As a result, a peak of selective reflection central wavelength 750 nm derived from liquid crystal composition 1, a peak of selective reflection central wavelength 650 nm derived from liquid crystal composition 3, a selective reflection central wavelength derived from liquid crystal composition 4 is a peak of 550 nm, As for the selective reflection center wavelength derived from the liquid crystal composition 5, a peak of 450 nm was observed.
The selective reflection center wavelength of each reflective layer is shown in Table 1.

The laminate 10 was set in a polarizing microscope so that the slow axis of the substrate 12 (PET film) coincides with the direction of the polarizer of the polarizing microscope, and each reflective layer was observed by incidence, resulting in a diffraction grating-like structure The formation of (= an undulation structure) was clearly confirmed.
The laminate 10 is cross-sectioned by an ultramicrotome, subjected to pretreatment, and the cross-section is observed by SEM (SU8030 SEM manufactured by Hitachi High-Technologies Corporation). It has been confirmed that it has become. The SEM photograph of this cross section is shown in FIG.

[Examples 2 to 5, Comparative Examples 1 to 3]
A laminate 10 is formed in the same manner as in Example 1 except that the liquid crystal composition used, the order of formation of the reflective layer by the liquid crystal composition, and the application amount of the liquid crystal composition (film thickness of the reflective layer) are changed. did.
The reflection wavelength of each laminate was measured in the same manner as in Example 1. As a result, in Examples 2 to 4, the peak of the selective reflection center wavelength of 850 nm derived from the liquid crystal composition 2 was observed instead of the peak of the selective reflection center wavelength of 750 nm derived from the liquid crystal composition 1. Further, in Example 5, the peak of the selective reflection center wavelength of 850 nm derived from the liquid crystal composition 2 is observed instead of the peak of the selective reflection center wavelength of 750 nm derived from the liquid crystal composition 1. The peak of the selective reflection center wavelength of 470 nm from which it originates was observed.

[Evaluation]
The following evaluation was performed about the laminated body 10 produced by Examples 1-5 and Comparative Examples 1-3.
<Haze and total light transmittance>
The haze and the total light transmittance were measured for the produced laminate. The haze and the total light transmittance were both measured using SH-4000 manufactured by Nippon Denshoku Kogyo Co., Ltd. The haze was measured according to JIS K 7136, and the total light transmittance was measured according to JIS K 7361.
If the haze is 5% or less, if the total light transmittance is 75% or more, it can be determined that both are good.

<Diffuse reflectivity evaluation>
The relative reflectance of each reflective layer with respect to a reference (white plate) was measured using a double beam measurement mode made by Murakami Color GCMS-3B.
Specifically, as shown in FIG. 5, the incident light from the light source 50 is irradiated from the normal direction of the surface of the sample 54 (laminate or white plate), and the pole relative to the normal direction of the surface of the sample 54 The reflected light was measured by the detector 52 disposed at a position where the angle θ was 45 °, and the relative reflectance of each reflective layer to the reference was measured.
If the relative reflectance is 5 or more, it can be judged that the diffuse reflectance is good.
The results are summarized in Table 2.

As shown in Table 2, each of the laminates of the present invention has a low haze of 5% or less, a high total light transmittance of 75% or more, and further has a 45 ° relative reflection amount of 5 or more. Diffuse reflectivity is also good. That is, the laminate of the present invention has both good transparency and diffuse reflectivity.
Specifically, when the examples and the comparative examples are compared, the amount of reflection of the examples 1, 2 and 5 is reduced to about 1/3 to 1/2 of the comparative examples 2 and 3, while The haze is reduced to about 1/5, and the ratio of the reflection amount to the haze is very high. Moreover, compared with Comparative Examples 2 and 3, Examples 1, 2 and 5 also have high total light transmittance.
Moreover, when Example 2 and Example 3 and Example 4 which use the same liquid crystal composition in the first to fourth layers are compared with each other, the selective reflection center wavelength of the reflective layer is increased from the substrate 12 upward. However, Example 2 gradually becoming short wavelength has good haze and total light transmittance as compared with Example 4 which does not satisfy this condition. Furthermore, in the third embodiment, the selective reflection central wavelength of the reflective layer gradually becomes shorter from the substrate 12 upward, even though the film thickness of the second and subsequent layers in the visible light region is thick, this condition Since the second embodiment has substantially the same haze and total light transmittance as Example 4 which does not satisfy the above, and has a large film thickness after the second layer in the visible light region, it has higher diffuse reflectance.
In addition, changing to the third layer which is the green light reflection layer 18 and the fourth layer which is the blue light reflection layer 20 instead of the four reflection layers, the green light whose selective reflection center wavelength is 470 nm in the third layer In Example 5 of the three-layer reflecting layer provided with a reflecting layer having both the characteristics of the reflecting layer 18 and the blue light reflecting layer 20, the haze and the total light transmittance equivalent to those of the other embodiments, and diffuse reflection Have sex.

On the other hand, Comparative Examples 1 to 3 in which the selective reflection center wavelength of the reflection layer of the first layer (the surface of the substrate 12) is a visible light region (650 nm) improve the haze and the total light transmittance. In order to achieve this, as in Comparative Example 1, it is necessary to make the first layer thinner, and as a result, the diffuse reflectivity deteriorates. On the other hand, as in Comparative Examples 2 and 3, by increasing the thickness of the first or subsequent reflective layer, the diffuse reflectance is increased, but the haze and the total light transmittance are significantly reduced. That is, unlike the laminate of the present invention, the laminate of the comparative example is not obtained while achieving both good transparency and diffuse reflectance.
From the above results, the effects of the present invention are clear.

DESCRIPTION OF SYMBOLS 10 laminated body 12 board | substrates 14 infrared light reflective layer 16 red light reflective layer 18 green light reflective layer 20 blue light reflective layer 24, 28, 32, 36 bright part 26, 30, 34, 38 dark part 42, 46 layer 50 light source 52 Detector 54 samples

Claims (16)

A substrate and a plurality of stacked reflective layers supported by the substrate,
The reflective layer is formed by immobilizing a cholesteric liquid crystal phase, and in the cross section of the reflective layer, light portions and dark portions derived from the cholesteric liquid crystal phase have a wavelike structure.
The laminated body characterized in that the reflective layer closest to the substrate has a selective reflection center wavelength in a wavelength range of 400 nm or less or a wavelength range of 700 nm or more.   The laminate according to claim 1, wherein the reflective layer closest to the substrate has a selective reflection center wavelength in a wavelength range of 700 nm or more.   The laminated body of Claim 1 or 2 in which the selective reflection center wavelengths of the said reflection layer mutually differ in all the reflection layers.   The laminated body of any one of Claims 1-3 whose direction of the circularly polarized light which the said reflection layer reflects is the same in all the reflection layers.   The layered product according to any one of claims 1 to 4 in which the selective reflection center wavelength of said reflection layer becomes short wavelength gradually toward the direction estranged from said substrate.   The laminated body of any one of Claims 1-5 whose number of the said reflection layers is four or less layers.   The laminate according to any one of claims 1 to 6, wherein the substrate has no tint and the total light transmittance is 70% or more. The selective reflection center wavelength of the reflective layer closest to the substrate is 700 to 1000 nm,
The laminate according to any one of claims 1 to 7, wherein the reflective layer has a selective reflection center wavelength of 600 nm or more and less than 700 nm, and the reflective layer at least one selective reflection center wavelength of 420 nm or more and less than 600 nm. body.   The layered product according to any one of claims 1 to 8 whose film thickness of said reflection layer nearest to said substrate is the thickest among a plurality of reflection layers.   The layered product according to any one of claims 1 to 9, wherein the formation surface of the reflective layer of the substrate is a flat surface.   The screen which has a laminated body of any one of Claims 1-10.   The transparent screen which has a laminated body of any one of Claims 1-10.   A light room screen having the laminate according to any one of claims 1 to 10. A layer formed by immobilizing a cholesteric liquid crystal phase, wherein in a cross section, the light part and the dark part derived from the cholesteric liquid crystal phase have a wavelike structure, and the selective reflection center wavelength is 400 nm or less or 700 nm or more Forming a reflective layer, and
Applying an upper layer composition containing a liquid crystal compound and a chiral agent to align the liquid crystal compound to form a cholesteric liquid crystal phase, thereby forming an upper reflective layer;
After performing the step of forming the non-visible light reflection layer, the step of forming the upper-layer reflection layer on the non-visible light reflection layer is performed, or further, the upper layer is formed on the upper-layer reflection layer formed. The manufacturing method of the laminated body which performs the process of forming a reflection layer once or more. The step of forming the non-visible light reflection layer comprises
A non-visible light reflecting layer composition containing a liquid crystal compound and a chiral agent is coated on a substrate, and the coated non-visible light reflecting layer composition is heated to align the liquid crystal compound to form a cholesteric liquid crystal phase. The manufacturing method of the laminated body of Claim 14 which performs the process which performs the process which cools or heats the said non-visible light reflection layer composition after that.   In the step of forming the upper reflective layer, the upper layer composition is applied when forming the at least one upper reflective layer, and then the upper layer composition is heated to orient the liquid crystal compound to form cholesteric. The manufacturing method of the laminated body of Claim 14 or 15 which is made into the state of a liquid crystal phase, and the process which cools or heats the said upper layer composition after that is performed.