JP2020027210A - Design material and method for manufacturing laminated polymer dispersion type liquid crystal device used for the same - Google Patents

Abstract

To provide a design material, such as a window and a partition that matches the ambient appearance and can achieve both protection of privacy in a room and improvement of living environment, and a method for manufacturing a laminated polymer dispersion type device used for the design material.SOLUTION: A design material 200 can change the transmittance of light upon energization, and comprises a laminated polymer dispersion type liquid crystal device 100 in which a first outer support 10, a first polymer/liquid crystal combined layer 20, a second polymer/liquid crystal combined layer 50, and a second outer support 60 are laminated in this order. The first outer support has a substrate 11 and a transparent conductive layer 12 laminated to each other, and the second outer support has a substrate 61 and a transparent conductive layer 62 laminated to each other. At least one of the first polymer/liquid crystal combined layer 20 and the second polymer/liquid crystal combined layer 50 has a dichroic dye.SELECTED DRAWING: Figure 1

Description

The present invention relates to a design material and a method for manufacturing a laminated polymer-dispersed liquid crystal element used for the design material.

A polymer-dispersed liquid crystal element is a dimming element in which the alignment state of liquid crystals changes depending on the presence or absence of an electric field, and can change light transmission (transparent state) and at least one of light scattering and absorption (opaque state). And is conventionally used in various situations.

For example, it is used for windows and wall materials of buildings, windows of vehicles such as cars, trains and airplanes, and partitions of offices and exhibition halls.
For example, Patent Literature 1 discloses that a polymer-dispersed liquid crystal light control structure is attached to a French window of a building, a skylight of a vehicle, and a general window.
Patent Document 2 discloses that a PDLC film is applied on a windshield of a vehicle and used as a light shielding device.

In addition to the above, the polymer-dispersed liquid crystal element is used for controlling a viewing angle of a liquid crystal display as disclosed in Patent Document 3, or used as a screen for a projector as disclosed in Patent Document 4.

However, in particular, when the above-described polymer dispersed liquid crystal element is used for windows of buildings and windows of vehicles, etc., the transmittance and / or chromaticity of the windows observed from inside and outside the room are the same. It has been difficult to achieve both windows suitable for exterior designs of vehicles and windows suitable for interior designs of buildings and vehicles. That is, the transmittance and / or chromaticity of the windows of buildings and vehicles cannot be different between when viewed from the inside and when viewed from the outside. Could not be configured. In addition, the window viewed from the outside cannot be made dark and the window viewed from the room cannot be made bright, and it has been difficult to achieve both protection of the privacy of the room and the like and improvement of the living environment.

JP-A-2017-37115 JP-T-2006-505867 JP 05-72529A JP 06-301005 A

The present invention has been proposed in view of the above-described conventional problems, and is provided with windows and partitions that are in harmony with the surrounding appearance and that can both protect the privacy of rooms and the like and improve the living environment. It is an object of the present invention to provide a design material and a method for producing a laminated polymer dispersed element used for the design material.

The present invention relates to a design material capable of changing the light transmittance by applying electricity, comprising a first outer support, a first polymer / liquid crystal composite layer, a second polymer / liquid crystal composite layer, and a second The outer support has a laminated polymer-dispersed liquid crystal element laminated in this order, and the first outer support and the second outer support each have a substrate and a transparent conductive layer laminated thereon. And wherein at least one of the first polymer / liquid crystal composite layer and the second polymer / liquid crystal composite layer has a dichroic dye.
The design material of the present invention preferably has an intermediate layer between the first polymer / liquid crystal composite layer and the second polymer / liquid crystal composite layer.
The intermediate layer can be an adhesive layer or a resin layer.
Further, the intermediate layer has an intermediate support having a pair of transparent conductive layers, and the laminated polymer dispersion type liquid crystal element has the first outer support and the first support formed by the intermediate support. Preferably, the polymer / liquid crystal composite layer is energized, and the second polymer / liquid crystal composite layer is energized by the second outer support and the intermediate support.
The intermediate support, wherein a first intermediate support and a second intermediate support are laminated via at least one selected from the group consisting of an air layer, an adhesive layer, and a resin layer, The first intermediate support and the second intermediate support are each formed by laminating a base material and a transparent conductive layer, and the laminated polymer-dispersed liquid crystal element includes the first outer support. And the first polymer / liquid crystal composite layer is energized by the first intermediate support, and the second polymer / liquid crystal composite layer is formed by the second outer support and the second intermediate support. Preferably, it is energized.
The intermediate layer has at least one intermediate polymer / liquid crystal composite layer and at least two intermediate supports, and the intermediate support is disposed on both sides of the intermediate polymer / liquid crystal composite layer. The intermediate polymer / liquid crystal composite layer can be energized by the intermediate supports disposed on both sides.
It is preferable that the design material further has an ultraviolet shielding layer.
The first polymer / liquid crystal composite layer and / or the second polymer / liquid crystal composite layer can have an alignment film.

The present invention also relates to a method for manufacturing a laminated polymer dispersed liquid crystal element used for a design material whose transmittance of light can be changed by energization, comprising a first outer support, a first polymer / liquid crystal. A first polymer-dispersed liquid crystal device having a composite layer and a coating layer in this order, and a second polymer-dispersed liquid crystal device having a second outer support, a second polymer / liquid crystal composite layer and a coating layer in this order Using a liquid crystal element, the first polymer dispersion type liquid crystal element and the second polymer dispersion so that the first outer support and the second outer support are arranged on both sides. The method includes a lamination step in which a liquid crystal element is laminated, wherein the first outer support and the second outer support are both a substrate and a transparent conductive layer laminated, and the first At least one of the polymer / liquid crystal composite layer and the second polymer / liquid crystal composite layer contains a dichroic dye. It is also a method for producing a laminated polymer dispersion type liquid crystal element, characterized by.
In the method for producing a laminated polymer dispersed liquid crystal device of the present invention, the coating for peeling off the covering layer in the first polymer dispersed liquid crystal device and the second polymer dispersed liquid crystal device before the laminating step. It is preferable to have a delamination step.
Further, the present invention provides a method for producing a laminated polymer dispersed liquid crystal element used for a design material whose transmittance of light can be changed by energization, comprising: a first outer support; a first polymer / liquid crystal composite layer; A first polymer-dispersed liquid crystal element having a first intermediate support in this order, a second outer support, a second polymer / liquid crystal composite layer, and a second intermediate support in this order. Using the second polymer-dispersed liquid crystal element having, the first outer support, the first polymer-dispersed liquid crystal element such that the second outer support is disposed on both sides And a lamination step in which the second polymer-dispersed liquid crystal element is laminated, wherein the first outer support, the first intermediate support, the second outer support, and the second intermediate The support is formed by laminating a substrate and a transparent conductive layer, and the first polymer / liquid crystal composite layer Method for producing a laminated polymer dispersed liquid crystal device in which at least one of the fine the second polymer / liquid crystal composite layer is characterized by having a dichroic dye is also one of the present invention.
In the above-mentioned laminating step in the method for producing a laminated polymer-dispersed liquid crystal element of the present invention, an adhesive or a resin can be used.
In the laminating step, the first polymer-dispersed liquid crystal element and the second polymer-dispersed liquid crystal element can be laminated via an air layer using a spacer.

Since the design material of the present invention has different reflection chromaticity and / or reflection luminance depending on the side to be observed, the design material is excellent in design, and is used for windows of buildings, windows of vehicles such as automobiles, trains, airplanes, offices and exhibition halls. And the like can be suitably used for partitioning.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic cross-sectional view showing an example of a design material according to the present invention, in which a design material (a) having a laminated polymer-dispersed liquid crystal layer in which two polymer / liquid crystal composite layers are laminated, and two polymer / liquid crystal composites. Design material (b) having a laminated polymer-dispersed liquid crystal layer in which the layers are laminated via an intermediate layer (adhesive), and two polymer / liquid crystal composite layers laminated via an intermediate layer (curable resin) Design material (c) having a laminated polymer-dispersed liquid crystal layer formed as described above. FIG. 3 is a schematic cross-sectional view showing a case where an intermediate layer has an intermediate support as an example of the design material of the present invention, and a design in which a pair of transparent conductive layers of the intermediate support are laminated via an air layer with a spacer interposed therebetween. A material (a), a design material (b) in which a pair of transparent conductive layers of an intermediate support are laminated via an adhesive or the like, and a pair of transparent conductive layers of the intermediate support are laminated via an intermediate base material Design material (c). FIG. 3 is a schematic cross-sectional view showing a case where one intermediate polymer / liquid crystal composite layer and two intermediate supports are provided as an example of the design material of the present invention.

Hereinafter, the present invention will be described. In addition, in order to facilitate understanding of the present invention, reference numerals in the accompanying drawings are added in parentheses, but the present invention is not limited to the illustrated embodiment.

As shown in FIG. 1A, the design material (200) of the present invention comprises a first outer support (10), a first polymer / liquid crystal composite layer (20), and a second polymer / liquid crystal. It has a laminated polymer dispersed liquid crystal element (100) in which a composite layer (50) and a second outer support (60) are laminated in this order.
Further, the first outer support (10) and the second outer support (60) are each formed by laminating the substrates (11) and (61) and the transparent conductive layers (12) and (62). It is.
At least one of the first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50) has a dichroic dye.

Here, the first and second outer supports (10) and (60) are such that both of the substrates (11) and (61) are on the outermost surface of the multilayer polymer dispersion type liquid crystal element (100). It is preferable to be laminated so as to be located.

With the above configuration, the laminated polymer-dispersed liquid crystal element (100) used in the design material (200) of the present invention has at least two polymer / liquid crystal composite layers, Since at least one of the layers has a dichroic dye, the design material of the present invention has a reflection chromaticity and / or reflection luminance when observing one surface, and a reflection chromaticity and / or reflection when observing the other surface. Alternatively, the reflection luminance can be different from the reflection luminance. That is, by using the design material of the present invention, it is possible to harmonize the design of the design material with the surrounding appearance on both sides of the surface to which the design material is applied (indoor / outside, and inside / outside the vehicle). Thus, the design of buildings and vehicles is improved, and it is possible to achieve both improvement of the living environment and protection of privacy.
Further, by changing the voltage applied to the first and second polymer / liquid crystal composite layers (20) and (50), it is possible to continuously control the low haze state to the high haze state. It is also possible to control.

The above-described reflection chromaticity and reflection luminance can be measured by a commonly used method. Specifically, for example, the reflection chromaticity and the reflection luminance can be measured using EZ Contrast manufactured by ELDIM.

The substrates (11) and (61) in the first outer support (10) and the second outer support (60) function as supports for supporting the transparent conductive layers (12) and (62). Any material may be used as long as it is not particularly limited, but a transparent film material can be suitably used.
The transparent film material is not particularly limited, and a transparent film material having flexibility can be used.

Examples of the transparent film material include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic resins such as polymethyl methacrylate (PMMA), polyolefin resins such as polypropylene (PP), and triacetyl cellulose ( A transparent film material such as a cellulose resin such as cellulose triacetate (TAC), a cycloolefin polymer (COP), and a polycarbonate (PC) resin can be suitably used. Among them, it is preferable to use polyethylene terephthalate from the viewpoint of mechanical properties and optical properties.

The thickness of the base materials (11) and (61) is not particularly limited, but is preferably 20 μm or more and 300 μm or less, and more preferably 50 μm or more and 150 μm or less, from the viewpoint of having a strength suitably functioning as a base material. Is more preferable.
The thickness of the substrate (11) in the first outer support (10) and the thickness of the substrate (61) in the second outer support (60) may be the same or different.

The transparent conductive layers (12) and (62) used for the first outer support (10) and the second outer support (60) are electrically connected to the first polymer / liquid crystal composite layer (20). ) And the second polymer / liquid crystal composite layer (50), whereby an electric field is applied, whereby the first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50) are included. This layer functions as an electrode for driving a liquid crystal material. Here, “driving” the liquid crystal material means changing the direction of liquid crystal molecules contained in the liquid crystal material.
Therefore, by applying an electric field to the first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50) using the transparent conductive layer, the polymer / liquid crystal composite layer is formed. The orientation direction of the liquid crystal molecules contained in (20) and (50) can be changed.

As the transparent conductive layers (12) and (62), a substantially uniform electric field can be applied to the first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50). Although there is no particular limitation, a transparent conductive material that is perceived as transparent is preferably used.
As the transparent conductive material, for example, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), AZO (Aluminum-doped Zinc Oxide), GZO (Gallium-doped Zinc Oxide), ATO (Antium Oxide) In addition to a metal oxide such as Zinc Oxide, a material containing a conductive polymer film, silver nanowires, carbon nanotubes, or the like can be used.
The sheet resistance and transmittance of the transparent conductive layers (12) and (62) are not particularly limited. For example, the sheet resistance may be 100Ω / □ or more and 300Ω / □ or less, and the transmittance may be 85% or more. preferable.

The first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50) change their transparency depending on the state of application of an electric field by the transparent conductive layers (12) and (62). This is a layer having a function of causing The first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50) are formed of polymer dispersed liquid crystal.

The polymer-dispersed liquid crystal is not particularly limited. For example, a liquid crystal in which liquid crystal droplets are dispersed in a transparent polymer material (PDLC: Polymer Dispersed Liquid Crystal). A polymer network type liquid crystal (PNLC: Polymer Network Liquid Crystal) in which a network of molecular resins is formed, a polymer stable type cholesteric liquid crystal (PSCT: Polymer Stabilized Cholesteric Texture) using a cholesteric liquid crystal, and the like can be given.
An example in which the first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50) are formed by the PDLC will be described.

One embodiment of the first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50) includes a polymer matrix and a liquid crystal material dispersed in the polymer matrix. .
As an example, the first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50) each include a polymerizable monomer, a photopolymerization initiator, and a liquid crystal having no polymerizable group. It can be formed by mixing materials and subjecting the liquid crystal to phase separation when the monomer is photopolymerized. As a result, the monomer is polymerized to form the polymer matrix of the first and second polymer / liquid crystal composite layers (20) and (50), and the liquid crystal material is dispersed in the polymer matrix.

The liquid crystal material is preferably, for example, a liquid material having no polymerizable group and containing liquid crystal molecules having a longitudinal direction.
The liquid crystal molecules having the above-described longitudinal direction have a refractive index anisotropy corresponding to the shape. That is, the refractive index in the direction perpendicular to the longitudinal direction of the liquid crystal molecules having the longitudinal direction is different from the refractive index in the direction parallel to the longitudinal direction of the liquid crystal molecules.
The liquid crystal material having no polymer group is not particularly limited, but, for example, a nematic material can be suitably used.
As a commercially available liquid crystal material, for example, a nematic material such as E7 manufactured by Merck can be used.
As the liquid crystal material, various materials as disclosed in JP-A-2007-009120 and JP-A-2011-246411 can be used.

When the design material (200) of the present invention is used as a normal type, positive liquid crystal molecules are used as the liquid crystal material. In this case, the direction of the liquid crystal molecules is irregular when no electric field is applied to the polymer / liquid crystal composite layer. Therefore, the normal type design material (200) is in a high haze state in a state where no electric field is applied, exhibits cloudiness or a predetermined color, and has low visibility. On the other hand, when an electric field is applied to the polymer / liquid crystal composite layer, the liquid crystal molecules are aligned. Therefore, the normal type design material (200) becomes colorless and transparent or a state close to the colorless state when an electric field is applied, whereby visibility through the design material (200) is enhanced.

When the design material (200) of the present invention is used as a reverse type, negative liquid crystal molecules are used as the liquid crystal material. In this case, the direction of the liquid crystal molecules becomes irregular when an electric field is applied to the polymer / liquid crystal composite layer. Therefore, the reverse type design material (200) is in a high haze state in a state where an electric field is applied, exhibits cloudiness or a predetermined color, and has low visibility. On the other hand, when no electric field is applied to the polymer / liquid crystal composite layer, the liquid crystal molecules are aligned. Therefore, the reverse type design material (200) becomes colorless and transparent or in a state close to it in a state where no electric field is applied, whereby visibility through the design material (200) is enhanced.

Further, in the design material (200) of the present invention, a normal type and a reverse type can be used in combination. In this case, one of the first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50) is a normal type and a liquid crystal material containing positive liquid crystal molecules is used, and the other is used. As the reverse type, a liquid crystal material including negative liquid crystal molecules can be used.

As the polymerizable monomer, any material capable of phase-separating the liquid crystal material having no polymerizable group and having a high light transmittance may be used. Resins having a (functional group) can also be used.
Examples of the polymerizable monomer include monofunctional (meth) acrylates such as methyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate. ) Polyfunctional (meth) acrylates such as acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
In addition to the above acrylates, cationic polymerizable monomers include alicyclic epoxides such as 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate and glycidyl such as bisphenol A diglycidyl ether. Ethers and the like can also be used.
The above polymerizable monomers can be used alone or in combination of two or more depending on the required performance, coating suitability, and the like.

The photopolymerization initiator is not particularly limited, and for example, benzoin and its alkyl etherified product, benzyl ketals, and acetophenones can be used.
Examples of the acetophenones include hydroxyacetophenone, aminoacetophenone, dialkoxyacetophenone, and halogenated acetophenone.
Commercial products of these photopolymerization initiators include, for example, Irgacure (registered trademark) 907, Irgacure 651, and Irgacure 184 manufactured by BASF.
The above photopolymerization initiators can be used alone or in combination of two or more.

The first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50) are composed of the first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer ( It is preferable to have a spacer having a function of maintaining the thickness of 50) at a predetermined thickness.
As the spacer, for example, a resin-made resin such as plastic beads having high light transmittance can be used. The shape of the spacer is not particularly limited, and may be spherical or irregular.

In the design material of the present invention, at least one of the first polymer / liquid crystal composite layer and the second polymer / liquid crystal composite layer contains a dichroic dye.
The dichroic dye has a longitudinal direction, and when the orientation direction of the liquid crystal material is changed by an electric field, the orientation is changed according to the change in the orientation of the liquid crystal material, and the design material is accordingly colored. It is a material that can be produced.
For this reason, the design material maintains a colorless and transparent state or nearly colorless and transparent state in a state where the liquid crystal material is arranged (low haze state), and a predetermined color in a state where the liquid crystal material is dispersed (high haze state). It becomes invisible while having a taste. When the polymer / liquid crystal composite layer does not contain a dichroic dye, the design material becomes invisible due to mere cloudiness when the orientation of the liquid crystal material is irregular (high haze state).
Here, when the predetermined color is set to the same color as the surrounding portion of the design material of the present invention, it is possible to prevent the appearance of the design material portion of the present invention from being different from that of the surrounding portion.
Further, the design may be positively imparted such that the color of the design material in the state where the liquid crystal material is arranged (low haze state) is different from the color of the surrounding portion.
As such a dichroic dye, for example, various known dyes as disclosed in JP-A-2007-009120 and JP-A-2011-246411 can be used.

In the design material of the present invention, at least one of the first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50) may have a dichroic dye. Each of the first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50) may have a dichroic dye.
As the dichroic dye used in the polymer / liquid crystal composite layer in the design material of the present invention, various known dichroic dyes can be used as described above, and it is not particularly limited. It is preferable to select according to the appearance of the object and the vehicle, and / or the application.
In the design material of the present invention, when the first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50) contain a dichroic dye, the first and second polymer layers may be used. The molecular / liquid crystal composite layers (20), (50) may contain the same dichroic dye or different dichroic dyes.

Further, in the design material of the present invention, the content of the dichroic dye contained in the first and / or second polymer / liquid crystal composite layers (20) and (50) is not particularly limited, but the low haze state Is preferably from 0.1 to 2.0%, more preferably from 0.5 to 1.0%, from the viewpoint of ensuring light transmittance.
When both the first and second polymer / liquid crystal composite layers (20) and (50) contain a dichroic dye, the content of the dichroic dye may be the same or different.

However, the first and / or second polymer / liquid crystal composite layers (20) and (50) are dichroic dyes so that both have different reflection chromaticity and / or reflection luminance in a high haze state. It is preferred that the type and / or content of is selected.
By being selected in this way, the reflection chromaticity and / or reflection luminance when observing one surface of the design material of the present invention, and the reflection chromaticity and / or reflection luminance when observing the other surface , Can be different. In other words, for example, even when the first and second polymer / liquid crystal composite layers (20) and (50) contain the same dichroic dye, their contents are different. The light absorption in the high haze state is different, which changes the reflected chromaticity and / or the reflected luminance, and makes it possible to make the color observed by human eyes different.

The first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50) may contain a leveling agent, a polymerization inhibitor, and the like, if necessary, in addition to the above-described materials.

The thicknesses of the first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50) are controlled from the viewpoint of controlling the alignment state of the liquid crystal material and suitably exhibiting a dimming function. , Preferably from 3 to 50 µm, more preferably from 5 to 20 µm, even more preferably from 10 to 16 µm.

Further, as shown in FIGS. 1B and 1C, the design material (200) of the present invention comprises a first polymer / liquid crystal composite layer (20) and a second polymer / liquid crystal composite layer (50). ) Can be provided with an intermediate layer (30).
The intermediate layer (30) can be an adhesive layer or a resin layer.
The pressure-sensitive adhesive layer is preferably formed of a pressure-sensitive adhesive. Examples of the pressure-sensitive adhesive include, but are not particularly limited to, an acrylic pressure-sensitive adhesive, a urethane pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, and a water-based pressure-sensitive adhesive. Can be. As the design material of the present invention, a material that can firmly adhere the first and second polymer / liquid crystal composite layers (20) and (50) and that does not foam even under high temperature and high humidity conditions. Since it is preferable, an acrylic pressure-sensitive adhesive is suitably used.

Further, the resin layer can be formed of a curable resin. Examples of the curable resin include a thermosetting resin and an ionizing radiation curable resin, and a suitable resin can be selected from the viewpoint of imparting transparency and hard coat properties.
In this specification, “resin” is a concept that also includes resin components such as monomers and oligomers.

Examples of the thermosetting resin include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), epoxy resins, polyurethane resins, aminoalkyd resins, melamine resins, guanamine resins, urea resins, thermosetting acrylics. Thermosetting resins such as resins are preferred. It is preferable to use a polyester resin from the viewpoint of imparting transparency and hard coat properties.

The ionizing radiation-curable resin is a resin composition that cures when irradiated with ionizing radiation. As the ionizing radiation, among electromagnetic waves or charged particle beams, those having an energy quantum capable of polymerizing or cross-linking molecules, for example, ultraviolet (UV) or electron beam (EB), X-rays, γ-rays, etc. Charged particles such as electromagnetic waves, α-rays and ion beams.

The ionizing radiation-curable resin can be appropriately selected from polymerizable oligomers and prepolymers conventionally used as resins having ionizing radiation-curing properties, and provides good transparency and curing characteristics. From the viewpoint, it is preferable that the resin hardly bleeds out, has applicability even when the solid content is about 95 to 100%, and hardly causes curing shrinkage when cured.
Further, from the viewpoints of storage stability and cost, it is preferable that the resin is an ultraviolet curable resin.

The UV-curable resin is not particularly limited, but it is preferable to use a (meth) acrylic resin from the viewpoint of obtaining good transparency and curing characteristics. In this specification, “(meth) acryl” means acryl or methacryl.
Examples of the (meth) acrylic resin include a polymer or a copolymer of a (meth) acrylic monomer, and the (meth) acrylic monomer is not particularly limited. For example, pentaerythritol tri (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, pentaerythritol (meth) tetraacrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate And isocyanuric acid EO-modified tri (meth) acrylate.
These (meth) acrylate monomers may have a part of the molecular skeleton modified, and have been modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol and the like. Things can also be used.
These (meth) acrylic monomers may be used alone or in combination of two or more. These (meth) acrylic monomers satisfy the range of the refractive index as described later and have excellent curing reactivity, and can improve the hardness of the obtained low refractive index layer.

The (meth) acrylic monomer preferably has a refractive index of 1.47 to 1.53. It is practically impossible to reduce the refractive index to less than 1.47, and if it exceeds 1.53, it may not be possible to obtain a UV-curable resin layer having a sufficiently low refractive index. This is because there is a possibility that a problem may occur when is used as a window.

Further, the (meth) acrylic monomer preferably has a weight average molecular weight of 250 to 1,000. If it is less than 250, the number of functional groups is reduced, and the hardness of the obtained ultraviolet curable resin layer may be reduced. When it exceeds 1,000, the functional group equivalent (the number of functional groups / molecular weight) generally becomes small, so that the crosslinking density becomes low and the hardness of the ultraviolet curable resin layer may become insufficient.
The weight average molecular weight of the (meth) acrylic monomer can be determined by gel permeation chromatography (GPC) in terms of polystyrene. As a solvent for the GPC mobile phase, tetrahydrofuran or chloroform can be used. The measurement column may be used in combination with a commercially available column for tetrahydrofuran or chloroform. Examples of the commercially available columns include Shodex GPC KF-801 and GPC-KF800D (both are trade names, manufactured by Showa Denko KK). As the detector, an RI (differential refractive index) detector and a UV detector may be used. Using such a solvent, column, and detector, the weight-average molecular weight can be appropriately measured by, for example, a GPC system such as Shodex GPC-101 (manufactured by Showa Denko KK).

In addition to the (meth) acrylic resin, the ultraviolet curable resin includes a curing agent for curing other resin components such as a fluorine atom-containing resin and a reactive group, and various additives for improving coating properties. Agents and solvents can be used as appropriate.

When the intermediate layer (30) is an adhesive layer or a resin layer, the upper limit of the thickness of the intermediate layer (30) is preferably 5 μm. If it exceeds 5 μm, the distance between the transparent conductive layers (12) and (62) becomes long, and the distance is applied to the first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50). This is because a high voltage (100 V or more) is required for driving the liquid crystal material because the electric field is low.

Further, as shown in FIGS. 2A to 2C, the intermediate layer (30) in the design material (200) of the present invention has an intermediate support having a pair of transparent conductive layers (42a) and (42b). (40).
Since the intermediate layer (30) has the intermediate support (40) having the pair of transparent conductive layers (42a) and (42b), the multilayer polymer-dispersed liquid crystal element (100) can have the first outer side. The first polymer / liquid crystal composite layer (20) is energized by the support (10) and the intermediate support (40), and the second polymer / liquid crystal composite layer (20) is energized by the second outer support (60) and the intermediate support (40). The molecular / liquid crystal composite layer (50) may be energized.
Therefore, the design material (200) of the present invention determines whether or not an electric field is applied and / or voltage with respect to the first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50). It can be changed and energized. Therefore, the presence or absence of application of an electric field to each of the first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50) is switched to (A) the first polymer / liquid crystal composite layer (20). ) ON: second polymer / liquid crystal composite layer (50) ON, (B) first polymer / liquid crystal composite layer (20) ON: second polymer / liquid crystal composite layer (50) OFF, (C) First polymer / liquid crystal composite layer (20) OFF: second polymer / liquid crystal composite layer (50) ON, (D) First polymer / liquid crystal composite layer (20) OFF: second polymer / liquid crystal The composite layer (50) can be turned off and four patterns can be controlled. For example, when all of the polymer / liquid crystal composite layers used in the design material of the present invention are in the normal mode, the design material of the present invention is applied to one surface near the first polymer / liquid crystal composite layer (20). According to observation, in the case of (A), the first and second polymer / liquid crystal composite layers (20) and (50) are in a low haze state and are colorless and transparent or in a state close to this. In the case of (B), only the second polymer / liquid crystal composite layer is in a high haze state, and the color of the second polymer / liquid crystal composite layer (50) is observed. In the cases (C) and (D), the first polymer / liquid crystal composite layer (20) is in a high haze state, and the color of the first polymer / liquid crystal composite layer (20) is observed.
Further, by changing the voltage applied to the first and second polymer / liquid crystal composite layers (20) and (50), the haze state can be continuously controlled from the low haze state to the high haze state. It is also possible to control. In this case, by changing the voltage applied to each of the first and second polymer / liquid crystal composite layers (20) and (50), the color density of the first polymer / liquid crystal composite layer (20) is changed. The color density of the second polymer / liquid crystal composite layer (50) can be controlled in each of the polymer / liquid crystal composite layers. For example, by controlling the first polymer / liquid crystal composite layer (20) (red) and the second polymer / liquid crystal composite layer (50) (blue) to an intermediate haze state, an intermediate color purple is developed. Can be done. Therefore, the color variation of the design material of the present invention can be increased.

The transparent conductive layer (42a) applies an electric field to the first polymer / liquid crystal composite layer (20) by being electrically connected to the transparent conductive layer (12) in the first outer support (10). This is a layer that functions as an electrode for driving the liquid crystal material included in the first polymer / liquid crystal composite layer (20). The transparent conductive layer (42b) applies an electric field to the second polymer / liquid crystal composite layer (50) by being electrically connected to the transparent conductive layer (62) in the second outer support (60), This is a layer that functions as an electrode for driving the liquid crystal material included in the second polymer / liquid crystal composite layer (50).
The transparent conductive layers (42a) and (42b) can use the same transparent conductive material as the transparent conductive layers (12) and (62) described above.

As shown in FIGS. 2A and 2B, the intermediate support (40) includes a first intermediate support (40a) and a second intermediate support (40b) each including an air layer, an adhesive layer, The first intermediate support (40a) and the second intermediate support (40b) are laminated via at least one selected from the group consisting of resin layers, and each of the first intermediate support (40a) and the second intermediate support (40b) is a substrate (41a). , (41b) and the transparent conductive layers (42a), (42b).
In this case, in the laminated polymer dispersed liquid crystal element (100), the first polymer / liquid crystal composite layer (20) is energized by the first outer support (10) and the first intermediate support (40a). The second polymer / liquid crystal composite layer (50) is energized by the second outer support (60) and the second intermediate support (40b).
In this case, the intermediate support (40) has a pair of transparent conductive layers (42a) and (42b) by the pair of first and second intermediate supports (40a) and (40b). .

When the pair of first and second intermediate supports (40a) and (40b) in the intermediate support (40) are laminated via an air layer, a pair of first intermediate supports is provided using a spacer. The distance between the body (40a) and the second intermediate support (40b) can be maintained. It is preferable that the bases (41a) and (41b) of the pair of first and second intermediate supports (40a) and (40b) are laminated so as to face each other.
Further, as the spacer, a spacer used in the polymer / liquid crystal composite layers (20) and (50) can be used. For example, a resin made of a resin having high light transmittance such as plastic beads can be used. The form of the spacer is not particularly limited, and may be spherical or another shape.
When a pair of first and second intermediate supports (40a) and (40b) are laminated via an air layer, the thickness of the air layer is the first polymer / liquid crystal composite layer (20). From the viewpoint of individually controlling the presence / absence of electric field application to the second polymer / liquid crystal composite layer (50), the thickness is preferably 3 to 20 μm, and more preferably 5 to 10 μm. If the upper limit is more than 20 μm, the thickness of the design material becomes thicker, and if it is lower than the lower limit of 3 μm, the first and second intermediate supports (40a) and (40b) are partially stuck to each other, resulting in spot-like unevenness. This is because there is a possibility of doing so.

When the pair of first and second intermediate supports (40a) and (40b) of the intermediate support (40) are laminated via an adhesive layer or a resin layer, the above-described intermediate layer (30) is used. ) Can be used. It is preferable that the bases (41a) and (41b) of the pair of first and second intermediate supports (40a) and (40b) are laminated so as to face each other.

When the pair of first and second intermediate supports (40a) and (40b) are laminated via an adhesive layer, the thickness of the adhesive layer is the first polymer / liquid crystal composite layer (20). From the viewpoint of individually controlling the presence or absence of electric field application to the second polymer / liquid crystal composite layer (50), the thickness is preferably 5 to 20 μm, and more preferably 5 to 10 μm. If the upper limit is more than 20 μm, the thickness of the design material is too thick, and if it is less than the lower limit of 3 μm, there is a possibility that a problem that adhesion reliability is lowered may occur.

When the pair of first and second intermediate supports (40a) and (40b) are laminated via a resin layer, the thickness of the resin layer is the first polymer / liquid crystal composite layer (20). From the viewpoint of individually controlling the presence / absence of electric field application to the second polymer / liquid crystal composite layer (50), the thickness is preferably 3 to 20 μm, and more preferably 5 to 10 μm. If the upper limit is more than 20 μm, the thickness of the design material is too thick, and if it is less than the lower limit of 3 μm, it may be difficult to keep the film thickness uniform.

Further, as shown in FIG. 2C, the pair of transparent conductive layers (42a) and (42b) of the intermediate support (40) can be laminated via the intermediate base material (43). .
The intermediate substrate (43) is not particularly limited, but a transparent film material can be suitably used. The above-mentioned transparent film has the above-mentioned flexibility, which can be suitably used as the base material (11) or (61) in the first outer support (10) and the second outer support (60). A transparent film material can be used.
When the pair of transparent conductive layers (42a) and (42b) are laminated via the intermediate base material (43), the thickness of the intermediate base material (43) is equal to the thickness of the first polymer / liquid crystal composite layer (20). ) And the second polymer / liquid crystal composite layer (50), from the viewpoint of individually controlling the presence or absence of application of an electric field, the thickness is preferably 25 to 100 μm, and more preferably 38 to 50 μm. If the upper limit is more than 100 μm, the thickness of the design material becomes thicker, and if it is less than the lower limit of 25 μm, wrinkles are generated due to heat when forming the transparent conductive layers (42a) and (42b), and the transparent conductive layer having uniform performance Is sometimes difficult to form.

As shown in FIG. 3, the intermediate layer (30) in the design material (200) of the present invention includes at least one intermediate polymer / liquid crystal composite layer (70) and at least two intermediate supports (40). And the intermediate support (40) is laminated on both sides of the intermediate polymer / liquid crystal composite layer (70), and the intermediate polymer / liquid crystal composite layer (70) is disposed on both sides. Electricity can be supplied by the two intermediate supports (40).
In this case, two intermediate supports (40) are arranged on both surfaces of the intermediate layer (30).
When the intermediate layer (30) has the above configuration, the intermediate polymer / liquid crystal composite layer (70) is energized by at least two intermediate supports (40) in the intermediate layer (30). it can.
Therefore, the design material (200) of the present invention is different from the first polymer / liquid crystal composite layer (20), the second polymer / liquid crystal composite layer (50) and the intermediate polymer / liquid crystal composite layer (70). The current can be supplied by changing the presence or absence of an electric field and / or the voltage. Therefore, the electric field application to each of the first polymer / liquid crystal composite layer (20), the intermediate polymer / liquid crystal composite layer (70), and the second polymer / liquid crystal composite layer (50) is switched, and six patterns are formed. Can be controlled.

For example, when all of the polymer / liquid crystal composite layers used in the design material (200) of the present invention are in the normal mode, one of the polymer / liquid crystal composite layers closer to the first polymer / liquid crystal composite layer (20) of the design material (200). When the first, middle and second polymer / liquid crystal composite layers (20), (70) and (50) are in a low haze state, they are observed as a colorless and transparent state or a state close thereto. . When the first and intermediate polymer / liquid crystal composite layers (20) and (70) are in a low haze state and the second polymer / liquid crystal composite layer (50) is in a high haze state, the second polymer / liquid crystal composite layer (50) is in a high haze state. The color of the liquid crystal composite layer (50) is observed. Next, when the first polymer / liquid crystal composite layer (20) is in a low haze state and the intermediate polymer / liquid crystal composite layer (70) is in a high haze state, the intermediate polymer / liquid crystal composite layer (70) Color is observed. Next, when the first polymer / liquid crystal composite layer (20) is in a high haze state, the color of the first polymer / liquid crystal composite layer (20) is observed.

Further, by changing the voltage applied to the first, intermediate and second polymer / liquid crystal composite layers (20), (70) and (50), it is possible to continuously control from a low haze state to a high haze state. Therefore, it is also possible to control the color shading. In this case, by changing the voltage applied to each of the first, intermediate and second polymer / liquid crystal composite layers (20), (70) and (50), the respective polymer / liquid crystal composite layers (20 ), (70) and (50) can be controlled.
For example, in the design material (200) of the present invention, the color of the first polymer / liquid crystal composite layer (20) is red, the color of the intermediate polymer / liquid crystal composite layer (70) is green, and the second polymer When the color of the liquid crystal / liquid crystal composite layer (50) is blue, the design material (200) is controlled by controlling whether or not an electric field is applied to each of the polymer / liquid crystal composite layers (20), (70), and (50). ) Are observed as a colorless or transparent state or a state close thereto, a red state, a green state, and a blue state. The presence / absence of an electric field applied to each of the polymer / liquid crystal composite layers (20), (70), and (50) and the voltage are determined. By controlling, it becomes possible to express intermediate colors of red, green, and blue, and various colors can be expressed.
Therefore, the color variation of the design material of the present invention can be further increased. Therefore, the design of the design materials such as windows and partitions in buildings and vehicles can be further improved.

By the way, a sealing material may be provided on the periphery of the laminated polymer dispersed liquid crystal element (100) in the design material (200) of the present invention. In particular, by providing a sealing material so as to cover the periphery of the polymer / liquid crystal composite layers (20), (50) and (70), the polymer / liquid crystal composite layers (20), (50) and (70) are provided. ) Can be prevented from leaking out. For this reason, the encapsulant is obtained by observing the laminated polymer dispersed liquid crystal device 100 from the normal direction to the plate surface, that is, in a plan view, the polymer / liquid crystal composite layers (20), (50), It is preferable to have a shape surrounding (70).
As the material of the sealing material, for example, the same resin as the polymer constituting the polymer matrix of the polymer / liquid crystal composite layers (20), (50), and (70) can be used.

Moreover, it is preferable that the laminated polymer dispersion type liquid crystal element (100) used for the design material (200) of the present invention has an ultraviolet shielding layer. This is because the provision of the ultraviolet shielding layer can prevent yellowing due to sunlight and / or certification, an increase in haze in a transparent state, and drive failure of the liquid crystal material. It is preferable that the above-mentioned ultraviolet shielding layer is used by arranging it in a direction in which ultraviolet irradiation is strong (for example, when applied to windows of buildings and vehicles, etc.).

The ultraviolet shielding layer is a layer having a function of imparting light resistance.
The above-mentioned ultraviolet shielding layer comprises a composition for an ultraviolet shielding layer containing a light resistant agent, a curable resin, a solvent, and the like, for a laminated polymer-dispersed liquid crystal element (100) used in the design material (200) of the present invention. It is formed by coating on an arbitrary surface and curing by heat treatment or irradiation with ionizing radiation or the like.

Examples of the light stabilizer include an ultraviolet absorber and a light stabilizer.
The ultraviolet absorber absorbs harmful ultraviolet rays and can improve light resistance over a long period of time.
In addition, the light stabilizer itself hardly absorbs ultraviolet light, but can improve light fastness by efficiently capturing harmful free radicals generated by ultraviolet light.

Examples of the ultraviolet absorber include inorganic ultraviolet absorbers such as titanium dioxide, cerium oxide, zinc oxide, and iron oxide, and organic ultraviolet absorbers such as benzotriazole, triazine, and benzophenone. . Above all, a triazine-based ultraviolet absorber is preferred from the viewpoint of suitably imparting light resistance to the design material.

As the triazine-based UV absorber, a hydroxyphenyltriazine-based UV absorber is more preferable. Examples of the hydroxyphenyltriazine-based ultraviolet absorber include 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5. -Triazine, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine , 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- Tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy 3- (2'-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine preferred. These can be used alone or in combination of two or more.

The content of the ultraviolet absorber is preferably 0.1 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, and 0.3 to 1.5 parts by mass with respect to 100 parts by mass of a curable resin described later. Parts are more preferred.
When the content of the ultraviolet absorbent is within the above range, the absorbent does not bleed out and a sufficient ultraviolet absorbing ability can be obtained, so that excellent light resistance can be obtained.

Examples of the light stabilizer include a hindered amine light stabilizer (HALS).
The hindered amine light stabilizer is preferably a hindered amine light stabilizer having a reactive functional group.
The reactive functional group is not particularly limited as long as it has reactivity with an ionizing radiation-curable resin or the like, and has, for example, an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group. Functional groups and the like are preferred, and at least one selected from these is preferred. Among them, a (meth) acryloyl group is preferred.
Such hindered amine light stabilizers having a reactive functional group include 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, bis (1,2,2,6,6-pentamethyl- 4-piperidyl) sebacate, bis (2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2, 2,6,6-pentamethyl-4-piperidinyl) sebacate, 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine) and the like are preferred.

The content of the light stabilizer is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass, and still more preferably 3 to 6 parts by mass with respect to 100 parts by mass of the curable resin.
When the content of the light stabilizer is within the above range, the light stabilizer does not bleed out and sufficient light stability can be obtained, so that excellent light resistance can be obtained.

The ultraviolet shielding layer preferably contains a curable resin.
Preferred examples of the curable resin include a thermosetting resin and an ionizing radiation-curable resin. Above all, ionizing radiation-curable resins are preferred from the viewpoint of imparting hard coat properties.
In this specification, “resin” is a concept that also includes resin components such as monomers and oligomers.

Preferred examples of the thermosetting resin include thermosetting resins such as polyester resin, epoxy resin, polyurethane resin, aminoalkyd resin, melamine resin, guanamine resin, urea resin, and thermosetting acrylic resin.

The ionizing radiation-curable resin is a resin composition that cures when irradiated with ionizing radiation. As the ionizing radiation, among electromagnetic waves or charged particle beams, those having an energy quantum capable of polymerizing or cross-linking molecules, for example, ultraviolet (UV) or electron beam (EB), X-rays, γ-rays, etc. Charged particles such as electromagnetic waves, α-rays and ion beams.

As the ionizing radiation-curable resin, can be appropriately selected from polymerizable oligomers and prepolymers conventionally used as resins having ionizing radiation-curable, and from the viewpoint of obtaining good curing characteristics, It is preferable that the resin does not easily bleed out, has applicability even when the solid content is about 95 to 100%, and hardly causes curing shrinkage when cured.

Examples of the polymerizable oligomer or prepolymer include oligomers and prepolymers having a radical polymerizable unsaturated group in the molecule, such as epoxy (meth) acrylate, urethane (meth) acrylate, and polyether urethane (meth) acrylate. And caprolactone urethane (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate oligomers and prepolymers. Of these, urethane (meth) acrylates are more preferred. Among these oligomers and prepolymers, polyfunctional polymerizable oligomers are preferable, and the number of functional groups is preferably 2 to 15 from the viewpoint of imparting a hard coat property with a high crosslinking density, and from the viewpoint of hardly causing curing shrinkage, 2-8 are more preferred, and 2-6 are even more preferred.
In addition, in this specification, (meth) acrylate means acrylate or methacrylate.

The ionizing radiation-curable resin includes, in addition to the polyfunctional polymerizable oligomer, a caprolactone-based urethane (meth) acrylate obtained by reacting a caprolactone-based polyol with an organic isocyanate and hydroxy (meth) acrylate, and a polybutadiene oligomer. Highly hydrophobic urethane (meth) acrylates such as polybutadiene (meth) acrylate having a (meth) acrylate group in the side chain can be mixed, and the light resistance can be further improved by mixing. Can be.
Of these, caprolactone-based urethane (meth) acrylate is preferred from the viewpoint of improving light resistance.
Further, in the present invention, mixing the above-mentioned polyfunctional polymerizable oligomers, in particular, a polyfunctional urethane (meth) acrylate and a caprolactone-based urethane (meth) acrylate, improves light resistance and hard coat property. In addition, it is preferable from the viewpoint of hardening shrinkage.

When using the ionizing radiation-curable resin, it is preferable to add about 0.1 to 5 parts by mass of a photopolymerization initiator to 100 parts by mass of the curable resin.
The photopolymerization initiator can be appropriately selected from commonly used photopolymerization initiators.

For the purpose of adjusting the viscosity of the curable resin and the like, a diluent such as a monofunctional (meth) acrylate such as methyl (meth) acrylate can be appropriately mixed as long as the object of the present invention is not impaired. .
One of the above monofunctional (meth) acrylates may be used alone, or two or more kinds may be used in combination, or a low molecular weight polyfunctional (meth) acrylate may be mixed.
As the diluent, in addition to the above monofunctional (meth) acrylate, an ordinary solvent may be used to ensure the coatability of the curable resin.

Examples of the solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol, diacetone alcohol), ketones (eg, acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclopentanone, cyclohexanone, heptanone, diisobutyl ketone, diethyl ketone, diacetone alcohol), ester (methyl acetate, ethyl acetate, butyl acetate, n-propyl acetate, isopropyl acetate, methyl formate, PGMEA) aliphatic Hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), Amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy-2-propanol), carbonate (dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate).
These solvents may be used alone or in combination of two or more.

The ultraviolet shielding layer can contain various additives within a range that does not hinder its performance.
Examples of the various additives include, for example, a polymerization inhibitor, a crosslinking agent, a scratch-resistant filler, an antistatic agent, an adhesion improver, an antioxidant, an antifouling agent, a leveling agent, a thixotropic agent, a coupling agent, and a plasticizer. , An antifoaming agent, a filler and the like.

As the thickness of the ultraviolet shielding layer, the thickness after curing is preferably from 1 to 20 μm, more preferably from 2 to 10 μm, and still more preferably from 3 to 6 μm, from the viewpoint of imparting excellent light resistance and transparency. It is more preferred that there be.
Further, by making the thickness of the ultraviolet shielding layer thinner, the occurrence of curing shrinkage can be reduced, and from the viewpoint that production stability and production efficiency can be improved, the thickness after curing is 2 to 4 μm. Is particularly preferred.

When the design material (200) of the present invention is used in the reverse mode, the first and second polymer / liquid crystal composite layers (20) and (50) are composed of the respective polymer / liquid crystal composite layers (20) and (20). 50) At least one of the surfaces has an alignment film. The first and second polymer / liquid crystal composite layers (20) and (50) are on the side facing the first outer support (10) and on the side facing the second outer support (60). It is preferable to have an alignment film on the side to be formed.
When the laminated polymer-dispersed liquid crystal element (100) in the design material (200) of the present invention has an intermediate polymer / liquid crystal composite layer (70), at least one of the surfaces has an alignment film. Having.
The alignment film has a function (alignment regulating force) of arranging (aligning) the liquid crystal material in the polymer / liquid crystal composite layers (20), (50), and (70) facing the alignment film in a predetermined direction.

The alignment film is not particularly limited. For example, various vertical alignment films applied to a VA liquid crystal display device or the like can be used, and for example, an alignment film formed of a polyimide alignment film, an LB film, or the like can be used. .

More specifically, as the vertical alignment film, for example, lecithin, silane-based surfactant, titanate-based surfactant, pyridinium salt-based polymer surfactant, silane coupling-based vertical alignment such as n-octadecyltriethoxysilane Film-forming compositions, such as soluble polyimides having long-chain alkyl groups and alicyclic structures in the side chains, and polyimide-based vertical alignment film compositions such as polyamic acids having long-chain alkyl groups and alicyclic structures in the side chains. It can be formed using a material. As the vertical alignment film composition, a polyimide vertical alignment film composition “JALS-2021” or “JALS-204” manufactured by JSR Corporation and “RN-1517” manufactured by Nissan Chemical Industries, Ltd. , "SE-1211" and "EXPOA-018".

As the solvent used in the alignment film composition, a solvent that can be used in the composition for the ultraviolet shielding layer can be appropriately selected and used.

When the alignment film composition contains a light stabilizer, the obtained alignment film can be used as an ultraviolet shielding layer.
As the light stabilizer, a light stabilizer that can be used in the above-described ultraviolet shielding composition can be appropriately selected and used.
The light-resistant agent is preferably 0.1 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, and still more preferably 0.3 to 1.5 parts by mass, based on 100 parts by mass of the composition for an alignment film. .

The thickness of the alignment film is not particularly limited, but is preferably, for example, in the range of 0.1 μm to 2.0 μm, and more preferably in the range of 0.2 μm to 1.0 μm.

Further, the present invention provides a method for manufacturing a laminated polymer-dispersed liquid crystal element (100) used for a design material (200), comprising a first outer support (10), a first polymer / liquid crystal composite layer (20). And a first polymer-dispersed liquid crystal element (80) having a coating layer in this order, a second outer support (60), a second polymer / liquid crystal composite layer (50) and a coating layer in this order. Using the second polymer-dispersed liquid crystal element (90), the first outer support (10) and the second outer support (60) are arranged such that the first outer support (10) and the second outer support (60) are arranged on both sides. The first and second outer supports (10) and (60) include a laminating step in which a polymer dispersed liquid crystal element (80) and a second polymer dispersed liquid crystal element (90) are laminated. In each case, the base material (11), (61) and the transparent conductive layer (12), (62) are laminated, The present invention also provides a method for manufacturing a laminated polymer-dispersed liquid crystal device, wherein at least one of the polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50) has a dichroic dye. This is one of the inventions.

With this configuration, the first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer are formed by the first outer support (10) and the second outer support (60). A multilayer polymer dispersion type liquid crystal element (100) having a configuration in which (50) is energized can be manufactured. The substrates (11) and (61) in the first and second outer supports are both arranged so as to be disposed on the outermost surface of the multilayer polymer dispersion type liquid crystal element (100). Preferably, the second outer supports (10), (60) are laminated.

Before the lamination step, a coating layer peeling step of peeling the coating layers of the first polymer dispersed liquid crystal element (80) and the second polymer dispersed liquid crystal element (90) may be provided.
By having the coating layer peeling step, it is possible to manufacture the laminated polymer-dispersed liquid crystal layer (100) having a small thickness.
In the case where the first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50) are directly laminated with a coating layer peeling step, a lamination method can be used.

In the laminating step, the first polymer-dispersed liquid crystal element and the second polymer-dispersed liquid crystal element may be stacked via an intermediate base having transparent conductive layers on both surfaces. it can.

The present invention also relates to a method for producing a multilayer polymer dispersion type liquid crystal element (100) used for a design material whose transmittance of light can be changed by energization, comprising: a first outer support (10); A first polymer-dispersed liquid crystal element (80) having one polymer / liquid crystal composite layer (20) and a first intermediate support (40a) in this order, and a second outer support (60) , A second polymer / liquid crystal composite layer (50), and a second polymer-dispersed liquid crystal element (90) having a second intermediate support (40a) in this order. The first polymer-dispersed liquid crystal element (80) and the second polymer-dispersed liquid crystal element (so that the support (10) and the second outer support (61) are arranged on both sides. 90) and a first outer support (10), a first intermediate support (40a), Each of the second outer support (60) and the second outer support (40b) includes the base material (11), (41a), (61), (41b) and the transparent conductive layer (12), (42a). , (61) and (42b) are laminated, and at least one of the first polymer / liquid crystal composite layer (20) and the second polymer / liquid crystal composite layer (50) contains a dichroic dye. The present invention also provides a method for manufacturing a laminated polymer-dispersed liquid crystal element, characterized by having the above.

In the laminating step, the first polymer dispersed liquid crystal element (80) and the second polymer dispersed liquid crystal element (90) can be laminated using an adhesive and / or a curable resin.
In the case where the first polymer-dispersed liquid crystal element (80) and the second polymer-dispersed liquid crystal element (90) each have a pair of transparent conductive layers, in the above-described laminating step, air is used by using a spacer. The first polymer-dispersed liquid crystal element (80) and the second polymer-dispersed liquid crystal element (90) can be laminated via the layers.

In the manufacturing method of the multilayer polymer dispersion type liquid crystal element (100) of the present invention, the same material as the material used in the design material (200) can be used.

The application of an electric field to the design material (200) of the present invention and the liquid crystal element (100) obtained by the method of manufacturing the multilayer polymer dispersion type liquid crystal element (100) is performed by a conductive wire from an external power supply. Is applied to the transparent conductive layers (12), (42a), (42b), and (62) of the liquid crystal display device (100), so that the polymer / liquid crystal composite layers (20), (50), An electric field is applied to 70). By applying the electric field in this manner, the alignment state of the liquid crystal molecules in the polymer / liquid crystal composite layers (20), (50), and (70) is switched, so that the low haze state and the high haze state can be switched. it can.

Hereinafter, the present invention will be described more specifically with reference to Examples of the present invention. However, the present invention is not limited to the following Examples.

<Preparation of liquid crystal mixed material 1>
A liquid crystal mixed material 1 was prepared by mixing 50 parts by mass of a nematic liquid crystal material having no polymerizable group, 47.5 parts by mass of isobornyl acrylate, and 2.5 parts by mass of Irgacure 651 manufactured by BASF as a photopolymerization initiator. did.

<Preparation of liquid crystal mixed material 2>
50 parts by mass of a nematic liquid crystal material having no polymerizable group, 47.5 parts by mass of isobornyl acrylate, 2.5 parts by mass of Irgacure 651 manufactured by BASF as a photopolymerization initiator, and a dichroic dye (Mitsui Chemicals, Inc.) A liquid crystal mixed material 2 was prepared by mixing 0.5 parts by mass of black (manufactured by Fine Inc.).

(Examples 1 and 2)
<Preparation of polymer dispersed liquid crystal element 1>
Beads are placed on a 51 μm-thick transparent electrode substrate (corresponding to the first or second outer support) in which an ITO film (transparent conductive layer) having a sheet resistance of 150 Ω / □ is formed on a 50 μm-thick PET film substrate. A spacer (manufactured by Sekisui Chemical Co., Ltd._Micropearl SP216) is sprayed, the liquid crystal mixed material 1 is dropped, and after lamination with another transparent electrode substrate, ultraviolet light is applied at an intensity of 1.0 mW / cm ² for 10 minutes. To cure the liquid crystal mixed material layer to produce a polymer dispersed liquid crystal element 1 (containing no dichroic dye) having a pair of transparent electrode substrates. The thickness of the liquid crystal mixed material layer (corresponding to the polymer / liquid crystal composite layer) in the obtained polymer dispersed liquid crystal element 1 was 16 μm.
<Preparation of polymer dispersed liquid crystal element 2>
Except for dropping the liquid crystal mixture material 2 instead of the liquid crystal mixture material 1, the polymer dispersion type liquid crystal element 2 having a pair of transparent electrode base materials (dichroic Including a dye). The thickness of the liquid crystal mixed material layer (corresponding to the polymer / liquid crystal composite layer) in the obtained polymer dispersed liquid crystal element 2 was 16 μm.

Next, a heat-welding type spacer (Micropearl_SP-205 manufactured by Sekisui Chemical Co., Ltd., having a diameter of 5 μm) was sprayed on the obtained polymer-dispersed liquid crystal element 1, and the obtained polymer-dispersed liquid crystal element 2 was dispersed. Are stacked and heated at 60 ° C. for 60 minutes to fix the polymer-dispersed liquid crystal element 1 and the polymer-dispersed liquid crystal element 2 in a state where the distance between the polymer-dispersed liquid crystal elements 1 and 2 is maintained at 5 μm. A design material 1 having a laminated polymer-dispersed liquid crystal element (corresponding to FIG. 2 (a)) was formed. In addition, the thickness of the air layer of the obtained design material 1 was 5 μm.

Further, an adhesive (SK Dyne manufactured by Soken Chemical Co., Ltd.) was applied to the obtained polymer dispersed liquid crystal element 1 with a thickness of 10 μm, and the obtained polymer dispersed liquid crystal element 2 was laminated on the adhesive. Then, a design material 2 having a laminated polymer-dispersed liquid crystal element 1 (corresponding to FIG. 2B) laminated via an adhesive according to Example 2 was produced.

(Example 3)
A bead spacer is provided on a 51 μm-thick transparent electrode substrate (corresponding to the first or second outer support) in which an ITO film (transparent conductive layer) having a sheet resistance of 150 Ω / □ is formed on a 50 μm-thick PET film substrate. (Sekisui Chemical Co., Ltd._Micropearl SP216) is sprayed, and the liquid crystal mixed material 1 is dropped. An ITO film (transparent conductive layer) having a sheet resistance of 150Ω / □ is provided on both sides of a 50 μm thick intermediate substrate (PET film). The formed intermediate support (51 μm) was laminated. Further, the liquid crystal mixed material 2 was dropped on the intermediate support, and a bead spacer (Micropearl SP216 manufactured by Sekisui Chemical Co., Ltd.) was sprayed on the intermediate support to form a 51 μm-thick transparent electrode base material (first or second outer support). After the lamination, the laminated liquid crystal material layer was cured by irradiating ultraviolet rays at an intensity of 1.0 mW / cm ² for 10 minutes to cure the liquid crystal mixed material layer. A design material 3 having the shape shown in FIG. The thickness of the liquid crystal mixture material layer (polymer / liquid crystal composite layer) formed of the liquid crystal mixture material 1 of the obtained design material 3 is 16 μm, and the thickness of the liquid crystal mixture material layer (polymer / liquid crystal mixture) formed of the liquid crystal mixture material 2 is large. The thickness of the liquid crystal composite layer) was 16 μm.

(Examples 4 to 6)
<Preparation of polymer dispersed liquid crystal element 3>
A bead spacer is provided on a 51 μm-thick transparent electrode substrate (corresponding to the first or second outer support) in which an ITO film (transparent conductive layer) having a sheet resistance of 150 Ω / □ is formed on a 50 μm-thick PET film substrate. (Sekisui Chemical Co., Ltd._Micropearl SP216) was sprayed, the liquid crystal mixed material 1 was dropped, a 50 μm-thick coated PET film was laminated, and after laminating, ultraviolet rays were applied at an intensity of 1.0 mW / cm ² for 10 minutes. Irradiation was performed to cure the liquid crystal mixed material layer, thereby producing a polymer dispersed liquid crystal element 3. The thickness of the liquid crystal mixed material layer (corresponding to the polymer / liquid crystal composite layer) in the obtained polymer dispersed liquid crystal element 3 was 5 μm.
<Preparation of polymer dispersed liquid crystal element 4>
A polymer dispersed liquid crystal element 4 (including a dichroic dye) was produced in the same manner as in the production of the polymer dispersed liquid crystal element 3 except that the liquid crystal mixed material 2 was dropped instead of the liquid crystal mixed material 1. The thickness of the liquid crystal mixed material layer (corresponding to the polymer / liquid crystal composite layer) in the obtained polymer dispersed liquid crystal element 4 was 5 μm.

The coated PET films of the obtained polymer-dispersed liquid crystal elements 3 and 4 are peeled off, and an adhesive (_SK Dyne manufactured by Soken Chemical Co., Ltd.) is applied on the liquid crystal mixed material layer of the polymer-dispersed liquid crystal element 3 after peeling. The polymer-dispersed liquid crystal element 4 coated at 5 μm and the coated PET film was peeled off on the adhesive was laminated so that the transparent electrode substrate was disposed outside, and the two-layer liquid crystal mixing according to Example 4 was performed. A design material 4 having a laminated polymer-dispersed liquid crystal element 4 (corresponding to FIG. 1B) laminated via a material layer (corresponding to a polymer / liquid crystal composite layer) adhesive layer was produced.

The coated PET films in the obtained polymer-dispersed liquid crystal elements 3 and 4 were peeled off, and 95 parts by mass of isobornyl acrylate and photopolymerization were started on the liquid crystal mixed material layer in the polymer-dispersed liquid crystal element 3 after peeling. An ultraviolet curable resin solution mixed with 5 parts by mass of Irgacure 651 manufactured by BASF was dropped as an agent, and the polymer dispersed liquid crystal element 4 from which the coated PET film was peeled was further placed so that the transparent electrode substrate was placed outside. Then, after lamination, an ultraviolet ray was irradiated at an intensity of 1.0 mW / cm ² for 10 minutes to cure the ultraviolet curable resin layer, and a two-layer liquid crystal mixed material layer (polymer / liquid crystal) according to Example 5. A design material 5 having a laminated polymer-dispersed liquid crystal element 5 (corresponding to FIG. 1C) in which a composite layer (corresponding to a composite layer) was laminated via an ultraviolet curable resin layer was produced. The thickness of the ultraviolet-curable resin layer of the obtained design material was 5 μm.

The coated PET films in the obtained polymer-dispersed liquid crystal elements 3 and 4 were peeled off, and the polymer-dispersed liquid crystal in which the coated PET film was peeled was placed on the liquid crystal mixed material layer in the polymer-dispersed liquid crystal element 3 after peeling. The polymer-dispersed liquid crystal elements 3 and 4 are laminated and laminated so that the liquid crystal mixed material layer in the element 4 is arranged, and the two liquid crystal mixed material layers (the polymer / liquid crystal composite layer) according to Example 6 are laminated. A design material 6 having a laminated polymer-dispersed liquid crystal element 6 (corresponding to FIG. 1A) on which the corresponding liquid crystal was directly laminated was prepared.

With respect to the obtained design materials 1 to 6, visibility evaluation with or without application of an electric field was performed from both sides of one surface and the other surface. As a result, in any of the design materials, in the high haze state, a cloudy color was observed on the surface near the polymer / liquid crystal composite layer containing no dichroic dye, and the dichroic dye (black) was observed. Black was observed on the surface near the polymer / liquid crystal composite layer included.
In the low haze state of the obtained design materials 1 to 6, a colorless and transparent state or a state close to this was observed.
Next, the obtained design materials 1 to 3 have a low haze state on one side and a low haze state on the other side because the two polymer / liquid crystal composite layers in the stacked polymer dispersion type liquid crystal elements 1 to 3 can be separately controlled. In the case of the high haze state, the color of the high haze state could be observed from both sides of one surface and the other surface. All of these were excellent in transparency and concealing property, were in harmony with the appearance assumed to be installed as a design material, and were not unnatural when viewed comprehensively.

ADVANTAGE OF THE INVENTION According to this invention, since it has the predetermined structure provided with the polymer / liquid crystal composite layer and the ultraviolet-ray shielding layer, it is excellent in light resistance, windows and wall materials of buildings, windows of vehicles such as automobiles, trains and airplanes, and the like. In addition, it is possible to provide a design material suitable for a partition or the like of an office or an exhibition hall.

Reference Signs List 10 first outer support 11 base 12 transparent conductive layer 20 first polymer / liquid crystal composite layer 30 intermediate layer 40 intermediate support 40a first intermediate support 40b second intermediate support 41a, 41b base 42a, 42b Transparent conductive layer 43 Intermediate substrate 50 Second polymer / liquid crystal composite layer 60 Second outer support 61 Substrate 62 Transparent conductive layer 70 Intermediate polymer / liquid crystal composite layer 80 First polymer dispersion type Liquid crystal element 90 Second polymer dispersed liquid crystal element 100 Stacked polymer dispersed liquid crystal element 200 Design material

Claims (13)

A design material whose light transmittance can be changed by energizing,
It has a laminated polymer-dispersed liquid crystal element in which a first outer support, a first polymer / liquid crystal composite layer, a second polymer / liquid crystal composite layer, and a second outer support are laminated in this order. ,
The first outer support and the second outer support are both laminated substrates and transparent conductive layers,
A design material, wherein at least one of the first polymer / liquid crystal composite layer and the second polymer / liquid crystal composite layer has a dichroic dye. The design material according to claim 1, further comprising an intermediate layer between the first polymer / liquid crystal composite layer and the second polymer / liquid crystal composite layer. The design material according to claim 2, wherein the intermediate layer is an adhesive layer or a resin layer. The intermediate layer has an intermediate support having a pair of transparent conductive layers,
In the laminated polymer dispersion type liquid crystal element, the first polymer / liquid crystal composite layer is energized by the first outer support and the intermediate support, and the second outer support and the intermediate support provide the second polymer / liquid crystal composite layer. The design material according to claim 2, wherein the polymer / liquid crystal composite layer is energized. The intermediate support has a first intermediate support and a second intermediate support laminated through at least one selected from the group consisting of an air layer, an adhesive layer, and a resin layer,
The first intermediate support and the second intermediate support are all laminated with a substrate and a transparent conductive layer,
In the laminated polymer dispersion type liquid crystal element, the first polymer / liquid crystal composite layer is energized by the first outer support and the first intermediate support, and the second outer support and the second intermediate support are connected to each other. The design material according to claim 4, wherein the second polymer / liquid crystal composite layer is energized by the support. The intermediate layer has at least one intermediate polymer / liquid crystal composite layer and at least two intermediate supports, and is laminated such that the intermediate support is disposed on both sides of the intermediate polymer / liquid crystal composite layer. The design material according to claim 4, wherein the intermediate polymer / liquid crystal composite layer is energized by the intermediate supports disposed on both sides. The design material according to claim 1, 2, 3, 4, 5, or 6, further comprising an ultraviolet shielding layer. The design material according to claim 1, 2, 3, 4, 5, 6, or 7, wherein the first polymer / liquid crystal composite layer and / or the second polymer / liquid crystal composite layer has an alignment film. A method for producing a laminated polymer-dispersed liquid crystal element used for a design material capable of changing light transmittance by energization,
A first polymer-dispersed liquid crystal element having a first outer support, a first polymer / liquid crystal composite layer, and a coating layer in this order;
Using a second outer support, a second polymer / liquid crystal composite layer, and a second polymer-dispersed liquid crystal element having a coating layer in this order,
The first polymer-dispersed liquid crystal element and the second polymer-dispersed liquid crystal element are stacked such that the first outer support and the second outer support are arranged on both sides. Laminating step,
The first outer support and the second outer support are both laminated substrates and transparent conductive layers,
A method for manufacturing a laminated polymer-dispersed liquid crystal device, wherein at least one of the first polymer / liquid crystal composite layer and the second polymer / liquid crystal composite layer has a dichroic dye. The laminated polymer-dispersed liquid crystal according to claim 9, further comprising, before the laminating step, a covering layer peeling step of peeling a covering layer in the first polymer dispersed liquid crystal element and the second polymer dispersed liquid crystal element. Device manufacturing method. A method for producing a laminated polymer-dispersed liquid crystal element used for a design material capable of changing light transmittance by energization,
A first polymer-dispersed liquid crystal element having a first outer support, a first polymer / liquid crystal composite layer, and a first intermediate support in this order;
Using a second outer support, a second polymer / liquid crystal composite layer, and a second polymer dispersion type liquid crystal element having a second intermediate support in this order,
The first polymer-dispersed liquid crystal element and the second polymer-dispersed liquid crystal element are stacked such that the first outer support and the second outer support are arranged on both sides. Laminating step,
The first outer support, the first intermediate support, the second outer support and the second intermediate support are both laminated substrates and transparent conductive layers,
A method for manufacturing a laminated polymer-dispersed liquid crystal device, wherein at least one of the first polymer / liquid crystal composite layer and the second polymer / liquid crystal composite layer has a dichroic dye. The method for producing a laminated polymer-dispersed liquid crystal device according to claim 9, 10 or 11, wherein an adhesive or a curable resin is used in the laminating step. The laminated polymer-dispersed liquid crystal according to claim 11, wherein in the laminating step, the first polymer-dispersed liquid crystal element and the second polymer-dispersed liquid crystal element are laminated via an air layer using a spacer. Device manufacturing method.

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