JP2013148687A - Light control film, and method of manufacturing light control film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel light control film with high flexibility and durability, which enables simple workability and inexpensive supply that have been impossible in a conventional light control film, and can be attached to an existing glass window for a use, and also has a light control function, and a crack prevention function (for crime prevention and disaster prevention), and a method of manufacturing the light control film.SOLUTION: A light control film has a light control layer between a pair of transference electrodes facing each other carried on a base material. The base material is a film base material, and the transference electrodes are combined electrodes that contain metal microparticles and a conductive polymer.

Description

  The present invention relates to a novel light control film. More specifically, the present invention relates to a new light control film whose performance is greatly improved by using a composite electrode containing metal fine particles and a conductive polymer, and The present invention relates to a method for producing a light control film.

  The liquid crystal conventionally used for a display etc. has the outstanding advantage that it can drive with a low voltage. However, many conventional liquid crystals require a polarizing plate, and as the name implies, it is a liquid, and it is necessary to completely seal the liquid so as not to leak.

  Compared to this, the recently developed polymer liquid crystal composite film has the advantage that it is solidified and plastic because it has a physical structure in which liquid crystal is wrapped in a polymer, and therefore it can be easily deformed into a film or the like. In addition, although the driving voltage is slightly high, it is also an advantage that a polarizing plate is not required.

  The polymer liquid crystal composite film has the advantages of low light absorption loss, high light scattering performance, high light utilization efficiency in the entire device, and bright display, and simple device configuration. It is applied to optical shutter applications such as light control glass and segment display applications such as watches.

  For optical shutter applications such as light control glass, the liquid crystal oriented by applying voltage is designed so that the refractive index for polarized light perpendicular to the incident light (referred to as ordinary light refractive index) and the refractive index of the polymer are almost the same. Thus, it shows a transparent state when a voltage is applied. On the other hand, when no voltage is applied, since the average direction of the liquid crystal in the liquid crystal / polymer composite is different for each liquid crystal droplet, the incident light does not coincide with the refractive index of the polymer and the transparency is lost. Thus, a glass whose transparency can be changed by turning on / off the voltage is realized.

  There are several types of polymer liquid crystal used in such a polymer liquid crystal composite film, for example, a type called NCAP (Nematic Curvilinear Aligned Phase) (Patent Document 1), a polymer dispersed liquid crystal (PDLC: A type called Polymer Dispersed Liquid Crystal (Patent Document 2 and Patent Document 3), a type called Polymer Network Liquid Crystal (PNLC) (Patent Document 4), and the like have been proposed.

  The PDLC and PNLC types have so far been mainly applied to optical members such as display elements and optical shutters, but in recent years, as shown in Non-Patent Document 1, a large-area light control film is used. Manufacturing is realized, and unlike the NCAP method, it is easy to manufacture in a uniform state and can be manufactured at low cost.

  In a light control film using this type of polymer liquid crystal composite film, ITO (indium tin oxide) is deposited on the film surface and used as a transparent electrode to drive the polymer liquid crystal (for example, Patent Document 5). , See Patent Document 6). However, since the electrode is ITO and is vulnerable to impact, the durability as a light control film is poor and insufficient. For this reason, although the light control film can be realized on a film basis in a laboratory (as a sample), it can be practically used only in a rigid form protected by glass. In addition, because ITO is used, the material is soaring and depleting (rare earth), film formation in a vacuum process and complicated patterning are necessary, and not only the electrode itself is expensive, but also protects the weakness of ITO. By becoming a glass product, it is very expensive as a light control film, and is very heavy and fragile in applications such as large windows. Therefore, the construction is difficult for ordinary people, and only products that must be installed by professional contractors can be provided to the market. These factors have greatly hindered the spread of light control films.

  Patent Document 7 discloses the use of a counter electrode in which a metal electrode is formed into a thin wire, a lattice, or a mesh on the other side of a single-sided electrode using ITO. According to this patent document, storage stability and weather resistance are disclosed. A dimming element with good properties can be obtained, but the use of an ITO electrode as a single-sided electrode is not sufficient in terms of stretchability and bendability, and a structure containing a conductive resin in the single-sided electrode is disclosed. However, there is still a need for improvement in weather resistance and moisture resistance.

U.S. Pat. No. 4,435,047 US Pat. No. 4,688,900 US Pat. No. 4,834,509 US Pat. No. 5,304,323 JP-A-6-3654 JP 2009-169252 A JP 2011-39283 A

Monthly display March, 2004 issue (P78)

  The present invention has been made in view of the above-described problems and situations, and a solution to that problem is to provide a flexible and highly durable light control film that could not be realized with conventional products. With its performance, it is possible to provide a simple workability and low-priced supply that cannot be realized with conventional light control films, and can be used by sticking to existing glass windows. It is providing the novel light control film which has a prevention function (crime prevention / disaster prevention function), and the manufacturing method of this light control film.

  As a result of studying the above problems, the present inventor has a light control film having a light control layer between a pair of opposed transparent electrodes carried on a base material, the base material being a film base material. In addition, the light control film, which is a composite electrode containing metal fine particles and a conductive polymer, provides a light control film having flexibility and high durability that cannot be realized with conventional products. As a result, the present invention was found.

  That is, the said subject which concerns on this invention is solved by the following means.

  1. A light control film having a light control layer between a pair of opposing transparent electrodes carried on a base material, wherein the base material is a film base material, and the transparent electrode contains fine metal particles and a conductive polymer A light control film characterized by being a composite electrode.

  2. 2. The light control film according to item 1, wherein the light control layer contains a polymer dispersed liquid crystal or a polymer network type liquid crystal.

  3. 3. The light control film according to item 1 or 2, wherein the metal fine particles are metal nanoparticles or metal nanowires.

  4). The light control film according to any one of Items 1 to 3, wherein the transparent electrode has a fine metal wire structure made of fine metal particles.

  5. The light control film according to item 4, wherein the metal fine wire structure is a stripe-like fine wire structure.

  6). 6. The light control film as described in 5 above, wherein the pair of transparent electrodes has a metal fine wire structure which is a stripe fine wire structure, and the stripe fine wire structures of the pair of transparent electrodes are orthogonal to each other. .

  7). The light control film according to any one of Items 1 to 6, wherein the conductive polymer contains poly (3,4-ethylenedioxythiophene).

  8). The light control film according to any one of Items 1 to 6, wherein the conductive polymer is a mixture of poly (3,4-ethylenedioxythiophene) and a nonconductive polymer. .

  9. 9. The light control film according to item 8, wherein the nonconductive polymer is a nonconductive polymer having a hydroxy group.

  10. 9. The light control film as described in 8 above, wherein the non-conductive polymer is a self-dispersing polymer having a dissociable group.

  11. It is a light control film as described in any one of said 1st term-10th, Comprising: This light control film has durability 100 times or more in the bending endurance test of axial radius 3mmR, It is characterized by the above-mentioned. Light control film.

  12 It is a light control film as described in any one of said 1st term-10th item, Comprising: This light control film has the durability of 100 g or more by 0.3 mmR scratch weight evaluation. Light film.

  13. The light control film according to any one of Items 1 to 12, wherein an adhesive layer and a release support are provided on a surface opposite to the surface having the transparent electrode of the substrate. .

  14 14. The light control film according to item 13, wherein the light control film is a long roll-shaped light control film.

  15. It is a manufacturing method of the light control film which manufactures the light control film as described in any one of said 1st term-14th, Comprising: Providing the said transparent electrode and the said light control layer by the apply | coating method or the printing method. The manufacturing method of the light control film characterized.

  16. The method for producing a light control film according to item 15, wherein the method of providing the transparent electrode is an ink jet printing method.

  17. Item 15. The method for producing a light control film according to Item 15, wherein the width of the substrate, the formation width of the transparent electrode, and the formation width of the light control layer satisfy the following relationship.

Substrate width> Transparent electrode formation width> Light control layer formation width18. After the transparent electrode and the light control layer are provided on the base material, the transparent electrode facing the transparent electrode is installed so that the base material width, the formation width of the transparent electrode, and the formation width of the light control layer satisfy the following relationship: 18. The method for producing a light control film according to item 17, characterized in that:

  Substrate width> Transparent electrode formation width> Light control layer formation width

  According to the above configuration of the present invention, ITO is used as a transparent electrode on a glass substrate by adopting a laminated configuration in which a dimming layer is supported by a pair of transparent electrodes prepared using a flexible electrode material on a film substrate. Therefore, it is possible to provide a flexible and highly durable light control film that cannot be realized with respect to the conventional light control member. In addition, the above-mentioned performance enables easy workability and low-priced supply that could not be realized with conventional light control films, and the existing sizes are pasted on various glass windows. It is possible to provide a novel light control film having a light control function and a crack prevention function (crime prevention / disaster prevention function), and a method for producing the light control film.

It is sectional drawing for demonstrating schematically the taper angle comprised between a transparent substrate and a metal fine wire. It is a figure for demonstrating ink jet printing roughly. It is the schematic which shows an example of an inkjet head. It is a schematic diagram which shows an example of formation of an extraction electrode, a transparent electrode, and a conductive polymer layer. It is a schematic diagram of a bending test. It is a schematic diagram explaining a preferable example of a structure of the light control film of this invention.

  The light control film of the present invention is a light control film having a light control layer between a pair of opposed transparent electrodes carried on a base material, the base material being a film base material, and the transparent electrode being It is a composite electrode containing fine metal particles and a conductive polymer. This feature is a technical feature common to the inventions according to claims 1 to 18.

  In addition to flexibility and high durability, the light control layer contains polymer dispersed liquid crystal or polymer network type liquid crystal, and provides a light control film that is uniform as a product and low in cost. Therefore, this is a preferred embodiment.

  As an embodiment of the present invention, the metal fine particles are preferably metal nanoparticles or metal nanowires in order to realize a flexible and highly durable light control film. The metal nanoparticles are preferably used in the form of a metal nano ink described later.

  The transparent electrode preferably has a fine metal wire structure made of fine metal particles, and the fine metal wire structure preferably has a stripe fine wire structure.

  The transparent electrode has a metal fine wire structure that is a pair of striped fine wire structures, and the pair of stripe fine wire structures are arranged in a vertical lattice structure shifted by 90 ° so that moire does not occur. An optical film can be provided, which is preferable.

  Furthermore, it is preferable that the conductive polymer contains the PEDOT, the conductive polymer is a mixture of the PEDOT and a nonconductive polymer, and the nonconductive polymer has a hydroxy group. It is preferable that the non-conductive polymer is a dissociable group-containing self-dispersing polymer.

  The light control film of the present invention preferably has a durability of 100 times or more in a bending durability test with an axial radius of 3 mmR, and preferably has a durability of 100 g or more in a scratch load evaluation of 0.3 mmR.

  As a supply form of the light control film of the present invention, it is a form in which an adhesive layer and a release support are provided on the surface opposite to the surface having the transparent electrode of the substrate, from the viewpoint of facilitating workability. It is preferable that it is supplied in the form of a long roll from the viewpoint of workability.

  In the method for producing a light control film of the present invention, it is preferable to provide the transparent electrode and the light control layer by a coating method or a printing method in order to increase productivity.

  Furthermore, it is preferable to manufacture the transparent electrode by an ink jet printing method in order to increase productivity.

  The light control film of the present invention is preferably manufactured so that the width of the base material, the formation width of the transparent electrode, and the formation width of the light control layer satisfy the following relationship, from the viewpoint of facilitating edge power feeding.

Width of base material> width of formation of transparent electrode> width of formation of light control layer Further, after forming the base material, the transparent electrode, and the light control layer so as to satisfy the above-mentioned relationship, an opposing transparent electrode of the transparent electrode may be provided. preferable.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In the present invention, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

<Configuration of light control film>
The light control film of the present invention includes at least a first electrode using a transparent electrode carried on a film base material and a second electrode using the transparent electrode disposed to face the first electrode, At least one light control layer is provided between the transparent electrode and the second electrode.

  The transparent electrode according to the present invention includes metal fine particles and a conductive polymer. That is, in the transparent electrode according to the present invention, it is essential that the two transparent electrodes facing each other contain the metal fine particles and the conductive polymer, and preferably both the facing electrodes are both the metal fine particles and the conductive polymer. It is preferable to contain as a main component. When the transparent electrode according to the present invention is used as a single electrode, in order to obtain the flexible and high bending resistance / film strength of the object of the present invention, it is equivalent to the transparent electrode composed of the metal fine particles and the conductive polymer according to the present invention. A combination with a tough electrode material is preferable.

  Furthermore, the transparent electrode according to the present invention is preferably provided with a layer containing metal fine particles and a conductive polymer as a single thin film on the substrate, the first conductive layer comprising metal fine particles or a metal oxide fine wire pattern, It may be a laminated electrode composed of a second conductive layer containing a conductive polymer. The first conductive layer and the second conductive layer may have an interface, or may be a unified layer without an interface. At the time of manufacturing such transparent electricity, the first conductive layer and the second conductive layer may be provided twice, or may be provided at a time.

  In any case, it is essential that the transparent electrode according to the present invention acting as a surface electrode is a layer containing metal fine particles and a conductive polymer.

  Hereinafter, each component will be described.

<Film base>
By providing a transparent electrode containing metal fine particles according to the present invention on a film substrate, a flexible light control film can be obtained. A transparent resin film may be used directly as the film substrate, or the transparent electrode may be transferred to a transparent resin film after the transparent electrode is produced on another substrate.

  There is no restriction | limiting in particular in the transparent resin film used for this invention, About the material, a shape, a structure, thickness, etc., it can select suitably from well-known things.

  For example, polyolefins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyester resin film such as modified polyester, polyethylene (PE) resin film, polypropylene (PP) resin film, polystyrene resin film, cyclic olefin resin, etc. Resin films, vinyl resin films such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin films, polysulfone (PSF) resin films, polyether sulfone (PES) resin films, polycarbonate (PC) resin films , Polyamide resin film, polyimide resin film, acrylic resin film, triacetyl cellulose (TAC) resin film, and the like. If the resin film transmittance of 80% or more in 0~780nm), can be preferably applied to the present invention. Among these, from the viewpoint of transparency, heat resistance, ease of handling, strength and cost, it is preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, or a polycarbonate film, and biaxially stretched. More preferably, it is a polyethylene terephthalate film or a biaxially stretched polyethylene naphthalate film.

  In order to ensure the wettability and adhesiveness of the coating solution, the transparent resin film can be subjected to a surface treatment or an easy adhesion layer. A conventionally well-known technique can be used about a surface treatment or an easily bonding layer. For example, the surface treatment includes surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment. Examples of the easy adhesion layer include polyesters, polyamides, polyurethanes, vinyl copolymers, butadiene copolymers, acrylic copolymers, vinylidene copolymers, epoxy copolymers, and the like. The easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.

  The total light transmittance of the transparent resin film used in the present invention is desirably 60% or more, preferably 70% or more, and particularly preferably 80% or more. The total light transmittance can be measured according to a known method using a spectrophotometer, a haze meter or the like.

  The thickness of the transparent resin film used in the present invention is preferably in the range of 1 to 1000 μm from the viewpoint of strength, handling and cost, more preferably 10 to 800 μm, and particularly preferably 20 to 500 μm.

  The base material is preferably provided with a gas barrier layer for the purpose of blocking oxygen and moisture in the atmosphere. As a material for forming the gas barrier layer, metal oxides such as silicon oxide, silicon nitride, silicon oxynitride, aluminum nitride, and aluminum oxide, and metal nitrides can be used. These materials have an oxygen barrier function in addition to a water vapor barrier function. In particular, silicon nitride and silicon oxynitride having favorable barrier properties, solvent resistance, and transparency are preferable. In addition, the barrier layer may have a multilayer structure as necessary. As a method for forming the gas barrier layer, a resistance heating vapor deposition method, an electron beam vapor deposition method, a reactive vapor deposition method, an ion plating method, or a sputtering method can be used depending on the material. The thickness of each inorganic layer constituting the gas barrier layer is not particularly limited, but typically it is preferably in the range of 5 nm to 500 nm per layer, more preferably 10 nm to 400 nm per layer. The gas barrier layer is preferably provided on at least one surface of the substrate, and more preferably on both surfaces.

  The base material is preferably treated with a known UV absorber / reflector to enhance UV shielding. These UV absorbers may be kneaded into the base material or provided as a separate layer on the base material. However, the transmittance of visible light (400-700 nm) is 80%, preferably 85% or more, more preferably 90% or more, and particularly preferably 92% or more. When the upper substrate is laminated on the standard white plate, The color misregistration is within ΔE = 2.0, more preferably within 1.5, still more preferably within 1.0, and particularly preferably within 0.5.

  Further, the surface of the substrate may be subjected to a protective layer treatment with a hard coat layer or the like. The hard coat layer is formed by uniformly applying a photo-radical generating material and a mixture of radical polymerizable monofunctional and / or polyfunctional monomers to a desired film thickness, and then irradiating the necessary amount of ultraviolet light with radical polymerization. It is a transparent and high-hardness polymer layer obtained by making it.

<Underlayer>
The transparent electrode according to the present invention may have an undercoat layer formed by applying a silane coupling agent to the substrate surface. In that case, a biaxially stretched polyethylene naphthalate film is more preferable.

<Transparent electrode>
The transparent electrode according to the present invention is characterized in that the two transparent electrodes facing each other are composite electrodes containing metal fine particles and a conductive polymer. The composite electrode includes a metal conductive layer made of fine metal particles and a polymer conductive layer made of a conductive polymer as its constituent elements, for example, a structure in which a conductive polymer is laminated on a metal conductive layer made of a metal fine wire pattern, and vice versa. A structure in which a metal conductive layer composed of a fine metal wire pattern is laminated on a conductive polymer layer, and a structure composed of a metal three-dimensional network structure composed of metal nanowires and a conductive polymer can be used satisfactorily. Uniform conductivity can be obtained as a whole.

<Metal fine particles>
The metal fine particles referred to in the present invention collectively refer to the following metal nanoparticles or metal nanowires, and act as a nanoscale metal conductive layer (metal conductor).

[Metal nanoparticles]
The metal nanoparticle as used in the present invention refers to a metal or metal oxide in the form of fine particles having a particle diameter from the atomic scale to the nm size. The average particle size of the fine particles is preferably 1 to 1000 nm, and the fine particles are generally preferably spherical, but may be indeterminate to be nearly spherical.

  In the transparent electrode according to the present invention, the metal nanoparticles function as a main conductor.

  Specific examples of the metal nanoparticles according to the present invention include metal oxides, metal salts, and metal complexes. Specific examples of the metal species include Ag, Cu, Au, Al, Rh, Ir, Co, Zn, Ni, In, Fe, Pd, Pt, Sn, and Ti. In the present invention, two or more kinds of metal fine particles can be used in combination, but from the viewpoint of conductivity, it is preferable to use at least an element selected from Ag, Cu, Au, Al, and Co. For example, when silver is used as the metal species, first silver oxide, second silver oxide, silver carbonate, silver acetate, acetylacetone silver complex and the like can be used as the metal nanoparticles. These metal nanoparticles can be used alone or in combination of two or more. In addition, there is no restriction | limiting in particular in these metal nanoparticles, For example, well-known means, such as a liquid phase method and a gaseous-phase method, can be used. Moreover, there is no restriction | limiting in particular in a specific manufacturing method, A well-known manufacturing method can be used.

  The preferable average particle diameter of these metal nanoparticles is in the range of 1 to 1000 nm, and is appropriately selected according to the influence on transparency, dispersibility, and the like. In particular, the average particle size is more preferably 500 nm or less, and more preferably 100 nm or less from the viewpoint of transparency. Further, it is more preferably 10 nm or more from the viewpoint of dispersibility and conductivity.

  In the present invention, those having an average particle diameter in the range of 3 to 300 nm are particularly preferable, and those having an average particle diameter in the range of 10 to 100 nm are more preferably used.

  Among these, in particular, when a resin film is used as the transparent substrate, silver nanoparticles having an average particle diameter of 10 to 100 nm are preferable because high conductivity can be obtained at a low heating temperature.

  In the present invention, the average particle diameter can be easily measured using a commercially available measuring apparatus using a light scattering method, specifically using a Zetasizer 1000 (manufactured by Malvern), The value measured by the laser Doppler method at S25 ° C. and 1 ml of the sample diluent.

  The metal nanoparticles can be used in combination with metal nanowires to be described later in the transparent electrode. In that case, the ratio of the metal nanowires to the metal nanoparticles is not particularly limited, but for example, 100: 100 to 100: 0. In the range of 1, it can be appropriately determined in consideration of conductivity, heat treatment conditions, transparency and the like.

[Metal nanowires]
The metal nanowire referred to in the present invention refers to a wire (wire shape) having an average diameter of 200 nm or less and an average length of 100 μm or less.

In the transparent electrode according to the present invention, metal nanowires can also be used as the main conductor as the metal fine particles. In the present invention, an element having a bulk conductivity of 1 × 10 ⁶ S / m or more can be used as the metal element of the metal nanowire. Specific examples of metal elements of the metal nanowire that can be preferably used in the present invention include Ag, Cu, Au, Al, Rh, Ir, Co, Zn, Ni, In, Fe, Pd, Pt, Sn, Ti, and the like. Can be mentioned. In the present invention, two or more kinds of metal nanowires can be used in combination, but from the viewpoint of conductivity, it is preferable to use at least a metal element selected from Ag, Cu, Au, Al, and Co.

  In the present invention, the means for producing the metal nanowire is not particularly limited, and for example, known means such as a liquid phase method and a gas phase method can be used. Moreover, there is no restriction | limiting in particular in a specific manufacturing method, A well-known manufacturing method can be used. For example, as a method for producing Ag nanowires, Adv. Mater. , 2002, 14, 833-837; Chem. Mater. , 2002, 14, 4736-4745, etc. As a method for producing Co nanowires, a method for producing Au nanowires is disclosed in JP 2006-233252A, and a method for producing Cu nanowires is disclosed in JP 2002-266007 A, etc. Reference can be made to Japanese Unexamined Patent Publication No. 2004-149871. In particular, Adv. Mater. And Chem. Mater. The method for producing Ag nanowires reported in 1 can produce silver nanowires easily and in large quantities in an aqueous system, and the conductivity of silver is the largest among metals, so that the production of metal nanowires according to the present invention is possible. It can be preferably applied as a method.

  In the present invention, the average diameter of the metal nanowires is preferably 200 nm or less from the viewpoint of transparency, and preferably 10 nm or more from the viewpoint of conductivity. If the average diameter is 200 nm or less, the influence of light scattering can be reduced, and a smaller average diameter is preferable because light transmittance reduction and haze deterioration can be suppressed. On the other hand, if the average diameter is 10 nm or more, the function as a conductor can be expressed significantly, and a larger average diameter is preferable because conductivity is improved. Therefore, it is more preferably 20 to 150 nm, and further preferably 40 to 150 nm.

  In the present invention, the average length of the metal nanowires is preferably 1 μm or more from the viewpoint of conductivity, and preferably 100 μm or less from the viewpoint of the effect on the transparency due to aggregation. More preferably, it is 1-50 micrometers, and it is still more preferable that it is 3-50 micrometers.

  In the present invention, the average diameter and the average length of the metal nanowires are obtained by taking an electron micrograph of a sufficient number of nanowires using a scanning electron microscope (SEM) or a transmission electron microscope (TEM), It can be obtained from the arithmetic average of the measured values. The length of the nanowire should be calculated in a straight line, but in reality, it is often bent, so the projection diameter and projected area of the nanowire can be determined from an electron micrograph using an image analyzer. The calculation is performed assuming a cylindrical body (length = projected area / projected diameter). The number of nanowires to be measured is preferably at least 100 or more, and more preferably 300 or more nanowires.

[Metal nano ink]
In the present invention, it is important to form a transparent conductive film on a film substrate and enhance its durability, and it is preferable to use metal nano-inks that can be fired at low temperature as metal nanoparticles that can be fired at low temperatures.

  The low temperature firing referred to in the present invention refers to a temperature range applicable to a film substrate, and refers to firing at less than 300 ° C, preferably less than 200 ° C, particularly preferably less than 150 ° C.

  Here, the metal nano ink refers to a form in which the metal nanoparticles are dispersed in a solvent such as water or alcohol.

  Any of the currently known metal nanoinks that can be fired at a low temperature can be suitably used in the present invention, but silver nanoinks are the most powerful and inexpensive as metal nanoinks currently available. However, the use of other highly conductive metal nanoparticles such as copper and Al, which are inexpensive at the original raw material cost, is a preferred embodiment, and the use of copper, Al, etc. as a metal thin wire according to the present invention is also a preferred embodiment.

  In the present invention, in particular, by changing a dry process metal such as a conventional metal deposition film / sputtering film to a nano ink type metal material, not only bending resistance, stretching resistance, and scratch resistance are increased, but also a conductive polymer is used in combination, Furthermore, by containing either a non-conductive polymer having a hydroxy group or a self-dispersing polymer having a dissociative group as an insulating resin, the bending resistance, stretching resistance, and scratch resistance are further improved, and weather resistance / humidity resistance It is possible to achieve compatibility with sex.

[Metal fine wire structure]
The transparent electrode according to the present invention preferably has a metal fine wire structure made of the above metal fine particles.

  A metal fine wire structure is a layer in which a layer containing a metal material is formed in a pattern so as to have an opening on a transparent substrate.

  The said opening part is a part which does not have a metal fine wire among transparent substrates, and is a translucent part of a metal pattern.

  There is no particular limitation on the shape of the pattern.

  The shape of the pattern may be, for example, a stripe shape (parallel line shape), a lattice shape, a honeycomb shape, or a random network shape. From the viewpoint of transparency, the stripe shape is particularly preferable. In the transparent electrode, the ratio of the opening to the entire surface electrode, that is, the opening ratio, is preferably 80% or more from the viewpoint of transparency.

  For example, when the conductive portion has a stripe shape, the aperture ratio of the stripe pattern having a line width of 100 μm and a line interval of 1 mm is approximately 90%.

  In general, the line width of the pattern is preferably in the range of 1 to 200 μm, more preferably in the range of 1.5 to 100 μm, and particularly preferably in the range of 2 to 50 μm.

  The height is preferably in the range of 0.05 to 2 μm, more preferably in the range of 0.1 to 1.5 μm, and particularly preferably in the range of 0.2 to 1.2 μm.

  The transparent electrode according to the present invention is preferably in the range of 0.1 to 2000Ω / □, more preferably in the range of 0.3 to 1000Ω / □, and in the range of 0.5 to 500Ω / □. Is more preferable, and the range of 1 to 250Ω / □ is particularly preferable. The surface specific resistance can be measured based on, for example, JIS K6911, ASTM D257, etc., and can be easily measured using a commercially available surface resistivity meter.

  The line width, height, and fine line pitch can be arbitrarily adjusted so as to achieve such sheet resistance. In the present application, ultra-thin lines, ultra-thin lines, etc., according to the user needs of the light control film, etc. Any of these measures can be suitably performed.

  In addition, the fine metal wire according to the present invention can be freely adjusted in line width, height, and pitch as described above, and in the present invention, the design of the fine metal wire along the light control film lineup becomes important. .

  In view of the above, the light control film having high transparency is preferably an ultrahigh-definition fine line having a line width of less than 30 μm, more preferably a fine line having a line width of less than 15 μm. Although the use of a high-definition screen is preferable for realizing such a thin line, it is preferable to apply ultrahigh-definition inkjet.

  On the other hand, it is preferable to reproduce the pattern of the metal wire glass in which the metal wire can be visually recognized at a constant pitch from the viewpoint of crime prevention as the light control film to be attached to the existing window glass which is the object of the present invention. From this point of view, it is preferable that the pitch is larger than 5 mm and the line width is larger than 100 μm. More preferably, the pitch is 10 mm or more, and the line width is 200 μm or more.

  In the present invention, since each of the counter electrodes of the light control film uses a transparent electrode containing metal fine particles and a conductive polymer, the fine wire structure is preferably a stripe shape, and in addition, the stripe-like fine wire structure of a pair of transparent electrodes Are preferably orthogonal to each other. The term “perpendicular” means that the direction of the other electrode is shifted within a range of 90 ° ± 10 ° with respect to one direction of the opposing electrodes. By using it in this way, it is possible to provide a high-quality lattice-like light control film from any angle without causing moire due to fine lines not on the same plane.

  There are no particular restrictions on the method for forming striped, grid-like, or honeycomb-like fine metal wires, and conventionally known methods can be used.

  As a method for forming the fine metal wire, for example, a photolithography method, a silver salt photographic technique, a method using a printing method, or the like can be used, and it is more preferable to use the printing method. This is because the fine metal wire formed by the printing method has a smaller taper angle and the thickness distribution of the transparent conductive layer on the fine metal wire is less likely to occur than the fine metal wire formed by the photolithographic method or silver salt photographic method. it is conceivable that.

  As shown in FIG. 1, the taper angle 1 means an inner angle formed by the transparent substrate 2 and the edge of the thin metal wire 3. The taper angle 1 can be measured by cutting the transparent substrate 2 and the fine metal wires 3 in cross section and observing them using a scanning electron microscope (SEM).

  Specifically, the known photolithography method is to form a conductor layer on the entire surface of the substrate using one or more physical or chemical forming techniques such as printing, vapor deposition, sputtering, plating, etc. Or after laminating | stacking metal foil on a base material with an adhesive agent, it can process into a desired stripe form, a lattice form, or a honeycomb form by etching using a well-known photolithography method.

  A method using silver salt photographic technology can be carried out with reference to, for example, [0076]-[0112] of JP-A-2009-140750 and Examples.

  The known printing method is a method of forming a pattern by printing a coating solution for fine metal wires containing fine metal particles.

  The coating solution for fine metal wires containing metal fine particles is a metal fine particle dispersion containing metal nanoparticles or metal nanowires.

  The metal fine particle dispersion contains metal nanoparticles or metal nanowires in a solvent such as water or alcohol, but may contain a binder, a dispersant for dispersing the metal nanoparticles or metal nanowires, if necessary.

  A metal pattern can be formed by a printing method such as a gravure printing method, a flexographic printing method, a screen printing method, or an ink jet printing method using a metal fine particle dispersion.

  For each printing method, a method generally used for forming an electrode pattern is applicable to the present invention. Specific examples of the gravure printing method include those described in JP 2009-295980 A, JP 2009-259826 A, JP 2009-96189 A, and JP 2009-90662 A, and the like. The methods described in Japanese Patent Application Laid-Open Nos. 2004-268319 and 2003-168560 are disclosed, and the screen printing methods are described in Japanese Patent Application Laid-Open Nos. 2010-34161, 2010-10245, and 2009-302345. An example is the method described in Japanese Patent Publication.

In particular, the formation of the transparent electrode according to the present invention preferably uses ink jet printing.
(1) Inkjet printing The transparent electrode according to the present invention is preferably formed by inkjet printing a coating solution for fine metal wires.

  Hereinafter, inkjet printing will be described.

  FIG. 2 is a schematic diagram showing an example of a method of applying a coating solution for fine metal wires on a film substrate in a certain area using a coating apparatus using an inkjet head.

  As shown in FIG. 2, the film substrate 10 is continuously running, and the fine metal wire coating liquid is ejected as droplets by the ink jet head 14 to form the transparent electrode 15 and pass through a drying zone (not shown). .

  The ink jet head 14 is not particularly limited. For example, the ink jet chamber has a diaphragm having a piezoelectric element in the ink pressure chamber, and a shear mode type (piezo type) that ejects the ejected liquid by the pressure change of the ink pressure chamber by the diaphragm. Or a thermal type head that discharges the ejected liquid from the nozzle by a rapid volume change due to film boiling of the coating liquid by the heat energy from the heat generating element. .

  The ink jet head 14 is connected to a mechanism for supplying the ejected liquid. The injection liquid is supplied from the tank 8A. In this example, the tank liquid level is made constant so that the injection liquid pressure in the ink jet head 14 is always kept constant. Therefore, it overflows from the tank 8A and returns the injected liquid to the tank 8B under natural flow. The supply of the injection liquid from the tank 8B to the tank 8A is performed by the pump 11, and the operation conditions are set so that the liquid level of the tank 8A is stably constant according to the injection conditions.

  In addition, when returning the injection liquid from the pump 11 to the tank 8A, it is performed after passing through the filter 12. As described above, it is preferable that the ejection liquid passes through the filter medium having an absolute filtration accuracy or a semi-absolute filtration accuracy of 0.05 to 50 μm at least once before being supplied to the inkjet head 14.

  Further, in order to perform the cleaning operation or the liquid filling operation of the inkjet head 14, the ejection liquid can be forcibly supplied from the tank 6 and the cleaning solvent from the tank 7 to the inkjet head 14 by the pump 9. Such tank pumps may be divided into a plurality of tanks for the ink jet head 14, pipe branches may be used, or a combination thereof may be used. In FIG. 2, a pipe branch 13 is used. Further, in order to sufficiently remove the air in the inkjet head 14, the ejection liquid is forcibly sent from the tank 6 to the inkjet 14 by the pump 9, and the ejection liquid is extracted from the air vent pipe described below to the waste liquid tank 4. May be sent.

  Furthermore, a heat exchanger may be provided between the tank 8A and the ink jet head 14 in order to keep the temperature of the ejected liquid in the ink jet head 14 constant, and the temperature of the ejected liquid such as a heat exchanger may be provided in the ink jet head 14. A fixed mechanism may be provided.

  The application procedure is shown below.

  First, in the procedure for filling the inkjet head 14 with the ejection liquid, the ejection liquid is forcibly passed from the tank 6 to the inkjet head 14 by the pump 9 at the standby position of the inkjet head 14. The ejected liquid discharged at this time is received by a catch pan (not shown). By this operation, the inkjet head 14 is filled with the ejection liquid, and after the air inside the head is removed, the nozzle surface (ejection surface) is cleaned.

  Next, the injection liquid is sent from the tank 8B to the tank 8A at a predetermined flow rate, and circulation is started by overflow. By closing the valve between the pump 9 and the inkjet head 14 and opening the valve between the pump 8 and the inkjet head 14, the ink can be ejected from the inkjet head 14. The film base 10 is conveyed at a predetermined speed, and the inkjet head 14 that has been prepared for injection is brought close to a predetermined distance of the film base 10 to start injection of an injection liquid under predetermined injection conditions. Since the liquid level of the tank 8A is kept constant by overflowing, the injection amount becomes stable.

The type of the ink-jet head 14 is arbitrary, but in the present invention, it is preferable to select a condition in which the amount of one droplet is several tens of picoliters and the ejection frequency is several hundred to several tens of thousands of Hz. In addition, if the speed is arbitrary and high, productivity will be improved. The frequency is adjusted so that the target wet film thickness is obtained with respect to the speed, and the injection is performed.
(2) Inkjet Head An example of the inkjet head 14 is shown in FIG.

  FIG. 3 is a schematic perspective view showing an example of an ink jet head having a partially broken surface. This figure shows the case of a shear mode type (piezo type) ink jet head.

  A controller 5 (see FIG. 2) for driving the piezoelectric substrate is connected to the inkjet head 14 via a connector (not shown). The control unit 5 selects the operation intensity and frequency of the piezoelectric substrate when the ejection liquid is ejected.

  The inkjet head 14 includes a piezoelectric substrate 201b formed by joining an upper piezoelectric substrate 201b1 and a lower piezoelectric substrate 201b2, a top plate 201c, and a nozzle plate 201d.

  A plurality of nozzles 201b3 having a predetermined length parallel to each other are opened on the piezoelectric base plate 201b by opening the nozzle plate 201d and closed on the opposite side, and a flat surface connected to the closed side of the nozzle 201b3. A flat surface 201b4 and side walls 201b5 on both sides of a nozzle (ink pressure chamber) 201b3.

  The plurality of nozzles may be alternately used as a nozzle for a coating solution pressure chamber and a nozzle for an air pressure chamber.

  This figure shows the case where it is used for a coating solution pressure chamber. 201c2 shows the 1st top plate which covers the upper surface of the piezoelectric base | substrate 201b, 201c1 shows the 2nd top plate which covers the upper surface of a 1st top plate.

  Reference numeral 201e denotes a coating liquid supply pipe for the coating liquid. The coating liquid supplied from the coating liquid supply pipe 201e is discharged from the nozzle discharge port 201d1.

  Reference numeral 201c3 denotes a storage portion for the coating liquid supplied from the coating liquid supply pipe 201e, and is supplied to each nozzle 201b3 for each coating liquid pressure chamber from each coating liquid supply port 201c4 communicating with each nozzle 201b3. .

  Each nozzle 201b3 is covered with a first top plate 201c2 and a nozzle plate 201d, so that a plurality of sealed channels (coating liquid pressure chambers) are formed.

  Reference numeral 201d1 denotes a nozzle discharge port that discharges the coating liquid in the form of droplets due to a change in the pressure of the coating liquid pressure chamber accompanying shear deformation of each side wall. The interval between the nozzle discharge ports is preferably 0.02 to 0.3 mm.

  Reference numeral 201f denotes a pipe used for bleeding the coating liquid. The pipe 201f is sealed by a valve or the like when the coating liquid is injected.

  The material of the first top plate and the second top plate is not particularly limited, and may be made of, for example, an organic material. However, alumina, aluminum nitride, zirconia, silicon, silicon nitride, silicon carbide, quartz, lead zirconate titanate ( PZT) and the like.

  A metal or resin is used as a base material constituting the nozzle plate 201d. For example, stainless steel, polyimide, polysulfone, polyethersulfone and the like can be preferably used. Particularly preferred is a polyimide resin, and DuPont: Kapton or Ube Industries, Ltd .: Upilex, etc. are preferred because they are excellent in dimensional stability, ink resistance, heat resistance and the like.

  The metal fine particle dispersion is preferably heated after pattern formation. Thereby, fusion of metal fine particles proceeds, and the metal fine wire becomes highly conductive, which is particularly preferable.

  The heating temperature is preferably 100 ° C. or more and 500 ° C. or less for metal fine particles. Although depending on the temperature and the size of the metal particles to be used, the time is preferably 10 seconds or longer and 30 minutes or shorter. From the viewpoint of productivity, it is preferably 10 seconds or longer and 15 minutes or shorter. More preferably, it is less than or equal to minutes.

  When using a resin substrate or a resin film for the base material, it is preferable to heat the substrate at a temperature that is 100 ° C. or higher and 250 ° C. or lower and that does not damage the substrate.

  There is no restriction | limiting in particular in the heat processing method, A well-known processing method can be used.

  For example, examples of the heat treatment mode include heating using a heater or IR heater, drying under reduced pressure, and the like, but are not limited thereto.

  As a method for forming a random network pattern, for example, as described in JP 2005-530005 A, a liquid containing metal fine particles is applied and dried to spontaneously form random conductive fine particles. A method of forming a network structure can be used.

<Conductive polymer>
The transparent electrode according to the present invention is a composite electrode formed by forming a transparent metal electrode containing metal fine particles and forming a conductive polymer layer so as to carry them. For example, the composite electrode according to the present invention can be formed by overcoating a conductive polymer-containing coating solution on a transparent metal electrode containing fine metal particles.

  As the conductive polymer according to the present invention, a conductive polymer containing a π-conjugated conductive polymer and a polyanion can be preferably used.

  Such a conductive polymer can be easily produced by oxidative polymerization of a precursor monomer that forms a π-conjugated conductive polymer described later in the presence of a suitable oxidizing agent, an oxidation catalyst, and a poly anion described later.

(Π-conjugated conductive polymer)
π-conjugated conductive polymers such as polythiophenes (including basic polythiophenes, the same shall apply hereinafter), polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans, polyparaphenylene vinylenes, polyazulenes A chain conductive polymer of polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, and polythiazyl compounds can be used.

  Of these, polythiophenes and polyanilines are preferable from the viewpoints of conductivity, transparency, stability, and the like. Most preferred is polyethylene dioxythiophene.

(Π-conjugated conductive polymer precursor monomer)
The precursor monomer has a π-conjugated system in the molecule, and a π-conjugated system is formed in the main chain even when polymerized by the action of an appropriate oxidizing agent.

  Examples of the precursor monomer include pyrroles and derivatives thereof, thiophenes and derivatives thereof, anilines and derivatives thereof, and the like.

  Specific examples of the precursor monomer include pyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, 3-decylpyrrole, 3-dodecylpyrrole, 3, 4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxylpyrrole, 3-methyl-4-carboxylpyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutylpyrrole, 3-hydroxypyrrole 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole, thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3 -Butylthiophene, 3-hexylchi Phen, 3-heptylthiophene, 3-octylthiophene, 3-decylthiophene, 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3-chlorothiophene, 3-iodothiophene, 3-cyanothiophene, 3-phenyl Thiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene, 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-butoxythiophene, 3-hexyloxythiophene, 3-heptyloxythiophene, 3- Octyloxythiophene, 3-decyloxythiophene, 3-dodecyloxythiophene, 3-octadecyloxythiophene, 3,4-dihydroxythiophene, 3,4-dimethoxythiophene, 3,4-diethoxythiol 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-didecyloxy Thiophene, 3,4-didodecyloxythiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene, 3,4-butenedioxythiophene, 3-methyl-4-methoxythiophene, 3-methyl -4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4-carboxyethylthiophene, 3-methyl-4-carboxybutylthiophene, aniline, 2-methylaniline, 3-isobutyl Aniline, 2-aniline sulfonic acid, 3-aniline A sulfonic acid etc. are mentioned.

(Poly anion)
The polyanion is an oligomer or polymer having a plurality of anionic groups (anionic groups).

  The polyanion is preferably a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted polyamide, a substituted or unsubstituted polyester, and a copolymer thereof. A compound composed of a structural unit having an anionic group and a structural unit having no anionic group is preferably used.

  The polyanion is a solubilized polymer that solubilizes the π-conjugated conductive polymer in a solvent.

  The anion group of the polyanion functions as a dopant for the π-conjugated conductive polymer, and improves the conductivity and heat resistance of the π-conjugated conductive polymer.

  The anion group of the polyanion may be any functional group capable of causing chemical oxidation doping to the π-conjugated conductive polymer. Among them, from the viewpoint of ease of production and stability, a monosubstituted sulfate ester Group, monosubstituted phosphate group, phosphate group, carboxy group, sulfo group and the like are preferable. Furthermore, from the viewpoint of the doping effect of the functional group on the π-conjugated conductive polymer, a sulfo group, a monosubstituted sulfate group, and a carboxy group are more preferable.

  Specific examples of polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, poly Isoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid, polyacrylic acid, etc. Can be mentioned. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.

  Moreover, the poly anion which has F in a compound may be sufficient.

  Specific examples include Nafion containing a perfluorosulfonic acid group (manufactured by Dupont) and Flemion (manufactured by Asahi Glass Co., Ltd.) made of perfluoro vinyl ether containing a carboxylic acid group.

  Among these, a compound having a sulfonic acid is more preferable because the washing resistance and solvent resistance of the transparent conductive layer are remarkably improved by performing the heat treatment.

  Furthermore, among these, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethylsulfonic acid, and polyacrylic acid butylsulfonic acid are preferable. These poly anions have high compatibility with the water-soluble binder described later, and can further increase the conductivity of the obtained conductive polymer.

  The degree of polymerization of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of solvent solubility and conductivity.

  Examples of the method for producing a polyanion include a method of directly introducing an anionic group into a polymer having no anionic group using an acid, a method of sulfonating a polymer having no anionic group with a sulfonating agent, an anionic group A method of producing by polymerization of the containing polymerizable monomer may be mentioned.

  Examples of the method for producing an anion group-containing polymerizable monomer by polymerization include a method for producing an anion group-containing polymerizable monomer in a solvent by oxidative polymerization or radical polymerization in the presence of an oxidizing agent and / or a polymerization catalyst.

  Specifically, a predetermined amount of the anionic group-containing polymerizable monomer is dissolved in a solvent, this is maintained at a constant temperature, and a solution in which a predetermined amount of an oxidizing agent and / or a polymerization catalyst is dissolved in the solvent is added to the predetermined amount. React with time. The polymer obtained by the reaction is adjusted to a certain concentration by the solvent. In this production method, an anionic group-containing polymerizable monomer may be copolymerized with a polymerizable monomer having no anionic group.

  The oxidizing agent, oxidation catalyst, and solvent used in the polymerization of the anionic group-containing polymerizable monomer are the same as those used in the polymerization of the precursor monomer that forms the π-conjugated conductive polymer.

  When the obtained polymer is a polyanionic salt, it is preferably transformed into a polyanionic acid. Examples of the method for converting to an anionic acid include an ion exchange method using an ion exchange resin, a dialysis method, an ultrafiltration method, and the like. Among these, the ultrafiltration method is preferable from the viewpoint of easy work.

  Ratio (solid content ratio) of π-conjugated conductive polymer and polyanion contained in the conductive polymer according to the present invention, “π-conjugated conductive polymer”: “Poly anion” is conductive and dispersible In view of the above, the mass ratio is preferably 1: 1 to 1:10. More preferably, it is in the range of 1: 2 to 1: 8.

The oxidant used when the precursor monomer forming the π-conjugated conductive polymer is chemically oxidatively polymerized in the presence of the polyanion to obtain the conductive polymer according to the present invention is, for example, J. Org. Am. Soc. 85, 454 (1963), which is suitable for the oxidative polymerization of pyrrole. For practical reasons, cheap and easy to handle oxidants such as iron (III) salts, eg FeCl ₃ , Fe (ClO ₄ ) ₃ , organic acids and iron (III) salts of inorganic acids containing organic residues Or use hydrogen peroxide, potassium dichromate, alkali persulfate (eg potassium persulfate, sodium persulfate) or ammonium, alkali perborate, potassium permanganate and copper salts such as copper tetrafluoroborate preferable. In addition, air and oxygen in the presence of catalytic amounts of metal ions such as iron, cobalt, nickel, molybdenum and vanadium ions can be used as oxidants at any time. The use of persulfates and the iron (III) salts of inorganic acids containing organic acids and organic residues has great application advantages because they are not corrosive.

  Examples of iron (III) salts of inorganic acids containing organic residues include iron (III) salts of alkanol sulfate half esters of alkanols such as lauryl sulfate; alkyl sulfonic acids of 1 to 20 carbons such as Methane or dodecanesulfonic acid; aliphatic carboxylic acid having 1 to 20 carbon atoms such as 2-ethylhexylcarboxylic acid; aliphatic perfluorocarboxylic acid such as trifluoroacetic acid and perfluorooctanoic acid; aliphatic dicarboxylic acid such as oxalic acid And in particular aromatic (optionally) alkyl-substituted sulfonic acids having 1 to 20 carbon atoms, such as the Fe (III) salts of benzenecenesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid.

In the present invention, a doping treatment can be performed in order to further increase the conductivity of the conductive polymer. As a dopant for the conductive polymer, for example, a sulfonic acid having a hydrocarbon group having 6 to 30 carbon atoms (hereinafter also referred to as “long-chain sulfonic acid”) or a polymer thereof (for example, polystyrene sulfonic acid), halogen , Lewis acid, proton acid, transition metal halide, transition metal compound, alkali metal, alkaline earth metal, MClO ₄ (M = Li ⁺ , Na ⁺ ), R ₄ N ⁺ (R═CH ₃ , C ₄ H ₉ , C ₆ H ₅ ), or R ₄ P ⁺ (R═CH ₃ , C ₄ H ₉ , C ₆ H ₅ ). Of these, the long-chain sulfonic acid is preferable.

  Moreover, the conductive polymer according to the present invention may contain a water-soluble organic compound. Among water-soluble organic compounds, compounds having an effect of improving conductivity by adding to a conductive polymer are known. Sometimes referred to as a dopant (or sensitizer). Seconds that can be used in the present invention. There is no restriction | limiting in particular in a dopant, It can select suitably from well-known things, For example, an oxygen containing compound is mentioned suitably. Especially, it is preferable that it is 1 type of the compound which has a hydroxyl group, a carbonyl group, an ether group, and a sulfoxide group.

  Examples of the compound having a hydroxy group include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, and glycerin. Among these, ethylene glycol and diethylene glycol are preferable. Examples of the compound having a carbonyl group include isophorone, propylene carbonate, cyclohexanone, and γ-butyrolactone. Examples of the compound having an ether group include diethylene glycol monoethyl ether. Examples of the compound having a sulfoxide group include dimethyl sulfoxide. These may be used alone or in combination of two or more, but at least one selected from dimethyl sulfoxide, ethylene glycol, and diethylene glycol is preferably used.

  In the conductive polymer according to the present invention, an additive such as a plasticizer, a stabilizer such as an antioxidant, a migration inhibitor, a surfactant, a dispersant, a colorant such as a dye or a pigment is added depending on the purpose. May be included.

  A commercially available material can also be preferably used for the conductive polymer according to the present invention.

  For example, a conductive polymer composed of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid (abbreviated as PEDOT-PSS) is available from Heraeus as CLEVIOS series, from Aldrich as PEDOT-PSS 483095, 560598, Nagase Chemtex. It is commercially available from the company as the Denatron series.

  Polyaniline is also commercially available from Nissan Chemical as the ORMECON series.

  The conductive polymer according to the present invention is preferably a mixture of the PEDOT and the nonconductive polymer, the nonconductive polymer is preferably a nonconductive polymer having a hydroxy group, and further the nonconductive polymer. Is preferably a self-dispersing polymer having a dissociable group.

(Non-conductive polymer having a hydroxy group)
As the nonconductive polymer having a hydroxy group according to the present invention, a compound represented by the following general formula (I) is preferably used.

（式中、Ｒは水素原子又はメチル基を表し、Ｑは−Ｃ（＝Ｏ）Ｏ−、又はＣ（＝Ｏ）ＮＲａ−を表す。Ｒａは水素原子又はアルキル基を表し、Ａは置換若しくは無置換アルキレン基、又は（ＣＨ_２ＣＨＲｂＯ）_ｘ−（ＣＨ_２ＣＨＲｂ）−を表す。Ｒｂは水素原子又はアルキル基を表し、ｘは平均繰り返しユニット数を表す。）
本発明に係る透明電極は、前記一般式（Ｉ）で表される構造単位を含むヒドロキシ基を有する非導電性ポリマーを導電性ポリマーと併用することが好ましい。こうした樹脂は導電性ポリマーと容易に混合可能であり、また、前述の第二ドーパントと同様な効果も有するため、樹脂を混合しても導電性保護層の抵抗値を大幅には劣化させず、条件によっては寧ろ抵抗値を下げることも可能である。

(In the formula, R represents a hydrogen atom or a methyl group, Q represents —C (═O) O—, or C (═O) NRa—. Ra represents a hydrogen atom or an alkyl group, and A represents a substituted or unsubstituted alkylene group, or _{(CH 2 CHRbO) x - (} CH 2 CHRb) - .Rb representing a represents a hydrogen atom or an alkyl group, x represents the average number of repeating units).
In the transparent electrode according to the present invention, it is preferable to use a non-conductive polymer having a hydroxy group containing the structural unit represented by the general formula (I) in combination with a conductive polymer. Such a resin can be easily mixed with a conductive polymer, and also has the same effect as the above-mentioned second dopant, so even if the resin is mixed, the resistance value of the conductive protective layer is not significantly deteriorated, Rather, the resistance value can be lowered depending on the conditions.

  In the present invention, the non-conductive polymer having a hydroxy group means a polymer that is water-soluble and dissolves 0.001 g or more in 100 g of water at 25 ° C. The solubility can be measured with a haze meter or a turbidimeter.

  The non-conductive polymer having a hydroxy group according to the present invention has a structure including at least the structural unit represented by the general formula (I), and may be a homopolymer represented by the general formula (I). Alternatively, other components may be copolymerized. When copolymerizing other components, the structural unit represented by the general formula (I) is preferably contained in an amount of 10 mol% or more, more preferably 30 mol% or more, and more preferably 50 mol% or more. More preferably.

  The water-soluble binder resin is preferably contained in the conductive protective layer in an amount of 40% by mass to 80% by mass, and more preferably 50% by mass to 70% by mass.

  In the structural unit having a hydroxy group represented by formula (I), R represents a hydrogen atom or a methyl group. Q represents -C (= O) O- or C (= O) NRa-, and Ra represents a hydrogen atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. Moreover, these alkyl groups may be substituted with a substituent. Examples of these substituents include alkyl groups, cycloalkyl groups, aryl groups, heterocycloalkyl groups, heteroaryl groups, hydroxy groups, halogen atoms, alkoxy groups, alkylthio groups, arylthio groups, cycloalkoxy groups, aryloxy groups, Acyl group, alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, ureido group, aralkyl group, nitro group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbamoyl group, Arylcarbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, acyloxy group, alkenyl group, alkynyl group, alkylsulfonyl group, arylsulfonyl group, alkyloxysulfonyl , Aryloxy sulfonyl group, alkylsulfonyloxy group, may be substituted with an aryl sulfonyloxy group. Of these, a hydroxy group and an alkyloxy group are preferable.

  The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

  The alkyl group may have a branch, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, and still more preferably 1 to 8. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, octyl group and the like.

  The number of carbon atoms in the cycloalkyl group is preferably 3-20, more preferably 3-12, and even more preferably 3-8. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

  The alkoxy group may have a branch, the number of carbon atoms is preferably 1-20, more preferably 1-12, still more preferably 1-6, and 1-4 Most preferably. Examples of the alkoxy group include a methoxy group, an ethoxy group, a 2-methoxyethoxy group, a 2-methoxy-2-ethoxyethoxy group, a butyloxy group, a hexyloxy group and an octyloxy group, and preferably an ethoxy group.

  The number of carbon atoms of the alkylthio group may be branched, and the number of carbon atoms is preferably 1-20, more preferably 1-12, even more preferably 1-6, Most preferably, it is 1-4. Examples of the alkylthio group include a methylthio group and an ethylthio group.

  The arylthio group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylthio group include a phenylthio group and a naphthylthio group.

  The number of carbon atoms of the cycloalkoxy group is preferably 3-12, more preferably 3-8. Examples of the cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

  The aryl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group.

  The aryloxy group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryloxy group include a phenoxy group and a naphthoxy group.

  The heterocycloalkyl group preferably has 2 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Examples of the heterocycloalkyl group include a piperidino group, a dioxanyl group, and a 2-morpholinyl group.

  The heteroaryl group preferably has 3 to 20 carbon atoms, and more preferably 3 to 10 carbon atoms. Examples of the heteroaryl group include a thienyl group and a pyridyl group.

  The acyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the acyl group include a formyl group, an acetyl group, and a benzoyl group.

  The alkylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylcarbonamide group include an acetamide group.

  The arylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the arylcarbonamide group include a benzamide group and the like.

  The alkylsulfonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the sulfonamide group include a methanesulfonamide group.

  The arylsulfonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the arylsulfonamide group include a benzenesulfonamide group and p-toluenesulfonamide group.

  The aralkyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms. Examples of the aralkyl group include a benzyl group, a phenethyl group, and a naphthylmethyl group.

  The alkoxycarbonyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Examples of the alkoxycarbonyl group include a methoxycarbonyl group.

  The aryloxycarbonyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

  The aralkyloxycarbonyl group preferably has 8 to 20 carbon atoms, and more preferably 8 to 12 carbon atoms. Examples of the aralkyloxycarbonyl group include a benzyloxycarbonyl group.

  The acyloxy group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

  The alkenyl group has preferably 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkenyl group include vinyl group, allyl group and isopropenyl group.

  The alkynyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkynyl group include an ethynyl group.

  The alkylsulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyl group include a methylsulfonyl group and an ethylsulfonyl group.

  The arylsulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylsulfonyl group include a phenylsulfonyl group and a naphthylsulfonyl group.

  The alkyloxysulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkyloxysulfonyl group include a methoxysulfonyl group and an ethoxysulfonyl group.

  The aryloxysulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryloxysulfonyl group include a phenoxysulfonyl group and a naphthoxysulfonyl group.

  The alkylsulfonyloxy group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyloxy group include a methylsulfonyloxy group and an ethylsulfonyloxy group.

  The arylsulfonyloxy group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylsulfonyloxy group include a phenylsulfonyloxy group and a naphthylsulfonyloxy group. The substituents may be the same or different, and these substituents may be further substituted.

In the structural unit having a hydroxy group represented by formula (I) according to the present invention, A represents a substituted or unsubstituted alkylene group, or — (CH ₂ CHRbO) _x — (CH ₂ CHRb) —. The alkylene group preferably has, for example, 1 to 5 carbon atoms, more preferably an ethylene group or a propylene group. These alkylene groups may be substituted with the substituent described above.

  Rb represents a hydrogen atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. Moreover, these alkyl groups may be substituted with the above-mentioned substituent. Furthermore, x represents the average number of repeating units, preferably 0 to 100, more preferably 0 to 10. The number of repeating units has a distribution, and the notation indicates an average value and may be expressed with one decimal place.

  Hereinafter, typical specific examples of the structural unit represented by the general formula (I) are shown, but the present invention is not limited thereto.

（解離性基を有する自己分散型ポリマー）
また本発明では、ヒドロキシ基を有する非導電性ポリマーに変えて解離性基を有する自己分散型ポリマーを使用することが好ましい。

(Self-dispersing polymer having a dissociable group)
In the present invention, it is preferable to use a self-dispersing polymer having a dissociable group instead of the non-conductive polymer having a hydroxy group.

  In the present invention, the self-dispersing polymer having a dissociable group refers to a polymer that does not contain a surfactant or an emulsifier that assists micelle formation and can be dispersed in an aqueous solvent as a single polymer. “Dispersible in an aqueous solvent” means that colloidal particles made of a binder resin are dispersed in the aqueous solvent without agglomeration. The size of the colloidal particles is generally about 0.001 to 1 μm (1 to 1000 μm). The colloidal particle size is preferably 3 to 500 nm, more preferably 5 to 300 nm, and still more preferably 10 to 100 nm. When the colloidal particles are large (when the colloidal particles are larger than 500 nm), the smoothness deteriorates when forming a film using the colloidal particles. Further, when the colloidal particles are extremely small (smaller than 3 nm), there are restrictions on the production of the colloidal particles such as causing aggregation of the particles, and the cost is increased. The size of the colloidal particles can be measured with a light scattering photometer.

  The aqueous solvent is not only pure water (including distilled water and deionized water) but also an aqueous solution containing acid, alkali, salt, etc., a water-containing organic solvent, or a hydrophilic organic solvent. Examples of the aqueous solvent include pure water (including distilled water and deionized water), alcohol solvents such as methanol and ethanol, and mixed solvents of water and alcohol.

  The self-dispersing polymer having a dissociable group according to the present invention is preferably transparent. The self-dispersing polymer having a dissociable group is not particularly limited as long as it is a medium that forms a film. Further, there is no particular limitation as long as there is no problem in bleeding out to the surface of the transparent electrode and electrode performance, but the polymer dispersion preferably does not contain a surfactant (emulsifier), a plasticizer for controlling the film forming temperature, or the like. .

  The average particle size of the self-dispersing polymer having a dissociable group according to the present invention is preferably 5 to 100 nm.

  The glass transition temperature (Tg) of the self-dispersing polymer having a dissociable group according to the present invention is preferably 25 to 80 ° C, more preferably 30 to 75 ° C, and further preferably 50 to 70 ° C. . The glass transition temperature Tg can be measured according to JIS K7121 (1987) using a differential scanning calorimeter (DSC-7 model manufactured by Perkin Elmer) at a temperature rising rate of 20 ° C./min.

  The pH at 25 ° C. of the dispersion of the self-dispersing polymer having a dissociable group is preferably 0.1 to 11.0, more preferably 3 from the viewpoint that it does not separate from the conductive polymer solution to be separately compatible. It is 0.0-9.0, More preferably, it is 4.0-7.0.

  Examples of the dissociable group used in the self-dispersing polymer having a dissociable group include an anionic group (sulfonic acid and its salt, carboxylic acid and its salt, phosphoric acid and its salt, etc.), a cationic group (ammonium salt, etc.) ) And the like. Such a dissociable group is not particularly limited, but an anionic group is preferable from the viewpoint of compatibility with the conductive polymer. The amount of the dissociable group is not particularly limited as long as the self-dispersing polymer can be dispersed in the aqueous solvent, and is preferably as small as possible because the drying load is reduced in a suitable manner in the process. Further, the counter species used for the anionic group and the cationic group are not particularly limited, but are preferably hydrophobic and in a small amount.

  The main skeleton of the self-dispersing polymer having a dissociable group is polyethylene, polyethylene-polyvinyl alcohol (PVA), polyethylene-polyvinyl acetate, polyethylene-polyurethane, polybutadiene, polybutadiene-polystyrene, polyolefin copolymer, polyamide (nylon). , Polyvinylidene chloride, polyester, polyacrylate, polyacrylate-polyester, polyacrylate-polystyrene, polyvinyl acetate, polyurethane-polycarbonate, polyurethane-polyether, polyurethane-polyester, polyurethane-polyacrylate, silicone, silicone-polyurethane, silicone- Polyacrylate, polyvinylidene fluoride-polyacrylate, polyfluoroolefin-polyvinyl ether And the like. Further, based on these skeletons, copolymerization using another monomer may be the main skeleton. Among these, a polyester resin emulsion having an ester skeleton, a polyester-acrylic resin emulsion, and a polyethylene resin emulsion having an ethylene skeleton are preferable.

  As commercial products, Polysol FP3000 (polyester resin, anion, core: acrylic, shell: polyester, manufactured by Showa Denko KK), Vironal MD1480 (polyester resin, anion, manufactured by Toyobo Co., Ltd.), Vironal MD1245 (polyester resin, anion, Toyobo Co., Ltd.) ), Bironal MD1500 (polyester resin, anion, manufactured by Toyobo Co., Ltd.), Bironal MD2000 (polyester resin, anion, manufactured by Toyobo Co., Ltd.), Bironal MD1930 (polyester resin, anion, manufactured by Toyobo Co., Ltd.), Plus Coat RZ105 (polyester resin, anion) , Manufactured by Mutual Chemical Co., Ltd.), Plus Coat RZ570 (polyester resin, anion, manufactured by Interactive Chemical Co., Ltd.), Plus Coat RZ571 (polyester resin, anion, manufactured by Interactive Chemical Co., Ltd.) Itec S-9242 (polyethylene resin, anion, manufactured by Toho Chemical Co., Ltd.), Movinyl 7720 (acrylic resin, nonion, manufactured by Nippon Synthetic Chemical Co., Ltd.), Movinyl 7820 (acrylic resin, nonion, manufactured by Nippon Synthetic Chemical Co., Ltd.) can be used. . In addition, the self-dispersing polymer having a dissociable group may contain one kind of those described above, or may contain a plurality of kinds.

  The conductive polymer according to the present invention can be dispersed in a self-dispersing polymer having a dissociable group and an aqueous solvent. The aqueous solvent is not only pure water (including distilled water and deionized water), but also an aqueous solution containing acid, alkali, salt, etc., a water-containing organic solvent, or a hydrophilic organic solvent. Examples of the aqueous solvent include pure water (including distilled water and deionized water), alcohol solvents such as methanol and ethanol, and mixed solvents of water and alcohol.

  The pH of the dispersion at 25 ° C. is not particularly problematic as long as desired conductivity is obtained, but is preferably 0.1 to 7.0, and more preferably 0.3 to 5.0.

  In order to control the surface tension of the dispersion, an organic solvent may be added to the dispersion. The organic solvent is not particularly limited as long as a desired surface tension can be obtained, but a monovalent, divalent or polyvalent alcohol solvent is preferable. The boiling point of the organic solvent is preferably 200 ° C. or lower, more preferably 150 ° C. or lower.

  The average particle diameter of the conductive polymer and the self-dispersing polymer having a dissociative group contained in the dispersion is preferably 5 to 100 nm, more preferably 7 to 80 nm, and still more preferably 10 to 50 nm. . Even if the average particle size is controlled, if the film-forming temperature of the self-dispersing polymer having a dissociable group used is too high, the film shape does not form within the drying temperature, and the particle shape remains and the average roughness of the film surface remains. Therefore, it is desirable to control the film forming temperature.

  Examples of a method for setting the average particle size of the dispersion to a desired range include a homogenizer, an ultrasonic disperser (US disperser), a dispersion technique using a ball mill, a reverse osmosis membrane, an ultrafiltration membrane, and a microfiltration membrane. The classification of the used particles can be used. Dispersion techniques using a homogenizer, an ultrasonic disperser (US disperser), a ball mill, etc. are all likely to increase in particle size at high temperatures. Therefore, the temperature during the dispersion operation is preferably 3 to 50 ° C. More preferably, it is 5-30 degreeC. Classification is not particularly limited as long as a membrane to be used is selected as necessary.

  Self-dispersing polymer particles having a dissociable group and conductive polymer particles in the dispersion are in a state where each particle is dispersed independently and the particle size is the sum of the particle sizes. In addition, particles having different compositions may be aggregated. Further, particles having different compositions may be partially mixed during the dispersion operation, or may be completely mixed to form particles.

  The use amount (solid content) of the self-dispersing polymer having a dissociable group is preferably 50 to 1000% by mass, more preferably 100 to 900% by mass, and still more preferably based on the solid content of the conductive polymer. Is 200-800 mass%.

  The particle size measurement method of the dispersion is not particularly limited, but is preferably a dynamic light scattering method, a laser diffraction method or an image imaging method, more preferably a dynamic light scattering method. The self-dispersing polymer particles and conductive polymer particles having dissociative groups are not measured with surfactants, and the particle size becomes unstable by dilution. A dense particle size measuring machine that can be used is preferable, and examples of such a concentrated particle size measuring device include a concentrated particle size analyzer (manufactured by Otsuka Electronics Co., Ltd.), the Zetasizer Nano Series (manufactured by Malvern), and the like.

[Other binders that can be uniformly dispersed in aqueous solvents]
In the present invention, other binders that can be uniformly dispersed in an aqueous solvent may be used, and any binder may be used as long as it is transparent.

  The binder that can be uniformly dispersed in the aqueous solvent is not particularly limited as long as it is a medium for forming a film. Examples of the binder that can be uniformly dispersed in the aqueous solvent include: acrylic resin emulsion, aqueous urethane resin, and the like. The acrylic resin emulsion is made of vinyl acetate, acrylic acid, a polymer of acrylic acid-styrene, or a copolymer with other monomers. In addition, the acid part is composed of a copolymer of an anionic lithium salt, sodium salt, potassium salt, ammonium salt, and a monomer having a nitrogen atom, and a cationic nitrogen atom forming a hydrochloride salt, Preferably it is anionic.

  Examples of aqueous urethane resins include water-dispersed urethane resins and ionomer-type aqueous urethane resins (anionic). The water-dispersed urethane resin includes a polyether-based urethane resin and a polyester-based urethane resin, preferably a polyester-based urethane resin.

  Examples of the ionomer-type water-based urethane resin include a polyester-based urethane resin, a polyether-based urethane resin, a polycarbonate-based urethane resin, and the like, preferably a polyester-based urethane resin and a polyether-based urethane resin.

  As commercial products, Boncoat AN-155-E, Boncoat AC-501, Boncoat AN-200, Boncoat R-3380-E (acrylic resin emulsion (anionic)), Bondick 1940NE (water-dispersed polyurethane resin, polyether) -Based urethane resin), Bondick 2210, Bondick 2220 (water-dispersed polyurethane resin, polyester-based urethane resin), Hydran 140SF, Hydran AP-40 (F), Hydran AP-40N (Ionomeric aqueous urethane resin, polyester-based urethane) Resin), Hydran HW-312B, Hydran WLS-201 (ionomer type water-based urethane resin, polyether urethane resin) (all manufactured by DIC Corporation) can be used. One or more binders that can be uniformly dispersed in the aqueous solvent can be used.

  The amount of the binder that can be uniformly dispersed in the aqueous solvent is preferably 1 to 200% by mass, more preferably 5 to 100% by mass with respect to the conductive polymer.

[Formation of conductive polymer layer]
As a method for forming a layer containing a conductive polymer according to the present invention (also simply referred to as a conductive polymer layer) on a transparent film substrate, both high productivity and reduction in production cost and environmental burden From the viewpoint of reduction, it is preferable to use a liquid phase film forming method such as a coating method or a printing method. As coating methods, known roll coating methods, bar coating methods, dip coating methods, spin coating methods, casting methods, die coating methods, blade coating methods, bar coating methods, gravure coating methods, curtain coating methods, spray coating methods, doctors A coating method or the like can be used. As a printing method, a letterpress (letter) printing method, a stencil (screen) printing method, a lithographic (offset) printing method, an intaglio (gravure) printing method, a spray printing method, an ink jet printing method, or the like can be used.

  After forming a conductive polymer layer by a liquid phase film-forming method, a drying process can be suitably performed. Although there is no restriction | limiting in particular as conditions for a drying process, It is preferable to process at the temperature of the range which does not damage a film base material or a conductive polymer layer. Moreover, after forming the conductive polymer layer containing the metal fine particles according to the present invention, it is possible to perform pressurization or pressurization heat treatment as needed at any timing. Thereby, higher conductivity can be obtained and the surface can be smoothed. In pressurization, surface-to-surface pressurization with the plate on the plate, nip roll pressurization with the film substrate passing between the rolls, and combined pressurization with the roll on the plate Can be adopted. Moreover, since it becomes effective when it heats at the time of pressurization, it is preferable to heat in the range of 40-300 degreeC. The heating time is adjusted in relation to the temperature and can be short at high temperatures and long at low temperatures. In the case of a nip roll, the heating method includes a method of heating the roll to a predetermined temperature in advance and a method of heating in a heating chamber such as an autoclave chamber.

  The dry film thickness of the conductive polymer layer can be appropriately selected in consideration of the sheet resistivity required from the transmittance of the conductive polymer layer and the size of the opening of the thin metal wire, but is preferably 30 to 2000 nm. . From the viewpoint of conductivity, the thickness is more preferably 200 nm or more, and from the viewpoint of transparency, it is more preferably 1000 nm or less.

  Although there is no restriction | limiting in particular as conditions of a drying process, It is preferable to dry-process at the temperature of the range which does not damage a base material and an electrode. Further, by performing the heat treatment, the solvent in the coating liquid can be evaporated, and the condensation reaction between the water-soluble binder of the conductive polymer layer or between the conductive polymer and the water-soluble binder can be promoted and completed. Thereby, the cleaning resistance and solvent resistance of the electrode are remarkably improved, and the device performance is further improved.

  The drying step and the heat treatment step may be the same step or may be performed separately. In the case of separate processes, drying and heat treatment may be continuous, and there may be a time pause between the two processes.

  There is no limitation on the conditions of the drying step and the heat treatment step, but the drying can be performed at a temperature of 80 ° C. or higher, for example, as a condition that allows the solvent to be evaporated quickly, and the upper limit is a temperature at which the conductive layer is not damaged. It is considered to be a possible region up to about ℃. The time is preferably in the range of about 10 seconds to 10 minutes.

  Further, the heat treatment is preferably performed at a temperature of 100 ° C. or higher and 300 ° C. or lower. When the temperature is lower than 100 ° C., the evaporation of the solvent in the coating solution is not completed, and thus the reaction promoting effect is small. When the temperature exceeds 300 ° C., a part of the conductive polymer is decomposed by heat, and the resistance of the conductive polymer layer is increased. The heat treatment time is preferably 1 minute or longer. The upper limit of the treatment time is not particularly limited, but is preferably 24 hours or less from the viewpoint of productivity. However, when the heat treatment temperature exceeds 200 ° C., it is preferable to keep it within 30 minutes.

  The heat treatment may be performed on-line or off-line after applying and drying the conductive layer. In the case of off-line, it is preferable to further perform under reduced pressure because it leads to accelerated drying of moisture.

  Examples of the heat treatment method include heating using a heater or IR heater, vacuum drying, induction heating, microwave heating, laser heating, plasma heating, etc. From the viewpoint of simplicity of temperature and humidity control, the heater is used. The heating used is preferred.

  In the present invention, the condensation reaction between the water-soluble binder of the conductive polymer layer or between the conductive polymer and the water-soluble binder can be promoted and completed using an acid catalyst. As the acid catalyst, hydrochloric acid, sulfuric acid or ammonium sulfate can be used. Moreover, in the poly anion used as a dopant for a conductive polymer, a dopant and a catalyst can be used together by using a sulfo group-containing poly anion. In addition, the heat treatment described above can be performed in combination with the use of an acid catalyst, which is preferable because it shortens the treatment time.

<Light control layer>
Next, the light control layer according to the present invention will be described.

  Examples of conventionally known light control layers include normal mode, reverse mode, and memory mode nuclear polymer-liquid crystal systems described in “Reflective Color Liquid Crystal Display Technology” P61 published by CMC Publishing. Is a polymer-dispersed liquid crystal (PDLC: Polymer Dispersed LC), a polymer network-type liquid crystal (PNLC: Polymer Network LC), or the like, and any of them can be suitably used.

  Further, as a polymer dispersion type and network type dimming material that does not use liquid crystal, US Pat. Nos. 3,756,700, 4,247,175, and 4,247,175 by Robert L. Saxe, 273,422, 4,407,565 and 4,422,963, or US Pat. No. 3,912,365 to FC Lowell, Earl Eye A light control material using light polarizing particles disclosed in US Pat. No. 4,078,856 of Thompson (RI Thompson) can be mentioned, and as a technique for making these particles into a polymer dispersion type, JP-A-2008-158042 and JP-A-2002-214653, which can also be suitably used.

  Furthermore, light control layers using electrochromism technology are also disclosed in Japanese Patent Application Laid-Open Nos. 2009-265437 and 2011-39283, and these known light control layers are preferably used in the electrode material according to the present invention. it can.

  For example, a light control film using a liquid crystal is disclosed in “Polymer encapsulated Nematic Liquid Crystals for Display and Light Control Applications”, “SID '85 Digest”, 1985, J. Org. L. Fergason, Society for Information Display, pages 68-70, announcing a light-scattering LCD (PDLC) in which nematic liquid crystals are microencapsulated, US Pat. Nos. 4,435,047, 4,579,423, No. 4,616,903, J.L. West, US Pat. No. 4,685,771, and the like.

  Furthermore, DIC Corp. And polymer network (PNLC) type liquid crystals in which pyridine-based liquid crystals are held in a polymer network, studied by Prof. Chisato Kajiyama of Kyushu University, etc. have been announced. It is usable without.

In particular,
1) Polymer dispersed liquid crystal by polymer phase separation method using curable resin such as liquid crystal material (nematic liquid crystal etc.) and epoxy 2) Liquid crystal by emulsion method using liquid crystal material (nematic liquid crystal etc.) and PVA or resin emulsion Capsule dispersion type 3) Polymer network technology by photopolymerization phase separation method using liquid crystal material (nematic liquid crystal etc.) and (di) acrylate 4) Photopolymerization phase using liquid crystal material (nematic liquid crystal etc.) and (di) acrylate Reflective light distribution grain fibril technology by separation method (IRIS type)
5) Memory type polymer network type liquid crystal technology by a photopolymerization phase separation method using a liquid crystal material (cholesteric liquid crystal or the like) and (di) acrylate.

  The liquid crystal used is preferably a nematic liquid crystal, a smectic liquid crystal, or a cholesteric liquid crystal, and particularly preferably a nematic liquid crystal. Further, in order to improve the performance, a cholesteric liquid crystal, a chiral nematic liquid crystal, a chiral smectic liquid crystal or the like, or a chiral compound or the like may be included as appropriate.

  In these technologies, nematic liquid crystals are important, and cyanobiphenyl liquid crystal materials have been developed for a long time, and cyanophenylcyclohexane liquid crystals with significantly improved response speed have been developed. Furthermore, with the practical use of liquid crystals, materials exhibiting liquid crystallinity in various temperature ranges are demanded, and alkylbiphenylcyclohexane liquid crystals, P-type ester liquid crystals, pyrimidine liquid crystals, phenylbicyclohexane liquid crystals and the like have been developed.

  Furthermore, 3-chloro-4-cyanophenol ester, 3-fluoro-4-cyanophenol ester derivative, tolan-based liquid crystal, alkenyl-based liquid crystal, cyclohexene-based liquid crystal, azine-based liquid crystal, and the like can be used. is there.

  In addition, as described above, in order to expand the use environment temperature range of the liquid crystal device, it is a preferable aspect to use a plurality of liquid crystals having different liquid layer temperatures, and usually 3 or more types, preferably 5 or more types are mixed and used. It is preferable to do.

  Specific examples of the liquid crystal material that can be used in the present invention include, for example, those of the compound group shown below. Depending on the required physical properties and applications, the characteristics of the liquid crystal material, that is, the phase transition temperature between the isotropic liquid and the liquid crystal, Considering the positive and negative of melting point, viscosity, birefringence index, dielectric anisotropy (Δε), or selecting and blending appropriately for the purpose of adjusting the solubility with other additives such as polymerizable compositions Can be used.

（式中、環Ａ、Ｂ及びＣは、それぞれ独立に、下記の環のいずれかを表し、

ｎは０〜２の整数、ｍは１〜４の整数を表し、Ｙ_１及びＹ_２は、それぞれ独立に、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−（ＣＨ_２）_４−、−ＣＨ_２ＣＨ_２ＣＨ_２Ｏ−、又は−ＣＨ_２＝ＣＨＣＨ_２ＣＨ_２を表し、Ｙ_３は、単結合、−ＣＯＯ−、又は−ＯＣＯ−を表し、Ｒ_１及びＲ_２はそれぞれ独立に水素原子、ハロゲン原子、シアノ基、炭素原子数１〜２０のアルキル基、アルコキシ基、アルケニル基、アルケニルオキシ基、フルオロアルキル基、又はフルオロアルコキシ基を表す。）で表される液晶化合物を用いることができる。 Liquid crystal materials include benzoic acid ester, cyclohexanecarboxylic acid ester, biphenyl, terphenyl, phenylcyclohexane, pyrimidine, pyridine, dioxane, cyclohexanecyclohexane ester, tolan, alkenyl, and fluoro. A compound represented by the general formula (II) such as cyano group and naphthalene group,

(Wherein, rings A, B and C each independently represent any of the following rings:

n represents an integer of 0 to 2, m represents an integer of 1 to 4, and Y ₁ and Y ₂ each independently represent a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —COO—, — OCO -, - C≡C -, - CH = CH -, - CF = CF -, - (CH 2) 4 -, - CH 2 CH 2 CH 2 O-, or an _{-CH 2} = CHCH 2 CH 2 Y ₃ represents a single bond, —COO—, or —OCO—, and R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, An alkenyl group, an alkenyloxy group, a fluoroalkyl group, or a fluoroalkoxy group is represented. ) Can be used.

  The content of the liquid crystal material in the light control layer forming material is preferably in the range of 50 to 99% by mass, more preferably in the range of 60 to 90% by mass.

  More recently, liquid crystal has been improved for the purpose of improving the bending resistance and weather resistance of the light control layer, which is very preferable when used in combination with the electrode material according to the present invention. The electrode material according to the present invention has very strong bending resistance and weather resistance, and hardly undergoes deterioration due to oxidation or UV irradiation. For this reason, the light control film obtained by these combinations can provide the ease of use and durability overwhelming the conventional light control film in the application nature as a film, and the sticking use in the window etc. which an ultraviolet-ray inserts.

  As a liquid crystal material that realizes these, for example, Japanese Patent Application Laid-Open No. 2011-105908 can be cited, and the bending resistance of the light control layer can be improved by a combination of these liquid crystal material and an acrylic photopolymerization material as a polymer network. This is a preferable mode.

  For example, a compound represented by the following general formula (III) is preferable.

（式中、Ｒ^１、及びＲ^２は、それぞれ独立して、炭素原子数１〜１０のアルキル基、又は炭素原子数２〜１０のアルケニル基を表し、該アルキル基、及びアルケニル基中の非隣接の１つ又は２つ以上の−ＣＨ_２−基は酸素原子、−ＣＯＯ−、又は−ＯＣＯ−で置き換えられていてもよく、環Ａ^１は、１，４−フェニレン基、１，４−シクロヘキシレン基、１，３−ジオキサン−２，５−ジイル基、又はピリミジン−２，５−ジイル基を表し、該１，４−フェニレン基は非置換であるか又は置換基として１個又は２個以上のフッ素原子、塩素原子、ＣＦ_３基、ＯＣＦ_３基又はＣＨ_３基を有することができ、Ｚ^１、及びＺ^２は、それぞれ独立して、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２−ＣＨ_２−、−ＣＦ_２−ＣＦ_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、又は−Ｃ≡Ｃ−を表し、Ｘ^１〜Ｘ^８は、それぞれ独立して、水素原子、フッ素原子、塩素原子、ＣＦ_３基、ＯＣＦ_３基、又はＣＨ_３基を表す。）で表される液晶化合物である。

(In the formula, each of R ¹ and R ² independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. One or more adjacent —CH ₂ — groups may be replaced by an oxygen atom, —COO—, or —OCO—, and ring A ¹ is a 1,4-phenylene group, 1,4- Represents a cyclohexylene group, a 1,3-dioxane-2,5-diyl group, or a pyrimidine-2,5-diyl group, and the 1,4-phenylene group is unsubstituted or has one or two substituents; It may have one or more fluorine atoms, chlorine atoms, CF ₃ groups, OCF ₃ groups or CH ₃ groups, and Z ¹ and Z ² are each independently a single bond, —COO—, —OCO—, _{-CH 2 -CH 2 -, - CF} 2 -CF 2 -, - _{H = CH -, - CF =} CF -, - CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2 -, or -C≡C- ^represents, X 1 to X ⁸ are each Independently, it represents a hydrogen atom, a fluorine atom, a chlorine atom, a CF ₃ group, an OCF ₃ group, or a CH ₃ group.

  Further, a general light control film tends to be preferred to have higher cloudiness. In order to obtain high turbidity, the Δn (refractive index anisotropy) of the liquid crystal composition should be large, and there is an optimum size for the polymer network structure or the particle size of the liquid crystal droplets. On the other hand, when a sufficiently high voltage is applied, the liquid crystal composition is aligned in the direction of the electric field, and the scattering property of the liquid crystal composition itself is lost. Here, if the difference between the refractive index of the polymer and the no (ordinary refractive index) of the liquid crystal composition is sufficiently small, light scattering does not occur and a transparent state is obtained. Therefore, in order to obtain high transparency, it is necessary to match the refractive index of the polymer with the refractive index of the liquid crystal composition. Also in these points, conventionally known knowledge can be preferably used.

  As described above, there are a plurality of resin matrices such as a photopolymerization system and an emulsion type as the resin matrix constituting the liquid crystal and resin composite as described above. Here, the emulsion type which is practically used in the market will be described.

  As resins, polyvinyl alcohol, polyethylene glycol, polyurethane and the like have been studied. Among these resins, polyurethane is excellent from the viewpoints of processability and heat resistance. In order to disperse the liquid crystal microparticles in the resin matrix, a phase separation method or an emulsion method can be used. As described above, the emulsion method has been put into practical use. In the emulsion method, a state in which liquid crystal microparticles are dispersed, that is, a state in which liquid crystal is “pseudo-encapsulated” is realized by stirring an emulsion containing a liquid crystal material at a high speed.

  A liquid crystal material and other necessary materials are added to the polymer emulsion to prepare a liquid crystal-resin composite material (liquid crystal emulsion).

  In order to form liquid crystal microparticles, a liquid crystal material is previously stirred in water to form liquid crystal microparticles, and this is mixed with a polymer emulsion. On the other hand, the liquid crystal material may be directly added to the polymer emulsion and stirred to form liquid crystal microparticles. A surfactant may be added as an emulsifier in order to make the shape and particle size of the liquid crystal microparticles uniform. As this surfactant, a nonionic surfactant is preferable, and a nonionic surfactant of HLB 8-18, particularly HLB 10-16 is more preferable. The HLB value (Hydrophile-Lipophile Balance) is a value representing the degree of affinity of a surfactant to water and oil (an organic compound insoluble in water). A product with higher lipophilicity has a lower HLB value, and a product with higher hydrophilicity has a higher HLB value.

  The mixing and stirring in the above may be performed using a homogenizer, homomixer, disperser, high-pressure emulsifier, blender, colloid mill, ultrasonic emulsifier or the like.

  Thus, an emulsion (liquid crystal emulsion) in which liquid crystal microparticles are dispersed is prepared.

  The median diameter D50 of the liquid crystal microparticles is preferably in the range of 1.5 to 4.5 μm. When the median diameter D50 exceeds 4.5 μm, the surface area per unit mass of the liquid crystal microparticles is reduced, and the shielding property when the voltage is released is lowered. On the other hand, when the median diameter D50 is less than 1.5 μm, the surface area per unit mass of the liquid crystal microparticles increases, but the effect of transmission and diffraction on the visible wavelength side longer wavelength side exceeds the increase in light scattering due to this. For this reason, as a result, the shielding performance when the voltage is released is also lowered.

  In order to obtain desired optical performance, it is desirable to adjust not only the median type of liquid crystal microparticles (liquid crystal capsules) but also the particle size distribution within an appropriate range. When the ratio of particles having a large particle diameter increases, scattering in the visible region is almost eliminated, and the shielding property in a voltage open state is lowered. Therefore, the ratio (D90 / D10) of the liquid crystal capsule diameter D10 at which the cumulative transmittance in the cumulative curve of the liquid crystal capsule diameter is 10% and the liquid crystal capsule diameter D90 at which the cumulative transmittance is 90% is D90 / It is preferable that D10 ≦ 3 × D50. More preferably, D90 / D10 ≦ 2.5 × D50.

  The median diameter D50 and particle size distribution of the liquid crystal microparticles can be controlled by adjusting the stirring speed and time. In this specification, a value measured by a laser diffraction method is adopted as the particle size of the liquid crystal microparticles.

  On the film substrate provided with the transparent electrode according to the present invention as described above, the light control layer solution thus prepared was rolled, bar coating, dip coating, spin coating, casting, die coating, It is preferable to form using a coating method such as a blade coating method, a bar coating method, a gravure coating method, a curtain coating method, a spray coating method, or a doctor coating method.

  The light control layer according to the present invention may be laminated directly on the transparent electrode, may be provided with any overcoat layer on the transparent electrode, or may be laminated after the cover film is bonded and formed. Can also be suitably used.

  The applied liquid crystal emulsion is dried to remove excess water / solvent. When a crosslinking agent is added, a crosslinked structure is introduced into the copolymer as it is dried. The emulsion may be dried at room temperature, or known heating may be applied within a range that does not damage the substrate.

  The film thickness of the liquid crystal-resin composite formed by applying the liquid crystal emulsion is preferably 10 to 35 μm, particularly preferably 15 to 25 μm, considering the balance between the transparency and shielding properties of the liquid crystal light control device.

(Formation width of each layer)
FIG. 6 is a schematic diagram illustrating a preferred example of the configuration of the light control film of the present invention.
A transparent electrode 52b is provided on the film substrate 51b, and a light control layer 53a is formed thereon. Furthermore, it is comprised from the transparent electrode 52a provided on the film base material 51a as a counter electrode on it. In the light control layer 53a, liquid crystal particles 54b are dispersed in a resin matrix (resin layer) 54a.
Here, it is preferable that a transparent electrode having a width Y is formed on a substrate having a width X, and a light control layer having a width Z is further formed thereon.
In this invention, it is preferable to provide the formation width of a base material, a transparent electrode, and a light control layer as follows. Thereby, the effect which makes it easy to take out an electrode without requiring complicated patterning is obtained.
That is, the transparent electrode and the light control layer may be provided on the base material so that the base material width (X), the transparent electrode formation width (Y), and the light control layer formation width (Z) are in the following order. , Roll-to-Roll samples can be used for two-point power supply, or even when the user's demand size is interrupted on two sides, the end power supply can be easily taken out. It is possible to realize production management by freely changing the cutting width, and to provide an inexpensive light control film that has never been available.

  Substrate width> Transparent electrode formation width> Light control layer formation width

  The difference between the width of the base material and the formation width of the transparent electrode is 0.1 mm or more (0.05 mm for each left and right) and preferably 20 mm or less (10 mm for each left and right), more preferably 1 mm or more (0.5 mm for each left and right) and 10 mm or less. (5 mm for each left and right).

  Similarly, the difference in formation width between the transparent electrode and the light control layer is also 0.1 mm or more (0.05 mm for each left and right), preferably within 20 mm (10 mm for each left and right), more preferably 1 mm or more (each 0.5 mm for each left and right), It is within 10 mm (5 mm for each left and right).

  After forming the transparent electrode and the light control layer on the base material so that the formation width of the base material, the transparent electrode, and the light control layer is as described above, another transparent electrode facing the transparent electrode can be installed. From the viewpoint of production process, it is preferable from the viewpoint of easy production.

  Even in the above manner, it is described in International Publication No. 2009/093657 pamphlet (FIG. 4: dimming layer single layer type) and JP-A-6-3654 (FIG. 1: dimming layer double layer type). Such a light control film is obtained. In this way, a light control film using a liquid crystal material in which the liquid crystal-resin composite is sandwiched between the two substrates with transparent electrodes in contact with the transparent electrodes is manufactured.

[Light control film element driving method]
The driving operation of the light control film element of the present invention may be simple matrix driving or active matrix driving. The simple matrix driving in the present invention is a driving method in which a current is sequentially applied to a circuit in which a positive line including a plurality of positive electrodes and a negative electrode line including a plurality of negative electrodes are opposed to each other in a vertical direction. I mean. By using simple matrix driving, there is an advantage that the circuit configuration and driving IC can be simplified and manufactured at low cost. The active matrix drive is a system in which scanning lines, data lines, and current supply lines are formed in a grid pattern, and are driven by TFT circuits provided in each grid pattern. Since switching can be performed for each pixel, there are advantages such as gradation and memory function.

[Light control film for pasting windows]
The light control film of the present invention enables simple workability and low-priced supply, which cannot be realized with conventional light control films, and can be used by being attached to an existing glass window. It is a new light control film that has both light function and crack prevention function (crime prevention / disaster prevention function).

  Therefore, when a 100 μm-thick polyethylene naphthalate film is used as the base material of the light control film of the present invention, it is preferable that it has a durability of 100 times or more in a bending durability test with a shaft radius of 3 mmR, and 0.3 mmR It is preferable that there is durability of 100 g or more in the scratch weight evaluation.

The bending durability test is performed by a winding method. The winding method is a kind of bending test, and is a test method in which a test piece is wound around a shaft or a mold by gradually applying a load so that the test piece has a specified shape. With this method, the number of tests is 100 times to determine how many mmR the shaft radius can withstand deterioration, and the durability is evaluated. The judgment of no deterioration is made within 10% of resistance change. (See Figure 5.)
Scratch load evaluation uses a wear resistance tester (HEIDON-18), a sapphire needle with a needle tip of 0.3 mmR, and a load from the back surface (first electrode side) of the light control film from 0 g to 200 g at intervals of 20 g. I scratched it. Drive the light control film before and after loading, and check the load area where there is no problem in operation.

  In order for the light control film of the present invention to have a durability of 100 times or more in a bending durability test with an axial radius of 3 mmR and a durability of 100 g or more in a scratch load evaluation of 0.3 mmR, the transparent film of the present invention is used. The most important factor is that the electrode is a composite electrode containing fine metal particles and a conductive polymer, but the combination of the liquid crystal material represented by the general formula (III) described above and an acrylic photopolymerization material as a polymer network It is also preferable to increase the strength of the light control layer itself.

  In the present invention, a dimming film for window pasting is provided by providing an adhesive layer for glass pasting and an easily peelable peeling support on the side opposite to the side having the transparent electrode of the dimming film obtained as described above. It is preferable that

  Examples of the resin film used for the release support include a polyester resin, a polyurethane resin, a polyvinyl chloride resin film, and the like, and a polyester resin film is particularly preferable in view of weather resistance, scratch resistance, cost, and the like. It is. The heat shrinkage rate of the film can be made desired by, for example, selecting a resin constituting the film, or appropriately selecting a stretching method after the film formation, heat treatment conditions, and the like. The thickness of the base film is not particularly limited, but is preferably in the range of 18 to 120 μm from the viewpoint of workability. Note that the shrinkage ratio in the vertical direction and the horizontal direction need not be the same, but if substantially the same, it is advantageous because the film can be applied without particularly worrying about the direction of the film.

  There is no restriction | limiting in particular in the adhesive used for the adhesion layer provided in a base film, For example, a natural rubber type, an acrylic type, a urethane type, and a polyester-type adhesive are used. Of these, acrylic pressure-sensitive adhesives are preferred from the viewpoint of weather resistance. The thickness of the adhesive layer is not particularly limited, but is preferably in the range of 5 to 20 μm.

  The release sheet used for the light control film for pasting a window is not particularly limited. For example, a resin film such as polyester or polypropylene, a paper obtained by applying a silicone resin to a paper such as a laminate paper, a coated paper, or a glass paper, or an alkyd resin. The one coated with a release agent is used.

  The thermal processing performed when applying the light control film for pasting a window is made to adhere to the glass surface while heating from the side of the release film to remove wrinkles, so the release film has less shrinkage than the base film. preferable. The shrinkage rate of the release film is preferably smaller than the shrinkage rate of the base film in both the vertical and horizontal directions.

  Although the thickness in particular of the peeling film used for this light control film for window pasting is not restrict | limited, It is preferable to exist in the range of 16 micrometers-75 micrometers.

  The base film can contain an ultraviolet absorber or an infrared absorber as necessary, or can be colored with a dye or a pigment, or can be appropriately printed in advance. You may make the said chemical | medical agent, dye, and pigment contain in an adhesion layer. Moreover, it is also possible to use a base film obtained by laminating a film containing these drugs or a colored film via an adhesive layer. Furthermore, in order to improve the scratch resistance, it is preferable to provide a hard coat layer on the outer surface (surface on which no adhesive layer is provided) of the base film.

  In the method for producing a light control film for pasting a window, an adhesive is applied to a surface of a release sheet on which a release agent is applied using a coater such as a roll coater, a knife coater, or a blade coater, and then bonded to a base film. A publicly known method such as a method or a method in which an adhesive is applied to one surface of a base film with the coater, dried, and bonded to a release sheet can be employed. The thickness of the light control film for pasting a window is not particularly limited, but is preferably in the range of 50 μm to 200 μm.

  After these processes, it is a particularly preferable aspect that the light control film for pasting a window is wound and provided in the form of a long roll.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
<Preparation of the light control film of Comparative Examples 1-6 and this invention 1 and 2>
[Preparation of light control layer material]
(Production example 1 of light control particles)
In order to produce light control particles, in a 500 ml four-necked flask equipped with a stirrer and a cooling tube, nitrocellulose 1 / 4LIG (trade name, manufactured by DLX8-13 Nobel) is 15% by mass, and the solvent is isoamyl acetate. (Reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.) 87.54 g of diluted solution, 44.96 g of isoamyl acetate, dehydrated CaI ₂ (water content 0.3%) (chemical, manufactured by Wako Pure Chemical Industries, Ltd.) 4 .5 g, 2.0 g of anhydrous methanol (for organic synthesis, manufactured by Wako Pure Chemical Industries, Ltd.) and 0.50 g of purified water (purified water, manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in a mixed solvent. Pyrazine-2,5-dicarboxylic acid dihydrate (Kanto Chemical Co., Ltd.), which is a substrate-forming substance of light adjusting particles, is dissolved in 4.5 g of iodine (special grade of JIS reagent, manufactured by Wako Pure Chemical Industries, Ltd.) 3 g) was added. After stirring at 45 ° C. for 3 hours to complete the reaction, the mixture was dispersed with an ultrasonic disperser for 2 hours.

  Next, in order to take out light control particles having a certain size from the reaction solution, the particles were separated using a centrifuge. First, the reaction solution was centrifuged at a speed of 500 G for 10 minutes to remove precipitates, and further centrifuged at 10000 G for 2 hours to remove suspended matters, and the precipitate particles were collected to obtain light-adjusted particles.

(Example of UV curable silicone resin production)
In a four-necked flask equipped with a Dean-Stark trap, condenser, stirrer, and heating device, 11.75 g of both-end silanol polydimethylsiloxane (Shin-Etsu Chemical Co., Ltd.), both-end silanol polydimethyldiphenylsiloxane (Shin-Etsu Chemical) 31 g, (3-acryloxypropyl) methyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 4 g, 2-ethylhexane tin (manufactured by Wako Pure Chemical Industries, Ltd.) 0.6 g, and heptane The mixture was refluxed at 100 ° C. for 3 hours to carry out the reaction.

  Next, 10.6 g of trimethylethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the reaction solution, and the mixture was refluxed for 2 hours for dealcoholization reaction. Thereafter, heptane was removed under reduced pressure at 80 ° C. for 3 hours under a vacuum of 60 Pa using a rotary evaporator to obtain an ultraviolet curable silicone resin (silicone resin having a substituent having an ethylenically unsaturated bond).

(Production example of light control suspension)
97 g of an isoamyl acetate dispersion of the light control particles obtained in (Preparation Example 1 of the light control particles) (dispersion in which 9 g of light control particles were dispersed in 88 g of isoamyl acetate) was used as a dispersion medium for the light control suspension. Butyl acrylate (Wako special grade, manufactured by Wako Pure Chemical Industries, Ltd.) / 2,2,2-trifluoroethyl methacrylate (for industrial use, manufactured by Kyoeisha Chemical Co., Ltd.) / 2-hydroxyethyl acrylate (Wako 1 Grade, manufactured by Wako Pure Chemical Industries, Ltd.) (monomer molar ratio: 18 / 1.5 / 0.5, weight average molecular weight: 2,200, refractive index 1.468) in addition to 59 g, 30 minutes with a stirrer Mixing was performed to obtain a mixed solution. Subsequently, using a rotary evaporator, the pressure was reduced at 80 ° C. under a vacuum of 60 Pa for 3 hours to remove isoamyl acetate from the mixed solution, and 29.5 g of decyl trimellitic acid (manufactured by Kao Corporation), dimethyl dodecaverate (Exfluor) To produce a stable liquid light-conditioning suspension free from particle sedimentation and agglomeration.

<Production of transparent electrode: ITO / Production of comparative electrode>
Using a non-alkali glass substrate (thickness 0.7 mm), ITO (indium tin oxide; refractive index 1.85) is deposited on the glass substrate by sputtering to a thickness of 100 nm, patterned, and then provided with this ITO transparent electrode The obtained substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes to produce a transparent electrode (Comparative Example 1).

  A 100 μm PEN film (Teonex Teijin Limited) was used. After depositing 100 nm of ITO (indium tin oxide; refractive index 1.85) on the surface of the PEN film by sputtering and patterning, the substrate provided with this ITO transparent electrode was ultrasonically washed with isopropyl alcohol and dried nitrogen It dried with gas and performed UV ozone washing | cleaning for 5 minutes, and produced the transparent electrode (comparative example 4).

<Preparation of transparent electrode: Composite electrode of metal nanoparticles + conductive polymer>
(1) Synthesis of conductive polymer 2.6 of poly (3,4-ethylenedioxythiophene) / Nafion (registered trademark) (hereinafter abbreviated as P-1) by the method described in Example 16 of Japanese Patent No. 4509787. % Dispersion was prepared.

(2) Synthesis of hydroxy group-containing polymer (2.1) Initiator 1: Synthesis of methoxy-capped oligoethylene glycol methacrylate 2-bromoisobutyryl bromide (7.3 g, 35 mmol) and triethylamine (2 .48 g, 35 mmol) and tetrahydrofuran (20 ml) were added, and the internal temperature was kept at 0 ° C. with an ice bath. In this solution, 30 ml of 33% THF solution of oligoethylene glycol (10 g, 23 mmol, ethylene glycol units 7-8, manufactured by Laporte Specialties) was added dropwise. After stirring for 30 minutes, the solution was brought to room temperature and further stirred for 4 hours. After THF was removed under reduced pressure by a rotary evaporator, the residue was dissolved in diethyl ether and transferred to a separatory funnel. Water was added and the ether layer was washed three times, and then the ether layer was dried with MgSO ₄ . The ether was distilled off under reduced pressure using a rotary evaporator to obtain 8.2 g (yield 73%) of initiator 1.

(2.2) Synthesis of hydroxy group-containing polymer by living polymerization (ATRP method) Initiator 1 (500 mg, 1.02 mmol), 2-hydroxyethyl acrylate (4.64 g, 40 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), 50: 50v 5 ml of a / v% methanol / water mixed solvent was put into a Schlenk tube, and the Schlenk tube was immersed in liquid nitrogen under reduced pressure for 10 minutes. The Schlenk tube was taken out of liquid nitrogen and replaced with nitrogen after 5 minutes. After performing this operation three times, bipyridine (400 mg, 2.56 mmol) and CuBr (147 mg, 1.02 mmol) were added under nitrogen, and the mixture was stirred at 20 ° C. After 30 minutes, the reaction solution was dropped onto a 4 cm Kiriyama funnel with filter paper and silica, and the reaction solution was recovered under reduced pressure. The solvent was distilled off under reduced pressure using a rotary evaporator and then dried under reduced pressure at 50 ° C. for 3 hours. As a result, 2.60 g (yield 84%) of a hydroxy group-containing polymer poly (2-hydroxyethyl acrylate) having a number average molecular weight of 13100, a molecular weight distribution of 1.17, a number average molecular weight of less than 1000 and a molecular content of 0%. Obtained. The structure and molecular weight were measured by ¹ H-NMR (400 MHz, manufactured by JEOL Ltd.) and GPC (Waters 2695, manufactured by Waters), respectively. The obtained polymer was diluted with water and adjusted to a 20% solution (hereinafter abbreviated as P-3).

(GPC measurement conditions)
Apparatus: Wagers 2695 (Separations Module)
Detector: Waters 2414 (Refractive Index Detector)
Column: Shodex Asahipak GF-7M HQ
Eluent: Dimethylformamide (20 mM LiBr)
Flow rate: 1.0 ml / min
Temperature: 40 ° C
(3) Preparation of extraction electrode The extraction electrode was formed by the following method.

  After vapor-depositing ITO with an average film thickness of 150 nm on an alkali-free glass substrate, the substrate was immersed in 2-propanol after the patterning shown in FIG. 4A by photolithography, and an ultrasonic cleaner Brandonic 3510J- Ultrasonic cleaning treatment for 10 minutes was performed by MT (manufactured by Nippon Emerson).

(4) Preparation of transparent electrode A metal conductive layer and a conductive polymer layer were laminated | stacked on the ITO surface on the transparent glass substrate for transparent electrodes obtained above, and the transparent electrode was produced.

(4.1) Formation of metal conductive layer A metal conductive layer was formed by the following method.

  Screen printing is performed on the above glass substrate using a silver nano ink (TEC-PA-010: manufactured by Inktec) with a grid pattern having a width of 50 μm and a pitch of 1 mm, and from the metal fine line pattern in the region of FIG. A metal conductive layer was formed. This was dried at 110 ° C. for 5 minutes, and further baked at 150 ° C. for 60 minutes.

  Note that STF-150IP (manufactured by Tokai Shoji Co., Ltd.) was used for screen printing.

  When the pattern of the metal conductive layer was measured with a high-intensity non-contact three-dimensional surface shape roughness meter WYKO NT9100 (manufactured by Biko Japan), the pattern width was 60 μm and the average height was 600 nm.

(4.2) Formation of conductive polymer layer On the patterned metal conductive layer, as a conductive polymer layer, conductive polymer (P-1, P-2), polymer having a hydroxy group (P-3) And the following coating liquid A which consists of a solvent (S-1-S-3) was used, and it coated so that the average dry film thickness might be set to 500 nm by the inkjet printing to the area | region of FIG.4 (c).

(Coating liquid A)
P-1: Poly (3,4-ethylenedioxythiophene) (PEDOT) / Nafion (registered trademark) (fluorinated polymer acid) 2.6% liquid 4.8 parts by mass P-2: CLEVIOS PH750 (manufactured by Heraeus) ) (Non-fluorinated polymer acid) 1.08% solution 34.7 parts by mass P-3: Poly (2-hydroxyethyl acrylate) aqueous solution (PHEA) 20% solution
3.8 parts by mass S-1: 2-propanol (IPA) 1.7 parts by mass S-2: propylene glycol (PG) 2.5 parts by mass S-3: propylene glycol monopropyl ether (PGPr) 2.5 parts by mass Part Next, it was dried at 80 ° C. for 5 minutes, and further heat-treated at 150 ° C. for 60 minutes to produce a transparent electrode (Comparative Example 3) composed of metal nanoparticles and a conductive polymer.

  The inkjet printer was controlled by an inkjet evaluation apparatus EB150 (manufactured by Konica Minolta IJ) using a desktop robot Shotmaster-300 (manufactured by Musashi Engineering Co., Ltd.) equipped with an ink jet head (manufactured by Konica Minolta IJ).

  In the same manner as above, a transparent electrode (Invention 2) made of metal nanoparticles and a conductive polymer was produced on a 100 μm PEN film (made by Teonex Teijin Ltd.).

<Preparation of transparent electrode: metal nanowire + conductive polymer>
[Preparation of transparent electrode]
On an alkali-free glass substrate, Chem. Mater. , 2002, 14, 4736-4745, silver nanowires having an average diameter of 60 nm and an average length of 5.5 μm were prepared, and the silver nanowires were filtered using a filter, and washed with water. Silver nanowire dispersion liquid W-10 (silver nanowire content: 0.5%) was prepared by redispersion in ethanol.

  Dispersion liquid W-10 was applied on a substrate so that the equivalent film thickness was 30 nm, and then dried at 80 ° C. Subsequently, the conductive polymer layer described above is provided by inkjet printing so that the converted thickness after drying is equivalent to 150 nm, dried at 80 ° C. for 5 minutes, and further heat-treated at 150 ° C. for 60 minutes to obtain metal nanoparticles and conductive A transparent electrode (Comparative Example 2) made of a conductive polymer was produced.

  In the same manner as described above, a transparent electrode (Invention 1) made of metal nanoparticles and a conductive polymer was produced on a 100 μm PEN film (made by Teonex Teijin Ltd.).

(Preparation of Al vapor deposition grid)
On a 100 μm PEN film (made by Teonex Teijin Ltd.), a thin film of aluminum is provided by a vacuum deposition method, and after applying a photoresist, the resist film is subjected to pattern exposure and development steps, a line width of 50 μm, a thickness of 2 μm, A fine grid-like transparent electrode (Comparative Example 5) having an interval between facing lines of 550 μm was obtained.

(Comparative Examples 1-6, Production of Light Control Film of Inventions 1 and 2)
The light control film was produced by the combination of Table 1 by using the produced said transparent electrode comparative examples 1-5 and this invention 1 and 2 as the 1st electrode and the 2nd electrode which opposes.

  In Comparative Example 6, the transparent electrode produced in Comparative Example 4 was used as the first electrode, and the transparent electrode produced in Invention 2 was combined as the second electrode.

  The light control layer prepared by the following procedure was disposed between the first electrode and the second electrode.

  10 g of the ultraviolet curable silicone resin obtained in the above (Production example of ultraviolet curable silicone resin), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by BASF Japan Ltd.) as a photopolymerization initiator Add 0.2 g of the light control suspension obtained in the above (Production Example of Light Control Suspension) to 0.3 g of dibutyltin dilaurate as a coloring inhibitor, and mix by ultrasonic for 1 minute. A light-modulating material was manufactured.

  This light-modulating material was applied to a base material provided with each transparent electrode using a wire bar so that the dry film thickness was 45 μm, and dried at 100 ° C. for 10 minutes.

On top of this, 1% by weight liquid containing silane coupling agents KBM-303 and KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.) dissolved in methyl ethyl ketone at a mass ratio of 50:50 is spray-dried, and then each coating layer is coated on the coating layer. pasted a transparent electrode having a counter electrode, the upper and lower from (from both sides) cumulative amount of light 2000 mJ / cm ² (measured in the laminated film in a metal halide lamp which is adjusted to the illuminance ^{275mW / cm 2; UV Power Pack} S / N 8601UV Comparative Examples 1-6, which have a light control layer dispersed in a silicone resin which is irradiated with ultraviolet rays of -A (320-390 nm) fusion) and the light-adjusting suspension is ultraviolet-cured as spherical droplets. The light control film of invention 1 and 2 was manufactured.

  The following evaluation was performed with respect to these light control films. Table 1 shows the combinations of these light control films and the evaluation results.

<Measurement and evaluation of transparent electrode>
(Surface specific resistance Rs)
The surface specific resistance of the conductive layer of each transparent electrode produced by the above method was measured and evaluated.

  For the surface specific resistance Rs (Ω / □), the surface specific resistance of the transparent conductor was measured by a four-terminal method using a resistivity meter Loresta GP manufactured by Dia Instruments.

(Transmissivity T)
As an evaluation of the transmittance T (%), which is an index of transparency, a total light transmittance was measured using a HAZE METER NDH5000 manufactured by Tokyo Denshoku Co., Ltd. to obtain a numerical value.

(appearance)
The colorability of the conductive layer was visually evaluated.

○ is almost neutral ○ △ is almost neutral and the metal wire is visible △ can be confirmed to be colored △ × can be confirmed and the metal wire is visible × is a strong color (Production of electrode production)
○: Good productivity ×: Poor productivity <Evaluation of light control film>
(scattering)
As evaluation of scattering properties, Haze was measured using HAZE METER NDH5000 manufactured by Tokyo Denshoku Co., Ltd., and evaluated according to the following criteria.

○ is equivalent to ITO (difference is less than 1)
△: Difference from ITO is less than 1 and less than 3 △: Difference from ITO is from 3 to less than 5 △: Difference from ITO is from 5 to less than 7 ×: Difference from ITO is 7 or more (bending test)
The light control film was subjected to a bending test by a winding method.

  The winding method is a kind of bending test, and is a test method in which a load is gradually applied so that the test piece has a specified shape, and the test piece is wound around a shaft or a mold.

  Specifically, the shaft radius was changed sequentially from 3 mmR at intervals of 5, 10, and 15 mmR, and a test was conducted to see how many mmR it can withstand without deterioration. Using a test piece of 100 mm × 100 mm, applying tension (10 g / cm) to the film so that it becomes a shape (turned back at 360 ° C.), bending it (10 g / cm), winding the test piece 301 around the shaft 303, and enduring up to how many mmR without deterioration. Tested. The number of tests was 100, the determination of no deterioration was made by resistance change, and the evaluation was made by the minimum radius where the resistance value change was within 10%.

  FIG. 5 is an explanatory diagram of the winding method.

○ is less than 3 mmR (no problem with 3 mmR)
○: 3 mm or more and less than 10 mm ×: 10 mm or more (Tensile test)
According to ASTM-D-882, the conductivity (surface specific resistance) after stretching the film by 5% was measured. The difference in performance before and after stretching was evaluated.

○: Change within 10% △: Greater than 10%, less than 100% (double)
X indicates more than 100% fluctuation (Durability: Scratch test)
Using a wear resistance tester (HEIDON-18), a sapphire needle having a needle tip of 0.3 mmR was used, and the load was scratched from the back surface (first electrode side) of the light control film from 0 g to 200 g at 20 g intervals. . The light control film was driven before and after the load, and a load region having no problem in operation was confirmed.

表１の結果から、本発明１及び２の調光フィルムは透過率が高く、外観に着色もなく、曲げ、引っ張り、耐久性に優れることから、従来製品では実現不可能であったフレキシブル性、且つ高耐久性の調光フィルムを提供できることが分かった。 ○ is 100g or more × is less than 100g

From the results in Table 1, the light control films of the present inventions 1 and 2 have high transmittance, are not colored in appearance, and are excellent in bending, pulling, and durability. And it turned out that a highly durable light control film can be provided.

  Moreover, since a transparent electrode can be produced by the apply | coating method or the printing method, productivity is also high.

Example 2
<Preparation of the light control film of this invention 3-5>
Next, the transparent electrode 2 of this invention was used as a 1st electrode and a 2nd electrode, and the adaptation of various light control layers was confirmed.

(Light control film of the present invention 3)
Electrochromic particles were prepared according to paragraph [0181] of JP2011-232488A.

<Preparation of electrochromic particles>
First, 2-chromoethyltrichlorosilane, 4,4′-bipyridine, and 1-bromohexane were sequentially reacted with titanium oxide nanoparticles to produce electrochromic particles 1.

(Preparation of laminate 1)
On the transparent electrode 2 of the present invention, the electrochromic particle dispersion was applied by spin coating. Subsequently, silane coupling agents KBM-303 and KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.) dissolved in methyl ethyl ketone were applied to the silica nanoparticle dispersion liquid (manufactured by C-I Kasei Co., Ltd.) by a spin coat method and 50:50. The 1% liquid contained in was spray-dried, and then the transparent electrode 2 of the present invention was bonded as a counter electrode on the coating layer.

  Thereafter, sintering was performed at 150 ° C. for 24 hours to obtain a light control film of the present invention 3 comprising a plurality of display electrodes and an electrochromic layer.

(Light control film of the present invention 4)
An emulsion type liquid crystal was prepared according to JP 2009-133922 A with reference to paragraphs [0111] to [0116].

<Emulsion type liquid crystal light control film>
Polyether urethane emulsion Neorez R-967 (Enomoto Kasei Co., Ltd .: 40% water non-volatile content) For 100 parts of this diluted polymer emulsion, nematic liquid crystal (JM1000XX (birefringence index Δn = 0.132): manufactured by Chisso Corporation ) 64 parts were added. This emulsion homogenizer (manufactured by Nippon Seiki Co., Ltd.) was stirred at a rotational speed of 133.3 revolutions / second (8000 rpm) for 10 minutes to obtain a liquid crystal emulsion.

  Subsequently, a polypropylene glycol diglycidyl ether as a crosslinking agent was dissolved in water to prepare a 50% aqueous crosslinking agent solution. While the liquid crystal emulsion obtained above was stirred at a low speed, the above-mentioned aqueous crosslinking agent solution was added to this liquid crystal emulsion. The addition ratio of the crosslinking agent aqueous solution was 4.8 parts of the crosslinking agent aqueous solution with respect to 100 parts of the polymer emulsion contained in the liquid crystal emulsion (100 parts of the polymer emulsion diluted with water). The liquid crystal ratio V1 in the liquid crystal emulsion for film formation thus obtained was 0.60.

  Next, the liquid crystal emulsion was applied on the transparent electrode 2 of the present invention with a wire bar and dried at 100 ° C. for 10 minutes to form a liquid crystal-resin composite on the PEN film. The film on which this liquid crystal-resin composite was formed was bonded using the transparent electrode 2 of the present invention as a counter electrode, and the light control film of the present invention 4 was obtained.

(Light Control Film of Invention 5)
JP, 2001-180264, A The following mixture was produced according to paragraphs [0033]-[0034].

  [Example 1] 95 parts of a cyano nematic liquid crystal (BL-009 manufactured by Merck) in which 2.5% by mass of a chiral agent (a mixture of S-811 manufactured by Merck and C15 manufactured by Merck) having a mass ratio of 1: 1 was dissolved. As an uncured curable compound, a mixture (mixture A) of 5 parts of the following compound and 0.15 part of 2,2-dimethoxy-2-phenylacetophenone was prepared.

次に、本発明の透明電極２を微量の直径１３μｍの樹脂ビーズを介して対向し、一部に切り欠けを設けて四辺に幅約３ｍｍで印刷したエポキシ樹脂により貼合してセルを作製した。このセルに上記混合物を真空注入法にて注入し、切り欠き部をエポキシ樹脂で封止した。このセルを、１２０℃に温度設定した恒温槽中に２０分間保持した後２５℃まで冷却した。その後、このセルを２５℃に保持した状態で、主波長が約３６５ｎｍのＨｇＸｅランプを用いて硝子面の両側からそれぞれ約３ｍＷ／ｃｍ^２の強度の紫外線を１０分間照射して、本発明５の調光フィルムを得た。

Next, the transparent electrode 2 of the present invention was opposed to each other through a small amount of resin beads having a diameter of 13 μm, and a cell was prepared by bonding with an epoxy resin having a notch formed in a part and printed with a width of about 3 mm on four sides. . The mixture was injected into this cell by a vacuum injection method, and the notch was sealed with an epoxy resin. The cell was kept in a thermostat set at 120 ° C. for 20 minutes and then cooled to 25 ° C. Thereafter, with the cell held at 25 ° C., ultraviolet light having an intensity of about 3 mW / cm ² was irradiated from both sides of the glass surface for 10 minutes using an HgXe lamp having a dominant wavelength of about 365 nm. A light control film was obtained.

  It was confirmed that all of the light control films 3 to 5 of the present invention described above have good drivability and operate well as a light control film. Moreover, all of these laminates showed good results in the bending, pulling and durability evaluation of Example 1.

Therefore, the light control film of the present invention from Example 2 can be used for any light control layer of electrochromic type, polymer dispersed liquid crystal (PDLC) or polymer network type liquid crystal (PNLC). confirmed.
Furthermore, since the light control layer which concerns on this invention can be manufactured by the apply | coating method, it is high productivity.

Example 3
<Preparation of the light control film of Comparative Examples 7-9 and this invention 4, 6-10>
Next, the operation and performance of the conductive polymer composition of the present invention and the transparent electrode with modified process conditions were verified.

  Hereinafter, it produced according to this invention 4 of Example 2, but it produced similarly except having changed the heating conditions after providing the conductive polymer layer in preparation of a transparent electrode as follows.

  Standard (similar to Invention 4 of Example 2) A transparent electrode dried at 80 ° C. for 5 minutes and further heat-treated at 150 ° C. for 60 minutes was prepared and used (the light control film of Invention 4).

(Light control film of the present invention 6)
A transparent electrode which was dried at 80 ° C. for 5 minutes and further heat-treated at 150 ° C. for 5 hours was prepared and used.

(Light control film of the present invention 7)
A transparent electrode that was dried at 80 ° C. for 5 minutes and then heat-treated at 150 ° C. for 96 hours was prepared and used.

  Furthermore, the sample which changed the conductive polymer layer into the following was produced.

<Manufacture of polyester resin>
(Polyester resin PP-1)
As an acid component, 2160 g of terephthalic acid (TPA), 1578 g of isophthalic acid (IPA), 505 g of sebacic acid (SEA), 931 g of ethylene glycol (EG) and 1953 g of neopentyl glycol (NPG) as an alcohol component were charged in an autoclave, 250 The esterification reaction was performed by heating at 4 ° C. for 4 hours. The raw material ratio was TPA / IPA / SEA / EG / NPG = 52/38/10/60/75 (molar ratio). Subsequently, after adding 3.3 g of zinc acetate dihydrate as a catalyst, the temperature of the system was raised to 260 ° C., and the pressure of the system was gradually reduced to 13 Pa after 1 hour. Under this condition, the polycondensation reaction is continued for another 5 hours, the system is brought to atmospheric pressure with nitrogen gas, the temperature of the system is lowered, and when the temperature reaches 255 ° C., 7.2 g of trimellitic anhydride is added, and at 255 ° C. for 2 hours. The depolymerization reaction was carried out with stirring. Thereafter, the system is put under pressure with nitrogen gas, the resin is discharged in a strand shape, and the pellet temperature is reduced by cutting with a pelletizer via a quenching bath having a water temperature of 35 ° C. Obtained. The number average molecular weight of the obtained polyester resin PP-1 was 14000, the acid value was 23, and the glass transition temperature (Tg) was 45.

<Production of aqueous polyester resin dispersion>
(Polyester resin aqueous dispersion E-1)
400 g of polyester resin PP-1 and 600 g of MEK are put into a glass 2 L container with a jacket, and the polyester resin is completely dissolved by stirring while heating through warm water at 60 ° C. in the jacket, and the solid content concentration is 40% by mass. 1000 g of a polyester resin solution was obtained. Next, cold water is passed through the jacket to keep the system temperature at 13 ° C., and while stirring at a rotational speed of 50 rpm, 23.8 g of triethylamine is added as a basic compound, followed by 13 ° C. distilled water at a rate of 100 g / min. 1107 g was added to carry out phase inversion emulsification. Subsequently, 1600 g of the obtained aqueous dispersion was placed in a 2 L flask, and the organic solvent was distilled off by distillation under normal pressure. Distillation was terminated when the amount of distillate reached 630 g, and after cooling to room temperature, 1.1 g of 25% by mass ammonia water was added while stirring the aqueous polyester resin dispersion. Then, it filtered with a 1000 mesh stainless steel filter, and obtained polyester resin aqueous dispersion E-1.

  The following coating solution B was applied onto a 100 μm PEN film (made by Teonex Teijin Ltd.) by adjusting the slit gap of the extrusion head so as to have a dry film thickness of 300 nm using an extrusion method. Heat-dried to form a conductive layer composed of a conductive polymer and a polyester resin, and the obtained conductive layer was heat-treated at 150 ° C. for 60 minutes using an oven to obtain a transparent electrode (preparation of the present invention 8). Optical film).

(Coating solution B)
Conductive polymer dispersion: PEDOT-PSS CLEVIOS PH510 (solid content concentration 1.89%, manufactured by HC Starck) 1.59 g
Polyester resin aqueous dispersion: E-1 0.35 g (solid content 70 mg)
Dimethyl sulfoxide (DMSO, 1/10 of the conductive polymer solution mass)
0.16g
Furthermore, said drying conditions were changed into the following and the transparent electrodes 9-10 which concern on this invention were produced.

(Light control film of the present invention 9)
A transparent electrode 9 which was dried at 80 ° C. for 5 minutes and further heat-treated at 150 ° C. for 5 hours was prepared and used.

(Light control film of the present invention 10)
A transparent electrode 10 that was dried at 80 ° C. for 5 minutes and then heat-treated at 150 ° C. for 96 hours was prepared and used.

  5% DMSO was added to PEDOT / PSS of CLEVIOS PH 500 (manufactured by Heraeus), spin-coated on a 100 μm PEN film (manufactured by Teonex Teijin Ltd.), and the transmittance T was adjusted to 85%. After spinning to the extent that the fluidity of the film is eliminated by spin rotation, the film is dried on a hot plate at 80 ° C. for 5 minutes, heat treated at 150 ° C. for 60 minutes to remove excess solvent, and the PEDOT-PSS layer A transparent electrode was formed and used.

(Light control film of Comparative Example 7)
Furthermore, the above drying conditions were changed to the following, and transparent electrodes 8 to 9 of comparative examples were produced.

(Light control film of Comparative Example 8)
A transparent electrode 8 which was dried at 80 ° C. for 5 minutes and further heat-treated at 150 ° C. for 5 hours was prepared and used.

(Light control film of Comparative Example 9)
A transparent electrode 9 which was dried at 80 ° C. for 5 minutes and further heat-treated at 150 ° C. for 96 hours was prepared and used.

  The light control layer used by this invention 4 of Example 2 was provided similarly to Example 2 with respect to these transparent electrodes, the light control film was produced, and the following evaluation was performed.

(Weatherability)
Using the "Xenon Weather Meter XL75" (manufactured by Suga Test Instruments Co., Ltd.), the prepared light control film was irradiated for 1 month under the irradiation conditions of a xenon lamp of 70,000 lux. The element condition after the test was confirmed visually.

○ is basically no problem drive ○ △ is slightly deteriorated (less than 5%)
Δ is partially degraded (5% or more but less than 20%)
△ × indicates deterioration in a large area (20% or more and less than 50%)
×: Deterioration occurs at 50% or more (storability)
The produced light control film was left in an environment of 40 ° C. and 80% for 1 month, returned to an environment of 23 ° C. and 50%, and after 1 week, the light control film was driven, and the device condition before and after storage was visually confirmed.

これら調光フィルムは、いずれも良好に動作することを確認した。またこれらの調光フィルムは、いずれも実施例１の曲げ、引っ張り、耐久性の観点で良好な結果を示した。しかしながら比較例７〜９のＰＥＤＯＴを使用した調光フィルムは応答が遅いばかりか、耐候性、保存性が著しく劣ることが確認され、耐候性、保存性試験後は応答しなくなった。本発明の調光フィルムは、試験後も駆動可能であり良好であり、特に解離性基を有する自己分散型ポリマーに相当する本発明８〜１０の調光フィルムは、ヒドロキシ基を有する非導電性ポリマーに対し、低熱量時の保存性、耐候性の観点でさらに優位にあることを確認した。 ○: Drive without problems ○ △: Slightly deteriorated at the edge (less than 5%)
△ indicates deterioration at the edge (5% or more but less than 20%)
△ × indicates deterioration to the inside (20% or more and less than 50%)
×: Deterioration progresses at 50% or more

These light control films were confirmed to work well. Moreover, all of these light control films showed the favorable result from the viewpoint of the bending of Example 1, a tension | pulling, and durability. However, the light control films using PEDOT in Comparative Examples 7 to 9 were not only slow in response but also confirmed to be extremely inferior in weather resistance and storage stability, and stopped responding after the weather resistance and storage stability tests. The light control film of the present invention can be driven even after the test and is good. In particular, the light control film of the present invention 8 to 10 corresponding to the self-dispersing polymer having a dissociable group is non-conductive having a hydroxy group. It was confirmed that the polymer is further superior in terms of storage stability and weather resistance at low heat.

Example 4
Under the conditions of the light control film 7 of the present invention, the pattern of the fine metal wires was changed to a stripe shape as follows to prepare a light control film. The counter electrode was bonded so that one and the other stripes were orthogonal, and a good light control film free from moire was obtained.

  The light control film of the present invention 12 was formed by forming a 10 μm fine line stripe using the electrostatic suction ink jet system described in FIG. 1 of JP 2010-99873 A.

(1.1) Electrostatic Suction Type Inkjet Device JP, 2010-98973, A The nozzle plate 11 of the ink-jet head 2 shown in FIG. 1 is made of polytetrafluoroethylene (PTFE) Teonex (manufactured by Teijin DuPont Films Ltd.). In actuality, droplets were ejected from the ejection holes 13 of the nozzle 10 onto the film substrate.

  The configuration of the inkjet head 2 is a one-stage structure in which the taper angle of the nozzle 10 is 4 ° and the small diameter portion 14 and the large diameter portion 15 are continuous.

  The silver nano ink was prepared by diluting PR030 (manufactured by Inctec) with N-methyl-2-pyrrolidone (NMP) to 10 cp.

  In the dot formation, the gap was 1 mm, 500 V was applied to the substrate side, and the head ink side was grounded to form a linear fine line pattern with a driving frequency of 30 kHz and a width of 10 μm. Further, the emission was formed by shifting by 1/3 pitch in the main scanning direction.

  The Cu ink of the light control film of the present invention 15 was prepared in the same manner except that the silver nano ink was changed to the following ink in the light control film of the present invention 11.

  In the production of the transparent electrode according to the present invention, a copper nanoparticle paste was prepared instead of the silver nanoparticle paste, formed in a stripe pattern, and subjected to the same heat treatment.

  The copper nanoparticle paste was prepared by dissolving 0.28 g of polyvinylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) having an average molecular weight of 10,000 in 0.72 g of ethylene glycol, glycerin, diethylene glycol, and 2,3-butanediol, 4.0 g of particles (manufactured by Sigma-Aldrich), three rolls, and a mixer were used for kneading. When 50 copper nanoparticles were observed, the aspect ratio was 2.0 or less.

表３によれば、本発明では実質的にストライプ線の見えない調光フィルムも、その反対に金属線のハッキリ見える疑似ワイヤー入り防犯ガラスのような仕上がりの調光フィルムも同一組成で作製可能であり、製品バリエーション上も非常に有用である。

According to Table 3, in the present invention, it is possible to produce a light control film with substantially the same stripe composition, and a light control film with a finished composition such as a security wire with pseudo wires that can clearly see a metal wire. Yes, it is very useful in terms of product variations.

  In addition, it has been confirmed that the low-temperature fired copper ink operates in the same manner, and there is a possibility that it can be developed into a cheaper product in the future.

Example 5
Two 100 μm PEN films having a substrate width of 180 mm were prepared.

  One film substrate was screen printed in the same manner as in Invention 11 of Example 4, and a 170 mm wide metal wire (stripe perpendicular to the substrate width) was provided at the center, heat-treated, and an ink jet on it. Similarly, by printing, a conductive polymer layer having a width of 170 mm was provided at the center and subjected to heat treatment, and a film a having a 170 mm transparent electrode provided on a 180 mm film substrate was produced.

  At the time of winding, the electrode was protected with a release film T788 (manufactured by Daicel Value).

  Similarly, another film substrate was screen-printed in the same manner as in Invention 11 of Example 4, and a 170 mm wide metal thin wire (stripe parallel to the substrate width) was provided at the center, and heat treatment was performed. Similarly, a conductive polymer layer having a width of 170 mm was provided at the center by ink-jet printing, followed by heat treatment, and a film b in which a 170 mm transparent electrode was provided on a 180 mm base material was produced.

  At the time of winding, the electrode was protected with a release film T788 (manufactured by Daicel Value).

  One film a was peeled off and released from the release film, and in the same manner as in Example 1, the light control layer was coated by die coating so that the coating width was 160 mm from the center and the dry film thickness was 45 μm, and dried in the same manner. Then, a 1% solution containing 50:50 of silane coupling agents KBM-303 and KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.) dissolved in methyl ethyl ketone is sprayed in an amount equivalent to 2 nm and dried at 100 ° C. for 1 minute. Thus, an electrode / light control layer laminate A was formed. Furthermore, the electrode / light control layer laminate A was protected with a release film T788 (manufactured by Daicel Value).

The electrode / light control layer laminate A and the film b are slit at the center, and then cut into 90 mm pieces to prepare each, and an extraction electrode is provided at the end where each light control layer is not provided. Laminate as follows. (The extraction electrodes may be extracted from the same side, or may be extracted from different surfaces (reverse surfaces, etc.).)
Then, from the top and bottom of the laminated film (from both sides) with a metal halide lamp adjusted to an illuminance of 275 mW / cm ² , an integrated light amount of 2000 mJ / cm ² (measurement; UV Power Pack S / N 8601 UV-A (320 to 390 nm) manufactured by Fusion) A light control film having a light control layer in which a light control suspension was dispersed and formed in a UV-cured silicone resin as a spherical droplet was produced. As shown in FIG. 6, the produced light control film is provided with each layer such that the base material width> the transparent electrode formation width> the light control layer formation width with respect to the base material width.

  20 light control films were produced from the 900 mm electrode / light control layer laminate A and the film b as described above, and it was confirmed that all of the produced light control films operated well. In addition, all of these laminates showed good results from the viewpoints of bending, pulling, and durability of Example 1. Since these laminates do not require a complicated manufacturing process or complicated patterning, it has been found that a very large amount of light control films can be manufactured with good reproducibility without waste, which is a preferable method.

Example 6
The light control film 11 of this invention and the light control film 4 of a comparative example are produced in roll shape, and the following adhesion layer liquid is provided so that it may become a dry film thickness of 25 micrometers by the die coat on one side, and it is 60 degree | times for 1 minute, After drying at 100 ° C. for 1 minute, a release polyester film [trade name “Supertech SP-PET38”, manufactured by Lintec Co., Ltd.] is bonded and aged at 45 ° C. for 3 days. The composition of the light control film was obtained.

  After providing the following adhesive layer liquid with an applicator at 25 μm on one side of the light control film 11 of the present invention and the light control film 4 of the comparative example, drying at 60 degrees for 1 minute, 100 degrees for 1 minute, A release polyester film [trade name “Supertech SP-PET38”, manufactured by Lintec Corporation] was bonded and aged at 45 ° C. for 3 days to obtain a structure of a release support, an adhesive layer, and a light control film.

(Preparation of adhesive layer solution)
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen gas inlet tube, 70 parts of ethyl acetate was charged and the temperature was raised to 78 ° C. a monomer liquid mixture containing 264 parts (2.1 mole parts) of n-butyl acrylate and 36 parts (0.5 mole parts) of acrylic acid, and 2,2′-azobis (2,4-dimethylvaleronitrile); An initiator solution in which 1 part was dissolved in 55 parts of ethyl acetate was subjected to radical polymerization by continuously dropping it over 4 hours from a separate dropping funnel while blowing nitrogen into the reaction vessel.

  After completion of the dropwise addition, the mixture was aged for 2 hours, and then an initiator solution prepared by dissolving 0.6 part of 2,2'-azobis (2,4-dimethylvaleronitrile) in 28 parts of ethyl acetate was continuously added for 2 hours using a dropping funnel. Added. Furthermore, after continuing the polymerization reaction at the boiling point (80 ° C.) for 2 hours, 1047 parts of ethyl acetate was added to obtain a solution (solid content concentration = 20%) of the (meth) acrylate copolymer precursor (A1). . Mw was 1.5 million.

  A 75% ethyl acetate solution of an isocyanate-terminated urethane prepolymer of trimethylolpropane as a crosslinking agent (B) was added to 100 parts of the above-mentioned (meth) acrylate copolymer (A1) (solid concentration = 20%) [trade name "Coronate L" manufactured by Nippon Polyurethane Co., Ltd. 1 part and 0.05 part of 3-glycidoxypropyltrimethoxysilane [trade name "KBM-403", Shin-Etsu Chemical Co., Ltd.] as silane coupling agent (C) Product] was uniformly mixed to prepare an adhesive (X1). The viscosity (measurement method: method described in JIS-K7117-2) of the pressure-sensitive adhesive (X1) was 7200 (mPa · s) at 25 ° C.

  This high-performance sheet was sized up to make a prototype, and a 50 cm × 1 m cut was prepared. The light control film 11 of Comparative Example 4 in which the transparent electrode was ITO and the light control film 11 having the transparent electrode according to the present invention were prepared. When the light control film was driven after the pasting / peeling operation was repeated 5 times on the window glass, the light control film using ITO was found to be defective, but the light control film using the transparent electrode of the present invention. No failure occurred.

DESCRIPTION OF SYMBOLS 1 Taper angle 2 Transparent substrate 3 Metal thin wire 4 Waste liquid tank 5 Control part 6 Tank 7 Tank 8A Tank 8B Tank 9 Pump 10 Film base material 11 Pump 12 Filter 13 Pipe branch 14 Inkjet head 15 Transparent electrode 201b Piezoelectric substrate 201c Top plate 201d Nozzle plate 201e Coating liquid supply pipe 201f Pipe 20 Transparent base material 22 Extraction electrode 24 Metal conductive layer 26 Conductive polymer layer 30 Film base material 31 Metal conductive layer 32 Conductive polymer layer 33 Light control layer 34 Light control suspension (spherical) )
35 Extraction electrode 51a, b Film substrate 52a, b Transparent electrode 53a Light control layer 54a Resin matrix 54b Liquid crystal particle 55a Power supply 56a Switch
301 Specimen 303 axis

Claims (18)

  A light control film having a light control layer between a pair of opposing transparent electrodes carried on a base material, wherein the base material is a film base material, and the transparent electrode contains fine metal particles and a conductive polymer A light control film characterized by being a composite electrode.   The light control film according to claim 1, wherein the light control layer contains a polymer dispersed liquid crystal or a polymer network type liquid crystal.   The light control film according to claim 1, wherein the metal fine particles are metal nanoparticles or metal nanowires.   The said transparent electrode has a metal fine wire structure which consists of metal nanoparticles, The light control film as described in any one of Claims 1-3 characterized by the above-mentioned.   The light control film according to claim 4, wherein the fine metal wire structure is a stripe fine wire structure.   6. The dimming device according to claim 5, wherein the pair of transparent electrodes has a metal fine wire structure that is a stripe-like thin wire structure, and the stripe-like thin wire structures of the pair of transparent electrodes are orthogonal to each other. the film.   The light control film according to any one of claims 1 to 6, wherein the conductive polymer contains poly (3,4-ethylenedioxythiophene).   The light control film according to claim 1, wherein the conductive polymer is a mixture of poly (3,4-ethylenedioxythiophene) and a nonconductive polymer.   The light control film according to claim 8, wherein the nonconductive polymer is a nonconductive polymer having a hydroxy group.   The light control film according to claim 8, wherein the non-conductive polymer is a self-dispersing polymer having a dissociable group.   It is a light control film as described in any one of Claims 1-10, Comprising: This light control film has durability 100 times or more in the bending durability test of axial radius 3mmR, It is characterized by the above-mentioned. .   It is a light control film as described in any one of Claims 1-10, Comprising: This light control film has durability of 100 g or more by the scratch load evaluation of 0.3 mmR, The light control film characterized by the above-mentioned.   The light control film according to any one of claims 1 to 12, wherein an adhesive layer and a release support are provided on a surface opposite to the surface having the transparent electrode of the base material.   The light control film according to claim 13, wherein the light control film is a long roll-shaped light control film.   It is a manufacturing method of the light control film which manufactures the light control film as described in any one of Claims 1-14, Comprising: The said transparent electrode and the said light control layer are provided by the apply | coating method or the printing method, It is characterized by the above-mentioned. Manufacturing method of light control film.   The method for producing a light control film according to claim 15, wherein the method of providing the transparent electrode is an ink jet printing method. The method for producing a light control film according to claim 15 or 16, wherein the width of the substrate, the formation width of the transparent electrode, and the formation width of the light control layer satisfy the following relationship.
Substrate width> Transparent electrode formation width> Light control layer formation width After the transparent electrode and the light control layer are provided on the base material, the transparent electrode facing the transparent electrode is installed so that the base material width, the formation width of the transparent electrode, and the formation width of the light control layer satisfy the following relationship: The manufacturing method of the light control film of Claim 17 characterized by the above-mentioned.
Substrate width> Transparent electrode formation width> Light control layer formation width

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