JP2016110010A - Light control film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light control film that prevents decrease in haze reduction rate caused by continuous motion.SOLUTION: The present invention provides a light control film having a light control layer between a pair of light-transmitting electrodes, where at least one of the light-transmitting electrodes is a light-transmitting electrode having a thin metallic wire pattern on a light-transmitting support, and the light control layer is a polymer dispersion-type liquid crystal body at least having a liquid crystal compound, a binder resin, and a nitrogen-containing heterocyclic compound.SELECTED DRAWING: None

Description

  The present invention relates to a light control film having improved reduction in haze reduction rate due to continuous operation.

  In recent years, dimming films whose haze changes when voltage is applied are used to block sunlight in houses, automobiles, trains, airplanes, etc., and to block lines of sight for partitions in offices and exhibition halls. Etc. are attracting attention.

  Generally, the light control film has a light control layer between a pair of light-transmitting electrodes. The light control layer is roughly classified into a light control layer using a liquid crystal compound and a light control layer using an electrochromic material. Especially, the light control film which used the liquid crystal compound as a light control layer has the advantage that a haze change response speed at the time of a voltage application is quick, and is examined widely. However, in a light control film using a liquid crystal compound as a light control layer, the liquid crystal compound leaks out unless the periphery of the light control layer is sealed. For this reason, there existed problems, such as low durability and the ability to cut the light control film after preparation to a free shape.

  As a solution to this problem, Japanese Patent Application Laid-Open No. 9-235555 (Patent Document 1) and Japanese Patent Application Laid-Open No. 1-198725 (Patent Document 2) use a polymer dispersed liquid crystal as a light control layer. A film has been proposed. In the polymer-dispersed liquid crystal body, the liquid crystal compound is dispersed in a binder resin so that it is not necessary to seal the periphery of the light control layer, and the light control film after production can be cut freely. Is also possible.

  In a general polymer dispersion type liquid crystal, the liquid crystal compound is randomly oriented when no voltage is applied, so that it becomes an opaque state with high haze. When a voltage is applied, the liquid crystal compound is aligned in a certain direction, so that the haze is reduced and the transparency is increased when no voltage is applied. This behavior is particularly preferable from the viewpoint of power consumption in the above-described line-of-sight shielding application that is often used in an opaque state.

  For example, JP 2010-145856 (Patent Document 3) discloses a polymer dispersion type formed by preparing a mixed solution in which a microcapsule containing a liquid crystal compound and a binder resin are mixed, and applying and drying the solution. A light control laminate having a liquid crystal body as a light control layer and ITO glass as a light transmissive electrode is disclosed. Japanese Patent Application Laid-Open No. 2011-105908 (Patent Document 4) discloses a polymer dispersion formed by coating and curing a liquid crystal composition containing a specific liquid crystal compound and a non-liquid crystalline polymerizable compound on a PET film with ITO. A light control film having a liquid crystal body as a light control layer is disclosed.

  At present, as the light transmissive electrode, an electrode in which an ITO film is deposited on a light transmissive support has been studied. However, in recent years, there has been a demand in the market for a specification that can apply a voltage to an arbitrary portion of the light control film, such as making only a partial region of the window glass on which the light control film is applied. Although being studied, patterning of the ITO film generally requires a plurality of processes such as formation of a resist film and etching, and there is a problem that productivity is low. Further, as the area of the light control film is increased, the resistance of the light transmissive electrode is also required to be reduced. In order to solve the problem, a method of forming a thin metal wire pattern on a light transmissive support instead of an ITO film to form a light transmissive electrode has been studied. In this method, the metal fine line pattern can be miniaturized because of the high electrical conductivity of the metal, and a light transmissive electrode having excellent total light transmittance can be obtained. For example, Japanese Patent Application Laid-Open No. 2013-148687 (Patent Document 5) discloses a light control film in which a light control layer contains a polymer-dispersed liquid crystal and a light transmissive electrode has a fine metal wire pattern.

  In general, it is desirable that the light control film has a high haze reduction rate when a voltage is applied relative to when no voltage is applied. However, a light control film having a fine metal wire pattern as a light-transmitting electrode and having a polymer dispersed liquid crystal body as a light control layer has a problem that the haze reduction rate decreases with continuous operation, and improvement is required. It was.

  On the other hand, for example, in Japanese Patent Application Laid-Open No. 2014-29671 (Patent Document 6), an adhesive layer containing a triazole compound as a metal corrosion inhibitor is provided on at least one of the first light transmissive electrode and the second light transmissive electrode. It is described that the operation failure with time can be improved by the conductive film for a touch panel.

JP-A-9-235555 JP-A-1-198725 JP 2010-145856 A JP 2011-105918 A JP2013-148687A JP 2014-29671 A

  The subject of this invention is providing the light control film which improved the fall of the haze reduction rate accompanying continuous operation | movement.

The above object of the present invention is achieved by the following invention.
(1) A light-controlling film having a light-controlling layer between a pair of light-transmitting electrodes, wherein at least one of the light-transmitting electrodes has a metal fine line pattern on a light-transmitting support A light control film, wherein the light control layer is a polymer-dispersed liquid crystal body containing at least a liquid crystal compound, a binder resin, and a nitrogen-containing heterocyclic compound.

  According to the present invention, it is possible to provide a light control film in which a decrease in the haze reduction rate due to continuous operation is improved.

Schematic sectional view of a light transmissive electrode of the light control film of the present invention 1 is a schematic cross-sectional view of an example of a light control film having a thin metal wire shown in (1-1) or (1-3) of FIG. Schematic sectional view of another example of a light control film having a fine metal wire shown in (1-2) of FIG. Schematic diagram of transparent document used in the example Schematic of the light transmissive electrode produced in the example

  Hereinafter, the present invention will be described in detail. First, the light transmissive electrode which comprises the light control film of this invention is demonstrated using figures. FIG. 1 is a schematic cross-sectional view of a light transmissive electrode included in the light control film of the present invention. The light control film of the present invention has a pair of light transmissive electrodes, at least one of which is a light transmissive electrode having a metal fine wire pattern on a light transmissive support. Examples of such fine metal wires include the configurations shown in (1-1) to (1-3) in FIG. 1, but are not limited thereto.

  The light transmissive electrode shown in (1-1) has the metal fine wire 12 which forms the metal fine wire pattern on the undercoat layer 15 on the light transmissive support 11 and provided as necessary. The fine metal wire 12 contains a metal 13 and a binder 14, and the metal 13 is held by the binder 14. In the drawing, the binder 14 does not exist in a portion where no metal exists (light transmitting portion). Although two methods shown below can be illustrated as a manufacturing method of such a metal fine wire pattern, it is not limited to this. As the first production method, for example, in accordance with the method disclosed in Japanese Patent Application Laid-Open No. 2014-181316, conductive metal ink or conductive paste containing the metal 13 and the binder 14 is printed on the light-transmissive support 11. The method of giving by a method etc. and obtaining a metal fine wire pattern is mentioned. Here, examples of the metal contained in the conductive metal ink and the conductive paste include copper, nickel, zinc, tin, and silver. As a second production method, for example, according to the method disclosed in Japanese Patent Application Laid-Open No. 2007-59270, a silver salt photosensitive material in which a silver halide emulsion layer is provided on a light transmissive support 11 is used as a conductive material precursor. And a method of forming a fine metal wire pattern using a curing development method. In this method, the fine metal wire 12 is formed by localizing the metal 13 made of silver in the binder 14 mainly composed of hardened gelatin.

  The light transmissive electrode shown in (1-2) is on the light transmissive support 11, and the binder 14 is present on the entire surface of the undercoat layer 15 provided as necessary. The metal 13 is localized in the metal wire 12 to form a metal wire pattern. As a method for producing such a fine metal wire pattern, the following direct development method can be exemplified, but it is not limited thereto. The direct development method is a silver salt light-sensitive material in which a silver halide emulsion layer is provided on a light-transmitting support 11 according to a method disclosed in, for example, JP-A Nos. 2004-221564 and 2007-12314. As a conductive material precursor, the metal 13 made of silver is localized in the binder 14 mainly composed of gelatin using a direct development method, thereby forming the fine metal wire 12.

  The light transmissive electrode shown in (1-3) is a thin metal wire formed on the light transmissive support 11 and on the undercoat layer 15 provided as necessary by a metal 13 not held by a binder. 12 is formed. Although two methods shown below can be illustrated as a manufacturing method of such a metal fine wire, it is not limited to this. The first method is, for example, according to the method disclosed in JP-A No. 2003-77350, JP-A No. 2005-250169, JP-A No. 2007-188655, JP-A No. 2004-207001, etc. A silver salt light-sensitive material having at least a physical development nucleus layer and a silver halide emulsion layer in this order on the body 11 is used as a conductive material precursor, and a so-called silver is formed by allowing a soluble silver salt forming agent and a reducing agent to act in an alkaline solution. There is a method in which a metal 13 made of silver is localized on a physical development nucleus layer using a salt diffusion transfer method to form a fine metal wire pattern. As a second method, for example, according to the method disclosed in Japanese Patent Application Laid-Open No. 2014-197531, a base layer containing a water-soluble polymer compound, a crosslinking agent, and a metal sulfide is provided on the light-transmissive support 11, and photosensitive. A photosensitive resist layer is laminated, the photosensitive resist layer is exposed to an arbitrary pattern, developed, and a resist image is formed. Then, electroless plating is performed to deposit the metal 13 on the base layer not covered with the resist image. A method of localizing and then removing the resist image (hereinafter, electroless-plated metal fine wire forming method) can be mentioned. Examples of the metal to be electrolessly plated include copper, nickel, zinc, tin, and silver.

  Among the above-described configurations, since the fine metal wire 12 does not contain a binder, a fine metal wire pattern having high conductivity can be obtained. Therefore, the configuration shown in (1-3), that is, on the light-transmitting support by the binder. A light transmissive electrode in which a fine metal wire pattern is formed by fine metal wires that are not held is particularly preferable. Moreover, it is preferable that a metal fine wire contains silver from a viewpoint of the electroconductivity obtained. Furthermore, the ratio of silver to the total amount of metal contained in the fine metal wire is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass. Examples of the metal that may be contained in the fine metal wire other than silver include copper, nickel, gold, and palladium.

  In the above-described configuration, plastic, glass, rubber, ceramics and the like are preferably used as the light transmissive support. These light transmissive supports preferably have a total light transmittance of 60% or more. Among plastics, a resin film having flexibility is preferably used because it is easy to handle. Specific examples of the resin film used as the light transmissive support include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic resins, epoxy resins, fluororesins, silicone resins, polycarbonate resins, Examples include acetate resin, triacetate resin, polyarylate resin, polyvinyl chloride, polysulfone resin, polyether sulfone resin, polyimide resin, polyamide resin, polyolefin resin, and cyclic polyolefin resin. Moreover, it is preferable that the thickness of a resin film is 25-300 micrometers. The light-transmitting support may have a known layer such as an easy-adhesion layer on the surface having the fine metal wire pattern, or may have these known layers on the opposite surface. .

  A method for producing the light transmissive electrode shown in FIG. 1 (1-3), which is a particularly preferred structure of the light transmissive electrode constituting the light control film of the present invention, will be described in detail below. First, the silver salt diffusion transfer method, which is the first method for producing the above-described light transmissive electrode shown in FIG. 1 (1-3), will be described.

  In the silver salt diffusion transfer method, a silver salt photosensitive material having at least a physical development nucleus layer and a silver halide emulsion layer in this order on a light-transmitting support is used as a conductive material precursor. The principle of the silver salt diffusion transfer method is described in US Pat. No. 2,352,014. That is, the exposed silver halide is developed, but the unexposed silver halide is dissolved in a soluble silver complex salt forming agent and transferred to the image receiving layer as a soluble silver complex salt. By depositing as silver, a positive silver image pattern is formed. Specifically, the silver halide grains in the image area which is an unexposed area are dissolved as a soluble silver complex salt by the soluble silver complex forming agent, and the soluble silver complex salt diffused to the vicinity of the physical development nucleus is reduced by a reducing agent such as hydroquinone, Deposited as metallic silver on the physical development nuclei. On the other hand, the silver halide grains in the exposed area remain in the silver halide emulsion layer and are reduced in situ by the action of the reducing agent. When the developed silver salt light-sensitive material is washed with water, the exposed silver is washed away together with the silver halide emulsion layer that is no longer needed, while the silver deposited in the vicinity of the physical development nuclei is exposed by washing with water, and a light-transmitting support. A fine metal wire 12 formed of a metal 13 made of silver that is not held by a binder is obtained.

  The physical development nucleus layer of the conductive material precursor used in the silver salt diffusion transfer method will be described. The physical development nuclei layer contains at least physical development nuclei. As the physical development nuclei, fine particles (average particle diameter of about 1 to several tens of nanometers) made of heavy metal or sulfide thereof are used. Examples thereof include colloids such as gold and silver, metal sulfides obtained by mixing water-soluble salts such as palladium and zinc and sulfides, and silver colloids and palladium sulfide are preferable. The content of physical development nuclei in the physical development nuclei layer is preferably about 0.1 to 10 mg per square meter in solid content.

  Other substances that the physical development nucleus layer may contain include polyacrylic acid, polyacrylamide, polyvinyl alcohol, polyvinyl pyrrolidone, a copolymer of maleic anhydride and styrene, gelatin, albumin, casein, polylysine, etc. Mucopolysaccharides such as protein, carrageenan, hyaluronic acid, aminated cellulose, polyethyleneimine, polyallylamine, polydiallylamine described in Chapter 2.6.4, “Chemical Reaction of Polymer” (Nobu Okawara, 1972, Chemical Dojinsha), Polymer compounds such as copolymers of allylamine and diallylamine, copolymers of diallylamine and maleic anhydride, copolymers of diallylamine and sulfur dioxide, vinyl acetate, vinyl chloride, styrene, methyl acrylate, butyl acrylate, methacrylate Ronitrile, butadiene , Homopolymer resins such as isoprene, ethylene / butadiene copolymer, styrene / butadiene copolymer, styrene / p-methoxystyrene copolymer, styrene / vinyl acetate copolymer, vinyl acetate / vinyl chloride copolymer, Vinyl acetate / diethyl maleate copolymer, methyl methacrylate / acrylonitrile copolymer, methyl methacrylate / butadiene copolymer, methyl methacrylate / styrene copolymer, methyl methacrylate / vinyl acetate copolymer, methyl methacrylate / vinylidene chloride copolymer Polymer, methyl acrylate / acrylonitrile copolymer, methyl acrylate / butadiene copolymer, methyl acrylate / styrene copolymer, methyl acrylate / vinyl acetate copolymer, acrylic acid / butyl acrylate copolymer, methyl acrylate Rate chloride copolymer, butyl acrylate-styrene copolymer, a polyester, a copolymer resin of various urethane and the like. Among the above-described polymer compounds and resins, it is preferable to use a polymer compound or resin having an amino group from the viewpoints of adhesion of thin metal wires to the light-transmitting support and conductivity.

  When the physical development nucleus layer contains a polymer compound, it preferably contains a crosslinking agent. The crosslinking agent is not particularly limited, inorganic compounds such as chromium alum, aldehydes such as formaldehyde, glyoxal, malonaldehyde, glutaraldehyde, N-methylol compounds such as urea and ethylene urea, mucochloric acid, 2,3-dihydroxy Aldehyde equivalents such as -1,4-dioxane, compounds having an active halogen such as 2,4-dichloro-6-hydroxy-s-triazine salt and 2,4-dihydroxy-6-chloro-triazine salt, Divinyl sulfone, divinyl ketone, N, N, N-triacryloylhexahydrotriazine, compounds having two or more active three-membered ethyleneimino groups, compounds having two or more epoxy groups in the molecule, for example, Sorbitol polyglycidyl ether and polyglycerol polyglycidyl -Diterpolyglycidyl ether, glycerol polyglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc., or other “chemical reaction of polymer” (Nobu Okawara 1972, Kagaku Dojinsha) Examples of known crosslinking agents such as the crosslinking agents described in Chapters 6 and 7, Chapters 5 and 2, and Chapters 9 and 3 can be given. It is preferable to use a compound having two or more epoxy groups in the molecule as a cross-linking agent from the viewpoints of adhesion of thin metal wires to the light-transmitting support and electrical conductivity.

  There is a preferred range in the halide composition of the silver halide emulsion contained in the silver halide emulsion layer of the conductive material precursor used in the silver salt diffusion transfer method, and it is preferable to contain 80 mol% or more of chloride, 90 It is particularly preferable that the mol% or more is chloride. Such a halide composition is preferable because the solubility of silver halide grains is enhanced when a soluble silver complex salt forming agent acts.

  The conductive material precursor used in the silver salt diffusion transfer method is preferably provided with an intermediate layer containing a polymer compound between the physical development nucleus layer and the silver halide emulsion layer. The intermediate layer is a layer that does not contain a crosslinking agent. By providing such an intermediate layer, the water-removability of the silver halide emulsion layer after development is improved. Although this intermediate layer is located closer to the light-transmitting support than the silver halide emulsion layer, the soluble silver complex salt precipitates in the vicinity of the physical development nucleus, and the intermediate layer is removed by washing with water after development. Therefore, the intermediate layer does not exist in the light transmissive electrode obtained by this method. Examples of the polymer compound contained in the intermediate layer include, but are not particularly limited to, polymer compounds that the physical development nucleus layer may contain.

  The developer contains a soluble silver complex salt-forming agent that dissolves unexposed silver halide. Such soluble silver complex salt forming agents include thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, sulfites such as sodium sulfite and potassium bisulfite, Oxazolidones, 2-mercaptobenzoic acid and derivatives thereof, cyclic imides such as uracil, alkanolamines, diamines, mesoionic compounds described in JP-A-9-171257, thioethers as described in USP 5,200,294 , 5,5-dialkylhydantoins, alkylsulfones, “The Theory of the Photographic Process (4th edition, p474-475)”, T. et al. H. Examples include compounds described in James.

  Among these soluble silver complex salt forming agents, alkanolamine is particularly preferable. A fine metal wire obtained by development with a processing solution containing an alkanolamine has a relatively low resistance value. Examples of the alkanolamine include N- (2-aminoethyl) ethanolamine, diethanolamine, N-methylethanolamine, triethanolamine, N-ethyldiethanolamine, diisopropanolamine, ethanolamine, 4-aminobutanol, N, N -Dimethylethanolamine, 3-aminopropanol, N-ethyl-2,2'-iminodiethanol, 2-methylaminoethanol, 2-amino-2-methyl-1-propanol and the like.

  The reducing agent contained in the developer used in the silver salt diffusion transfer method includes hydroquinone, catechol, pyrogallol, methylhydroquinone, chlorohydroquinone and other polyhydroxybenzenes, ascorbic acid and its derivatives, 1-phenyl-4,4-dimethyl. 3-pyrazolidones such as -3-pyrazolidone, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, para A known reducing agent such as phenylenediamine can be used. These reducing agents can be used alone or in combination. The developer used for the silver salt diffusion transfer method can contain other alkali agents such as sodium hydroxide and potassium hydroxide, pH buffering agents such as phosphoric acid and carbonic acid alone or in combination, sodium sulfite, potassium sulfite, etc. Of preservatives.

  Next, an electroless plated metal fine wire forming method, which is a second method for producing the above-described light transmissive electrode shown in FIG. 1 (1-3), will be described.

  In the electroless-plated metal fine wire forming method, a conductive material precursor is formed of a laminate having a base layer containing a water-soluble polymer compound, a crosslinking agent and a metal sulfide on a light-transmitting support, and a photosensitive resist layer in this order. Used as

Examples of the water-soluble polymer compound contained in the underlayer include a water-soluble anionic polymer compound, a nonionic polymer compound, and an amphoteric polymer compound. The anionic polymeric compounds, naturally occurring compounds, or semi-synthetic, or can be used in any of the synthesized compounds, for example, -COO ^- group, -SO ₃ ^- include those having a group. Specific examples of water-soluble anionic polymer compounds include gum arabic, alginic acid, pectin and the like as naturally derived compounds, and gelatin derivatives such as carboxymethyl cellulose and phthalated gelatin, sulfated starch as semi-synthetic products. , Sulfated cellulose, lignin sulfonic acid and the like. Synthetic products include maleic anhydride (including hydrolyzed) copolymers, acrylic acid (including methacrylic acid) polymers and copolymers, vinyl benzene sulfonic acid polymers and copolymers. And carboxy-modified polyvinyl alcohol. Examples of the water-soluble nonionic polymer compound include polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose and the like. Examples of the water-soluble amphoteric polymer compound include gelatin.

  Among the water-soluble polymer compounds described above, gelatin, gelatin derivatives, and polyvinyl alcohol are preferable. Particularly, when polyvinyl alcohol is used, a metal fine wire having particularly excellent conductivity is obtained in addition to excellent adhesiveness, which is preferable. Polyvinyl alcohol is preferably completely or partially saponified polyvinyl alcohol from the viewpoint of film formation and film toughness of the underlayer, and particularly preferably polyvinyl alcohol having a saponification degree of 80% or more. Moreover, 500-6000 are preferable and, as for the average degree of polymerization of polyvinyl alcohol, 1000-5000 are more preferable. The polyvinyl alcohol used in the present invention includes, in addition to general polyvinyl alcohol, cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, and other polyvinyl alcohol derivatives. Polyvinyl alcohol may be used individually by 1 type, and may use 2 or more types together.

The water solubility of the above water-soluble polymer compound means that the amount dissolved in water at 25 ° C. is at least 0.5 mass%, preferably 5 mass% or more. The content of the water-soluble polymer compound in the underlayer is preferably 1 to 1000 mg / ^{m 2} as solid content, more preferably from 5 to 200 mg / ^{m 2.}

  In addition to the water-soluble polymer compound described above, the base layer of the conductive material precursor used in the electroless plating fine metal wire forming method contains a urethane resin from the viewpoint of toughness of the base layer, and from the viewpoint of the conductivity of the fine metal wire To preferred. Examples of the urethane resin include polyether-based urethane resins synthesized from polyether polyol and polyisocyanate, and polyether-based urethane resins synthesized from polycarbonate polyol and polyisocyanate, and any of them can be preferably used. The urethane resin is preferably an aqueous dispersion (emulsion).

  Examples of the crosslinking agent contained in the base layer of the conductive material precursor used in the electroless plating fine metal wire forming method include the crosslinking agent that may be contained in the physical development nucleus layer. From the viewpoint of electrical conductivity of the fine metal wire, an aldehyde compound is preferably used as the crosslinking agent, and polyvalent aldehyde compounds such as glyoxal, malonaldehyde, and glutaraldehyde are particularly preferable. The content of the crosslinking agent in the underlayer is preferably 1 to 200% by mass with respect to the solid content of the water-soluble polymer compound.

The metal sulfide contained in the base layer of the conductive material precursor used in the electroless plating fine metal wire forming method is mainly heavy metal sulfide fine particles (particle size is about 1 to several tens of nm). Examples of metal sulfides include colloidal particles such as gold and silver, and metal sulfides obtained by reacting sulfides with water-soluble salts such as palladium, zinc, and tin. The content of the metal sulfide in the underlayer is preferably 0.1 to 10 mg / m ² as a solid content.

  The photosensitive resist contained in the photosensitive resist layer of the conductive material precursor used in the electroless plated metal fine wire forming method will be described. As the photosensitive resist, it is possible to use a composition widely known as a substance whose solubility in a developer composed of water or various organic solvents changes upon exposure. As the photosensitive resist, there are known a negative type in which the solubility in a developer is lowered by exposure and a positive type in which the solubility in a developer is increased by exposure. From the viewpoint of preventing the temporal change in the photosensitive performance due to contact with the underlayer and from the viewpoint of obtaining finer fine metal wires, it is particularly preferable to use a positive photosensitive resist.

  As the positive photosensitive resist, a known positive photosensitive resist capable of dissolving and removing a portion that can be dissolved by exposure with an aqueous developer containing an alkaline compound is preferably used. A quinonediazide positive photoresist is particularly preferable. The quinonediazide-based positive photoresist contains an alkali-soluble resin and a photosensitizer that is a photodecomposition component. The alkali-soluble resin is preferably a cresol novolak resin, and the photosensitizer is preferably a naphthoquinone diazide sulfonate ester.

  Examples of the alkaline compound contained in the aqueous developer include inorganic alkalis such as sodium carbonate, sodium hydroxide, potassium hydroxide, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, amino alcohols such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc. And quaternary ammonium salts, cyclic amines such as pyrrole and piperidine, and the like. The aqueous developer may contain a known additive such as a surfactant.

  In addition to the above-described photosensitive resist, the photosensitive resist layer is, for example, an epoxy resin or acrylic resin compatible with an alkali-soluble resin, a polyvinyl ether as a plasticizer, other stabilizers, leveling for the purpose of improving toughness. Agents, dyes, pigments and the like may be contained.

  When the above-described photosensitive resist layer is exposed and developed to form a resist image, the underlying layer not covered with the resist image is exposed. In the electroless plating metal wire forming method, electroless plating is applied to the exposed underlayer. As the electroless plating method, known electroless plating methods such as copper plating, nickel plating, zinc plating, tin plating, silver plating, etc. can be used. Among them, electroless silver is used from the viewpoint of conductivity of fine metal wires. Plating is preferred.

  As an electroless silver plating method, for example, two solutions of an ammoniacal silver nitrate solution containing silver nitrate and ammonia and a reducing agent solution containing a reducing agent and a strong alkali component are applied so as to be mixed on the surface of the exposed underlayer. An example is a method in which metallic silver is deposited on the underlayer by a redox reaction.

  As the reducing agent solution, a reducing agent solution containing a reducing agent such as an aldehyde compound such as glucose or glyoxal, a hydrazine compound such as hydrazine sulfate, hydrazine carbonate or hydrazine hydrate, and a strong alkali component typified by sodium hydroxide. Such a reducing agent solution may contain sodium sulfite, sodium thiosulfate, or the like.

  The ammoniacal silver nitrate solution preferably contains an additive from the viewpoint of the conductivity of the fine metal wire pattern. As additives, monoethanolamine, tris (hydroxymethyl) aminomethane, 2-amino-2-hydroxymethyl-1,3-propanediol, 1-amino-2-propanol, 2-amino-1-propanol, diethanolamine And amino alcohol compounds such as diisopropanolamine, triethanolamine and triisopropanolamine, and amino acids such as glycine, alanine and sodium glycine or salts thereof.

  As a method of applying two liquids of an ammoniacal silver nitrate solution and a reducing agent solution so as to be mixed on the surface of the conductive material precursor on which a resist image having an arbitrary pattern is formed, the two liquids are mixed in advance, A method of immersing a conductive material precursor on which a resist image has been formed in this mixed liquid. Two liquids are mixed in advance, and this mixed liquid is sprayed onto the surface of the conductive material precursor on which the resist image has been formed using a spray gun or the like. A method of spraying using a concentric spray gun having a structure in which two liquids are mixed and immediately discharged in the head of the spray gun, and a method of spraying and spraying two liquids from a double-head spray gun having two spray nozzles. There is a method of spraying the liquid simultaneously using two separate spray guns, and any of them can be preferably used. When two liquids are mixed in advance, from the viewpoint of the stability of the liquid after mixing, the liquid after mixing can be quickly applied to the surface of the conductive material precursor on which a resist image having an arbitrary pattern is formed. Particularly preferred.

  The resist image remaining after electroless plating is removed using a known stripping solution suitable for the photosensitive resist contained in the used photosensitive resist layer. As the stripping solution, an organic solvent that swells the resist image or an alkaline aqueous solution is generally used. From the viewpoint of reducing environmental load, it is preferable to use an alkaline aqueous solution. Examples of the alkaline compound contained in the aqueous alkaline solution include the alkaline compounds described above as the main component of the aqueous developer. The stripping solution may contain a known additive such as a surfactant.

  In the present invention, for the purpose of improving the resistance value increase of the fine metal wire over time, after forming the fine metal wire, a reducing substance, a water-soluble phosphorus oxo acid compound, a water-soluble compound as described in JP-A-2008-34366 A functional halogen compound may be allowed to act. Alternatively, for the purpose of improving the adhesion between the light control layer of the present invention and the fine metal wire, the metal fine wire is treated with a treatment liquid containing an enzyme such as a proteolytic enzyme as described in JP-A-2007-12404. In order to reduce the metal reflection of the fine metal wires and reduce the visibility, for example, as described in JP 2011-209626 A, a blackening treatment by a sulfurization reaction may be performed.

  The thin metal wire pattern of the light transmissive electrode will be described. The fine metal line pattern can take any geometrical shape, but in order to achieve the object of the present invention, at least a part of the fine metal line pattern, such as a mesh shape or a stripe shape, is considered to be light transmissive as a whole. It is preferable to have a shape and a pattern that have both conductivity and conductivity. Examples of such fine line patterns include triangles such as regular triangles, isosceles triangles, right triangles, squares, rectangles, rhombuses, parallelograms, trapezoids, etc., (positive) hexagons, (positive) octagons, (positive) Repetitive patterns combining (positive) n-gons such as dodecagons, (positive) icosahedrons, circles, ellipses, stars, etc., and these units may be used alone or in combination of two or more types. Can do. Further, even if the side is not a straight line, it may be constituted by, for example, a zigzag line or a wavy line. Furthermore, stripes and brickwork patterns as disclosed in JP-A-2002-223095, or random figures described in JP-A-2011-216377, JP-A-2013-37683, etc. Can be used. The line width of the fine metal wires constituting the fine metal line pattern is preferably 20 μm or less, more preferably 10 μm or less. If the thickness of the thin metal wire is too thick, troubles such as bubbles are likely to occur between the light-transmitting electrode and the light control layer, but if it is too thin, the conductivity is insufficient. Therefore, the preferable thickness of the fine metal wire is 0.01 to 3 μm, and more preferably 0.05 to 1 μm.

  Next, the light control layer which comprises the light control film of this invention, and the other light transmissive electrode which the light control film of this invention has is demonstrated using figures. FIG. 2 is a schematic cross-sectional view of an example of a light control film having the fine metal wires shown in (1-1) or (1-3) of FIG. FIG. 3 is a schematic cross-sectional view of an example of a light control film having the fine metal wires shown in FIG. In the present invention, the light control layer is a polymer dispersed liquid crystal body containing a liquid crystal compound, a binder resin, and a nitrogen-containing heterocyclic compound. In the present invention, the polymer dispersed liquid crystal body is shown in FIGS. Means that the liquid crystal compound phase 42 is a structure dispersed in the binder resin phase 43. In the polymer dispersed liquid crystal, the nitrogen-containing heterocyclic compound is contained in the liquid crystal compound phase 42 and / or the binder resin phase 43. The other light transmissive electrode 44 which the light control film of this invention has is light transmissive so that it may mention later other than the light transmissive electrode shown by (1-1)-(1-3) of FIG. A known non-metallic conductive film such as a metal oxide such as ITO, a conductive polymer such as polythiophene, or graphene may be provided on the support. In the present invention, having a light control layer between a pair of light transmissive electrodes means that the metal of the light transmissive electrode has a fine metal wire pattern on a light transmissive support as shown in FIGS. This means that the fine line pattern and the metal fine line pattern or non-metal conductive film of the other light-transmitting electrode 44 are in contact with the dimming layer and sandwich the dimming layer.

  The polymer dispersed liquid crystal constituting the light control layer 41 of the light control film of the present invention will be described. As described above, in the polymer dispersion type liquid crystal, the liquid crystal compound phase is dispersed in the binder resin phase, and the spherical liquid crystal compound phase 42 is dispersed in the binder resin phase 43 in FIGS. Although an example is shown, the shape is not limited to this, for example, as described in Patent Document 1, a liquid crystal compound phase exists in a discontinuous droplet form in a binder resin phase, so-called Polymer Dispersed Liquid Crystal structure (hereinafter referred to as PDLC structure) or a so-called Polymer Network Liquid Crystal structure (hereinafter referred to as PNLC) in which a liquid crystal compound phase is present in a continuous network in the binder resin phase as described in Patent Document 2. Any structure exemplified as (structure) is preferably used It can be. The light control layer 41 may be configured by mixing both the PDLC structure and the PNLC structure. The PDLC structure in which the liquid crystal compound phase is present in the form of discontinuous droplets in the binder resin phase is preferable because the liquid crystal compound is less likely to be lost when the light control film is broken and is easy to handle.

  The method for forming the polymer dispersed liquid crystal is not particularly limited, and a known method can be used. Among them, the formation method shown below is easy, and a light control film having a uniform light control layer is obtained, which is particularly preferable. First, a liquid light control layer forming material containing a liquid crystal compound, a liquid monomer or oligomer, a polymerization initiator, and a nitrogen-containing heterocyclic compound is prepared. Next, the liquid light control layer forming material is applied onto the light transmissive electrode. The binder resin phase 43 is formed by polymerizing the monomer or oligomer applied on the light transmissive electrode by light or heat. In the step of forming the binder resin phase 43, the binder resin and the liquid crystal compound are phase-separated to form a PDLC structure or a PNLC structure. By polymerizing monomers and oligomers by light irradiation, the risk of phase separation between the binder resin phase and the liquid crystal compound phase becoming non-uniform due to temperature changes can be suppressed. Is particularly preferred.

  As the liquid crystal compound, a known liquid crystal compound can be used. For example, nematic type, smectic type, and cholesteric type liquid crystal compounds can be exemplified, and a light control film having a high haze reduction rate upon application of a voltage can be obtained. Therefore, it is particularly preferable to use a nematic type liquid crystal compound.

  Nematic liquid crystal compounds include biphenyl compounds, terphenyl compounds, phenylcyclohexyl compounds, biphenylcyclohexyl compounds, phenylbicyclohexyl compounds, phenyl benzoate compounds, cyclohexyl phenylbenzoate compounds, phenylbenzoate phenyl compounds Biphenyl carboxylic acid phenyl compounds, azomethine compounds, azo compounds, and azooxy compounds, stilbene compounds, bicyclohexyl compounds, phenylpyrimidine compounds, biphenylpyrimidine compounds, pyrimidine compounds, and biphenylethyne compounds Etc. The above nematic liquid crystal compounds are commercially available, and examples thereof include BL038, BL006, E7, E44, E48, TL213 (above, manufactured by Merck Co., Ltd.), JC1041XX (above, manufactured by JCN Corporation), and the like. Can also be preferably used.

  Examples of liquid crystal compounds other than nematic liquid crystal compounds include polyesters as smectic liquid crystal compounds, and examples of cholesteric liquid crystal compounds include cholesteryl linoleate, cholesteryl oleate, cellulose, cellulose derivatives, and polypeptides. be able to.

  The monomer, oligomer, and polymerization initiator that can be used for forming the binder resin contained in the polymer dispersed liquid crystal constituting the light control layer of the light control film of the present invention will be described. A monomer and an oligomer are not specifically limited, The well-known monomer and oligomer which a polymer has transparency can be used. Among them, it is preferable to use an acrylic monomer because of its excellent transparency.

  The acrylic monomer in the present invention means a monomer having an acrylic group or a methacryl group. Acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, ( T-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic (Meth) acrylic acid alkyl esters such as 3,5,5-trimethylhexyl acid, isooctyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (meth ) Methoxytriethylene glycol acrylate, 3-methoxypropyl (meth) acrylate, (Meth) acrylic acid alkoxyalkyl esters such as 3-ethoxypropyl, polar group-containing acrylic esters such as (meth) acrylic acid-4-hydroxybutyl, aminoethyl (meth) acrylate, di (meth) ) Hexanediol acrylate, butanediol di (meth) acrylate, di (meth) acrylic acid (poly) ethylene glycol, di (meth) acrylic acid (poly) propylene glycol, di (meth) acrylic acid neopentyl glycol, di (Meth) acrylic acid pentaerythritol, tri (meth) acrylic acid pentaerythritol, hexa (meth) acrylic acid dipentaerythritol, tri (meth) acrylic acid trimethylolpropane, tri (meth) acrylic acid tetramethylolmethane, (meth) Allyl acrylate, ( Data) vinyl acrylate, polyfunctional (meth) acrylic acid esters and the like, etc. can be exemplified. “(Meth) acryl” means “acryl” and / or “methacryl”, and the same applies to others. The above acrylic monomers are commercially available. For example, Aronix M-110, Aronix M-220, Aronix M-309, Aronix M-400 (manufactured by Toagosei Co., Ltd.), KAYARAD R-551, KAYARAD R- 604, KAYARAD R-712, KAYARAD HX-220, KAYARAD HX-620 (manufactured by Nippon Kayaku Co., Ltd.), Biscote # 260, Biscote # 295, Biscote # 300, Biscote # 312 (above, Osaka Organic Chemical Industry) Etc.) and any of them can be preferably used.

  In addition to acrylic monomers, monomers and oligomers that can be used to form a binder resin contained in the polymer dispersed liquid crystal constituting the light control layer of the light control film of the present invention include acrylic oligomers and vinyl ether monomers. Can be illustrated. An acrylic oligomer means an oligomer having at least one acrylic group. Examples of the acrylic oligomer include urethane acrylate, epoxy acrylate, and polyester acrylate. The above acrylic oligomers are commercially available. As urethane acrylates, Aronix M-1100, Aronix M-1200 (above, manufactured by Toagosei Co., Ltd.), UA-1100H, UA-160TM (above, Shin-Nakamura Chemical Co., Ltd.) Co., Ltd.), beam sets 505A-6, 550B, 575 (above, manufactured by Arakawa Chemical Industry Co., Ltd.) and the like. Examples of epoxy acrylates include Unidic V-5500, Unidic V-5502 (above, DIC ( ), Epoxy ester 80MFA, epoxy ester 3000MK (above, manufactured by Kyoeisha Chemical Co., Ltd.) and the like, and polyester acrylates such as Aronix M-7100, Aronix M-8100 (above, Toagosei Co., Ltd.) , EBECRYL436, EBECRYL450, EBE RYL810 (above, Daicel Orunekusu Ltd. Co.) and the like can be exemplified, any of them can be preferably used.

  The vinyl ether monomer means a monomer having a vinyl ether group. The vinyl ether monomer is not particularly limited, and methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl Examples thereof include alkyl monovinyl ethers such as vinyl ether, alkyl divinyl ethers such as 1,4-butanediol divinyl ether and triethylene glycol divinyl ether, and hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether and cyclohexanedimethanol monovinyl ether. The above vinyl ether monomers are commercially available, and can be purchased from, for example, Nippon Carbide Industries Co., Ltd. or BASF Japan Co., Ltd.

  As monomers and oligomers that can be used for forming the binder resin contained in the polymer dispersed liquid crystal constituting the light control layer of the light control film of the present invention, Macromolecules, 1998, No. 31, Examples thereof include NOA65 (Noland UV curable adhesive) published on pages 6806 to 6812.

  The polymer-dispersed liquid crystal body constituting the light control layer of the light control film of the present invention has a higher haze reduction rate when voltage is applied when the liquid crystal compound occupies more within the allowable range of rigidity and durability. A high light control film can be obtained. Therefore, the proportion of the liquid crystal compound in the polymer-dispersed liquid crystal body is preferably 50 to 90% by mass, particularly preferably 55 to 90% by mass.

  A polymerization initiator means the compound which starts the polymerization reaction of an above-described monomer or oligomer with light or a heat | fever, A well-known thing can be used as a polymerization initiator in the light control film of this invention. Specifically, benzoin, benzophenone, benzoin ethyl ether, benzoin isopropyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 -Phenylpropan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvalero Although a nitrile etc. can be illustrated, it is not limited to this. Using a polymerization initiator that initiates a polymerization reaction by light is more dangerous than using a polymerization initiator that initiates a polymerization reaction by heat, because the phase separation between the binder resin phase and the liquid crystal compound phase becomes uneven due to temperature changes. Therefore, it is particularly preferable from the viewpoint of productivity and uniformity of the light control film.

  From the viewpoint of curability of the monomer and oligomer, the polymerization initiator is preferably 0.3 to 5% by mass, particularly preferably 0.5 to 3% by mass, based on the total mass of the light control layer.

  The nitrogen-containing heterocyclic compound contained in the polymer dispersed liquid crystal constituting the light control film of the present invention will be described. The nitrogen-containing heterocyclic compound means a compound having a 5- or 6-membered ring structure (hereinafter referred to as a nitrogen-containing heterocyclic structure) containing at least one nitrogen in a ring structure composed of nonmetallic atoms. The nitrogen-containing heterocyclic compound may have a condensed ring. Examples of the nitrogen-containing heterocyclic structure having no condensed ring include imidazole, triazole, tetrazole, pyrrole, pyridine, thiazole, thiadiazole, oxazole, oxadiazole, imidazolone, pyrazoline, pyrazole, oxazoline, thiazoline, selenazoline, selenazole, pyrimidine, Examples include pyridazine, triazine, oxazine, tetrazine and pyrrolidine. Examples of the nitrogen-containing heterocyclic structure having a condensed ring include benzimidazole, benzotriazole, benzoxazole, benzothiazole, benzoselenazole, quinolidine, indolizine, indole, quinoline, benzotriazine, and tetrazaindene. Among the above, benzimidazoles, benzotriazoles, mercaptotetrazoles, and tetrazaindenes represented by the following general formulas A-1, A-2, A-3, A-4, and A-5 are continuously operated. This is particularly preferable from the viewpoint of improving the accompanying decrease in the haze reduction rate.

In general formulas A-1, A-2, A-3, A-4, and A-5, R _{1 to} R ₁₈ are each a hydrogen atom, a hydroxy group, a mercapto group, a halogen atom (fluorine, chlorine, bromine, iodine, etc.) ), Cyano group, sulfo group, carboxyl group, amino group, alkyl group (methyl, ethyl, propyl, cyclohexyl group, etc.), aralkyl group (benzyl group, etc.), alkoxy group (methoxy, ethoxy group, etc.), aryloxy group ( Phenoxy, naphthoxy group, etc.), amide group, sulfonamide group, ureido group, urethane group, sulfamoyl group, carbamoyl group, aryl group (phenyl, naphthyl group, etc.), alkylthio group (methylthio, hexylthio group, etc.), arylthio group (phenylthio) Group), phosphoric acid amide group, nitro group. These groups may form a salt and may further have a substituent. Examples of the substituent include the groups mentioned as R _{1 to} R ₁₈ and alkyloxycarbonyl groups. When R ₁₂ and R ₁₃ in the general formula A-4, or R ₁₆ and R ₁₇ in the general formula A-5 are particularly an alkyl group, they may be bonded to each other to form a ring.

  Specific examples of the nitrogen-containing heterocyclic compound represented by General Formula A-1 are shown below, but are not limited thereto. Among these, nitrogen-containing heterocyclic compound A-1-2 is preferable.

  Specific examples of the nitrogen-containing heterocyclic compound represented by General Formula A-2 are shown below, but are not limited thereto. Among these, nitrogen-containing heterocyclic compounds A-2-1, A-2-2, A-2-4, A-2-5, and A-2-6 are preferable.

  Specific examples of the nitrogen-containing heterocyclic compound represented by General Formula A-3 are shown below, but are not limited thereto. Among these, nitrogen-containing heterocyclic compounds A-3-1 and A-3-3 are preferable.

  Specific examples of the nitrogen-containing heterocyclic compound represented by General Formula A-4 or A-5 are shown below, but are not limited thereto. Among these, nitrogen-containing heterocyclic compound A-4-1 is preferable.

  Specific examples of the nitrogen-containing heterocyclic compounds that can be used in the present invention other than the nitrogen-containing heterocyclic compounds exemplified as the general formulas A-1 to A-5 described above include the nitrogen-containing compounds described above as shown below. Compounds having a heterocyclic structure and having no substituent (A-6- 1 to A-6-4) and triazines (A-7-1 to A-7-3) having a mercapto group Can be mentioned.

  The content of the nitrogen-containing heterocyclic compound in the light control layer is not particularly limited, but if it is too small, the effect of improving the decrease in the haze reduction rate due to continuous operation may be diminished, and if it is too large, precipitation of the nitrogen-containing heterocyclic compound In some cases, haze increases due to, and polymerization reaction of monomers and oligomers may be inhibited. Therefore, the nitrogen-containing heterocyclic compound content in the light control layer is preferably from 0.1 to 7% by weight, particularly preferably from 0.5 to 5% by weight, based on the total weight of the light control layer.

  In order to allow the nitrogen-containing heterocyclic compound to be contained in the light control layer, it is preferable to dissolve and add the nitrogen-containing heterocyclic compound to the liquid light control layer forming material described above because a uniform polymer dispersed liquid crystal can be formed. In order to improve the solubility of the nitrogen-containing heterocyclic compound, a known organic solvent such as alcohols, ketones and esters may be added to the liquid light control layer forming material. When adding an organic solvent to the liquid light-control layer forming material, after applying the liquid light-control layer forming material and before polymerizing the monomer or oligomer, an organic solvent drying process is performed by warm air or natural drying to remove the organic solvent It is preferable to do.

  The liquid light control layer forming material may contain other known additives such as surfactants, ultraviolet absorbers, infrared absorbers, colorants (pigments, dyes, etc.) and antioxidants.

  The other light transmissive electrode 44 of the light control film of this invention is demonstrated. The light-transmitting electrode is not particularly limited as long as it is a material having both light-transmitting property and conductivity, and a thin metal wire pattern composed of the thin metal wires 12 shown by (1-1) to (1-3) in FIG. In addition to the light-transmitting electrode having a non-metallic conductive film on the light-transmitting support, for example, ITO (indium tin oxide), IZO (indium zinc oxide), ZnO (zinc oxide), FTO (fluorine-doped tin oxide) , Metal oxides such as ATO (aluminum doped tin oxide), GTO (gallium doped tin oxide), GZO (gallium doped zinc oxide), conductive polymers such as polythiophene, polyacetylene, polypyrrole, polyaniline, graphene, etc. Examples include, but are not limited to, light transmissive electrodes having a non-metallic conductive film.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to a following example, unless the summary is exceeded.

<Preparation of light control film 1>
As the light transmissive support, a polyethylene terephthalate film having a thickness of 100 μm (Toray Industries, Inc. Lumirror U34, which has been easily bonded) was used. The total light transmittance of this light transmissive support was 92%.

  Next, according to the following formulation, physical development nuclei (palladium sulfide sol) are prepared, a physical development nucleation layer coating solution containing the physical development nuclei is prepared, applied onto a light-transmitting support, and dried to develop physical development nuclei. A layer was provided. Thereafter, the mixture was heated at 50 ° C. for 1 day.

<Preparation of palladium sulfide sol>
Liquid A Palladium chloride 5g
Hydrochloric acid 40ml
1000ml distilled water
B liquid sodium sulfide 8.6g
1000ml distilled water
Liquid A and liquid B were mixed with stirring, and 30 minutes later, the solution was passed through a column filled with an ion exchange resin to obtain palladium sulfide sol.

<Physical development nucleus layer coating solution 1> per 1 m ^{2 of the} palladium sulfide sol 0.4 mg
0.2% aqueous 2% glyoxal solution
Surfactant (S-1) 4mg
Denacol EX-830 5mg
(Polyethylene glycol diglycidyl ether manufactured by Nagase ChemteX Corporation)
10 mass% SP-200 aqueous solution 0.5g
(Nippon Shokubai polyethyleneimine)

  Subsequently, an intermediate layer having the following composition, a silver halide emulsion layer, and a protective layer were coated on the physical development nucleus layer in order from the side closest to the light-transmitting support to obtain a conductive material precursor. The silver halide emulsion was prepared by a general double jet mixing method for photographic silver halide emulsions. This silver halide emulsion was prepared such that 95 mol% of silver chloride and 5 mol% of silver bromide had an average particle size of 0.15 μm. The silver halide emulsion thus obtained was subjected to gold sulfur sensitization using sodium thiosulfate and chloroauric acid according to a conventional method. The silver halide emulsion thus obtained contains 0.5 g of gelatin per gram of silver.

<Intermediate layer composition / per 1 m ² >
Gelatin 0.5g
Surfactant (S-1) 5mg
Dye 1 5mg

<Silver halide emulsion layer composition per 1/1 m ² >
Gelatin 0.5g
Silver halide emulsion 4.0g Equivalent to silver 1-Phenyl-5-mercaptotetrazole 3mg
Surfactant (S-1) 20mg

<Protective layer composition / per 1 m ² >
1g of gelatin
Amorphous silica matting agent (average particle size 3.5μm) 10mg
Surfactant (S-1) 10mg

  The conductive material precursor thus obtained and the transparent original shown in FIG. 4 were brought into close contact with each other, and exposed through a resin filter that cut light of 400 nm or less with a contact printer using a mercury lamp as a light source. In FIG. 4, the fine metal line pattern equivalent portion 21 is a mesh having a unit figure of a square having a line width of 7 μm and a fine wire interval of 300 μm, and the fine metal line pattern equivalent portion 21 is connected to the terminal equivalent portion 22.

  After the exposure, the film was immersed in the following diffusion transfer developer for 90 seconds at 20 ° C., and then the silver halide emulsion layer, intermediate layer, and protective layer were washed away with warm water at 40 ° C. and dried. Thus, on the light transmissive support, a light transmissive electrode 1 having a fine metal wire pattern composed of fine metal wires of the form (1-3) in FIG. 1 was obtained.

<Diffusion transfer developer composition>
Potassium hydroxide 25g
Hydroquinone 18g
1-phenyl-3-pyrazolidone 2g
Potassium sulfite 80g
N-methylethanolamine 15g
Potassium bromide 1.2g
Total volume 1000ml with water
Adjust to pH = 12.2.

  FIG. 5 is a schematic view of the light transmissive electrode 1. A black part (line drawing part) is the metal fine wire 12 in FIG. As for the correspondence between the transparent original shown in FIG. 4 and the light-transmissive electrode 1 shown in FIG. 5, the fine metal wire pattern equivalent portion 21 in FIG. 4 corresponds to the fine metal wire pattern portion 31 in FIG. The terminal equivalent portion 22 corresponds to the terminal portion 32 of FIG. As a result of observation using a confocal microscope (Latertech Co., Ltd., Optics C130), the line width and fine line interval of the thin metal wire pattern 31 that is a light-transmitting electrode are as follows. It was the same as the fine wire interval, and the other shapes were exactly the same. Moreover, the thickness of the metal fine wire evaluated using the confocal microscope was 0.10 micrometer.

Next, according to the following prescription, a liquid light-modulating layer forming material is prepared, applied on the above-described light-transmissive electrode 1 (excluding the terminal portion) so as to have a thickness of 20 μm, and subsequently as the light-transmissive electrode 2, An ITO film (manufactured by Toyobo Co., Ltd.) having an ITO film formed on a polyethylene terephthalate film was placed so that the ITO film was on the light control layer side. Then, light was irradiated with the light quantity of 1000 mJ / cm < ² > using the high pressure mercury lamp from the polyethylene terephthalate film side of the ITO film, and the monomer in the liquid light control layer forming material was polymerized. In this way, the light control film 1 which has a light control layer between a pair of transparent electrodes was obtained.

<Liquid light control layer forming material composition>
E7 (nematic liquid crystal compound, manufactured by Merck & Co., Inc.) 79 g
3,5,5-trimethylhexyl acrylate 15g
KAYARAD HX-620 (acrylic monomer, Nippon Kayaku Co., Ltd.)
5g
2,2-dimethoxy-1,2-diphenylethane-1-one (polymerization initiator)
1g
Nitrogen-containing heterocyclic compound A-1-2 2 g
It stirred well after adding a nitrogen-containing heterocyclic compound, and it confirmed that the powdery undissolved substance did not remain | survive.

<Preparation of light control film 2>
A light control film 2 was obtained in the same manner as the preparation of the light control film 1 except that the nitrogen-containing heterocyclic compound A-2-1 was used instead of the nitrogen-containing heterocyclic compound A-1-2.

<Preparation of light control film 3>
A light control film 3 was obtained in the same manner as the preparation of the light control film 1 except that the nitrogen-containing heterocyclic compound A-2-2 was used instead of the nitrogen-containing heterocyclic compound A-1-2.

<Preparation of light control film 4>
A light control film 4 was obtained in the same manner as the preparation of the light control film 1 except that the nitrogen-containing heterocyclic compound A-2-4 was used instead of the nitrogen-containing heterocyclic compound A-1-2.

<Preparation of light control film 5>
A light control film 5 was obtained in the same manner as the preparation of the light control film 1 except that the nitrogen-containing heterocyclic compound A-2-5 was used instead of the nitrogen-containing heterocyclic compound A-1-2.

<Preparation of light control film 6>
A light control film 6 was obtained in the same manner as the preparation of the light control film 1 except that the nitrogen-containing heterocyclic compound A-3-1 was used in place of the nitrogen-containing heterocyclic compound A-1-2.

<Preparation of light control film 7>
A light control film 7 was obtained in the same manner as the preparation of the light control film 1 except that the nitrogen-containing heterocyclic compound A-3-3 was used instead of the nitrogen-containing heterocyclic compound A-1-2.

<Preparation of light control film 8>
A light control film 8 was obtained in the same manner as the preparation of the light control film 1 except that the nitrogen-containing heterocyclic compound A-4-1 was used instead of the nitrogen-containing heterocyclic compound A-1-2.

<Preparation of light control film 9>
A light control film 9 was obtained in the same manner as in the preparation of the light control film 1 except that the nitrogen-containing heterocyclic compound A-6-2 was used instead of the nitrogen-containing heterocyclic compound A-1-2.

<Preparation of light control film 10>
The light control film 10 was obtained similarly to preparation of the light control film 1 except having used the nitrogen-containing heterocyclic compound A-6-3 instead of the nitrogen-containing heterocyclic compound A-1-2.

<Preparation of light control film 11>
A light control film 11 was obtained in the same manner as in the preparation of the light control film 1 except that the nitrogen-containing heterocyclic compound A-7-2 was used in place of the nitrogen-containing heterocyclic compound A-1-2.

<Preparation of light control film 12>
The light control film 12 was obtained in the same manner as the preparation of the light control film 1 without using the nitrogen-containing heterocyclic compound A-1-2.

<Preparation of light control film 13>
In place of the nitrogen-containing heterocyclic compound A-1-2, the light-controlling film 13 was obtained in the same manner as the preparation of the light-controlling film 1 except that the following non-nitrogen-containing heterocyclic compound B-1 was used.

<Checking the initial operation of the light control film>
When the haze when no alternating voltage was applied was measured for each of the light control films 1 to 13, it was confirmed that the haze was uniform in the surface and the polymer dispersed liquid crystal constituting the light control layer was uniform. The haze at this time was set to 1 (unit:%). Next, when an AC voltage of 70 V was applied between the terminal portion of the light transmissive electrode 1 and the ITO film of the light transmissive electrode 2 for each of the light control films 1 to 13, the haze of the light control film was lowered. The haze at this time was set to 2 (unit:%). When voltage application was completed, it was confirmed that the haze of the light control film was recovered to a haze value of 1. The haze reduction rate from the haze value 1 to the haze value 2 was calculated by the following formula and used as the haze reduction rate (unit:%) immediately after the production of the light control films 1 to 13. The results are shown in Table 1. A haze computer HZ-2 manufactured by Suga Test Instruments Co., Ltd. was used for haze measurement.

Haze reduction rate immediately after production = {(haze value 1−haze value 2) / haze value 1} × 100

<Evaluation of haze reduction rate change with continuous operation>
An AC voltage of 70 V was continuously applied to each of the light control films 1 to 13 for one month. Thereafter, once the voltage application was finished and the haze of each light control film was measured again after being left for 24 hours, it was the same as the haze value 1. When AC voltage 70V was applied again, the haze of the light control film fell. The haze at this time was set to 3 (unit:%). The haze reduction rate from the haze value 1 to the haze value 3 was calculated by the following formula, and used as the haze reduction rate (unit:%) after continuous operation of the light control films 1 to 13. The results are shown in Table 1.

Haze reduction rate after continuous operation = {(haze value 1−haze value 3) / haze value 1} × 100

  From the results in Table 1, the effectiveness of the present invention can be seen.

DESCRIPTION OF SYMBOLS 11 Light transmissive support body 12 Metal fine wire 13 Metal 14 Binder 15 Undercoat layer 21 Metal fine wire pattern equivalent part 22 Terminal equivalent part 31 Metal fine wire pattern part 32 Terminal part 41 Light control layer 42 Liquid crystal compound phase 43 Binder resin phase 44 The other Light transmissive electrode

Claims (1)

  A light-control film having a light-control layer between a pair of light-transmitting electrodes, wherein at least one of the light-transmitting electrodes is a light-transmitting electrode having a metal fine line pattern on the light-transmitting support, A light control film, wherein the light control layer is a polymer dispersed liquid crystal containing at least a liquid crystal compound, a binder resin, and a nitrogen-containing heterocyclic compound.