JP2009106903A - Manufacturing method of metallic luster coat - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metallic luster coat capable of forming a metallic luster coat on an arbitrary substrate such as plain paper, plastics, fiber, and glass at low temperature in a short time with a small number of processes, and excellent in adhesion to equipment and materials in addition to the above-described characteristics, its forming method, and a product using the metallic luster coat. <P>SOLUTION: A method of manufacturing the metallic luster coat comprises the step of coating the substrate with a material for forming a metallic luster coat including a metal nano-particle coated with a protective material having ionic properties and having an average particle size of 1-100 nm. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a metallic luster coating obtained by using a material containing metallic nanoparticles that are coated with an ionic protective substance and have an average particle diameter of 1 to 100 nm, and a method for forming the same.

  Conventionally, when forming images of characters, figures, and patterns with specular reflectivity, metal such as aluminum is vapor-deposited on the entire surface of the substrate, and then unnecessary portions are removed with chemicals, etc. There is a method of forming a predetermined image having Alternatively, masking corresponding to an image to be formed in advance is performed, then silver fine powder is vapor-deposited on the entire surface of one side of the substrate to be printed by a metal vapor deposition step, and then the masking is removed, thereby remaining. There is a method of forming a predetermined image having specular reflectivity composed of the above-described portions.

  On the other hand, as a printing method, as disclosed in JP-A-9-268269 and JP-A-2003-315511, mirror ink using scaly metallic powder or aluminum foil pieces is printed by gravure printing, flexographic printing or screen printing, and mirror surface is used. A method of imparting reflectivity has been performed.

The above-mentioned conventional vapor deposition method requires a large amount of equipment because it requires a vapor deposition process, and it is very expensive. In addition, a process for removing unnecessary parts, and a metal for non-patterned parts The number of processes such as recovery and reuse of the product increases, resulting in poor productivity and a great cost for producing a product. Also, pattern formation using chemicals often uses powerful drugs such as strong acids, which requires wastewater treatment and is not preferable from the viewpoint of environmental conservation. In addition, the base material on which the chemical solution can be used is limited and lacks versatility. In addition, although scaly metallic powder and aluminum foil pieces are expensive, in the pattern forming method having specular reflectivity by printing using scaly metallic powder and aluminum foil pieces, about 3 μm is required to obtain specularity and concealment. This is disadvantageous in terms of cost.
Japanese Patent Laid-Open No. 9-268269 JP 2003-315511 A

  Accordingly, an object of the present invention is to provide a metallic glossy coating that does not have the above-described conventional problems and a method for forming the metallic glossy coating.

  More specifically, the present invention can form a metallic gloss film in a small number of steps at a low temperature and in a short time on an arbitrary substrate such as ordinary paper, plastic, fiber, glass, etc. An object of the present invention is to provide a metallic glossy coating having excellent adhesion to equipment, a method for forming the same, and a product using the metallic glossy coating.

    That is, the present invention is characterized in that a metallic glossy film-forming material containing metal nanoparticles having an average particle diameter of 1 to 100 nm and coated with an ionic protective substance is formed on a substrate. The present invention relates to a method for producing a metallic gloss coating.

    The present invention also relates to the above-mentioned method for producing a metallic glossy coating, wherein the metallic glossy coating-forming material containing metallic nanoparticles contains at least one liquid medium.

  The present invention also relates to the above-described method for producing a metallic luster coating, characterized in that after the coating is formed, the coating is dried at a temperature not higher than the boiling point of the liquid medium having the highest boiling point among the liquid media.

  The present invention also relates to the above-described method for producing a metallic glossy coating, wherein the metallic glossy coating-forming material containing metallic nanoparticles contains at least one of a leveling agent, an antifoaming agent, and a lubricant.

    In the present invention, the metal forming the metal nanoparticles is gold, silver, copper, nickel, platinum, palladium, aluminum, zinc, chromium, iron, cobalt, molybdenum, zirconium, ruthenium, iridium, tantalum, mercury, indium. Further, the present invention relates to a method for producing the above metallic glossy coating, which is an alloy or a mixture of one or more selected from tin, lead, and tungsten.

  Moreover, this invention relates to the manufacturing method of the said metallic luster film whose metal which forms a metal nanoparticle is silver.

  Moreover, this invention relates to the manufacturing method of the said metallic gloss coating whose metal nanoparticle is obtained by reduce | restoring a metal compound in a liquid medium.

  Further, the present invention is obtained by reducing a metal compound using a carbodihydrazide represented by the following formula (1) or a polybasic acid polyhydrazide represented by the following formula (2). It is related with the manufacturing method of the said metallic luster film.

（式中、Ｒはｎ価の多塩基酸残基を表す。）

(In the formula, R represents an n-valent polybasic acid residue.)

  Further, the present invention provides the metallic glossy coating, characterized in that the metal nanoparticles coated with an ionic protective substance are brought into contact with a substance having an ion exchange capacity for the protective substance on a substrate. It relates to a manufacturing method.

  The present invention also provides a metal comprising metal nanoparticles coated with a protective substance having ionicity on an ion exchange layer after forming an ion exchange layer containing a substance having ion exchange ability on a substrate. The present invention relates to a method for producing the above-mentioned metallic glossy film, characterized in that a film for forming a glossy film is formed.

  In addition, the present invention provides a metallic nanoparticle layer after forming a metallic glossy film-forming material containing metallic nanoparticles coated with a protective substance having ionicity on a base material to form a metallic nanoparticle layer. The present invention relates to a method for producing a metallic glossy coating, comprising forming an ion exchange layer containing a substance having ion exchange capacity thereon.

  The present invention also relates to a method for producing a metallic gloss coating, comprising printing a metallic gloss coating material containing metal nanoparticles.

  The present invention also relates to the above-described method for producing a metallic luster coating, which comprises coating a metallic luster coating-forming material containing metal nanoparticles.

  The present invention further relates to a method for producing a metallic glossy coating, wherein a heat and pressure treatment is performed after the coating is formed.

  Moreover, this invention relates to the metallic glossy film manufactured with the said manufacturing method.

  With the metallic glossy coating obtained by applying the material containing the metal nanoparticles of the present invention and the method for forming the metallic glossy coating, the metallic glossy coating can be formed at a low temperature and in a short time. In addition, it is possible to form a metallic gloss film on any base material such as normal paper, plastic, fiber, glass, etc., and since it has excellent adhesion to the base material, it can be applied to any kind of base material. Can be used for applications. In addition, the material containing metal nanoparticles used for forming the metallic gloss coating of the present invention has characteristics suitable for various printing methods such as gravure printing, flexographic printing, and ink jet printing, or various coating methods. Therefore, a metallic gloss coating, an image and a pattern can be formed only in necessary portions with a small number of steps, which is very advantageous in terms of productivity and cost as compared with the conventional method.

  Since the metallic glossy coating of the present invention has good specular reflectivity by controlling the drying temperature, for example, a display member, an optical member, an illumination member, a medical member, an automobile member, a coating member It can be used for packaging members, building members and the like.

  Hereinafter, the present invention will be described in more detail. However, the present invention is not limited to the following description or embodiments without departing from the technical idea of the present invention.

First, the metallic gloss coating of the present invention is obtained by printing or coating a material containing metal nanoparticles having an average particle diameter of 1 to 100 nm, which is coated with an ionic protective substance, and contains metal nanoparticles. The material is characterized in that it may contain at least one liquid medium.

  The metal forming the metal nanoparticles is not particularly limited as long as it has a metallic luster when it becomes a film, but among others, gold, silver, copper, nickel, palladium, platinum, aluminum, zinc, chromium, iron, Cobalt, molybdenum, zirconium, ruthenium, iridium, tantalum, mercury, indium, tin, lead, and tungsten are preferable, and gold, silver, copper, nickel, cobalt, tin, lead, chromium, and zinc are used in terms of gloss and cost. Further, it is preferable that aluminum is silver, tin, chromium, lead, and aluminum in terms of metallic luster and cost. These metals can be used alone, or two or more of them can be used as an alloy, a mixture, or a mixture other than an alloy and an alloy.

  In the present invention, the metal nanoparticles are coated with an ionic protective substance. The protective substance prevents aggregation of the metal nanoparticles, and improves the dispersion stability of the metal nanoparticles in the material when, for example, a material for forming a metallic glossy film containing metal nanoparticles such as ink and paint is used. Therefore, it is preferable to use a substance having an ionic property having an affinity for the surface of the metal nanoparticle as a substance that can achieve such an object. Examples of the ionic protective substance include compounds having one or more ionic groups in the compound, and have one or both of a cationic group and an anionic group. As the ionic group having an affinity for the metal surface, generally, for example, an anionic group such as a hydroxyl group, a cyano group, a carboxyl group, a sulfonic acid group, phosphoric acid, a phosphate ester, such as an amino group, an amide Groups, cationic groups such as quaternary ammonium, mercapto group, sulfenyl group, sulfanediyl group and the like are not limited thereto. These ionic groups may be contained in the main chain of the compound, or may be contained in the side chain or both the side chain and the main chain.

  Examples of the compound having one or more ionic groups having an affinity for the metal nanoparticle surface include pigment dispersants, surfactants, coupling agents, fatty acids, amines, acid amides, thiols, sulfides. Compounds and the like.

  The pigment dispersant that can be used as a protective substance in the present invention is not particularly limited as long as it has one or more ionic groups having affinity for the surface of the metal nanoparticles in the compound. Absent. A wide variety of pigment dispersants are already on the market, and any of these commercially available pigment dispersants can be used as a protective material for metal nanoparticles in the present invention. Examples of commercially available pigment dispersants that can be used as protective substances in the present invention include, for example, Floren DOPA-15B, Floren DOPA-17 (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse 3000, Solsperse 9000, Solsperse 17000, Solsperse 24000, Solsperse. 28000, Solsperse 32000, Solsperse 35100, Solsperse 36000, Solsperse 41000 (manufactured by Nippon Lubrizol Corporation), SMA1000, SMA2000, SMA3000, SMA1440, SMA17352, SMA2625, SMA3840 (manufactured by Kawa Crude Chemical Co., Ltd.), EFKA4009, EFKA4046, EFKA4047 EFKA4080, EFKA4010, EFKA4015, EFKA4020, E KA4050, EFKA4055, EFKA4060, EFKA4080, EFKA4400, EFKA4401, EFKA4402, EFKA4403, EFKA4300, EFKA4330, EFKA4340, EFKA6220, EFKA6225, EFKA6230, EFKA6525, EFKA6700, EFKA6745, EFKA6780, EFKA6782, EFKA6903, EFKA6906, EFKA6950, EFKA7462, EFKA8502, EFKA8503, EFKA8511, EFKA8512, EFKA8580, EFKA8590 (all manufactured by Efka Additives), Addisper PB821, Addisper PB711, Addisper PB822, Famex L-12, Addisper PN411 Addispar PA111 (all manufactured by Ajinomoto Fine Techno Co., Ltd.), TEXAPHOR-UV20, TEXAPHOR-UV21, TEXAPHOR-UV61 (all manufactured by Cognis Japan Co., Ltd.), Disperbyk-101, Disperbyk-102, Disperbyk-103, Disperbyk-106 Disperbyk-110, Disperbyk-111, Disperbyk-140, Disperbyk-142, Disperbyk-145, Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-164, DisperDik-164, DisperDik-164 170, Di Superbyk-171, Disperbyk-174, Disperbyk-180, Disperbyk-182, Disperbyk-2000, Disperbyk-2001, Disperbyk-2050, Disperbyk-2070, Disperbyk-2090 , Disparon KS-873N, Disparon 7004, Disparon 1831, Disparon 1850, Disparon 1860, Disparon 2150, Disparon DA-400N, Disparon PW36, Disparon DA-703-50, Disparon DA-725, Disparon DA-705, Disparon DA-7301 , Disparon DA-325, Disparon A-375, DISPARLON DA-234, DISPARLON DN-900, DISPARLON DA-1200 (Kusumoto Chemicals Ltd. any), and the like. These pigment dispersants may be used singly or in combination of two or more, or may be used in combination of the pigment dispersant and the protective substance of the present invention other than the pigment dispersant.

  In addition, surfactants are generally known to be anionic, nonionic, zwitterionic, and cationic. In the present invention, any of these may be used as a protective substance. it can. The surfactant used in the present invention is not particularly limited as long as it is a compound known as a surfactant, but from the viewpoint of easy availability, a compound that is commercially available as a surfactant. Is preferably used. Examples of anionic, nonionic, zwitterionic, and cationic surfactants are specifically shown below, but the surfactants that can be used in the present invention are limited to the following. is not.

  Examples of the anionic surfactant include higher fatty acid salt, alpha sulfo fatty acid methyl ester salt, alkyl sulfonate, alkyl benzene sulfonate, alkyl sulfate ester salt, alkyl ether sulfate ester salt, monoalkyl phosphate ester salt, alpha Examples include oleic sulfonate, alkane sulfonate, sulfosuccinate, alkyl ether sulfonate, alkyl ether carboxylate, and methyl taurate.

  Examples of the nonionic surfactant include glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol alkyl ether, polyethylene glycol alkyl phenyl ether, polyethylene glycol fatty acid ester, polyoxyethylene fatty acid ester. , Fatty acid alkanolamide, polyoxyethylene alkyl ether, alkyl glucoside, polyoxyethylene alkyl phenyl ether, fatty acid monoglyceride and the like.

  Examples of zwitterionic surfactants include amino acids, alkylamino fatty acid salts, alkylbetaines, alkylamine oxides, and polyacrylamides.

  Examples of the cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, N-methylbishydroxyethylamine fatty acid ester hydrochloride, alkylpyridinium halide, and the like.

  In addition, these are classified into different forms, such as reactive surfactants such as fluorosurfactants and allyl reactive surfactants, polymer interfaces such as cationic cellulose derivatives, polycarboxylic acids, and polystyrenesulfonic acids. Activators are also known. These are also commercially available as wetting and dispersing agents, but any of the aforementioned surfactants including such wetting and dispersing agents can be used as a protective substance in the present invention. Examples of these surfactants are EFKA5010, EFKA5044, EFKA5244, EFKA5054, EFKA5055, EFKA5063, EFKA5064, EFKA5065, EFKA5066, EFKA5070, EFKA5071 and EFKA5207k. 101, Disperbyk-108, Disperbyk-130 (all manufactured by Big Chemie Japan Co., Ltd.) and the like.

  These surfactants can be used alone or in combination of two or more. Moreover, in this invention, it can also use as a protective substance of a metal nanoparticle combining the protective substance of this invention other than surfactant and surfactant.

  As coupling agents, silane coupling agents, titanate coupling agents, aluminum coupling agents, zirconium coupling agents and the like are generally known, and any of these may be used in the present invention. Can be used as a protective substance. Hereinafter, some commercially available coupling agents that can be used in the present invention are exemplified, but the coupling agent used in the present invention is not limited to the following.

  Examples of the silane coupling agent include KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE403, KBM-1403, KBM-502, KBM-503, KBE-502. , KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-6123, KBE-585, KBM -703, KBM-802, KBM-803, KBE-945, KBE-846, KBE-9007 (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

  Examples of titanate-based coupling agents include Preneact KR-TTS, Preneact KR-46B, Preneact KR-55, Preneact KR-41B, Preneact KR-38S, Preneact KR-138S, Preneact KR-238S, Preneact 338X, Preneact KR-44, Preneact KR-9SA (both manufactured by Ajinomoto Fine Techno Co., Ltd.) and the like.

  Examples of the aluminum coupling agent include Preneact AL-M (manufactured by Ajinomoto Fine Techno Co., Ltd.).

  Examples of the zirconium-based coupling agent include Kenliact (manufactured by Kenrich Petrochemicals Co., Ltd.).

  These coupling agents may be used singly or in combination of two or more, or may be used in combination with the protective agent of the present invention other than the coupling agent and the coupling agent. .

  The fatty acid used in the present invention is not particularly limited, and those generally known as fatty acids can be used, for example, linear saturated fatty acids, linear unsaturated fatty acids, branched fatty acids, tertiary fatty acids and the like. Can be mentioned.

  Examples of linear saturated fatty acids include propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecyl acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, Examples include heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, mellicic acid, and laccelic acid.

  Examples of linear unsaturated fatty acids include acrylic acid, crotonic acid, isocrotonic acid, undecylenic acid, oleic acid, elaidic acid, celetic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, propiolic acid. Examples include acids and stearol acids. Of these, caproic acid, enanthic acid, caprylic acid, myristic acid, oleic acid, stearic acid and the like can be mentioned in consideration of stability and low-temperature decomposability.

  Examples of branched fatty acids include isobutyric acid, isovaleric acid, 2-ethylhexanoic acid, 2-ethylisohexanoic acid, 2-propylheptanoic acid, 2-butyloctanoic acid, 2-isobutylisooctanoic acid, 2-pentylnonanoic acid, 2-isopentylnonanoic acid, 2-hexyldecanoic acid, 2-hexylisodecanoic acid, 2-butyldodecanoic acid, 2-isobutyldodecanoic acid, 2-heptylundecanoic acid, 2-isoheptylundecanoic acid, 2-isopeptyliso Undecanoic acid, 2-dodecylhexanoic acid, 2-isododecylhexanoic acid, 2-octyldodecanoic acid, 2-isooctyldodecanoic acid, 2-octylisododecanoic acid, 2-nonyltridecanoic acid, 2-isononylisotridecane Acid, 2-decyldodecanoic acid, 2-isodecyldodecanoic acid, 2-decylisododecane 2-decyltetradecanoic acid, 2-octylhexadecanoic acid, 2-isooctylhexadecanoic acid, 2-undecylpentadecanoic acid, 2-isoundecylpentadecanoic acid, 2-dodecylheptadecanoic acid, 2-isododecylisoheptadecanoic acid 2-decyloctadecanoic acid, 2-decylisooctadecanoic acid, 2-tridecylheptadecanoic acid, 2-isotridecylisoheptadecanoic acid, 2-tetradecyloctadecanoic acid, 2-isotetradecyloctadecanoic acid, 2-hexa Decylhexadecanoic acid, 2-hexadecyltetradecanoic acid, 2-hexadecylisohexadecanoic acid, 2-isohexadecylisohexadecanoic acid, 2-pentadecylnonadecanoic acid, 2-isopentadecylisonononadecanoic acid, 2-tetradecyl Behenic acid, 2-isotetradecylbe Phosphate, 2-tetradecyl Isobe hen acid, 2-iso-tetradecyl Isobe hen acid, isoheptanoic acid, isomyristic acid, isopalmitic acid, isostearic acid, isoarachic acid.

  Examples of the tertiary fatty acid include pivalic acid, neononanoic acid, neodecanoic acid, equacid 9 (produced by Idemitsu Petrochemical Co., Ltd.), equacid 13 (produced by Idemitsu Petrochemical Co., Ltd.), and the like.

  These fatty acids are preferably those having 3 to 22 carbon atoms. Moreover, you may use individually by 1 type, may be used in combination of 2 or more types, and may use combining the protective substances of this invention other than a fatty acid and a fatty acid.

  Examples of amine compounds include alkylamines such as primary amines, secondary amines, tertiary amines, and quaternary amine salts, diamines, alkanolamines, and the like, such as butylamine, octylamine, dodecylamine, Hexadodecylamine, octadecylamine, cocoamine, tallowamine, hydrogenated tallowamine, primary amines such as oleylamine, laurylamine, and stearylamine, secondary amines such as dicocoamine, dihydrogenated tallowamine, and distearylamine, dodecyldimethyl Tertiary amines such as amine, didodecylmonomethylamine, tetradecyldimethylamine, octadecyldimethylamine, cocodimethylamine, dodecyltetradecyldimethylamine, and trioctylamine, naphthalenediamine, stearyl Propylene diamine, octamethylene diamine, and diamines such nonanediamine, 2-methyl-aminoethanol, diethanolamine, butoxypropyl amine, diethyl methyl amine, 2-dimethylaminoethanol, and the like alkanolamines such as methyldiethanolamine.

  Although it does not specifically limit as an acid amide compound, For example, carboxylic acid amide and aminocarboxylate are mentioned.

  The thiol compound is not particularly limited. For example, acid thiols such as mercaptoacetic acid, mercaptopropionic acid, thiodipropionic acid, mercaptosuccinic acid, thioacetic acid, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, allyl Aliphatic thiols such as mercaptan, dimethyl mercaptan, mercaptoethanol, aminoethyl mercaptan, thiodiethylamine, alicyclic thiols such as cyclohexylthiol, aromatic thiols such as thiophenol, thiodiethylene glycol, thiodiglycolic acid, ethylenethio And thioglycols such as glycol.

  Although it does not specifically limit as said sulfide compound, For example, dimethyl sulfide, diethyl sulfide, methylpropyl sulfide, etc. are mentioned.

  In the present invention, the protective substance having ionicity is preferably used in the range of 0.1 to 2000 parts by weight in the total amount of the protective substance with respect to 100 parts by weight of the metal nanoparticles, but in the range of 0.1 to 100 parts by weight. More preferably, it is used. This is because when the amount of the protective substance used is less than 1 part by weight, the effect of the protective substance cannot be obtained and the metal nanoparticles are aggregated. On the other hand, when the amount exceeds 2000 parts by weight, the presence of an excessive protective substance that does not contribute to stabilization adversely affects the reflectance and physical properties when used as a metallic luster coating or the like.

As a method of coating these protective substances on metal nanoparticles, a method of coating metal nanoparticles with a protective substance by mixing metal nanoparticles prepared in advance and the protective substance in a dry or wet manner, metal nanoparticles, etc. A method of forming metal nanoparticles in the presence of a protective substance to produce metal nanoparticles coated with the protective substance when using a metal salt of a substance that functions as a protective substance, such as a fatty acid metal salt, using a reducing agent, etc. For example, a method of obtaining metal nanoparticles coated with a protective substance by reduction is known. Any of these methods is a known method, and an appropriate method may be used.

The metal nanoparticles of the present invention are preferably fine particles having an average particle diameter in the range of 1 to 100 nm, and more preferably 1 to 50 nm from the viewpoint of film formability and low temperature. It is known that metal nanoparticles having a particle diameter in this range cause fusion of metals in a temperature range that is dramatically lower than the melting point inherent to the metal due to the melting point lowering of the nanoparticles. Therefore, by using metal nanoparticles having an average particle diameter of 1 to 100 nm, it becomes possible to form a metallic glossy coating having excellent specular reflectivity at a low temperature in a short time. A glossy metallic film can also be formed on paper and plastic substrates. On the other hand, when the average particle diameter exceeds the upper limit of the above range, not only the reflectivity is lowered, but also the fusion property and physical properties at low temperature may be inferior, which is not preferable.

  Furthermore, as a method for obtaining metal nanoparticles in the above average particle size range, for example, a gas phase method such as a gas evaporation method, a liquid phase method in which a metal compound is reduced using ultrasonic waves, ultraviolet rays, or a reducing agent in a liquid phase. (For example, refer to JP-A-11-80647 and JP-A-61-276907), or a method such as a melting method or an electrolytic method. In the present invention, in consideration of production costs and man-hours, a method obtained by a liquid phase method in which a metal compound is reduced in a liquid medium using ultrasonic waves, ultraviolet rays or a reducing agent is more preferable.

  Moreover, in this invention, the metal nanoparticle obtained by reduce | restoring a metal compound using the polybasic acid polyhydrazide shown by the carbodihydrazide shown by following formula (1) or the following formula (2) in a liquid medium. A particle dispersion can be preferably used (for details, refer to PCT / JP2006 / 320493). In this method, since the reduction reaction proceeds rapidly without heating to a high temperature, aggregation of the metal nanoparticles after the reaction is suppressed, and metal nanoparticles having a uniform particle diameter can be obtained. For this reason, the metal nanoparticle dispersion obtained by this method is excellent in fluidity and stability. For example, when used as an ink, a metallic glossy film having a good metallic luster and / or a high glossiness even when dried at a low temperature. Or a pattern can be formed. In this method, for example, by using a fatty acid metal salt as a metal salt, metal nanoparticles coated with a protective substance containing a fatty acid can be directly produced, and the metal nanoparticles obtained by this method have various properties. Since it is excellent, in this invention, the metal nanoparticle obtained by this method can be preferably used for forming a metallic glossy film.

（式中、Ｒはｎ価の多塩基酸残基を表す。）

(In the formula, R represents an n-valent polybasic acid residue.)

  Examples of the polybasic acid polyhydrazide represented by the above formula (2) include dibasic acid dihydrazide, tribasic acid trihydrazide, and tetrabasic acid tetrahydrazide. Examples of the dibasic acid dihydrazide include malonic acid. Dihydrazide, Succinic acid dihydrazide, Glutaric acid dihydrazide, Adipic acid dihydrazide, Sebacic acid dihydrazide, Dodecanoic acid dihydrazide, Isophthalic acid dihydrazide, Terephthalic acid dihydrazide, Tartarodihydrazide, Pimelic acid dihydrazide, Suberic acid dihydrazide dihydrazide 1,6-naphthoic acid dihydrazide, 1,4-naphthoic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, itaconic acid dihydrazide, etc. .

  Examples of the tribasic acid trihydrazide include citric acid trihydrazide, trimellitic acid trihydrazide, nitriloacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, and the like. Examples of the tetrabasic acid tetrahydrazide include ethylenediaminetetraacetic acid tetrahydrazide and pyromellitic acid tetrahydrazide. Examples of polybasic acid polyhydrazides other than the above include polyacrylic acid polyhydrazide.

  These polybasic acid polyhydrazides can be used singly or in combination of two or more, and can also be used in combination with carbodihydrazide.

  Carbodihydrazide or polybasic acid polyhydrazide may be added as a solid or dissolved in a solvent. However, in order for the reaction to proceed more uniformly and efficiently, it may be added dissolved in a solvent. preferable.

  Furthermore, in consideration of purification after the reaction, it is preferably added as an aqueous solution. In the case of adding as an aqueous solution, it is preferable to use adipic acid dihydrazide, succinic acid dihydrazide, or glutaric acid dihydrazide in consideration of solubility in water. In the carbodihydrazide or polybasic acid polyhydrazide, one or more of hydrogen may be substituted with a functional group such as a hydroxyl group.

  The amount of carbodihydrazide or polybasic acid polyhydrazide added in the method for producing metal nanoparticles of the present invention varies depending on the type and concentration of the metal compound, but is usually necessary for at least metal to be reduced and deposited from the metal compound solution. Any stoichiometric amount may be used. Since the reducing agents used in the production method of the present invention are dihydrazides and have two or more functional groups having a reducing ability, the stoichiometric ratio necessary for the reduction precipitation of the metal is hydrazide groups. It is preferable to add in terms of conversion. When removing the aqueous phase after the reduction, excess reducing agent can be removed at the same time, so a reducing agent with a stoichiometric ratio or more may be used, and the upper limit is not particularly defined. Considering the cost, it is preferably 6 times or less of the addition amount necessary for reducing the metal compound at a stoichiometric ratio in terms of hydrazide.

  In the production method of the present invention, as described above, a metal fine particle dispersion can also be obtained by a method in which a liquid medium and a metal compound are mixed and then reduced by adding carbodihydrazide or polybasic acid polyhydrazide. However, after mixing the liquid medium with carbodihydrazide or polybasic acid polyhydrazide, the metal compound can be added to reduce the mixture.

  Although the said metal compound is not specifically limited, The form of a fatty acid salt and an inorganic salt is known well, About a fatty acid salt, it can obtain easily using a well-known method. For example, commercially available sodium fatty acid or fatty acid sodium salt obtained by mixing fatty acid and sodium hydroxide in water, dissolved in pure water, and adding an equal amount of the metal inorganic salt to be obtained, The fatty acid metal salt compound can be easily obtained by suction filtration of the precipitated fatty acid metal salt compound, followed by drying.

  The inorganic salt of the metal is not particularly limited. For example, chlorides such as chloroauric acid, chloroplatinic acid, and silver chloride; nitrates such as silver nitrate; acetates such as silver acetate and copper acetate (II); Examples include perchlorates such as acid silver, sulfates such as copper (II) sulfate, carbonates, silicates, phosphates, and the like, which can be appropriately selected according to the desired metal.

  These metal inorganic salts may be used alone or in combination of two or more.

  In the method for producing metal nanoparticles of the present invention, the liquid medium in which the fatty acid metal salt compound is dispersed is not particularly limited, but considering a process such as removal of impurities, a non-aqueous solvent that is phase-separated from water is preferable. It is preferable to add an aqueous solution of carbodihydrazide or polybasic acid polyhydrazide as a reducing agent after dispersing the metal salt compound of fatty acid in a non-aqueous solvent.

  At this time, the reduction reaction occurs only when the fatty acid metal salt compound comes into contact with the reducing agent present as an aqueous droplet in the non-aqueous solvent, and the reduced metal is quickly stabilized in the non-aqueous solvent. Therefore, local reactions are unlikely to occur, and therefore, fine metal fine particles having a uniform particle diameter can be obtained. Moreover, since excess reducing agents, salt residues, and the like are present in the aqueous phase, they can be purified by simply leaving after the reaction and removing the aqueous phase, which is preferable.

The non-aqueous solvent is not particularly limited as long as it is phase-separated from water.
Examples include chloroform, cyclohexane, benzene, normal hexane, toluene, cyclohexanone, 1-methoxyisopropanol acetate, diethyl ether, methyl isobutyl ketone, carbon tetrachloride, methylene chloride, ethyl acetate, butyl acetate, petroleum ether, silicon oil, and the like.

  Moreover, a reactive organic solvent can also be used as a non-aqueous solvent. Although it does not specifically limit as a reactive organic solvent, For example, ethylenically unsaturated monomers, such as (meth) acrylic acid, a (meth) acrylate compound, a vinyl ether compound, a polyallyl compound, etc. are mentioned. A non-aqueous solvent may be used individually by 1 type, or may be used in combination of 2 or more types.

  In the method for producing metal nanoparticles of the present invention, the reduction reaction is preferably performed in the presence of a protective substance. At this time, the protective substance is present at the nonpolar solvent phase and at the interface between the nonpolar solvent and the aqueous phase. It is thought that it helps the movement of the metal nanoparticles from the aqueous phase and stabilizes the extracted metal nanoparticles.

  The reduction reaction in the method for producing metal nanoparticles of the present invention is sufficiently completed even at room temperature, but the reaction may be performed by heating. However, if the temperature is too high, the Brownian motion of the metal particles becomes violent, and aggregation may easily occur, and the protective substance may be denatured by heat. Therefore, the reduction reaction is preferably performed at 90 ° C. or lower. More preferably, it is carried out at 70 ° C. or lower.

  In the method for producing metal nanoparticles of the present invention, it may be carried out in the atmosphere through the reaction, but in order to prevent oxidation and sulfidation of the generated metal fine particles, or to prevent generation of side reactions due to the presence of oxygen, for example, Alternatively, the reaction may be performed in an inert gas atmosphere such as nitrogen or argon.

  In the method for producing metal nanoparticles of the present invention, after removing the aqueous phase as necessary, a part of the non-aqueous solvent can be removed using a method such as heating or distillation under reduced pressure, and concentrated to an arbitrary concentration. . In addition, after completely removing the non-aqueous solvent, a solvent different from that used in the synthesis may be added and redispersed depending on the purpose, thereby adjusting the metal nanoparticle dispersion at an arbitrary concentration. The solvent at this time may be a non-aqueous solvent or an aqueous solvent, but is preferably a solvent in which a protective substance existing in the vicinity of the metal fine particles is dissolved.

  The method for removing the non-aqueous solvent is not particularly limited. For example, heating, vacuum distillation, and when a dispersant is used, a poor solvent that does not dissolve the dispersant is added depending on the dispersant. It is also possible to redisperse in an arbitrary solvent after taking out as a solid by precipitating metal fine particles.

The material containing metal nanoparticles coated with an ionic protective substance is characterized by containing at least one liquid medium, but the liquid medium that can be used is not particularly limited, and is a printing / coating method. The base material, viscosity, surface tension, drying temperature, solubility of the protective substance, etc. can be freely selected. In addition, as described above, the liquid medium used for the material containing the metal nanoparticles coated with the ionic protective substance does not need to be the same as the liquid medium used when the metal nanoparticles are synthesized, and is free. Can be selected.

  Examples of the liquid medium used in the material containing the metal nanoparticles of the present invention include ester solvents, ketone solvents, glycol ether solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, alcohol solvents, Examples include glycol solvents, ether solvents, and water. These solvents may be used alone or in combination of two or more. Hereinafter, each of these solvents will be described in more detail.

  Examples of the ester solvent include ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate. , Acetic acid (iso) amyl, cyclohexyl acetate, ethyl lactate, 3-methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, methyl monochloroacetate, monochloro Examples include ethyl acetate, butyl monochloroacetate, methyl acetoacetate, ethyl acetoacetate, butyl propionate, isoamyl propionate, and γ-butyrolactone.

  Examples of ketone solvents include acetone, acetophenone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, acetonyl acetone, isophorone, cyclohexanone, and methyl. Examples include cyclohexanone and 2- (1-cyclohexenyl) cyclohexanone.

  Examples of glycol ether solvents include ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol mono n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono n-propyl ether, dipropylene glycol mono n-butyl ether, triethylene glycol monomethyl ether , Triethylene glycol Of ethyl ether, triethylene glycol mono n-propyl ether, triethylene glycol mono n-butyl ether, tripropylene glycol monoethyl ether, tripropylene glycol mono n-propyl ether, tripropylene glycol mono n-butyl ether, and these monoethers Examples thereof include dialkyl ethers such as acetate ester, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl isobutyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol diethyl ether.

  Examples of the aliphatic hydrocarbon solvent include n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-dodecane, No. 0 solvent L, M, H, (Manufactured by Nippon Oil Corporation), normal paraffin SL, L, M (manufactured by Nippon Oil Corporation), isoparaffinic solvents include isohexane, 2,2,3-trimethylpentane, isooctane, 2,2,5- Trimethylhexane, Paraol 100, 130, 50, 750 (Showa Shell Sekiyu KK) Isopar L, M (Exxon Petrochemical Co., Ltd.), Isosol 200, 300, 400 (manufactured by Nippon Oil Corporation), Supersol FP2, 25, 30, 38 (both manufactured by Idemitsu Kosan Co., Ltd.), cycloparaffinic solvents include cyclopentane, Lucyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, naphthesol 160, 200, 220, MS-20P (manufactured by Nippon Oil Corporation), AF solvent 4, 5, 6, 7 (all Nippon Oil) Co., Ltd.), tetrahydronaphthalene, decahydronaphthalene, turpentine oil, p-pentadiene, limonene, industrial volatile oil Nos. 1, 2, 3, 4, 5, ligroin and the like.

  Examples of the aromatic hydrocarbon solvent include toluene, xylene, ethylbenzene, naphthalene, tetralin, solvent naphtha, and aromatic mixed hydrocarbon.

  Examples of the alcohol solvent include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, heptanol, n-amyl alcohol, sec-amyl alcohol, n-hexyl alcohol, tetrahydrofurfuryl alcohol, furfuryl alcohol, allyl alcohol, ethylene chlorohydrin, octyldodecanol, 1-ethyl-1-propanol, 2-methyl-1-butanol, isoamyl alcohol, t-amyl alcohol, sec-isoamyl alcohol, neoamyl alcohol, hexyl alcohol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, heptyl alcohol, n-octyl Alcohol, 2-ethylhexyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, benzyl alcohol, α-terpineol, terpineol C, L-α-terpineol, dihydroterpineol, terpinyloxyethanol, dihydroterpinyl Oxyethanol tersolve MTPH, tersolve DTO-210, tersolve THA-90, tersolve THA-70 (manufactured by Nippon Terpene Chemical Co., Ltd.) cyclohexanol, 3-methoxybutanol, diacetone alcohol, 1,4-butanediol, octanediol, etc. Fine oxocol 140N, fine oxocol 1600, fine oxocol 180, fine oxocol 180N, fine oxocol 20 0 (manufactured by Nissan Chemical Industries, Ltd.) side-chain higher alcohols, etc., and the like.

  Examples of the glycol solvent include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-butylene glycol, hexylene glycol, polyethylene glycol, dipropylene glycol and the like.

  Examples of the ether solvent include ethyl ether, isopropyl ether, dioxane, dibutyl ether, methyl-t-butyl ether, terpinyl methyl ether, dihydroterpinyl methyl ether, and cyclic ether solvents such as tetrahydrofuran, 1, Examples include 3-dioxolane.

  A reactive organic solvent can also be used as the liquid medium. Although it does not specifically limit as a reactive organic solvent, For example, ethylenically unsaturated monomers, such as (meth) acrylic acid, a (meth) acrylate compound, a vinyl ether compound, a polyallyl compound, etc. are mentioned.

  Other liquid media include dimethyl carbonate, ethyl methyl carbonate, di-n-butyl carbonate, and furfural.

  The liquid medium may be used alone or in combination of two or more.

  Although different depending on various conditions such as a metallic glossy film-forming material containing metal nanoparticles and a film-forming method, these liquid media are usually 0.01 to 100% by weight of the metallic glossy film-forming material containing metal nanoparticles. It can be used by adding 99% by weight, preferably 0.1 to 95% by weight.

In order to improve the metallic luster of the resulting metallic luster coating, the material for forming a metallic luster coating including the metal nanoparticles of the present invention contains at least one or more of a leveling agent, an antifoaming agent, and a lubricant. It is preferable. In order to obtain a good metallic luster, it is necessary to suppress light scattering that occurs on the metal surface and causes a decrease in reflectance. Leveling agents, antifoaming agents, and lubricants function to adjust the surface tension of materials containing metal nanoparticles and increase the affinity with the substrate, so when a material containing metal nanoparticles is applied on the substrate. It is possible to form a coating film having a uniform metallic surface and a smooth surface, and a coating film for metallic luster having excellent metallic luster can be obtained.

  Examples of the leveling agent used in the coating layer forming material containing the conductive substance of the present invention include Surfinol 104PA, Surfinol 420, Surfinol 440, Surfinol 465, Surfinol 485, Surfinol 504, Surfinol SE. -F (all manufactured by Air Products Japan Co., Ltd.), EFKA3030, EFKA3031, EFKA3033, EFKA3034, EFKA3035, EFKA3232, EFKA3KA, EFKA3239, EFKA3522, EFKA3522, EFKA3523, EFKA3523 , EFKA3600, EFKA36 0, EFKA3772, EFKA3777, EFKA3778 (all manufactured by Efka Additives), BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-340, BYK-344, BYK-370, BYK-375, BYK-377, BYK-350, BYK- 352, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-392, BYK-UV3500, BYK-UV3510, BYK-UV3570, BYK-Siclean 3700, BYK-301, BYK-302, BYK-307, BY -325, BYK-331, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK-348, BYK-375, BYK-380N, BYK-381, Byketol-OK, Byketol-Special Byketol-WS (all manufactured by Big Chemie Japan Co., Ltd.), Disparon 1970, Disparon 230, Disparon LF-1970, Disparon LF-1982, Disparon LF-1983, Disparon LF-1984, Disparon LF-1985 (all Etc.). The leveling agent can be added and used in an amount of usually 0.005 to 10% by weight, preferably 0.01 to 5% by weight, in 100% by weight of the material for forming a coating layer containing a conductive substance.

  Examples of the antifoaming agent used in the coating layer forming material containing the conductive material of the present invention include Surfinol DF-70, Surfinol DF-75, Surfinol DF-210, Surfinol DF-695 (all Air Products Japan Co., Ltd.), EFKA2022, EFKA2023, EFKA2025, EFKA2028, EFKA2035, EFKA2038, EFKA2040, EFKA2048, EFKA2527, EFKA2550, EFKA2721, EFKA2722, EFKA2722, EFKA2722, 052, BYK-053, BYK-054, BYK-055, BYK-057, BYK-1752, BYK-1790, BYK-060N, BYK-0 3, BYK-065, BYK-067A, BYK-070, BYK-077, BYK-080A, BYK-088, BYK-141, BYK-354, BYK-392, BYK-011, BYK-012, BYK-017, BYK-018, BYK-019, BYK-020, BYK-021, BYK-022, BYK-023, BYK-024, BYK-025, BYK-028, BYK-038, BYK-044, BYK-080A, BYK- 094, BYK-1610, BYK-1615, BYK-1650, BYK-1730, BYK-1770 (all manufactured by Big Chemie Japan Co., Ltd.), Disparon OX-880EF, Disparon OX-881, Disparon OX-883, Disparon OX- 77EF, Disparo OX-710, Disparon OX-8040, Disparon 1922, Disparon 1927, Disparon 1950, Disparon 1951, Disparon P-410EF, Disparon P-420, Disparon P-425, Disparon PD-7 (all manufactured by Enomoto Kasei Co., Ltd.) Is mentioned. The antifoaming agent can be used by adding 0.005 to 10% by weight, preferably 0.01 to 5% by weight, in 100% by weight of the coating layer forming material containing a conductive substance.

Examples of the lubricant used in the material for forming a coating layer containing the conductive material of the present invention include CERAFLOUR914, CERAFLOUR915, CERAFLOUR916, CERAFLOUR950, CERAFLOUR970, CEAFLOUR980, CEAFLOUR998, CERAFLUR990, CERAFLUUR990, CERALO990, CERALO990, CERALOUR990. AQUACER 515, AQUACER 526, AQUACER 531, AQUACER 537, AQUACER 539, AQUACER 593, AQUAMAT 263, AQUAMAT 270, CERACOL79, CERACOL601, CERA AK103, CERAFAK106, CERAFAK110, CERATIX8461, CERATIX8463 (both manufactured by BYK Japan KK), and the like. The lubricant can be used by adding 0.005 to 10% by weight, preferably 0.01 to 5% by weight, in 100% by weight of the material for forming a coating layer containing a conductive substance.

The material containing the metal nanoparticles coated with the ionic protective substance of the present invention has improved film strength and metallic luster when formed into a film, and improved adhesion to the printed / applied body. In order to optimize the characteristics of the material when applied to the coating method, a resin and / or a precursor thereof may be added as necessary.

  The resin and / or precursor thereof is not particularly limited. For example, polyurethane resin, (unsaturated) polyester resin, alkyd resin, butyral resin, acetal resin, polyamide resin, (meth) acrylic resin, styrene / (meta ) Acrylic resin, polystyrene resin, nitrocellulose, benzylcellulose, cellulose (tri) acetate, casein, shellac, gelatin, gilsonite, rosin, rosin ester, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, Ethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, carboxymethylethyl Cellulose, carboxymethylnitrocellulose, ethylene / vinyl alcohol resin, styrene / maleic anhydride resin, polybutadiene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinylidene fluoride resin, polyvinyl acetate resin, ethylene / vinyl acetate resin, chloride Vinyl / vinyl acetate resin, vinyl chloride / vinyl acetate / maleic acid resin, fluororesin, silicone resin, epoxy resin, phenoxy resin, phenol resin, maleic acid resin, urea resin, melamine resin, benzoguanamine resin, ketone resin, petroleum resin, Examples include chlorinated polyolefin resins, modified chlorinated polyolefin resins, and chlorinated polyurethane resins.

  Examples of the resin precursor include compounds having an ethylenically unsaturated double bond such as (meth) acrylic acid, (meth) acrylate compounds, and vinyl ether compounds. These compounds having an ethylenically unsaturated double bond may be monofunctional or polyfunctional. These compounds can also be used individually by 1 type, and can also be used in combination of 2 or more type. In the present invention, “(meth) acrylic acid” is used to include acrylic acid and methacrylic acid. Similarly, the term “(meth) acrylate” is used to mean including acrylate and methacrylate. The same applies to other (meth) acryloyl.

  Among the (meth) acrylate compounds, examples of the monofunctional (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl ( (Meth) acrylate, butanediol monoacrylate, 2- (dimethylamino) ethyl (meth) acrylate, 2- (diethylamino) ethyl methacrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 2-methoxyethyl acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, acryloylmorpholine, N-vinylformamide, cyclohexyl (meth) acrylate, dicyclope Tanyl (meth) acrylate, glycidyl (meth) acrylate, isobornyl (meth) acrylate, phenoxy (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-phenoxyethyl (meth) ) Acrylate, isooctyl (meth) acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 3-methoxybutyl acrylate, benzyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol Acrylate, methoxydipropylene glycol acrylate, methylphenoxyethyl acrylate, dipropylene glycol (Meth) acrylate, (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-hydroxy-3-acryloyloxypropyl ( And (meth) acrylate and 2-methacryloyloxyethyl isocyanate.

  Examples of the polyfunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and ethoxylated 1,6-hexanediol. Diacrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol diacrylate, 1, 4-butanediol di (meth) acrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol Acrylate, dimethylol-tricyclodecane diacrylate, neopentyl glycol diacrylate hydroxypivalate, 1,3-butylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) Acrylate, cyclohexanedimethanol di (meth) acrylate, dimethylol dicyclopentane diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylolpropane triacrylate Acrylate, tetramethylol methane triacrylate, pentaerythritol tetraacrylate Caprolactone-modified trimethylolpropane triacrylate, ethoxylated isocyanuric acid triacrylate, tri (2-hydroxyethyl isocyanurate) triacrylate, propoxylate glyceryl triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate , Ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, neopentyl glycol oligoacrylate, 1,4-butanediol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate, urethane Acrylate, epoxy Examples include acrylate, polyester acrylate, rosin-modified acrylate, and the like.

  Among the vinyl ether compounds, examples of the monofunctional vinyl ether compound include hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexyl vinyl ether, and the like. Examples of the polyfunctional vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, pentaerythritol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, neopentyl glycol divinyl ether, 1 , 4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, trimethylolpropane divinyl ether, 1,4-dihydroxycyclohexane divinyl ether, 1,4-dihydroxymethylcyclohexane divinyl ether, bisphenol A diethoxydivinyl ether, glycerol Trivinyl ether, sorbitol tetravinyl ether, Trimethylolpropane trivinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol hexavinyl ether, and ditrimethylolpropane tetra vinyl ether.

  Furthermore, examples of the compound having an ethylenically unsaturated double bond other than the above compounds include N-vinylacetamide, tris (acryloxyethyl) isocyanurate, polyethylene glycol dimethacrylate, methoxypolyethylene glycol methacrylate, tribromophenyl (meta ) Acrylate, pentaerythritol diacrylate monostearate, 2-methallyloyloxyethyl hexahydrophthalate, stearyl acrylate, tetramethylpiperidyl methacrylate, and the like.

  Although these resins and / or precursors thereof vary depending on various conditions, they are usually 0.01 to 99% by weight, preferably 0.1 to 95%, in 100% by weight of the metallic gloss coating material containing metal nanoparticles. It can be added and used so that it may become weight%.

When forming the material containing the metal nanoparticles coated with the protective substance having ionicity of the present invention, the metal nanoparticles coated with the protective substance may be mixed with a liquid medium, an antifoaming agent, or leveling as necessary. Mixed with an agent, a lubricant, a dispersant, a resin and / or a precursor thereof, and dispersed using a conventionally known method such as a ball mill, an attritor, a sand mill, a jet mill, a three-roll mill, a paint shaker, or the like, or Then, it may be stirred and mixed using a conventionally known method, for example, a mixer or a dissolver.

The method for producing a metallic glossy coating according to the present invention is characterized in that metal nanoparticles coated with a protective substance having ionicity are brought into contact with a substance having an ion exchange capacity for the protective substance. As an aspect of bringing the metal nanoparticles coated with these ionic protective substances into contact with the substance having ion exchange capacity for the protective substances, (I) metal nanoparticles coated with the ionic protective substances And a layer containing a substance having an ion exchange capacity for the protective substance (ion exchange layer) as an adjacent layer, or (II) a substance having an ion exchange ability with a protective substance having an ionicity, There is a method of including them in a state where they are in contact with each other in the same layer. As a method for producing a metallic glossy coating by the method (I), for example, (I-1) an ion exchange layer containing a substance having an ion exchange ability with respect to a protective substance is formed, and then on the ion exchange layer And a method of forming a metallic glossy film by forming a coating layer containing metal nanoparticles coated with an ionic protective substance, and (I-2) an ionic protective substance on a substrate A coating layer containing metal nanoparticles coated with is formed, and then an ion exchange layer containing a substance having an ion exchange ability with respect to the protective substance is formed on the coating layer to form a metallic gloss coating. The method of doing is mentioned. In addition, as a method for producing a metallic glossy coating by the method (II), for example, a metal nanoparticle coated with a protective substance having ionicity on a substrate and a substance having an ion exchange capacity for the protective substance are used. The method of forming the layer which consists of the film forming material containing is mentioned. These layers are a film-forming material containing metal nanoparticles coated with an ionic protective substance, a film-forming material containing a substance having an ion exchange capacity for the protective substance, or an ionic protective substance. Examples thereof include a method of coating a base material with a coated metal nanoparticle and a substance having an ion exchange ability with respect to the protective substance by, for example, coating or printing to form a metallic glossy coating layer. However, in the method for producing a metallic glossy coating of the present invention, the metal nanoparticles coated with the protective substance having ionicity and the substance having ion exchange capacity for the protective substance may be in contact with each other by any method. The method of bringing the metal nanoparticles coated with a protective substance having ionicity into contact with a substance having an ion exchange capacity for the protective substance is not limited to the above exemplified method.

In the present invention, the metal nanoparticles are coated and stabilized with a protective substance having ionic properties. However, when the metal nanoparticles are brought into contact with the substance having ion exchange ability, the protective substance becomes a metal nanoparticle by the substance having ion exchange ability. For example, F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , ClO ₃ ⁻ , SO ₄ ²⁻ , NO ₃ ⁻ , CrO ₄ ⁻ , CO ₃ ^{2 −} , PO ₄ ³⁻ , HPO ₄ ²⁻ , H ₂ PO ₄ ⁻ , OH ⁻ , H ⁺ , Li ⁺ , K ⁺ , Na ⁺ , Rb ⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Al ³⁺ The surface of the metal nanoparticles with high active energy is exposed by being exchanged with ions such as NH ⁴⁺ . As a result, the metal nanoparticles lose their dispersion stability and agglomerate and become easy to fuse, so even when forming a coating at a low temperature such as room temperature, the coating of the metal nanoparticles proceeds promptly and the metallic gloss coating It is thought that it can be formed.

Next, a substance having an ion exchange ability for the protective substance, which is brought into contact with the metal nanoparticles coated with the protective substance having ionic properties, will be described.

  In the present invention, the substance having ion exchange ability refers to a substance exhibiting an ion exchange reaction.

  In general, an ion exchange reaction is a phenomenon in which ions in a solid or a liquid exchange with ions of the same sign in an external solution in contact with the ion, and an anion exchange reaction and a cation exchange reaction are caused by the exchanged ions. is there. The substance having ion exchange ability can be selected according to the ion of the protective substance having ionicity covering the metal nanoparticles.

First, a case where an ion exchange reaction is used with a substance having anion exchange ability will be described. The anionic protective substance is not particularly limited as long as it can cause an anion exchange reaction with a substance having anion exchange ability. For example, a hydroxyl group, a cyano group, a carboxyl group, a sulfonic acid group in the molecule. And protective substances having an ionic group such as a phosphoric acid group and a phosphoric acid ester. These ionic groups may be contained in the main chain of the compound, or may be contained in the side chain or both the side chain and the main chain. Examples of the compound having one or more ionic groups in the compound include a pigment dispersant, a surfactant, a coupling agent, and a fatty acid. In the present invention, the protective substance to be combined with the substance having anion exchange ability preferably contains a dispersant. Further, the dispersant is preferably a fatty acid, and among the fatty acids, saturated or having 3 to 22 carbon atoms. It is preferably an unsaturated fatty acid. This is because when metallic nanoparticles coated with a protective substance containing a fatty acid are used, it is possible to form a metallic gloss coating at a lower temperature and in a shorter time.

  Examples of the substance having anion exchange ability used in the present invention include those having an ionic group or anion exchange group involved in anion exchange in the molecule. Examples of the ionic group and anion exchange group that participate in anion exchange include ammonium groups, phosphonium groups, sulfonium groups, amino groups, primary amines, secondary amines, and tertiary amines.

Examples of the substance having an anion exchange ability of the present invention include an anion exchange resin, a cationic compound such as a cation activator, and an inorganic anion exchanger.

  In general, an anion exchange resin can be prepared by aminating a crosslinked polymer matrix composed of a styrene / divinylbenzene copolymer after chloromethylation. The chloromethyl group is easily introduced by reacting chloromethyl ether in the presence of an anhydrous aluminum chloride catalyst. Amination is a reaction in which a chloromethyl group is treated with an amine, and various anion exchange resins can be produced depending on the type of amine. The anion exchange resins include strong basic anion exchange resins and weak basic ion exchange resins, and those in which a quaternary ammonium group is introduced using trimethylamine are strongly basic type I and 4 using dimethylethanolamine. The graded product is said to be strongly basic type II. Moreover, when a primary to tertiary amine is introduced, a weakly basic ion resin is obtained. The above styrene / divinylbenzene copolymer is obtained by suspension polymerization, and transparent and homogeneous crosslinked spherical particles are generally called gel type, while high boiling point such as water-insoluble aromatic hydrocarbons. A porous material obtained by adding an organic solvent to a porous material is called a macroporous type, and a porous material obtained by adding an organic solvent such as 2-butanol that hardly swells the produced polymer is called an MR resin. In the present invention, any anion exchange resin including these anion exchange resins can be used as a substance having anion exchange ability.

  On the other hand, examples of the cationic compound include a quaternary ammonium salt or a compound having a quaternary ammonium salt. Quaternary ammonium salts can generally be made by reacting tertiary amines with alkyl halides. Examples of the quaternary ammonium salt include cyclic quaternary ammonium salts such as N-methylpiperidine methiodide having a nitrogen atom in the ring and quinoline methiodide, benzalkonium chloride, benzethonium chloride, and alkyltrimethyl halide. Cationic activators such as ammonium, alkylpyridinium halides, and halogenates of higher amines can be mentioned, and any of these can be used as the substance having anion exchange ability of the present invention.

  Similarly, resin compounds into which these quaternary ammonium bases are introduced, and resin compounds into which ammonium groups, phosphonium groups, sulfonium groups, amino groups, primary amines, secondary amines, and tertiary amines are introduced. Can be used. Examples of the resin compound include acrylic resins, urethane resins, polyamine resins, acrylamide resins, allylamine polymerization resins, diallylamine polymerization resins, and the like. Further examples include dicyandiamidine and dicyandiamide polymerization resins, cation-modified resins obtained by directly cation-modifying resins, and resin beads obtained by crosslinking an allylamine polymerized resin, for example.

Examples of the acid group of the quaternary ammonium salt include F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , ClO ₃ ⁻ , SO ₄ ²⁻ , NO ₃ ⁻ , CrO ₄ ⁻ , and CO ₃ ^{2. _{-, PO 4 3-, HPO 4}} 2-, H 2 PO 4 -, OH - like any acid groups can also be used.

Examples of inorganic ion exchangers, so-called solid bases, include activated carbon, tin oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, aluminum oxide, zirconium oxide, titanium dioxide and other metal oxides, magnesium carbonate, calcium carbonate Metal carbonates such as ZnO / ZrO ₂ , MgO / TiO ₂ , CaO / P ₂ O ₅ , SiO ₂ / CaO / MgO, SiO ₂ / Al ₂ O ₃ , SiO ₂ / SrO, SiO ₂ / BaO, ZnO / SiO ₂ , TiO ₂ / ZrO ₂ , Al ₂ O ₃ / TiO ₂ , SiO ₂ / ZrO ₂ , Al ₂ O ₃ + ZrO ₂ , SiO ₂ / TiO ₂ , MoO ₃ / SiO ₂ , MoO ₃ / Al ₂ O ₃ , Al ₂ O ₃ / composite oxide such as MgO, zeolite, Na / MgO, K / MgO, metal vapor deposited metal oxide such as Na / _Al 2 _{O 3 , KNH 2 / Al 2 O 3} , EuNH / K-Y imine supported metal oxides such _{as, KF / Al 2 O 3,} LiCO 3 / alkali metal salts such as SiO ₂ and the like. Further, as the inorganic ion exchanger, for example, silica, colloidal silica, titania coated with, for example, aluminum oxide and the like, and the surface charge cationized can be used.

  The substances having anion exchange ability may be used alone or in combination of two or more.

  Next, a case where an ion exchange reaction is used with a substance having a cation exchange capacity will be described. The cationic protective substance is not particularly limited as long as it is a substance that can cause a cation exchange reaction with a substance having a cation exchange ability. For example, the molecule contains a nitrogen atom and / or a sulfur atom. It is preferable that a nitrogen atom and / or a sulfur atom exist as a basic group. Examples of the basic group include an amino group, an amide group, a mercapto group, a sulfenyl group, and a sulfanediyl group. These ionic groups may be contained in the main chain of the compound, or may be contained in the side chain or both the side chain and the main chain. Examples of the compound having one or a plurality of ionic groups in the compound include pigment dispersants, surfactants, coupling agents and the like.

  Although it does not specifically limit as a substance which has cation exchange ability of this invention, For example, solid acids, such as cation exchange resin and anionic compounds, such as an anion activator, an inorganic cation exchanger, are mentioned.

  Moreover, the resin compound which introduce | transduced the acidic group which takes part in a cation exchange can be used similarly. Examples of the resin compound include acrylic resins, polyester resins, vinyl resins, epoxy resins, styrene resins, and phenol resins. Furthermore, an anion-modified resin obtained by directly anion-modifying the resin can also be used.

The cation exchange resin generally has a sulfonic acid group or a carboxylic acid group as an ion exchange group, and rarely has a phosphoric acid group, a phosphonic acid group, an arsenic acid group, or a selenic acid group. .

  A cation exchange resin having a sulfonic acid group as an ion exchange group works as a strong acidity, a carboxylic acid group works as a weak acidity, and the others work as a medium acidity. In the present invention, any of strong acid, weak acid, and medium acid cation exchange resins can be used.

  As said cation exchange resin, what is generally marketed as a cation exchange resin can be used.

  Examples of strong acid cation exchange resins include Diaion SK104, Diaion SK1B, Diaion SK110, Diaion SK112, Diaion PK208, Diaion PK212, Diaion PK216, Diaion PK218, Diaion PK220, and Diaion PK228. Diaion UBK08, Diaion UBK10, Diaion UBK12, Diaion UBK510L, Diaion UBK530, Diaion UBK550, Diaion UBK535, and Diaion UBK555 (manufactured by Mitsubishi Chemical Corporation).

  Examples of the weakly acidic cation exchange resin include Diaion WK10, Diaion WK11, Diaion WK100, and Diaion WK40L (manufactured by Mitsubishi Chemical Corporation).

  One of these may be used alone, or two or more may be used in combination, or a cation exchange resin and other substances having cation exchange ability may be used in combination.

  Examples of the anionic compounds include anionic surfactants, fatty acids, compounds containing carboxyl groups, sulfonic acid groups, and phosphoric acid groups, and salts thereof.

  It does not specifically limit as an anionic surfactant, What is known as an anionic surfactant can be used. For example, higher fatty acid salt surfactants such as alkyl carboxylates, alkyl ether carboxylates, alkyl succinates, alkyl sulfonates, alkyl sulfate esters, alkane sulfonates, alkyl benzene sulfonates, alkyl ether sulfones Acid salt, alkyl ether sulfate ester salt, sulfosuccinate ester salt, sulfonate surfactant such as methyl taurate, alpha olein sulfonate, alpha sulfo fatty acid methyl ester salt, alkyl phosphate ester or phosphate ester salt Surfactant etc. are mentioned.

  These may be used alone or in combination of two or more, or may be used in combination with an anionic surfactant and other substances having cation exchange ability.

  The fatty acid is not particularly limited, and those generally known as fatty acids can be used.

  Examples of linear saturated fatty acids include propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecyl acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, Examples include heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, mellicic acid, and laccelic acid.

  Examples of linear unsaturated fatty acids include acrylic acid, crotonic acid, isocrotonic acid, undecylenic acid, oleic acid, elaidic acid, celetic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, propiolic acid. Examples include acids and stearol acids.

  Examples of branched fatty acids include isobutyric acid, isovaleric acid, 2-ethylhexanoic acid, 2-ethylisohexanoic acid, 2-propylheptanoic acid, 2-butyloctanoic acid, 2-isobutylisooctanoic acid, 2-pentylnonanoic acid, 2-isopentylnonanoic acid, 2-hexyldecanoic acid, 2-hexylisodecanoic acid, 2-butyldodecanoic acid, 2-isobutyldodecanoic acid, 2-heptylundecanoic acid, 2-isoheptylundecanoic acid, 2-isopeptyliso Undecanoic acid, 2-dodecylhexanoic acid, 2-isododecylhexanoic acid, 2-octyldodecanoic acid, 2-isooctyldodecanoic acid, 2-octylisododecanoic acid, 2-nonyltridecanoic acid, 2-isononylisotridecane Acid, 2-decyldodecanoic acid, 2-isodecyldodecanoic acid, 2-decylisododecane 2-decyltetradecanoic acid, 2-octylhexadecanoic acid, 2-isooctylhexadecanoic acid, 2-undecylpentadecanoic acid, 2-isoundecylpentadecanoic acid, 2-dodecylheptadecanoic acid, 2-isododecylisoheptadecanoic acid 2-decyloctadecanoic acid, 2-decylisooctadecanoic acid, 2-tridecylheptadecanoic acid, 2-isotridecylisoheptadecanoic acid, 2-tetradecyloctadecanoic acid, 2-isotetradecyloctadecanoic acid, 2-hexa Decylhexadecanoic acid, 2-hexadecyltetradecanoic acid, 2-hexadecylisohexadecanoic acid, 2-isohexadecylisohexadecanoic acid, 2-pentadecylnonadecanoic acid, 2-isopentadecylisonononadecanoic acid, 2-tetradecyl Behenic acid, 2-isotetradecylbe Phosphate, 2-tetradecyl Isobe hen acid, 2-iso-tetradecyl Isobe hen acid, isoheptanoic acid, isomyristic acid, isopalmitic acid, isostearic acid, isoarachic acid, and methacrylic acid.

  Examples of the tertiary fatty acid include pivalic acid, neononanoic acid, neodecanoic acid, equacid 9 (produced by Idemitsu Petrochemical Co., Ltd.), equacid 13 (produced by Idemitsu Petrochemical Co., Ltd.), and the like.

  Examples of fatty acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate), anhydrous Maleic acid, succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, alkenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylcyclohexene tetracarboxylic anhydride, polyadipic acid Anhydride, polyazeline acid anhydride, poly sebacic acid anhydride and the like can be mentioned.

  Examples of the dibasic acid include oxalic acid, malonic acid, sebacic acid, maleic acid, fumaric acid, itaconic acid and the like.

  One of these may be used alone, or two or more may be used in combination, or a fatty acid and other substances having cation exchange ability may be used in combination.

Inorganic cation exchangers, so-called solid acids include, for example, clay minerals such as zeolite, kaolinite, montmorillonite, chlorite, vermiculite, halloysite, mica, brittle mica, silicon oxide, aluminum oxide, zinc oxide, titanium oxide, oxidation Metal oxides such as magnesium, zirconium oxide, chromium oxide, SiO ₂ / CaO, SiO ₂ / SrO, ZnO / MgO, ZnO / Sb ₂ O ₃ , SiO ₂ / MgO, TiO ₂ / B ₂ O ₃ , ZnO / SiO 2 ZnO / ZrO ₂ , Al ₂ O ₃ / Bi ₂ O ₃ , SiO ₂ / WO ₃ , SiO ₂ / V ₂ O ₅ , Al ₂ O ₃ / MoO ₃ , Al ₂ O ₃ / WO ₃ , Al ₂ O _{3 / V 2 O 5, SiO 2} / Al 2 O 3, SiO 2 / ZrO 2, Cr 2 O 3 / Al 2 O 3 _{SiO 2 / BeO, SiO 2 /} Y 2 O 3, SiO 2 / La 2 O 3, SiO 2 / Ga 2 O 3, TiO 2 / Al 2 O 3, TiO 2 / ZrO 2, Al 2 O 3 / ZrO 2 , ZnO / Al ₂ O ₃ , SiO ₂ / MoO _{3 and} other composite oxides.

  The substances having cation exchange ability may be used alone or in combination of two or more.

Next, a film forming material (ion exchange layer forming material) containing a substance having an ion exchange ability with respect to an ionic protective substance will be described.

  When forming an ion exchange layer containing a substance having ion exchange ability, an appropriate liquid medium is used according to the characteristics of the substance having ion exchange ability, the method of applying or printing the ion exchange layer forming material, and the like. be able to. Further, if necessary, an antifoaming agent, a leveling agent, a lubricant, a dispersing agent, other resins other than resins having ion exchange ability and / or precursors thereof, inorganic or organic having or without ion exchange ability Fine particles or the like can also be added. These are appropriately dispersed by using, for example, a ball mill, attritor, sand mill, jet mill, three-roll mill, paint shaker or the like, or produced by stirring and mixing using, for example, a mixer or a dissolver. be able to.

  The liquid medium used for producing the ion exchange layer forming material is the same liquid medium as that used for producing the metallic gloss coating layer forming material containing metal nanoparticles, for example, an ester-based medium. Solvents, ketone solvents, glycol ether solvents, aliphatic solvents, aromatic solvents, alcohol solvents, glycol solvents, ether solvents, water, etc. can be used. Can also be used. Specific examples of each of these solvents can also be the same as those mentioned in the production of the material for forming a metallic glossy coating layer containing metal nanoparticles. However, in the present invention, the solubility in a resin having an ion exchange ability can be used. For this reason, water, alcohol solvents, glycol ether solvents, glycol solvents, mixed solvents of these solvents and water, and the like are preferably used as the solvent for the ion exchange layer forming material. Further, antifoaming agents, leveling agents, lubricants, dispersants and the like that are used as necessary may be the same as those used in the production of the material for forming a metallic glossy coating layer containing metal nanoparticles.

  On the other hand, other resins other than the resin used as a substance having ion exchange ability and / or precursors thereof are adhesiveness to a substrate on which a film forming material containing a substance having ion exchange ability is applied or printed, It is added for the purpose of enhancing the adhesion to the metallic glossy coating containing metallic nanoparticles coated with a protective substance or protecting the metallic glossy coating formed. Other resins added for this purpose include, for example, polyurethane resins, saturated or unsaturated polyester resins, alkyd resins, butyral resins, acetal resins, polyamide resins, (meth) acrylic resins, styrene / (meth) acrylic resins. , Polystyrene resin, nitrocellulose, benzylcellulose, cellulose (tri) acetate, casein, shellac, gelatin, gilsonite, rosin, rosin ester, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, hydroxy Ethyl methyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, carboxymethyl ethyl cellulose , Carboxymethylnitrocellulose, ethylene / vinyl alcohol resin, styrene / maleic anhydride resin, polybutadiene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinylidene fluoride resin, polyvinyl acetate resin, ethylene / vinyl acetate resin, vinyl chloride / Vinyl acetate resin, vinyl chloride / vinyl acetate / maleic acid resin, fluorine resin, silicone resin, epoxy resin, phenoxy resin, phenol resin, maleic acid resin, urea resin, melamine resin, benzoguanamine resin, ketone resin, petroleum resin, chlorine Chlorinated polyolefin resin, modified chlorinated polyolefin resin, chlorinated polyurethane resin and the like. These resins are appropriately selected according to the base material, the film formation method, the conductive film characteristics, etc., in order to achieve the purpose of addition. Among these, polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, (meth) acrylic resin, styrene / (meth) acrylic resin, polyester because of the adhesion of the anion exchange layer coating to the substrate and the strength of the coating. Resins, polyurethane resins and the like are preferable. These other resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Of the above resins, phenolic resins, epoxy resins, melamine resins, urea resins, polyester resins, alkyd resins, etc., curing amines, acid anhydrides, mercaptos, imidazoles, isocyanates, dicyandiamides, dihydrazides, etc. By using a combination of agents, physical properties such as solvent resistance and chemical resistance of the obtained coating can be enhanced.

  Moreover, as a precursor of resin, the compound which has ethylenically unsaturated double bonds, such as (meth) acrylic acid, a (meth) acrylate compound, a vinyl ether compound, is mentioned, for example. These compounds having an ethylenically unsaturated double bond may be monofunctional or polyfunctional. These compounds can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  Among the (meth) acrylate compounds, examples of the monofunctional (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl ( (Meth) acrylate, butanediol monoacrylate, 2- (dimethylamino) ethyl (meth) acrylate, 2- (diethylamino) ethyl methacrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 2-methoxyethyl acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, acryloylmorpholine, N-vinylformamide, cyclohexyl (meth) acrylate, dicyclope Tanyl (meth) acrylate, glycidyl (meth) acrylate, isobornyl (meth) acrylate, phenoxy (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-phenoxyethyl (meth) ) Acrylate, isooctyl (meth) acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 3-methoxybutyl acrylate, benzyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol Acrylate, methoxydipropylene glycol acrylate, methylphenoxyethyl acrylate, dipropylene glycol (Meth) acrylate, (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-hydroxy-3-acryloyloxypropyl ( And (meth) acrylate and 2-methacryloyloxyethyl isocyanate.

  Examples of the polyfunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and ethoxylated 1,6-hexanediol. Diacrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol diacrylate, 1, 4-butanediol di (meth) acrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol Acrylate, dimethylol-tricyclodecane diacrylate, neopentyl glycol diacrylate hydroxypivalate, 1,3-butylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) Acrylate, cyclohexanedimethanol di (meth) acrylate, dimethylol dicyclopentane diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylolpropane triacrylate Acrylate, tetramethylol methane triacrylate, pentaerythritol tetraacrylate Caprolactone-modified trimethylolpropane triacrylate, ethoxylated isocyanuric acid triacrylate, tri (2-hydroxyethyl isocyanurate) triacrylate, propoxylate glyceryl triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate , Ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, neopentyl glycol oligoacrylate, 1,4-butanediol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate, urethane Acrylate, epoxy Examples include acrylate, polyester acrylate, rosin-modified acrylate, and the like.

  Among the vinyl ether compounds, examples of the monofunctional vinyl ether compound include hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexyl vinyl ether, and the like. Examples of the polyfunctional vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, pentaerythritol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, neopentyl glycol divinyl ether, 1 , 4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, trimethylolpropane divinyl ether, 1,4-dihydroxycyclohexane divinyl ether, 1,4-dihydroxymethylcyclohexane divinyl ether, bisphenol A diethoxydivinyl ether, glycerol Trivinyl ether, sorbitol tetravinyl ether, Trimethylolpropane trivinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol hexavinyl ether, and ditrimethylolpropane tetra vinyl ether.

  Furthermore, examples of the compound having an ethylenically unsaturated double bond other than the above compounds include N-vinylacetamide, tris (acryloxyethyl) isocyanurate, polyethylene glycol dimethacrylate, methoxypolyethylene glycol methacrylate, tribromophenyl (meta ) Acrylate, pentaerythritol diacrylate monostearate, 2-methallyloyloxyethyl hexahydrophthalate, stearyl acrylate, tetramethylpiperidyl methacrylate, and the like.

  When an anion exchange layer forming material containing a resin precursor is cured by electron beam irradiation, radical polymerization occurs due to molecular chain scission of the resin precursor (compound having an ethylenically unsaturated double bond). . On the other hand, when curing by irradiating with ultraviolet rays, it is common to add a photopolymerization initiator to the film-forming material.

  Examples of the photopolymerization initiator include benzophenone, thioxanthone, acetophenone, benzoin, acylphosphine oxide, bisimidazole, acridine, carbazole-phenone, triazine, and oxime initiators. Can be used. The photopolymerization initiator can be used in an amount of 1 to 20 parts by weight with respect to 100 parts by weight of the resin precursor.

  The photopolymerization initiator will be described more specifically. Examples of the benzophenone photopolymerization initiator include benzophenone, benzoylbenzoic acid, 4-phenylbenzophenone, 4,4-diethylaminobenzophenone, and 3,3-dimethyl-4. -Methoxybenzophenone, 4-benzoyl-4-methyldiphenyl sulfide and the like. Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorooxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, and isopropylxanthone. Examples of the acetophenone photopolymerization initiator include 2-methyl-1-[(4-methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethyl-2-hydroxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-phenoxydichloroacetophenone, diethoxyacetophenone 1-hydroxycyclohexyl phenyl ketone and the like. Examples of the benzoin photopolymerization initiator include benzoin methyl ether, benzoin isobutyl ether, and benzyl methyl ketal. Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) acylphosphine oxide, and the like. Examples of bisimidazole initiators include 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis ( o-chlorophenyl) -4,5,4 ′, 5′-tetra (4-methylphenyl) -1,2′-biimidazole and the like. Examples of the acridine initiator include 1,7-bis (9-acridyl) heptane. Examples of the carbazole-phenone initiator include 3,6-bis (1-keto-2-methyl-2-morpholinopropyl). ) -9-octylcarbazole and triazine photoinitiators include, for example, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- ( p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6- Bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6 Bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6 -Triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine and the like. Other examples include oxime initiators.

  The material for forming an ion exchange membrane of the present invention containing a resin precursor can contain a photopolymerization accelerator and a sensitizer together with a photopolymerization initiator. Examples of the photopolymerization accelerator and sensitizer include triethanolamine, triisopropanolamine, 4,4-dimethylaminobenzophenone, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy) and the like. And aliphatic and aromatic amines.

  In addition, a material for forming an ion exchange layer containing a precursor of a resin can contain a (thermal) polymerization inhibitor for the purpose of improving the stability of the material. Examples of (thermal) polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, 2,6-t-butyl-p-cresol, 2,3-dimethyl-6-t-butylphenol, anthraquinone, Examples include phenothiazine and N-nitrosophenylhydroxylamine aluminum salt.

  Other resins or their precursors can be used by adding 0.01 to 99% by weight, preferably 0.1 to 95% by weight, in 100% by weight of the anion exchange layer forming material. .

  Furthermore, the ion exchange layer forming material of the present invention can contain organic or inorganic fine particles with or without ion exchange capacity, as necessary. For example, when the organic fine particles and / or inorganic fine particles are contained in the film forming material, the substance having ion exchange ability is uniformly present in the ion exchange layer, and thereby the substance having ion exchange ability. When is contacted with the conductive fine particles, the ion exchange reaction is more efficiently performed.

  Moreover, it is preferable that the average particle diameter of the microparticles | fine-particles which have or do not have the said ion exchange ability to be used is 0.001-20 micrometers. Use of fine particles having an average particle diameter of more than 20 μm is not preferable because not only the conductivity development effect is inferior but also the stability and physical properties of the film-forming material are lowered. The fine particles can be added and used in an amount of usually 1 to 99% by weight, preferably 5 to 95% by weight in 100% by weight of the anion exchange layer forming material.

  Examples of the inorganic fine particles with or without the ion exchange ability include clay, diatomaceous earth, aluminum silicate, calcium silicate, magnesium silicate, hydrotalcite, talc, kaolin, calcined kaolin, saponite, mordenite, barium sulfate, magnesium sulfate. , Iron (II) sulfate, calcium sulfate, magnesium hydroxide, zinc oxide, zinc hydroxide, zinc sulfide, lead oxide, magnesium phosphate, aluminum chloride, synthetic amorphous silica, colloidal silica, aluminum hydroxide, lithopone, zeolite , And montmorillonite. Among these inorganic fine particles, amorphous silica and colloidal silica are preferable.

  On the other hand, as the organic fine particles, for example, natural products such as starch, acrylics such as polymethyl methacrylate, polystyrenes, styrene / acrylics, nylons such as nylon 6, nylon 12 and nylon 6-12, high density polyethylene, Examples thereof include olefin-based, polyester-based, phenol-based, and benzoguanamine-based resin fine particles such as low-density polyethylene, polypropylene, and tetrafluoroethylene.

  These fine particles can be used singly or in combination of two or more.

  When metal nanoparticles coated with a protective substance having ionicity and a substance having ion exchange capacity for the protective substance are brought into contact with each other in the same layer, the metal nanoparticles coated with the protective substance having ionicity and the metal nanoparticles A material containing a substance having an ion exchange ability with respect to a protective substance may be a liquid medium, an antifoaming agent, a leveling agent, a lubricant, if necessary, with a metal nanoparticle coated with an ionic protective substance and a substance having an ion exchange ability. , Dispersants, other resins other than resins having ion exchange ability and / or precursors thereof, inorganic or organic fine particles having or without ion exchange ability, etc., and conventionally known methods such as ball mills, attritors, sand mills, etc. , Jet mill, three roll mill, paint shaker, etc., or conventionally known Method, for example, a mixer, stirred with a dissolver, can be prepared by mixing. Liquid media, antifoaming agents, leveling agents, lubricants, dispersants, other resins other than resins having ion exchange ability and / or precursors thereof, inorganic having or not having ion exchange ability Alternatively, the organic fine particles can be selected from materials similar to those used in manufacturing a material containing metal nanoparticles coated with a protective substance having ionicity or a substance containing a substance having ion exchange ability. What is necessary is just to select suitably according to the base material to be coated, the coating or printing method, the film properties after coating, and the metallic luster properties.

  The thickness of the ion exchange membrane of the present invention is not particularly limited, but is generally 0.1 to 200 μm, preferably about 1 to 100 μm.

  Next, the method for applying the metallic gloss coating of the present invention will be described. The method and film shape for applying the material for forming a metallic glossy film of the present invention are not particularly limited, but it is preferable to select appropriately according to the purpose of use, the form of application, the substrate and the like.

  For example, when applying a specific pattern such as a design package, when applying only to a desired location, when the coating area is small, and when the substrate is a film, when you want to finely control the film thickness Are preferably formed by printing a metallic glossy film-forming material containing metal nanoparticles.

  Also, for example, when you want to form a metallic glossy coating over a large area and high range at once, such as for large area reflector applications, if you want to increase the amount of coating, the base material is glass, resin molding, curved surface, plate-like substance In the case of a substrate that cannot be handled by a printing method such as, it is preferable to form a metallic glossy film-forming material containing metal nanoparticles by coating.

As the printing method, a generally known method can be used, and is not particularly limited. For example, gravure printing, flexographic printing, inkjet printing, screen printing, offset printing, gravure offset printing, dispenser printing, pad Printing etc.

  As the coating method, a generally known method can be used and is not particularly limited. For example, spray coating, spin coating, die coating, lip coating, knife coating, dip coating, curtain coating, roll coating, Bar coat etc. are raised.

  The thickness of the metallic glossy coating in the present invention is not particularly limited and can be appropriately selected depending on the application. In general, however, the metallic glossy coating is about 0.01 to 20 μm, preferably 0. .05 to about 10 μm. In particular, when used in applications such as a reflector, although depending on the substrate, if it is 0.01 μm or less, light may be transmitted and the reflectance may be lowered, which is not preferable.

  The base material for forming the metallic gloss film is not particularly limited, and any of those generally known as base materials such as paper, plastic film, glass, fiber and the like can be used. The substrate may not be in the form of a film or a sheet. Moreover, what formed the film on the base material may be used as a base material, and it may be appropriately selected and used from these conventionally known base materials according to the application. Hereinafter, these base materials will be described in more detail.

  As the paper substrate, for example, various processed papers such as synthetic paper, polyethylene coated paper, impregnated paper, water-resistant processed paper, insulating processed paper, and stretch processed paper can be used in addition to coated paper and uncoated paper. Among these, coated paper and processed paper are preferable from the viewpoint of obtaining a stable metallic luster as the metallic luster coating. In the case of coated paper, the higher the smoothness, the better the metallic luster, which is preferable.

  Examples of the plastic substrate include groups made of commonly used plastics such as polyester, polyethylene, polypropylene, cellophane, vinyl chloride, vinylidene chloride, polystyrene, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, nylon, polyimide, and polycarbonate. Material can be used. Corona discharge treatment on the surface of the plastic film, if necessary, for the purpose of improving the adhesion of the metallic gloss coating to be formed, and improving the reproducibility of the metallic gloss coating and metal coating pattern to be applied and printed. Or a plasma treatment, or a resin coating agent such as polyurethane, polyisocyanate, organic titanate, polyethyleneimine, or polybutadiene can be applied.

  Any glass substrate that is generally used as glass for a substrate can be used. For example, soda lime glass, micro sheet glass, non-alkali glass, Pyrex glass (registered trademark), Vycor glass, quartz glass and the like can be mentioned.

  Examples of the fiber substrate include plant fibers such as cotton and hemp, animal fibers such as silk and wool, polyester, acrylic, nylon, vinylon, polypropylene, polyvinyl chloride, polyethylene, polyvinylidene chloride, polyurethane and other chemical fibers, Examples thereof include regenerated fibers such as rayon, polynosic, and cupra. In addition, as the fiber structure, for example, any of woven fabric, knit, non-woven fabric and the like can be used.

  For example, in order to improve the adhesion to the metallic gloss coating, the base material is provided with an adhesion improving layer using an anchor agent or the like, or is subjected to pretreatment such as ultraviolet treatment, corona discharge treatment, and plasma treatment. May be.

In the present invention, a metallic glossy film can be obtained by applying a metallic glossy film-forming material containing metal nanoparticles coated with an ionic protective substance and then drying it as necessary. At this time, it is preferable that the drying temperature is appropriately selected according to the substrate to be used, the printing method, and the liquid medium. In particular, in the case of forming a metallic glossy film, in the material for forming the metallic glossy film containing metal nanoparticles. It is preferable to dry at a temperature not higher than the boiling point of the liquid medium having the highest boiling point among the liquid medium contained in the medium. When forming a conductive film using a material containing metal nanoparticles, in order to obtain good conductivity, the liquid medium contained in the conductive material is quickly volatilized to remove organic components such as resins and compounds. In order to achieve this, it is said that heat treatment is preferably performed at as high a temperature as possible. However, if rapid heating is performed after the coating is formed, moisture in the atmosphere is absorbed in the coating due to the heat of vaporization when the liquid medium volatilizes. Good metallic luster coating and base material due to whitening phenomenon easily occurring due to penetration, rough surface of coating due to large amount of organic components coming off from coating at once, and generation of bubbles in coating There is a risk that the adhesiveness cannot be obtained. Therefore, a good metallic gloss coating can be obtained by drying at the temperature of the boiling point of the liquid medium with the highest boiling point among the liquid media contained in the metallic gloss coating material containing metal nanoparticles, and controlling the speed of film formation. Is preferable.

The drying method is not particularly limited and can be appropriately selected depending on the drying temperature, printing method, and base material, but energy such as hot air drying, vacuum drying, infrared ray, near infrared ray, far infrared ray, ultraviolet ray, electron beam, microwave, etc. It can also be dried using a wire or the like.

  Further, after the metallic gloss coating is formed, an overprint varnish, various coating agents and the like may be applied for the purpose of further protection. As these various varnishes and coating agents, those conventionally used in the printing field may be used. These varnishes and coating agents can be used in either normal heat drying type or active energy ray curable type.

  Moreover, when forming an ion exchange layer on the film layer containing an electroconductive substance, this ion exchange layer can also be functioned as a protective layer of an electroconductive film layer.

  In the present invention, for the purpose of improving the metallic luster and reflectivity, other metallic luster coatings can be laminated. In that case, the form of lamination is not particularly limited, and a metallic gloss coating material containing metal nanoparticles is laminated on the formed metallic glossy coating, or an ion exchange layer is formed on the formed metallic glossy coating. It can be laminated by applying a material for forming a metallic glossy coating thereon, or a functional layer such as an adhesive layer can be provided on the metallic glossy coating, and then a metallic glossy coating can be formed. is there.

In addition, after applying an adhesive on the metallic glossy film, the circuit board and the film can be protected by laminating a paper base material or a plastic film by bonding or melt extrusion of plastic. Of course, the protective layer can also be formed by adhering a base material previously coated with an adhesive and an adhesive.

  The metallic gloss coating formed by the method of the present invention promotes fusion and metallization of metal nanoparticles, smoothes the formed metallic gloss coating surface, and obtains a better metallic gloss coating. A treatment such as a heat treatment or a heat and pressure treatment such as a calendar treatment can also be performed. In order to obtain a better metallic luster, any method may be selected according to the type of the base material to be used, and it can be performed by a calendar process, a press roll machine, a press machine, a laminator or the like. The treatment conditions may be performed in a range that does not affect the substrate, but the treatment temperature is 50 to 150 ° C., the pressurization condition is 0.5 to 2.0 MPa, and the pressurization time is in the range of 10 seconds to 10 minutes. Preferably it is done. When using a press roll machine, the linear pressure of the roll is preferably in the range of 1 to 25 kg / cm. Moreover, the base-material conveyance speed at the time of a press can be performed in the range of 1-30 m / min.

Since the metallic gloss coating of the present invention can be formed at a low temperature and has good adhesion to various substrates, it can be used on any substrate known as a conventional substrate. It can be formed. In addition, it can be applied to various printing methods and coating methods, and can obtain an arbitrary film thickness. Further, by controlling the temperature, it is possible to form a metallic glossy film with excellent characteristics. It can be used as a glossy coating.

  The use of the metallic luster coating of the present invention is not particularly limited as long as it is a field where the metallic luster of the present invention can be used, and can be appropriately applied depending on the level of metallic luster. Printing members such as stickers and cards, packaging members such as shrink labels, decorative members such as decorations for sporting goods, musical instruments, and paints, optical members such as display members, light guide plates, and reflectors for backlights , Lighting member, medical member, automotive member, coating member, glittering decorative label, decorative member, building member such as signboard, anti-counterfeiting member, anti-counterfeiting member such as hologram reflector, glossy yarn, fabric, dyeing It can be used for fiber members and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these. In the examples, “parts” represents “parts by weight” and “%” represents “% by weight”.

[Metal Nanoparticle Synthesis Example 1]
Attach 200 parts of toluene and 38.9 parts of silver oleate to a separable four-necked flask with a condenser, thermometer, nitrogen gas inlet tube, and stirring device, and stir at room temperature in a nitrogen atmosphere. After that, 2.3 parts of diethylaminoethanol (0.2 mol times with respect to 1 mol of metal) was added and dissolved as a dispersant. Thereafter, when 73.1 parts of an aqueous 20% succinic acid dihydrazide (hereinafter abbreviated as SUDH) solution (2 mol times of hydrazide group with respect to 1 mol of metal) was dropped, the liquid color changed from pale yellow to dark brown. In order to further promote the reaction, the temperature was raised to 40 ° C. to advance the reaction. After standing and separating, excess reducing agent and impurities were removed by taking out the aqueous layer. Distilled water was added several times to the toluene layer, and washing and separation were repeated to obtain a silver fine particle dispersion toluene solution. The obtained silver fine particle dispersion had an average particle diameter of 7 ± 2 nm and a silver concentration of 73%.

[Metal nanoparticle synthesis example 2]
A silver fine particle dispersion was obtained in the same manner as in Synthesis Example 1 except that the starting metal salt was changed to 22.3 parts of silver hexanoate. The obtained silver fine particle dispersion had an average particle diameter of 5 ± 2 nm and a silver concentration of 80%.

[Metal Nanoparticle Synthesis Example 3]
A silver fine particle dispersion was obtained in the same manner as in Synthesis Example 1 except that the starting metal salt was changed to 20.9 parts of silver pentanoate. The obtained silver fine particle dispersion had an average particle diameter of 5 ± 1 nm and a silver concentration of 82%.

[Metal Nanoparticle Synthesis Example 4]
Red copper fine particles in the same manner as in Synthesis Example 1 except that the metal salt of the raw material was changed to 26.6 parts of copper pentanoate and the reducing agent was changed to 292.3 parts of 20% SUDH aqueous solution (4 mol times of hydrazide group with respect to 1 mol of metal). A dispersion was obtained. The average particle diameter of the copper fine particles of the obtained copper fine particle dispersion was 7 ± 2 nm, and the copper concentration was 50%.

[Metal Nanoparticle Synthesis Example 5]
2. A separable four-necked flask was equipped with a cooling tube, thermometer, nitrogen gas inlet tube, and stirring device, 91.1 parts of toluene while introducing nitrogen gas, and Solsperse 32000 as a pigment dispersant (manufactured by Nippon Lubrizol Corporation) After 2 parts were charged and dissolved, 73.1 parts of a 20% succinic acid dihydrazide aqueous solution (2 mol times of hydrazide group with respect to 1 mol of metal) was added dropwise with stirring at 50 ° C. to generate uniform droplets. 100 parts of 1M silver nitrate aqueous solution was weighed into a beaker, and 27.3 parts of 25% aqueous ammonia (4 mol times with respect to 1 mol of metal) was added dropwise with stirring, and then added dropwise into the toluene solution, and the reaction was allowed to proceed at 30 ° C. After allowing to stand and separate, the aqueous phase was taken out, and the excess reducing agent and impurities were washed by repeating washing and separation several times with distilled water to obtain a silver fine particle dispersion toluene solution. The obtained silver fine particle dispersion was fluid, had strong absorption at 417 nm, the average particle diameter of silver fine particles was uniform at 7 ± 2 nm, and the silver concentration was 78%.

[Metal Nanoparticle Synthesis Example 6]
4. A separable four-necked flask was equipped with a cooling tube, a thermometer, a nitrogen gas inlet tube, and a stirrer, while introducing nitrogen gas, 91.1 parts of toluene, and Solsperse 32000 as a pigment dispersant (manufactured by Nippon Lubrizol Corporation) After 9 parts were charged and dissolved, 73.1 parts of a 20% succinic acid dihydrazide aqueous solution (2 mol times of hydrazide group with respect to 1 mol of metal) was added dropwise with stirring at 50 ° C. to generate uniform droplets. 100 parts of 1M chloroauric acid aqueous solution was weighed into a beaker, and 27.3 parts of 25% ammonia water (4 mol times with respect to 1 mol of metal) was added dropwise with stirring and then dropped into the toluene solution, and the reaction was allowed to proceed at 30 ° C. It was. After allowing to stand and separate, the aqueous phase was taken out, and the excess reducing agent and impurities were washed by repeating washing and separation several times with distilled water to obtain a silver fine particle dispersion toluene solution. The obtained silver fine particle dispersion was fluid, had strong absorption at 531 nm, the average particle size of silver fine particles was uniform as 5 ± 2 nm, and the gold concentration was 70%. The yield of the gold fine particle dispersion was 83%.

[Metal Nanoparticle Synthesis Example 7]
Attach 200 parts of toluene and 26.6 parts of silver pentanoate to a separable four-necked flask with a condenser, a thermometer, a nitrogen gas inlet pipe, and a stirrer while stirring at room temperature in a nitrogen atmosphere. Then, 2.3 parts of diethylaminoethanol (0.2 mol times with respect to 1 mol of metal) and 2.8 parts of oleic acid (0.1 mol times with respect to 1 mol of metal) were added and dissolved as a dispersant. After that, when 3.2 parts of hydrazine (2 mol times with respect to 1 mol of metal) was added, a violent reaction occurred and a precipitate was formed. After leaving and separating, the aqueous layer is taken out to remove precipitates, excess reducing agent and impurities, and distilled water is added to the toluene layer several times, followed by washing and separation to obtain a silver fine particle dispersion toluene solution. Obtained. The average particle diameter of the silver fine particles of the obtained silver fine particle dispersion was 20 ± 5 nm, and the silver concentration was 30%.

[Example 1]
Acetone, which is a poor solvent, was added to the silver nanoparticle dispersion coated with pentanoic acid obtained in Synthesis Example 3, and the silver nanoparticles were taken out as a solid and dried. The obtained silver nanoparticles were dissolved in ethylene glycol monobutyl ether and adjusted to a silver concentration of 20% to obtain a material for forming a metallic glossy film. A pattern was formed by inkjet printing on the obtained material on a polyester film (“Ester E5100” manufactured by Toyobo Co., Ltd., thickness: 100 μm) and dried at 150 ° C. for 30 minutes to obtain a metallic glossy coating.

[Example 2]
As a substance having anion exchange capacity, 60 parts of a cationic resin (Mitsubishi Chemical Corporation “Saftmer ST-3000”, solid content 25%), 40 parts of a liquid medium (water / isopropyl alcohol = 1/1, weight ratio) The mixture was mixed and stirred for 20 minutes using a dissolver to obtain a paint containing a substance having anion exchange ability. Next, using this paint having anion exchange ability, it was coated on a polyester film (“Ester E5100” manufactured by Toyobo Co., Ltd., thickness: 100 μm) using a bar coater, and then dried at 75 ° C. for 5 minutes. As a result, an anion exchange layer having a coating film thickness of 6 μm after drying was obtained.
Next, after the silver nanoparticle dispersion coated with oleic acid obtained in Synthesis Example 1 was concentrated under reduced pressure, methyl ethyl ketone (hereinafter referred to as MEK) and ethylcyclohexane (hereinafter referred to as ECH) were added. A material for forming a metallic glossy film was obtained by adjusting the concentration to 15% and the ratio of toluene / MEK / ECH to 1: 1: 1 by weight. Thereafter, a pattern was formed on the anion exchange layer with a small gravure printing machine and dried to obtain a metallic glossy coating. At this time, the drying temperature of the printing press was set to 70 ° C. by actual measurement.

[Example 3]
As a substance having anion exchange capacity, 60 parts of a cationic resin (Mitsubishi Chemical Corporation “Saftmer ST-3000”, solid content 25%), 40 parts of a liquid medium (water / isopropyl alcohol = 1/1, weight ratio) The mixture was mixed and stirred for 20 minutes using a dissolver to obtain a paint containing a substance having anion exchange ability. Next, using this paint having anion exchange ability, it was coated on a polycarbonate using a bar coater and then dried at 75 ° C. for 5 minutes, so that the anion exchange with a thickness of 6 μm after drying was performed. A layer was obtained.
Next, the silver nanoparticle dispersion coated with pentanoic acid obtained in Synthesis Example 3 was concentrated under reduced pressure, adjusted to a silver concentration of 10%, and a metallic glossy film forming material was obtained. Thereafter, the obtained material was applied onto the anion exchange layer using a die coater and dried to obtain a metallic gloss coating. At this time, the drying temperature of the printing press was set to 50 ° C. by actual measurement.

[Example 4]
15 parts of cationic resin (“Palset JK-510” manufactured by Meisei Chemical Co., Ltd., solid content 20%) as a substance having anion exchange ability, colloidal silica (Nissan Chemical Industries as a substance having no anion exchange ability) “Snowtex O” manufactured by Co., Ltd., 60 parts of solid content 20%) and 25 parts of a liquid medium (water / isopropyl alcohol = 1/1) are mixed and stirred for 20 minutes using a dissolver to provide anion exchange capacity. A printing ink containing the substance was obtained. Using this printing ink having anion exchange ability, the entire surface is solid-printed on a polyester film (“Ester E5100” manufactured by Toyobo Co., Ltd., thickness 100 μm) with a small gravure printing machine, dried, and the coating thickness is 5 μm. An anion exchange layer was obtained. The drying temperature of the printing press was set to 60 ° C.
Next, after the silver nanoparticle dispersion coated with hexanoic acid obtained in Synthesis Example 2 was concentrated under reduced pressure, methyl ethyl ketone (hereinafter referred to as MEK) and ethylcyclohexane (hereinafter referred to as ECH) were added. A material for forming a metallic glossy film was obtained by adjusting the concentration to 15% and the ratio of toluene / MEK / ECH to 1: 1: 1 by weight. Then, the obtained material was formed into a pattern on the anion exchange layer with a small gravure printing machine and dried to obtain a metallic gloss coating. At this time, the drying temperature of the printing press was set to 70 ° C. by actual measurement.

[Example 5]
15 parts of cationic resin (“Palset JK-510” manufactured by Meisei Chemical Co., Ltd., solid content 20%) as a substance having anion exchange ability, colloidal silica (Nissan Chemical Industries as a substance having no anion exchange ability) “Snowtex O” manufactured by Co., Ltd., 60 parts of solid content 20%) and 25 parts of a liquid medium (water / isopropyl alcohol = 1/1) are mixed and stirred for 20 minutes using a dissolver to provide anion exchange capacity. A printing ink containing the substance was obtained. Using this printing ink having anion exchange ability, the entire surface is solid-printed on a polyester film (“Ester E5100” manufactured by Toyobo Co., Ltd., thickness 100 μm) with a small gravure printing machine, dried, and the coating thickness is 5 μm. An anion exchange layer was obtained. The drying temperature of the printing press was set to 60 ° C.
Next, acetone as a poor solvent was added to the silver nanoparticle dispersion coated with pentanoic acid obtained in Synthesis Example 3, and the silver nanoparticles were taken out as a solid and dried. The obtained silver nanoparticles were dissolved in ethylene glycol monobutyl ether and adjusted to a silver concentration of 20% to obtain a material for forming a metallic glossy film. A pattern was formed on the obtained anion exchange layer by ink jet printing on the obtained anion exchange layer and dried at 100 ° C. for 20 minutes to obtain a metallic gloss coating.

[Example 6]
15 parts of cationic resin (“Palset JK-510” manufactured by Meisei Chemical Co., Ltd., solid content 20%) as a substance having anion exchange ability, colloidal silica (Nissan Chemical Industries as a substance having no anion exchange ability) “Snowtex O” manufactured by Co., Ltd., 60 parts of solid content 20%) and 25 parts of a liquid medium (water / isopropyl alcohol = 1/1) are mixed and stirred for 20 minutes using a dissolver to provide anion exchange capacity. A printing ink containing the substance was obtained. Using this printing ink having anion exchange ability, the entire surface is solid-printed on a polyester film (“Ester E5100” manufactured by Toyobo Co., Ltd., thickness 100 μm) with a small gravure printing machine, dried, and the coating thickness is 5 μm. An anion exchange layer was obtained. The drying temperature of the printing press was set to 60 ° C.
Next, after the copper nanoparticle dispersion coated with pentanoic acid obtained in Synthesis Example 4 was concentrated under reduced pressure, methyl ethyl ketone (hereinafter referred to as MEK) and ethylcyclohexane (hereinafter referred to as ECH) were added, and copper was added. A material for forming a metallic glossy film was obtained by adjusting the concentration to 15% and the ratio of toluene / MEK / ECH to 1: 1: 1 by weight. Then, the obtained material was formed into a pattern on the anion exchange layer with a small gravure printing machine and dried to obtain a metallic gloss coating. At this time, the drying temperature of the printing press was set to 70 ° C. by actual measurement.

[Example 7]
15 parts of polyvinyl alcohol resin (“Poval PVA-117” manufactured by Kuraray Co., Ltd.) as other resin, anionic colloidal silica (“Snowtex 40” manufactured by Nissan Chemical Industries, Ltd.), solid content 40 %) 60 parts and a liquid medium (water / isopropyl alcohol = 1/1) 25 parts were mixed and stirred for 60 minutes using a dissolver to obtain a paint containing a substance having a cation exchange ability. Next, using this paint having a cation exchange capacity, the whole surface was solid-printed on a polyester film (“Ester E5100” manufactured by Toyobo Co., Ltd., thickness 100 μm) with a small gravure printing machine, dried, and then the coating thickness An anion exchange layer having a thickness of 6 μm was obtained. The drying temperature of the printing press was set to 70 ° C.
Next, acetone as a poor solvent was added to the silver nanoparticle dispersion coated with sol32000 obtained in Synthesis Example 5, and the silver nanoparticles were taken out as a solid and dried. The obtained silver nanoparticles were dissolved in ethylene glycol monobutyl ether and adjusted to a silver concentration of 20% to obtain a material for forming a metallic glossy film. A pattern was formed on the obtained cation exchange layer by ink jet printing on the obtained material and dried at 100 ° C. for 20 minutes to obtain a metallic glossy coating.

[Example 8]
15 parts of polyvinyl alcohol resin (“Poval PVA-117” manufactured by Kuraray Co., Ltd.) as other resin, anionic colloidal silica (“Snowtex 40” manufactured by Nissan Chemical Industries, Ltd.), solid content 40 %) 60 parts and a liquid medium (water / isopropyl alcohol = 1/1) 25 parts were mixed and stirred for 60 minutes using a dissolver to obtain a paint containing a substance having a cation exchange ability. Next, using this paint having a cation exchange capacity, the whole surface was solid-printed on a polyester film (“Ester E5100” manufactured by Toyobo Co., Ltd., thickness 100 μm) with a small gravure printing machine, dried, and then the coating thickness An anion exchange layer having a thickness of 6 μm was obtained. The drying temperature of the printing press was set to 70 ° C.
Next, acetone as a poor solvent was added to the gold nanoparticle dispersion coated with sol32000 obtained in Synthesis Example 6, and the gold nanoparticles were taken out as a solid and dried. The obtained silver nanoparticles were dissolved in ethylene glycol monobutyl ether and adjusted to a gold concentration of 20% to obtain a material for forming a metallic glossy film. A pattern was formed on the obtained cation exchange layer by ink jet printing on the obtained material and dried at 100 ° C. for 20 minutes to obtain a metallic glossy coating.

[Example 9]
As a substance having anion exchange capacity, 60 parts of a cationic resin (Mitsubishi Chemical Corporation “Saftmer ST-3000”, solid content 25%), 40 parts of a liquid medium (water / isopropyl alcohol = 1/1, weight ratio) The mixture was mixed and stirred for 20 minutes using a dissolver to obtain a paint containing a substance having anion exchange ability. Next, using this paint having anion exchange ability, it was coated on a polycarbonate using a bar coater and then dried at 75 ° C. for 5 minutes, so that the anion exchange with a thickness of 6 μm after drying was performed. A layer was obtained.
Next, the silver nanoparticle dispersion coated with pentanoic acid obtained in Synthesis Example 7 was concentrated under reduced pressure and adjusted to a silver concentration of 10% to obtain a metallic glossy film-forming material. Thereafter, the obtained material was applied onto the anion exchange layer using a spin coating method and dried at 50 ° C. for 10 minutes to obtain a metallic glossy coating.

[Example 10]
15 parts of cationic resin (“Palset JK-510” manufactured by Meisei Chemical Co., Ltd., solid content 20%) as a substance having anion exchange ability, colloidal silica (Nissan Chemical Industries as a substance having no anion exchange ability) “Snowtex O” manufactured by Co., Ltd., 60 parts of solid content 20%) and 25 parts of a liquid medium (water / isopropyl alcohol = 1/1) are mixed and stirred for 20 minutes using a dissolver to provide anion exchange capacity. A printing ink containing the substance was obtained. Using this printing ink having anion exchange ability, the entire surface is solid-printed on a polyester film (“Ester E5100” manufactured by Toyobo Co., Ltd., thickness 100 μm) with a small gravure printing machine, dried, and the coating thickness is 5 μm. An anion exchange layer was obtained. The drying temperature of the printing press was set to 60 ° C.
Next, after the silver nanoparticle dispersion coated with hexanoic acid obtained in Synthesis Example 2 was concentrated under reduced pressure, methyl ethyl ketone (hereinafter referred to as MEK) and ethylcyclohexane (hereinafter referred to as ECH) were added. BYK-051 (BIC Chemie Japan Co., Ltd.) is used as a leveling agent for the purpose of improving the metallic luster and adjusting the weight ratio to 15: 1 and the toluene / MEK / ECH ratio to be 1: 1: 1. (Product made by the company, solid content 20%) is added to 0.5 parts, 0.1 parts in 100 parts by weight of the material for forming a metallic glossy film, and stirred for 10 minutes using a dissolver to form a metallic glossy film Material was obtained. Then, the obtained material was formed into a pattern on the anion exchange layer with a small gravure printing machine and dried to obtain a metallic gloss coating. At this time, the drying temperature of the printing press was set to 70 ° C. by actual measurement.

[Example 11]
15 parts of cationic resin (“Palset JK-510” manufactured by Meisei Chemical Co., Ltd., solid content 20%) as a substance having anion exchange ability, colloidal silica (Nissan Chemical Industries as a substance having no anion exchange ability) “Snowtex O” manufactured by Co., Ltd., 60 parts of solid content 20%) and 25 parts of a liquid medium (water / isopropyl alcohol = 1/1) are mixed and stirred for 20 minutes using a dissolver to provide anion exchange capacity. A printing ink containing the substance was obtained. Using this printing ink having anion exchange ability, the entire surface is solid-printed on a polyester film (“Ester E5100” manufactured by Toyobo Co., Ltd., thickness 100 μm) with a small gravure printing machine, dried, and the coating thickness is 5 μm. An anion exchange layer was obtained. The drying temperature of the printing press was set to 60 ° C.
Next, acetone as a poor solvent was added to the silver nanoparticle dispersion coated with pentanoic acid obtained in Synthesis Example 3, and the silver nanoparticles were taken out as a solid and dried. OX-880EF (manufactured by Enomoto Kasei Co., Ltd., solid content 50) was used as an antifoaming agent in order to dissolve the obtained silver nanoparticles in ethylene glycol monobutyl ether to adjust the silver concentration to 20% and to further improve the metallic luster. %) 0.2 part and 0.1 part of 100 parts by weight of the metallic glossy film-forming material were added and stirred for 10 minutes using a dissolver to obtain a metallic glossy film-forming material. A pattern was formed on the obtained anion exchange layer by ink jet printing on the obtained anion exchange layer and dried at 100 ° C. for 20 minutes to obtain a metallic gloss coating.

[Example 12]
As a substance having anion exchange capacity, 60 parts of a cationic resin (Mitsubishi Chemical Corporation “Saftmer ST-3000”, solid content 25%), 40 parts of a liquid medium (water / isopropyl alcohol = 1/1, weight ratio) The mixture was mixed and stirred for 20 minutes using a dissolver to obtain a paint containing a substance having anion exchange ability. Next, using this paint having anion exchange ability, it was coated on a polycarbonate using a bar coater and then dried at 75 ° C. for 5 minutes, so that the anion exchange with a thickness of 6 μm after drying was performed. A layer was obtained.
Next, the silver nanoparticle dispersion coated with pentanoic acid obtained in Synthesis Example 3 is concentrated under reduced pressure, adjusted to have a silver concentration of 10%, and further used as a lubricant for the purpose of improving metal gloss. CERAFAK103 (Bic Chemie Japan Co., Ltd., solid content 6%) is added to 1.6 parts and 0.1 part in 100 parts by weight of the metallic gloss coating material, and stirred for 10 minutes using a dissolver. Thus, a material for forming a metallic glossy film was obtained. Thereafter, the obtained material was applied onto the anion exchange layer using a die coater and dried to obtain a metallic gloss coating. At this time, the drying temperature of the printing press was set to 50 ° C. by actual measurement.

[Example 13]
The silver nanoparticle dispersion coated with pentanoic acid obtained in Synthesis Example 3 was concentrated under reduced pressure and adjusted to a silver concentration of 10% to obtain a metallic glossy film-forming material. Thereafter, the obtained material was applied onto the glass substrate using a spin coat method and dried at 50 ° C. to obtain a metallic gloss forming film. At this time, the drying temperature of the printing press was set to 50 ° C. by actual measurement.
Next, 60 parts of a cationic resin (“Saftamer ST-3000” manufactured by Mitsubishi Chemical Corporation, solid content 25%) as a substance having anion exchange capacity, liquid medium (water / isopropyl alcohol = 1/1, weight ratio) 40 parts were mixed and stirred for 20 minutes using a dissolver to obtain a paint containing a substance having anion exchange ability. Next, using this paint having anion exchange ability, a metal gloss forming film was applied using a bar coater and then dried at 75 ° C. for 5 minutes to obtain a metal gloss film.

[Example 14]
Next, after the silver nanoparticle dispersion coated with hexanoic acid obtained in Synthesis Example 2 was concentrated under reduced pressure, methyl ethyl ketone (hereinafter referred to as MEK) and ethylcyclohexane (hereinafter referred to as ECH) were added. A material for forming a metallic glossy film was obtained by adjusting the concentration to 15% and the ratio of toluene / MEK / ECH to 1: 1: 1 by weight. Then, the obtained material was formed into a pattern on a polyester film (“Ester E5100” manufactured by Toyobo Co., Ltd., thickness: 100 μm) with a small gravure printing machine and dried to obtain a metallic gloss coating. At this time, the drying temperature of the printing press was set to 70 ° C. by actual measurement.
Next, 15 parts of a cationic resin ("Palset JK-510" manufactured by Meisei Chemical Co., Ltd., solid content 20%) as a substance having anion exchange ability, and colloidal silica (as a substance having no anion exchange ability) “Snowtex O” manufactured by Nissan Chemical Industries, Ltd., 60 parts of solid content (20%) and 25 parts of liquid medium (water / isopropyl alcohol = 1/1) are mixed, and stirred for 20 minutes using a dissolver and anions. A printing ink containing a substance having exchange ability was obtained.
Next, using the ink having the anion exchange ability, a solid gravure printing machine was used to perform solid printing on the entire surface of the coating layer, followed by drying to obtain a metallic gloss coating. The drying temperature of the printing press was set to 60 ° C. by actual measurement.

[Example 15]
After obtaining a metallic glossy coating in the same manner as in Example 5, the coating was calendered using a press roll machine under the conditions of a heating temperature of 70 ° C., a pressing condition of 1 MPa, and a pressing time of 5 minutes.

[Example 16]
A metallic glossy coating was obtained in the same manner as in Example 3 except that the drying temperature of the printing press at the time of applying the metallic glossy coating forming material was set to 100 ° C. as an actual measurement value.

[Example 17]
A metallic glossy coating was obtained in the same manner as in Example 4 except that the drying temperature of the printing press at the time of applying the metallic glossy coating forming material was set to 150 ° C. as an actual measurement value.

[Example 18]
15 parts of polyvinyl alcohol resin (“Poval PVA-117” manufactured by Kuraray Co., Ltd.) as other resin, anionic colloidal silica (“Snowtex 40” manufactured by Nissan Chemical Industries, Ltd.), solid content 40 %) 60 parts and a liquid medium (water / isopropyl alcohol = 1/1) 25 parts were mixed and stirred for 60 minutes using a dissolver to obtain a paint containing a substance having a cation exchange ability. Next, using this paint having a cation exchange capacity, it was coated on a glass using a bar coater and then dried at 75 ° C. for 5 minutes, so that the cation exchange with a coating thickness of 6 μm after drying was performed. A layer was obtained.
Next, acetone as a poor solvent was added to the silver nanoparticle dispersion coated with sol32000 obtained in Synthesis Example 5, and the silver nanoparticles were taken out as a solid and dried. The obtained silver nanoparticles were dissolved in ethylene glycol monobutyl ether and adjusted to a silver concentration of 20% to obtain a material for forming a metallic glossy film. A pattern was formed on the obtained cation exchange layer by ink jet printing on the obtained cation exchange layer and dried at 200 ° C. for 20 minutes to obtain a metallic gloss coating.

[Comparative Example 1]
Mirror ink MIR-9100 (deposited aluminum foil dispersion type) manufactured by Teikoku Manufacturing Co., Ltd. was applied onto a polyester film (“Ester E5100” manufactured by Toyobo Co., Ltd., thickness 100 μm) to a thickness of 3 μm using a bar coater. And dried in an oven at 120 ° C. for 30 minutes to obtain a metallic gloss coating.

  The gloss values and substrate adhesion of the metallic gloss coatings obtained in Examples 1 to 18 and Comparative Examples were evaluated by the following methods. The results are shown in Table 1.

[Gloss value]
The gloss value was measured through an N filter that attenuates the amount of light at an incident angle of 60 ° and a reflection angle of 60 ° of a gloss meter manufactured by Murakami Color Giken.
[Base material adhesion]
A cellophane adhesive tape (made by Nichiban Co., Ltd., width 12 mm) is attached to a polyester film (“E5100” manufactured by Toyobo Co., Ltd., thickness 100 μm), a conductive circuit or conductive film formed on a glass substrate or polycarbonate. When the cellophane adhesive tape was peeled off rapidly, the degree of the peeled coating film was evaluated according to the following evaluation criteria.
(Evaluation criteria)
○: hardly peeled (peeled area less than 10%)
Δ: Partially peeled (peeled area 10% or more and less than 50%)
X: Almost peeled (peeling area 50% or more)

  The results obtained in Examples 1 to 18 show that the material for forming a metallic glossy film comprising metal nanoparticles having an average particle diameter of 1 to 100 nm and coated with an ionic protective substance, which is a feature of the present invention. In addition, since metal nanoparticles coated with a protective substance having ionicity are brought into contact with a substance having an ion exchange capacity for the protective substance, the metal nanoparticles are rapidly fused, which is not conventional. It shows that an unobtained metallic luster is obtained. In addition, by selecting a reducing agent when synthesizing metal nanoparticles, uniform particles can be obtained, which in turn improves the smoothness of the surface of the resulting metallic gloss coating and improves the metallic gloss. Yes. Moreover, in Examples 10-13, the gloss value is improving by including any of a leveling agent, an antifoamer, and a lubricant in the metallic gloss film forming material. This is considered to be because the wettability with the base material at the time of forming the metallic gloss coating is improved. Furthermore, the surface smoothness of the surface of the metal film was improved by applying a heat and pressure treatment after the formation of the metal gloss film, and the effect of dramatically improving the gloss value was obtained.

  As is clear from the results of the comparative examples, with the conventional mirror ink using aluminum vapor-deposited foil as a raw material, the obtained metallic gloss coating could not obtain sufficient performance.

  The metallic luster coating of the present invention can be applied to all fields where metallic luster can be used. Depending on the level of metallic luster, for example, printing members such as tickets, labels, stickers and cards, packaging members such as shrink labels, Design materials for decoration of sporting goods, musical instruments, paintings, etc., optical members such as display members, light guide plates, reflectors for backlights, illumination members, medical members, automotive members, coatings It can be used for members, glittering decorative labels, decorative members, building members such as signboards, anti-counterfeiting members, anti-counterfeiting members such as hologram reflectors, fiber members such as glossy yarns, fabrics, and dyeings.

Claims (15)

  A method for producing a metallic glossy coating, comprising: forming a metallic glossy coating-forming material comprising metal nanoparticles having an average particle diameter of 1 to 100 nm, coated with an ionic protective substance, on a substrate. .   2. The method for producing a metallic glossy coating according to claim 1, wherein the metallic glossy coating-forming material containing metallic nanoparticles contains at least one liquid medium.   3. The method for producing a metallic glossy coating according to claim 2, wherein after the coating is formed, the coating is dried at a temperature not higher than the boiling point of the liquid medium having the highest boiling point among the liquid medium.   The method for producing a metallic glossy coating according to any one of claims 1 to 3, wherein the material for forming a metallic glossy coating containing metal nanoparticles contains at least one of a leveling agent, an antifoaming agent, and a lubricant.   Metals forming the metal nanoparticles are gold, silver, copper, nickel, platinum, palladium, aluminum, zinc, chromium, iron, cobalt, molybdenum, zirconium, ruthenium, iridium, tantalum, mercury, indium, tin, lead, and The method for producing a metallic gloss coating according to any one of claims 1 to 4, which is an alloy or a mixture of one or more selected from tungsten.   The method for producing a metallic glossy coating according to any one of claims 1 to 5, wherein the metal forming the metal nanoparticles is silver.   The method for producing a metallic glossy coating according to any one of claims 1 to 6, wherein the metal nanoparticles are obtained by reducing a metal compound in a liquid medium. The metal nanoparticles are obtained by reducing a metal compound using a carbodihydrazide represented by the following formula (1) or a polybasic acid polyhydrazide represented by the following formula (2). The manufacturing method of the metallic glossy film in any one of -7.

(In the formula, R represents an n-valent polybasic acid residue.)   The metal according to any one of claims 1 to 8, wherein metal nanoparticles coated with a protective substance having ionicity are brought into contact with a substance having an ion exchange capacity for the protective substance on a substrate. A method for producing a glossy coating.   After forming an ion exchange layer containing a substance having ion exchange capacity on a substrate, a metallic gloss film forming material containing metal nanoparticles coated with a protective substance having ionicity on the ion exchange layer 10. The method for producing a metallic glossy coating according to claim 9, wherein a coating is formed.   On the base material, after forming a metal glossy film forming material containing metal nanoparticles coated with a protective substance having ionicity to form a metal nanoparticle layer, ion exchange ability is provided on the metal nanoparticle layer. The method for producing a metallic glossy coating according to claim 9, wherein an ion exchange layer containing the substance is formed.   The method for producing a metallic glossy coating according to any one of claims 1 to 11, wherein a metallic glossy coating-forming material containing metallic nanoparticles is printed.   The method for producing a metallic glossy coating according to any one of claims 1 to 11, wherein the metallic glossy coating-forming material containing metallic nanoparticles is coated.   The method for producing a metallic glossy coating according to any one of claims 1 to 13, further comprising performing a heat and pressure treatment after the coating is formed.   A metallic glossy film produced by the production method according to claim 1.