JP2018172461A - Brilliant color developing resin composition, brilliant color developing article and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a brilliant color developing resin composition which enables strong color development by control of a zeta potential of the surface without particularly changing a type and a size of metal, and can form various brilliant color developing coated films with a simple method such as a coating and drying process, in other words, with a method applicable as industrial production.SOLUTION: A brilliant color developing resin composition contains metal nanoparticles (A), a reflection material (B), a cellulose-based resin (C) and a solvent (D). The metal type of the metal nanoparticles (A) is preferably at least one selected from gold, silver, copper and aluminum. The brilliant color developing resin composition contains the metal nanoparticles (A), the reflection material (B), the resin (C) and the solvent (D), and is (1) or (2): (1) an absolute value of a zeta potential (Aζ) of the metal nanoparticles (A) of a standard deviation (Aζ) of zeta potential distribution or more and a difference therebetween of 70 mV or less; and (2) an absolute value of a zeta potential (Aζ) of the metal nanoparticles (A) of less than the standard deviation (Aζ) of zeta potential distribution and a difference therebetween of 20 mV or less.SELECTED DRAWING: None

Description

  The present invention relates to a glittering colored resin composition containing metal nanoparticles. The present invention also relates to a brilliant color product using a brilliant color resin composition containing metal nanoparticles and a method for producing the same.

  In general, when producing a glossy colored coating film such as a metallic feeling or a pearl feeling, it is known to apply and dry a paint mixed with a pigment and a reflecting material on a substrate. However, depending on the required color of the coating film, it is essential to change the pigment type and the accompanying change in the dispersant and binder resin, so it is necessary to prepare various materials and use many paints.

Patent Document 1 describes that a coating film is formed from a paint containing a metal colloid brightening agent composed of a core material and metal colloid particles (claims 1, 13, and 14).
In Patent Document 2, metal nanoparticles are dispersed in an organic solvent, the organic solvent containing the metal nanoparticles is spread on a water surface, the organic solvent is volatilized, and the metal nanoparticles are arranged in a two-dimensional direction. A two-dimensional crystal film is formed by self-organization, the metal reflective surface is brought into contact with the two-dimensional crystal film of the metal nanoparticles formed on the water surface, and the metal nanoparticle layer is transferred to the metal reflective layer. A coloration method for forming on a surface is described (claim 9). The coloration method uses an LB film (Langmuir-Blodgett film) method, and the orange-red-pink-purple-blue color is changed by changing the number of metal nanoparticle layers transferred to the metal reflecting surface. It has been reported that a color with vivid metallic luster is produced.

JP 2004-32355 A WO2013 / 039180

In the paint described in Patent Document 1, different types of metal colloid particles or metal colloid particles having different particle diameters are required depending on the required coating color, and various metal colloid particles must be prepared.
In addition, the coloration method described in Patent Document 2 utilizes transfer of an LB film, and cannot be used for general purposes because it is an industrially unsuitable method for mass production.
Further, at that time, the surface state of the metal nanoparticles and the state of interaction with the reflecting material are not sufficiently exhibited, and sufficient color development is not obtained.

  The present invention enables strong color development by controlling the zeta potential of the surface without particularly changing the metal species and the size thereof, and can easily apply a wide variety of glittering colored coating films such as coating and drying processes. It is an object of the present invention to provide a glittering colored resin composition which can be formed by a general method, that is, a method applicable to industrial production.

The inventors of the present invention have reached the present invention as a result of intensive studies to solve the above-mentioned problems.
A glittering colored resin composition comprising metal nanoparticles (A), a reflector (B), a resin (C) and a solvent (D), wherein the glittering color satisfies the following condition (1) or (2) The present invention relates to a color resin composition.
(1) The absolute value of the zeta potential (Aζ) of the metal nanoparticles (A) is not less than the standard deviation (Aζ _σ ) of the zeta potential distribution, and the difference is not more than 70 mV.
(2) The absolute value of the zeta potential (Aζ) of the metal nanoparticles (A) is less than the standard deviation (Aζ _σ ) of the zeta potential distribution, and the difference is 20 mV.
It is as follows.

  When the zeta potential (Aζ) of the metal nanoparticles (A) is positive, the zeta potential (Bζ) of the reflector (B) is positive, or the zeta potential (Aζ) of the metal nanoparticles (A) is negative. In this case, it is preferable that the zeta potential (Bζ) of the reflective material (B) is negative.

  The metal species of the metal nanoparticles (A) is preferably at least one selected from the group consisting of gold, silver, copper and aluminum.

  It is preferable that the reflective material (B) is flaky, has an average particle diameter of 1 to 100 μm, and an average thickness of 0.01 to 1 μm.

  The reflective material (B) is preferably aluminum.

  The present invention also provides a glittering colored article having a substrate (E) and a glittering colored coating film that is a dry coating film of the glittering colored resin composition described in any one of the present inventions. About.

  Furthermore, this invention relates to the manufacturing method of the glittering colored article which apply | coats the glittering colored resin composition as described in any of the said this invention to a base material (E), and dries.

A method for producing a glittering colored resin composition comprising metal nanoparticles (A), a reflector (B), a resin (C) and a solvent (D), wherein the glittering property is (1) or (2) The present invention relates to a method for producing a colored resin composition.
(1) The absolute value of the zeta potential (Aζ) is equal to or greater than the standard deviation (Aζ _σ ) of the zeta potential distribution, and the difference between the dispersion of the metal nanoparticles (A) and the reflector (B) is 70 mV or less. The dispersion, resin (C) and solvent (D) are mixed.
(2) The dispersion of the metal nanoparticles (A), the absolute value of the zeta potential (Aζ) is less than the standard deviation (Aζ _σ ) of the zeta potential distribution, and the difference is 20 mV or less, and the reflector (B) The dispersion, resin (C) and solvent (D) are mixed.

A dispersion of metal nanoparticles (A) having a positive zeta potential (Aζ) and a dispersion of a reflector (B) having a positive zeta potential (Bζ);
Or
A dispersion of metal nanoparticles (A) having a negative zeta potential (Aζ) and a dispersion of a reflector (B) having a negative zeta potential (Bζ) are mixed;
The present invention relates to a method for producing the glittering colored resin composition described above.

  The present invention can form a wide variety of glittering colored coating films by a simple method such as coating and drying processes, that is, a method applicable to industrial production, without particularly changing the metal species and the size thereof. In addition, the glittering colored resin composition can be stably provided.

  Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. Not specific to the content.

As the metal nanoparticles (A) in the present invention, metal species capable of forming localized plasmons can be employed. Examples of such metal species include gold, silver, copper, aluminum, platinum, palladium, rhodium, iridium, ruthenium, and osnium. Among these, noble metals such as gold, silver, copper, and aluminum having a large localized plasmon absorption are preferable, and silver is more preferable in terms of stability, cost, and plasmon absorption band. Moreover, you may comprise a metal nanoparticle layer by mixing many types of metal seed | species. The particle size of the metal nanoparticles is preferably 1 nm to 60 nm, more preferably 5 nm to 20 nm.
Moreover, since the said metal nanoparticle exists stably in ink, you may be covered with the dispersing agent. The dispersant is a compound or resin having a functional group having an affinity for the particle surface. Examples of the functional group having affinity include, but are not limited to, polar groups such as amino group, quaternary ammonium group, hydroxyl group, cyano group, carboxyl group, thiol group and sulfonic acid group. The affinity group 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. The compound having a functional group having affinity for the particle surface may be any of organic fatty acids, organic amines, alkanethiols, inorganic substances, and inorganic oxides. As the resin having a functional group having an affinity for the particle surface, those commercially available as a pigment dispersant can be used.

  The organic fatty acid is not particularly limited, for example, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, Palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, mellicic acid, lacteric acid, 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, stearic acid and the like. Among them, in view of stability and low temperature decomposability, caproic acid, enanthic acid, caprylic acid, myristic acid, oleic acid, stearic 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-heptylundecane Acid, 2-isoheptylundecanoic acid, 2-isopeptylisoundecanoic acid, 2-dodecylhexanoic acid, 2-isododecylhexanoic acid, 2-octyldodecanoic acid, 2-isooctyldodecanoic acid, 2-octylisododecanoic acid 2-nonyltridecanoic acid, 2-isononylisotridecanoic acid, 2- Decyldodecanoic acid, 2-isodecyldodecanoic acid, 2-decylisododecanoic acid, 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-hexadecylhexadecanoic acid, 2-hexadecyltetradecanoic acid, 2-hexadecylisohexadecanoic acid, 2-isohexadecylisohexadecanoic acid, 2-pentadecylnonadecane Acid, 2-isopentade Ruisononadecanoic acid, 2-tetradecylbehenic acid, 2-isotetradecylbehenic acid, 2-tetradecylisobehenic acid, 2-isotetradecylisobehenic acid, pivalic acid, neononanoic acid, neodecanoic acid, equacid 9 (Idemitsu Petrochemicals ), Ecacid 13 (made by Idemitsu Petrochemical), etc. Among these fatty acids, when the fatty acid is a linear fatty acid having 3 to 22 carbon atoms, it has excellent lipophilicity and stability in a non-aqueous solvent, and has a low decomposition temperature and excellent low-temperature sinterability. Therefore, it is preferable. These may be used alone or as a mixture of two or more.

  Although it does not specifically limit as organic fatty acid, For example, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, isoamylamine, n-hexylamine, 2-ethylhexylamine, n-heptylamine, n-octylamine, isooctylamine, nonylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, docodecylamine, cyclopropylamine, cyclopentylamine, cyclohexylamine, arylamine, hydroxyamine, ammonium hydroxide, methoxyamine, 2-ethanolamine, methoxyethylamine, 2-hydroxypropylamine, methoxypropylamine, cyanoethylamine, ethoxyamine, n-butoxya Min, 2-hexyloxyamine, methoxyethoxyethylamine, methoxyethoxyethoxyethylamine, diethylamine, dipropylamine, diethanolamine, hexamethyleneimine, morpholine, piperidine, piperazine, ethylenediamine, propylenediamine, hexamethylenediamine, triethylenediamine, 2,2 -(Ethylenedioxy) bisethylamine, triethylamine, triethanolamine, pyrrole, imidazole, pyridine, aminoacetaldehyde dimethyl acetal, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aniline, anisidine, aminobenzonitrile, Benzylamine and its derivatives, and polymerization such as polyarylamine and polyethyleneimine And ammonium compounds such as ammonium carbamate, ammonium carbonate, ammonium bicarbonate, ethylammonium ethyl carbamate, isopropylammonium isopropyl. Carbamate, n-butylammonium n-butylcarbamate, isobutylammonium isobutylcarbamate, t-butylammonium t-butylcarbamate, 2-ethylhexylammonium 2-ethylhexylcarbamate, octadecylammonium octadecylcarbamate, 2-methoxyethylammonium 2-methoxyethylcarbamate, 2-cyanoethylammonium 2-cyanoe Tylcarbamate, dibutylammonium dibutylcarbamate, dioctadecylammonium dioctadecylcarbamate, methyldecylammonium methyldecylcarbamate, hexamethyleneimineammonium hexamethyleneiminecarbamate, morpholinium morpholinecarbamate, pyridiniumethylhexylcarbamate, triethylenediaminiumisopropylbicarbamate, benzyl Ammonium benzylcarbamate, triethoxysilylpropylammonium triethoxysilylpropylcarbamate, ethylammonium ethyl carbonate, isopropylammonium isopropyl carbonate, isopropylammonium bicarbonate, n-butylammonium n-butylcarbonate, isobuty Ammonium isobutyl carbonate, t-butylammonium t-butyl carbonate, t-butylammonium bicarbonate, 2-ethylhexylammonium 2-ethylhexylcarbonate, 2-ethylhexylammonium bicarbonate, 2-methoxyethylammonium 2-methoxyethylcarbonate, 2-methoxy Ethyl ammonium bicarbonate, 2-cyanoethyl ammonium 2-cyanoethyl carbonate, 2-cyanoethyl ammonium bicarbonate, octadecyl ammonium octadecyl carbonate, dibutyl ammonium dibutyl carbonate, dioctadecyl ammonium dioctadecyl carbonate, dioctadecyl ammonium bicarbonate, methyl decyl ammonium methyl Decyl carbonate, hexamethyleneimine ammonium hexamethyleneimine carbonate, morpholine ammonium morpholine carbonate, benzylammonium benzyl carbonate, triethoxysilylpropylammonium triethoxysilylpropyl carbonate, pyridinium bicarbonate, triethylenediaminium isopropyl carbonate, triethylenediaminium bicarbonate , And derivatives thereof. These may be used alone or as a mixture of two or more.

  Although it does not specifically limit as alkanethiol, For example, methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, tridecane Examples include thiol, tetradecanethiol, pentadecanethiol, hexadecanethiol, heptadecanethiol, octadecanethiol, nonadecanethiol, and icosanethiol. These may be used alone or as a mixture of two or more.

  As the dispersion resin, commercially available ones can be used. For example, Solsperse 3000, Solsperse 9000, Solsperse 17000, Solsperse 24000, Solsperse 28000, Solsperse 32000, Solsperse 35100, Solsperse manufactured by Nippon Lubrizol Co., Ltd. 36000, Solsperse 41000, EFKA4009, EFKA4046, EFKA4047, EFKA4080, EFKA4010, EFKA4050, EFKA4300, EFKA4630, EFKA4300, EFKA4630 PB822, Ajispa PN411, Addispar PA111, TEXAPHORUV20, TEXAPHORUV21, TEXAPHORP61, Big Chemie Japan Co., Ltd. Disperbyk-101, Disperbyk-103, Disperbyk-106, Disperbyk-110, DisperDik-110, DisperDik 162, Disperbyk-163, Disperbyk-164, Disperbyk-166, Disperbyk-167, Disperbyk-168, Disperbyk-170, Disperbyk-171, Disperbyk-174, Disperbyk-180, Disperbyk-180 The present invention is not limited to these. The dispersion resin may be used alone or in combination of two or more.

Further, in order for the metal nanoparticles (A) to be stably present in the ink or to be uniformly arranged at the time of forming the coating film, it is preferable that the distribution of the surface zeta potential does not extend over the plus region and the minus region. Since the surface zeta potential distribution does not extend between the positive and negative regions, electrostatic aggregation is less likely to occur in the ink, and the bias of the metal nanoparticles can be suppressed during coating film drying, resulting in stable color development. can get. Therefore, in order to obtain stable color development, the absolute value of the zeta potential (Aζ) of the metal nanoparticles is preferably not less than the standard deviation (Aζ _σ ) of the zeta potential distribution, and the difference is preferably 70 mV or less. Alternatively, the absolute value of the zeta potential (Aζ) of the metal nanoparticles is preferably less than the standard deviation (Aζ _σ ) of the zeta potential distribution, and the difference is preferably 20 mV or less.

  In addition to changing the zeta potential by changing the metal species, the zeta potential can also be controlled by changing the dispersant around the metal nanoparticles.

The zeta potential and the standard deviation of the zeta potential in the present invention will be described. A dispersion or powder is measured by a measurement method such as electrophoresis or ultrasonic vibration, and the zeta potential and its distribution are determined.
The standard deviation of the zeta potential distribution indicates the distribution state of the zeta potential, and the state of the dispersion or powder can be grasped by the zeta potential and the standard deviation.
There are various methods for measuring the zeta potential. In the present invention, the zeta potential is measured by electrophoresis. For example, ZETER SIZER NANO ZSP manufactured by Malvern can be used.

The reflective material (B) in the present invention is made of metal flakes such as aluminum, zinc, copper, bronze, nickel, titanium, and stainless steel, or glass, titanium mica, titanium oxide-coated synthetic mica, titanium oxide and silicon oxide-coated mica, and oxidation. Examples thereof include titanium-coated glass flakes, titanium oxide-coated silica flakes, titanium oxide-coated alumina flakes, silica-coated mica, silica-coated synthetic mica, silica-coated glass flakes, titanium oxide flakes, and silica-coated aluminum. Having interference light has an effect of enhancing the color emitted by the metal colloid. Commercially available products include, for example, mica titanium, Bengala coated mica, Bengala coated mica titanium, carmine coated mica titanium, bitumen coated mica titanium, titanium oxide coated synthetic phlogopite, Bengala / titanium oxide coated synthetic phlogopite, titanium oxide coated glass flakes, Titanium oxide-coated alumina flakes (Silona Silver from Merck, etc.), Titanium oxide-coated silica flakes (Silona Magic Move, from Merck), iron oxide / silica-coated aluminum, iron oxide / silica-coated iron oxide, titanium oxide and oxidation Silicon-coated mica (such as Timron Splendid Gold manufactured by Merck and Sirona Caribbean Blue) and titanium oxide-coated glass flakes (Metashine MC1080RR manufactured by Nippon Sheet Glass Co., Ltd., Reflex Series manufactured by Engelhard) can be used. Meta Aluminum that can reflect the visible light region with high efficiency in order to produce a lick feeling is more preferable.
The reflective material is preferably in the form of a flake that reflects light more strongly and specularly in order to give a metallic feel. Further, if the thickness is too small, the regular reflection becomes weak, and if it is too thick, the dispersibility deteriorates. Similarly, when the average particle diameter is too small, regular reflection is weakened, and when it is too thick, dispersibility is deteriorated. Therefore, when the reflector is flaky, it is preferable that the average thickness is 0.01 to 1 μm and the average particle diameter is 1 to 100 μm. Further, the average thickness is preferably 0.1 to 0.67 μm and the average particle size is preferably 5 to 30 μm. Furthermore, the average thickness is preferably 0.2 to 0.4 μm, and the average particle size is preferably 9 to 20 μm. The average particle thickness (μm) is a value determined by the formula [4000 / water surface covering area (cm ² / g)], and the measurement method is, for example, “Aluminum Handbook” (April 15, 1972). 9th edition, Japan Light Metal Association; Asakura Shoten), page 1243.

  The reflective material (B) also affects the stable color development at the time of color development, regarding the relationship between the sign of the zeta potential (Bζ) and the zeta potential (Aζ) of the metal nanoparticles (A). When the symbol is the same symbol, aggregation is unlikely to occur in the ink due to electrostatic repulsion between the materials, and the bias of the metal nanoparticles can be suppressed when the coating film is dried, and stable color development can be obtained. Therefore, in order to obtain stable color development, the zeta potential (Bζ) of the reflective material (B) has the same sign as the zeta potential (Aζ) of the metal nanoparticles (A), that is, the metal nanoparticles (A). When the zeta potential (Aζ) is positive, the zeta potential (Bζ) of the reflector (B) is also positive, and when the zeta potential (Aζ) of the metal nanoparticles (A) is negative, the zeta potential of the reflector (B). The potential (Bζ) is also preferably negative.

  As the resin (C) in the present invention, specifically, acrylic resin, maleic acid resin, fumaric acid resin, high acid value resin of styrene / maleic acid copolymer resin, polyester resin, polyolefin resin, phenoxy resin, polyimide resin, Polyamide resin or vinyl acetate emulsion, acrylic emulsion, synthetic rubber latex, epoxy resin, phenol resin, D A P resin, urethane resin, fluororesin, silicone resin, ethyl cellulose and polyvinyl alcohol can be added as inorganic binder Examples thereof include, but are not limited to, silica sol, alumina sol, zirconia sol, titania sol and the like.

The following are known as specific names, but the use of anything other than those described in this section is not excluded when the above properties are possessed. Examples of acrylic resins include BR-102, BR-105, BR-117, BR-118, BR-1122, MB-3058 (manufactured by Mitsubishi Rayon Co., Ltd.), Alflon UC-3000, Alflon UG-4010, Alflon UG. -4070, Alflon UH-2041, Alflon UP-1020, Alflon UP-1021, Alflon UP-1061 (manufactured by Toagosei Co., Ltd.), polyester resins, Byron 220, Byron 500, Byron UR1350 (Toyobo Co., Ltd.) , Marquide No1 (manufactured by Arakawa Chemical Co., Ltd.), epoxy resin, Adeka Resin EP-4088S, Adeka Resin EP-49-23 (manufactured by Adeka Co., Ltd.), 871 (manufactured by Japan Epoxy Resin Co., Ltd.), phenolic resin, Restoto As PL-4348, Resitop PL-6317 (manufactured by Gunei Chemical Co., Ltd.), phenoxy resin, 1256, 4275 (manufactured by Japan Epoxy Resin Co., Ltd.), Tamanoru 340 (manufactured by Arakawa Chemical Industries, Ltd.), and DAP resin , Dup A, Dup K (manufactured by Daiso Co., Ltd.), urethane resin, Millionate MS-50 (manufactured by Nippon Polyurethane Industry Co., Ltd.), ethyl cellulose, etcell STANDARD4, etcel STANDARD7, etcel STANDARD20, etcel STANDARD100, etcel 200, Etcell 300 (manufactured by Nisshinsei Co., Ltd.) and polyvinyl alcohol include, but are not limited to, RS-1713, RS-1717, RS-2117 (manufactured by Kuraray Co., Ltd.) and the like. . The resins can be used alone or in combination of two or more.

  As a solvent (D) in this invention, the solvent which can melt | dissolve and disperse | distribute a metal nanoparticle (A), a reflecting material (B), and resin (C) is preferable. Specifically, alcohol solvents, ester solvents, ketone solvents, glycol ether solvents, ether solvents, hydrocarbon solvents, carbonate solvents, and the like are preferable.

  Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, sec-butanol, isobutanol, n-butanol, octyl (2-ethylhexyl) alcohol, cyclohexanol, furfuryl alcohol, methylcyclohexanol, tetotahydrofurfuryl alcohol, Examples include, but are not limited to, benzyl alcohol, phenylethyl alcohol, pine oil, ethylene glycol, diethylene glycol, glycerin, and triethanolamine.

  Examples of ester solvents include methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, cyclohexyl acetate, glycol diacetate, ethyl lactate, and dimethyl carbonate. It is not limited to these.

  Examples of the ketone solvent include, but are not limited to, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, diisobutyl ketone, mesityl oxide, diacetone alcohol, isophorone, methylcyclohexanone, acetophenone, and cyclohexanone.

  Examples of glycol ether solvents include monoethers such as ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, and ethylene glycol monobutyl ether, and acetates thereof; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, and the like, and acetic acid esters thereof, but are not limited thereto.

  Examples of ether solvents include, but are not limited to, ethyl ether, isopropyl ether, dioxane, morpholine, n-butyl ether, phenyl ether and benzyl ether.

  Examples of the hydrocarbon solvent include n-hexane, cyclohexane, methylcyclohexane toluene, xylene, ethylbenzene, isopropylbenzene, diethylbenzene, diphenylethane, cyclohexene, dipentene, chloroform, carbon tetrachloride, propylene dichloride, trichloroethane, and mineral spirits. However, it is not limited to these.

Examples of the carbonate solvent include, but are not limited to, dimethyl carbonate, diethyl carbonate, propylene carbonate, and ethylene carbonate.
The solvent can be used alone or in combination of two or more.

<Method for producing glittering colored resin composition>
The production method of the glittering colored resin composition in the present invention is not particularly limited, and the metal nanoparticles (A), the reflector (B), the resin (C), and the solvent (D) are uniformly mixed. Any known method that is generally used can be used.

  Specifically, for example, each component constituting the glittering colored resin composition is formulated, shaker, ultrasonic agitation, disper, mechanical stirrer, paint conditioner (manufactured by Red Devil), ball mill, sand mill (simmal) Enterprises "Dynomill" etc.), Attritor, Pearl Mill (Eirich "DCP Mill" etc.), Coball Mill, Homomixer, Homogenizer (M-Technica "Claremix" etc.), Wet Jet Mill (Genus Corporation) Examples thereof include a method of mixing, kneading or dispersing with “Genus P Y” manufactured by Nanogenizer, “Nanomizer” manufactured by Nanomizer Co., Ltd.), microbead mill (“Super Apeck Mill”, “Ultra Apeck Mill” manufactured by Kotobuki Industries Co., Ltd.), and the like.

  In addition, the glittering colored resin composition of the present invention includes a monofunctional monomer, an ultraviolet absorber, an antioxidant, a thermal stabilizer, a light stabilizer, an antistatic agent, a surfactant, if necessary. Storage stabilizers, leveling agents, light stabilizers and the like can also be used.

<Bright color coating>
The glittering colored coating film formed from the glittering colored resin composition of the present invention is obtained by applying and drying the glittering colored resin composition on the substrate (E).
As a coating method, a known method can be used, for example, a method using a lot or a wire bar, a microgravure, a gravure, a die, a curtain, a lip, a slot, a spray, a roll coater, a silk screen, an ink jet or Various coating methods such as spin can be used.
The thickness of the glittering colored coating film is not particularly limited, but is usually preferably 0.5 to 20 μm.

  The substrate (E) in the present invention is not particularly limited, and examples thereof include a polyimide film, a polyparaphenylene terephthalamide film, a polyether nitrile film, a polyether sulfone film, a polyethylene terephthalate film, and a polyethylene naphthalate film. , Polybutylene terephthalate film, polycarbonate film, polyvinyl chloride film, polyacryl film, glass, ceramic, alloy and metal. Further, an ITO (tin-doped indium oxide) layer, a metal layer (aluminum, gold, silver, etc.) or the like may be formed on the entire surface or a part of the substrate.

<Drying process of glittering colored coating film>
In the glittering colored resin composition applied on the substrate (E), the reflective material (B) first settles, and then the metal nanoparticles (A) are reflected by the self-organization in the drying process (the reflective material (B)). B) Laminate on top.
The number of stacked metal nanoparticles (A) can be controlled by the ratio of metal nanoparticles (A) or resin (C). Specifically, the number of stacked layers increases as the ratio of metal nanoparticles (A) increases, and the number of stacked layers decreases as it decreases. When the resin (C) ratio increases, the number of metal nanoparticles (A) dispersed in the resin increases, the number of layers on the reflector (B) decreases, and when the resin (C) ratio decreases, the coating liquid viscosity decreases. However, the self-organization in the drying process is not successful, and the number of layers on the reflective material (B) is reduced.

  Moreover, a lamination | stacking state can also be controlled by the relationship of the zeta potential of a metal nanoparticle (A) and a reflector (B). When the signs of the zeta potentials of the metal nanoparticles and the reflective material are the same, the electrostatic repulsion of both can suppress aggregation in the ink, and even when the paint film is dried, to the paint film surface that affects color development Of particles can be promoted. As a result, it is possible to stably exhibit high color developability.

<Coloring mechanism>
(Near Field effect)
When light is irradiated from the outside onto the reflective material (B) on which the metal nanoparticles (A) are laminated, localized plasmons are excited around the metal nanoparticles (A). When the metal nanoparticle layers are regularly arranged in a planar shape, localized plasmons excited by individual metal nanoparticles (A) adjacent to each other in the two-dimensional direction are bonded to each other in the plane direction. It absorbs light having a longer wavelength than the metal nanoparticles (A).

  A part of the light transmitted through the metal nanoparticle layer is reflected by the reflective material (B) of the underlayer, and enters the metal nanoparticle layer again from the back surface. Thereby, the direct light from the outside and the reflected light on the reflecting material surface enter the metal nanoparticle layer with a slight time difference. This creates a complex interaction between the localized plasmons excited in the individual metal nanoparticle layers. As a result, the resonance absorption peak exhibits a longer wavelength shift depending on the number of stacked metal nanoparticles (A).

(Far Field effect)
The metal nanoparticles (A) have an extremely large effective dielectric constant only at the wavelength at which the localized plasmon is excited. That is, it has a metamaterial property in which the refractive index greatly changes depending on the wavelength in a narrow wavelength region. Because of this metamaterial property, when light reflected by the reflector (B) is incident on the back surface of the metal nanoparticle (A), the light of a specific wavelength depends on the number of layers. It is strongly confined in the structure.

  As described above, the metal nanoparticle is obtained by the near field effect in which the localized plasmon is excited by both the direct light and the reflected light from the reflector (B) and the far field effect of the light confinement between the metal nanoparticle layers. The layer is colored in a color different from the original color of the metal nanoparticles (A) depending on the number of layers.

  In general, it is known that absorption by localized plasmons can be changed depending on the type, size, and shape of the metal nanoparticles (A), and the color gamut of the color can be expanded by combining with the above mechanism.

In the glittering colored resin composition of the present invention, the constituent elements can be changed at an arbitrary ratio, whereby the color and color developability at the time of coating change. When there are too few metal nanoparticles (A), color development will become weak, and when there are too many, absorption will spread and color development will worsen. Therefore, in the total 100 mass% of the metal nanoparticles (A), the reflector (B), and the resin (C), the metal nanoparticles (A) are preferably 0.6 to 12.5 mass%, and further 1.3. It is preferable to set it to -9.4 mass%.
If the amount of the reflective material (B) is too small, a reflective surface that sufficiently covers the substrate cannot be formed. If the amount of the reflective material (B) is too large, the adhesiveness with the substrate is deteriorated, so the metal nanoparticles (A) and the reflective material (B) In the total 100% by mass of the resin (C), the reflector (B) is preferably 1 to 98.4% by mass, more preferably 30 to 82% by mass, and further preferably 30 to 50% by mass. preferable.
If the amount of the resin (C) is too small, the viscosity of the glittering colored resin composition becomes low, the precipitation and aggregation of the metal nanoparticles during drying is promoted, and sufficient color development cannot be obtained. Is dispersed in the resin and cannot be accumulated on the reflective material (B), so that sufficient color development cannot be obtained and a dispersed color appears. Therefore, the addition amount is preferably controlled so that the viscosity of the glittering colored resin composition is 100 to 25000 mPa · s, and more preferably 300 to 5000. Alternatively, the resin (C) is preferably 1 to 20% by mass and more preferably 3 to 15% by mass in the total 100% by mass of the metal nanoparticles (A), the reflective material (B) and the resin (C). preferable.

  If the amount of the solvent (E) is too small, it will be difficult to disperse, and if it is too large, the viscosity of the glittering colored resin composition will be low, the precipitation and aggregation of metal nanoparticles during drying will be difficult to promote, and the color development will be reduced. . Therefore, it is preferable to control the addition amount so that the viscosity of the glittering colored resin composition is 100 to 25000 mPa · s, and more preferably 300 to 5000 mPa · s. Or 50-97 mass% is preferable at the mass% density | concentration in a glittering colored resin composition, and it is preferable to set it as 72-90 mass% further.

  Thus, according to the glittering colored coating film of the present invention, the metal nanoparticles (A) are laminated on the reflector (B) by a simple method such as coating and drying the glittering colored resin composition. By changing the number of layers, different colors can be obtained. Therefore, the glittering colored coating film can be colored in a plurality of different colors using a single metal species, and there is no need to prepare different types of metals and pigments for different colors as in the prior art. Moreover, since the surface of the glittering colored coating film thus obtained is colored in a vivid color having a metallic luster, the design of the surface of various articles can be enhanced.

  Next, the present invention will be described specifically by way of examples. In the examples, “parts” and “%” are all based on mass unless otherwise specified.

It describes about the manufacturing method of the resin type dispersing agent 1 used by a present Example.
<Production Method of Resin Type Dispersant 1>
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 15.0 parts of methyl methacrylate, 2-methoxyethyl acrylate 60. 0 parts, 5.0 parts of methacrylic acid, and 20 parts of t-butyl acrylate were charged and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C., and 6.0 parts of 3-mercapto-1,2-propanediol and 0.1 part of 2,2′-azobisisobutyronitrile were added to 45.4 parts of methoxypropyl acetate. The solution dissolved in was added and reacted for 10 hours. It was confirmed that 95% had reacted by solid content measurement. At this time, the weight average molecular weight was 4000. Next, 9.7 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 31.7 parts of methoxypropyl acetate, and 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst 0.2 part was added and it was made to react at 120 degreeC for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After completion of the reaction, the solvent was dried with a vacuum dryer to obtain a resin-type dispersant 1 having an acid value of 71 mgKOH / g and a weight average molecular weight of 9,500.

<Production method of metal nanoparticles (A)>
The metal nanoparticles (A) will be described. The average particle diameter of the metal nanoparticles is obtained by observing 100 nanoparticles with a transmission electron microscope (TEM) and calculating an average value.
The zeta potential was measured by using ZETA SIZER NANO ZSP manufactured by Malvern, and the z (potential) zeta potential in toluene (Aζ) and the standard deviation of the zeta potential distribution (Aζ _σ ) were measured using Huckel as the F (Ka) parameter. At this time, the measurement solution was adjusted to 0.01% by weight% concentration and measured.

Production Example 1 Production of silver nanoparticles 1 (for comparative example)
Attach 200 parts of toluene and 22.3 parts of silver hexanoate to a separable four-necked flask with a condenser, a thermometer, a nitrogen gas inlet tube, and a stirrer, and stir 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. Thereafter, when 73.1 parts of a 20% aqueous 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, the excess reducing agent and impurities are removed by taking out the aqueous phase. Further, distilled water is added to the toluene layer several times, washing and separating are repeated, and then dried to obtain silver nanoparticles 1. Obtained. The average particle diameter of the silver nanoparticles 1 was 13 nm, and the zeta potential (Aζ) of the toluene dispersion having a concentration of 0.01% by mass was 14.8 mV, and the standard deviation (Aζ _σ ) of the zeta potential distribution was 112 mV.

Production Example 2 Production of silver nanoparticle 2 10 parts of silver nanoparticle 1, 0.02 part of stearyl-3-mercaptopropionate (manufactured by SC Organic Chemical Co., Ltd.) and 100 parts of toluene were mixed, and an ultrasonic cleaner The mixture was stirred for 15 minutes and dried to obtain silver nanoparticles 2. The zeta potential (Aζ) of the toluene dispersion of the two silver nanoparticles was 46.9 mV, and the standard deviation (Aζ _σ ) of the zeta potential distribution was 34.6 mV.

Production Example 3 Production of Silver Nanoparticle 3 10 parts of silver nanoparticle 1, 0.02 part of oleic acid, and 100 parts of toluene were mixed, stirred for 15 minutes in an ultrasonic cleaner, dried, and silver nanoparticles 3 were obtained. Obtained. The zeta potential (Aζ) of the toluene dispersion of silver nanoparticles 3 was 31.8 mV, and the standard deviation (Aζ _σ ) of the zeta potential distribution was 35.5 mV.

Production Example 4 Production of Silver Nanoparticle 4 10 parts of silver nanoparticle 1, 0.02 part of ricinoleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 parts of toluene are mixed and stirred for 15 minutes with an ultrasonic cleaner. And dried to obtain silver nanoparticles 4. The zeta potential (Aζ) of the toluene dispersion of silver nanoparticles 4 was 30 mV, and the standard deviation (Aζ _σ ) of the zeta potential distribution was 48.6 mV.

Production Example 5 Production of silver nanoparticles 5 10 parts of silver nanoparticles 1, 0.017 parts of resin-type dispersant 1 and 100 parts of toluene are mixed, stirred for 15 minutes in an ultrasonic cleaner, dried, and silver Nanoparticles 5 were obtained. The resulting zano potential (Aζ) of the toluene dispersion of the silver nanoparticles 5 was 42.5 mV, and the standard deviation (Aζ _σ ) of the zeta potential distribution was 52.3 mV.

Production Example 6 Production of Silver Nanoparticle 6 10 parts of silver nanoparticle 1, 0.017 part of Solsperse 24000 (manufactured by Nihon Lubrizol) and 100 parts of toluene were mixed and stirred for 15 minutes with an ultrasonic cleaner. The silver nanoparticles 6 were obtained by drying. The resulting silver dispersion 6 of the silver nanoparticles 6 had a zeta potential (Aζ) of −65 mV and a standard deviation of the zeta potential distribution (Aζ _σ ) of 42 mV.

Production Example 7 Production of Silver Nanoparticle 7 10 parts of silver nanoparticle 1, 0.02 part of oleylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 parts of toluene were mixed and stirred for 15 minutes with an ultrasonic cleaner. It was made to dry and the dispersion liquid of the silver nanoparticle 7 was obtained. The resulting zano potential (Aζ) of the toluene dispersion of the silver nanoparticles 7 was −99.7 mV, and the standard deviation (Aζ _σ ) of the zeta potential distribution was 34.5 mV.

Production Example 8 Production of gold nanoparticle 8 A separable four-necked flask was equipped with a cooling tube, a thermometer, a nitrogen gas introduction tube and a stirrer, and 91.1 parts of toluene was introduced while introducing nitrogen gas, and a resin-type dispersion as a pigment dispersant 5.9 parts of Agent 1 was charged and dissolved, and then 73.1 parts of a 20% aqueous succinic acid dihydrazide solution (a ratio of 2 mol of hydrazide group to 1 mol of metal) was added dropwise with stirring at 50 ° C. Drops were generated. 100 parts of 1M chloroauric acid aqueous solution was weighed into a beaker, and 27.3 parts of 25% aqueous ammonia (a ratio of 4 mol of ammonia to 1 mol of metal) was added dropwise with stirring, and then dropped into the toluene solution and reacted at 30 ° C. Proceeded. After leaving and separating, excess reducing agent and impurities are removed by taking out the aqueous phase, and distilled water is added several times to the toluene layer, washing and separation are repeated, and then dried to obtain gold nanoparticles 8. Obtained. The average particle diameter of the obtained gold nanoparticles 8 is 5 nm, the zeta potential (Aζ) of the toluene dispersion of the obtained gold nanoparticles 8 is 35.2 mV, and the standard deviation (Aζ _σ ) of the zeta potential distribution is 28. It was 3 mV.

Production Example 9 Production of Copper Nanoparticles 9 Except for changing the gold pentanoate of Production Example 8 to 26.6 parts of copper pentanoate and reducing agent to 292.3 parts of a 20% SUDH aqueous solution (4 mol times hydrazide group to 1 mol of metal). Produced copper nanoparticles 9 in the same manner as in Production Example 8. The average particle diameter of the obtained copper nanoparticles 1 is 7 nm, the zeta potential (Aζ) of the toluene dispersion of the obtained copper nanoparticles 9 is −13.4 mV, and the standard deviation (Aζ _σ ) 31 of the zeta potential distribution is 31. .8 mV.

Production Example 10 Production of Silver Nanoparticle 10 (for Comparative Example)
After 250.0 g of 40 mass% silver nitrate aqueous solution was taken in Kolben and diluted with 176.6 g of acetone, 11.2 g of Solsperse 24000 (manufactured by Nippon Lubrizol Co., Ltd.) was dissolved. After Solsperse 24000 was completely dissolved, 262.0 g of dimethylaminoethanol was added to obtain a bright and concentrated silver colloid solution. The obtained silver colloid solution was heated under reduced pressure to remove acetone. Since Solsperse 24000 is insoluble in water, the silver colloid protected by Solsperse 24000 was precipitated and precipitated as the amount of acetone decreased. The supernatant aqueous layer was removed by decantation, and the precipitate was washed with ion-exchanged water, and then completely dried to obtain a solid of silver nanoparticles 10. The average particle diameter of the obtained silver nanoparticles 8 is 7 nm, the zeta potential (Aζ) of the toluene dispersion of the obtained silver nanoparticles 10 is −14.9 mV, and the standard deviation (Aζ _σ ) of the zeta potential distribution 39 0.7 mV.

[Example 1]
Silver nanoparticles 2 were dispersed in toluene to obtain a dispersion 1 of metal nanoparticles having a concentration of 1.81%.
“Etocel 300 (manufactured by Nisshin Kasei Co., Ltd.)” as resin (C) was dissolved in toluene as the solvent (D) to obtain a resin solution 1 having a 7.5% concentration.
Dispersion liquid of the metal nanoparticles 1: 2.38 parts (including 0.043 parts of metal nanoparticles), reflector 1: 6 parts, resin solution 1: 3.84 parts (resin (C) is added in an amount of 0. Into 288 parts), toluene (10.56 parts) was added as a solvent (D) and stirred for 1 minute in a disper to obtain a glittering colored resin composition (solid content 19%).
2 g of the resulting glittering colored resin composition was dropped onto a PET film (100 μm manufactured by Toyobo Co., Ltd.), applied with an No. 15 applicator, and the coating film was sufficiently dried at room temperature (24 ° C.) to give a glitter. A sexually colored coating film was obtained. According to the methods described later, the color tone, color strength, hue uniformity, and gloss were evaluated.

[Examples 2 to 39]
As shown in Table 2, the glittering colored resin composition and the glittering coloration were the same as in Example 1 except that the types of the metal nanoparticles (A), the reflector (B), and the resin (C) were changed. A coating film was obtained and evaluated in the same manner.

[Comparative Examples 1-5]
Comparative Examples 1 to 5 use silver nanoparticles 1 and obtain a glittering colored resin composition and a glittering colored coating film in the same manner as in Example 1 except that the resins shown in Table 2 were used. Evaluation was performed in the same manner.

[Comparative Example 6]
Comparative Example 6 was obtained in the same manner as in Example 1 except that the silver nanoparticles 10 were used, and a brightly colored resin composition and a brightly colored coating film were obtained and evaluated in the same manner.

The reflectors (B) used in the examples and comparative examples are listed below.
The zeta potential (Bζ) is ZETA SIZER NANO ZSP manufactured by Malvern, the F (Ka) parameter is set to Huckel, and the zeta potential (Bζ) in a dispersion of toluene with a concentration of 0.01% by mass is set. It was measured. At this time, the measurement solution was adjusted to 0.01% by weight% concentration and measured.
Reflector 1: Toyo Aluminum Co., Ltd. 5620NS (Aluminum flakes with an average particle diameter of 19 μm dispersed in mineral spirit, a dispersion with a concentration of 71%, zeta potential (Bζ) of 31.7 mV)
Reflector 2: WXM5660 manufactured by Toyo Aluminum Co., Ltd. (aluminum flakes with an average particle size of 9 μm dispersed in mineral spirit, a dispersion with a concentration of 63%, zeta potential (Bζ) is −202.5 mV)
Reflector 3: PDM-20L manufactured by Topy Industries, Ltd. (synthetic mica, average particle size 20 μm, zeta potential (Bζ) is +52 mV)

Resins (C) used in Examples and Comparative Examples are listed below.
Resin 1: Cellulose resin, “Etocel 300 (manufactured by Nisshin Kasei Co., Ltd.)”
Resin 2: Acrylic resin, “Foret GS-1000 (manufactured by Soken Chemical Co., Ltd.)”
Resin 3: Urethane resin, “8UA-017 (Taisei Fine Chemical Co., Ltd.)”
Resin 4: Polyester resin 1, “Byron 200 (Toyobo Co., Ltd.)”

Color tone: Judged by visual color judgment and peak position of absorption spectrum.
Model: U-4100 spectrophotometer manufactured by Hitachi, Ltd.
Scan speed: 300 nm / min
Measurement range: 250-800nm

Color intensity: The appearance of the glittering colored coating film was visually evaluated.
(Double-circle): Exhibiting quite strong color development.
○: A strong color is exhibited.
Δ: Clearly colored.
X: Almost no coloration. (The color of the reflective metal itself)

Hue uniformity: The appearance of the glittering colored coating film was visually evaluated.
○: No hue unevenness was observed.
Δ: Slight color unevenness was observed.
×: Hue unevenness was observed.

Glossiness: The reflection glossiness of the glossy colored coating was visually evaluated.
○: A strong gloss was felt.
Δ: A glossy feeling was felt.
X: The glossiness was not felt.

As shown in Examples 1 to 39 in Table 1, in all Examples, good results were obtained in terms of color development, hue uniformity, and gloss.
As shown in Examples 1 to 7, it was confirmed that the color tone changed due to the difference in the content of the metal nanoparticles.
As shown in Examples 1-10, 13-16, 19-20, 23-24, 27-29, 31-34, 37.39, the sign of the zeta potential of the metal nanoparticles and the sign of the zeta potential of the reflector It was confirmed that the same sign indicates strong color development.
As shown in Examples 37 and 38, it was confirmed that the color tone changed due to the difference in the metal type.

On the other hand, as shown in Comparative Examples 1 to 6 in Table 1, good color development was not observed when the composition did not contain a resin or when the physical properties of the silver nanoparticles did not satisfy the following conditions.
(1) The absolute value of the zeta potential (Aζ) of the metal nanoparticles (A) is not less than the standard deviation (Aζ _σ ) of the zeta potential distribution, and the difference is not more than 70 mV.
(2) The absolute value of the zeta potential (Aζ) of the metal nanoparticles (A) is less than the standard deviation (Aζ _σ ) of the zeta potential distribution, and the difference is 20 mV or less.

  From the above, the glittering colored resin composition of the present invention and the glittering colored coating film obtained by a simple method such as applying and drying the same are in terms of color development intensity, hue uniformity, and gloss. Excellent high design properties can be provided, and further properties such as strong color development can be provided by controlling parameters such as the concentration of metal nanoparticles, metal species, zeta potential of metal nanoparticles, and the combination of metal nanoparticles and reflectors. be able to.

Claims (9)

A glittering colored resin composition comprising metal nanoparticles (A), a reflective material (B), a resin (C) and a solvent (D), wherein the glittering colored resin composition is (1) or (2) object.
(1) The absolute value of the zeta potential (Aζ) of the metal nanoparticles (A) is not less than the standard deviation (Aζ _σ ) of the zeta potential distribution, and the difference is not more than 70 mV.
(2) The absolute value of the zeta potential (Aζ) of the metal nanoparticles (A) is less than the standard deviation (Aζ _σ ) of the zeta potential distribution, and the difference is 20 mV or less. When the zeta potential (Aζ) of the metal nanoparticles (A) is positive, the zeta potential (Bζ) of the reflector (B) is positive,
Or
When the zeta potential (Aζ) of the metal nanoparticles (A) is negative, the zeta potential (Bζ) of the reflector (B) is negative.
The glittering colored resin composition according to claim 1.   The glittering colored resin composition according to claim 1 or 2, wherein the metal species of the metal nanoparticles (A) is at least one selected from the group consisting of gold, silver, copper and aluminum.   The glittering colored resin composition according to any one of claims 1 to 3, wherein the reflective material (B) is flaky, has an average particle diameter of 1 to 100 µm, and an average thickness of 0.01 to 1 µm.   The glittering colored resin composition according to any one of claims 1 to 4, wherein the reflective material (B) is aluminum.   A glittering colored article comprising a substrate (E) and a glittering colored coating film which is a dry coating film of the glittering colored resin composition described in any one of claims 1 to 5.   A method for producing a glittering colored article, wherein the substrate (E) is coated with the glittering colored resin composition according to any one of claims 1 to 5 and dried. A method for producing a glittering colored resin composition comprising metal nanoparticles (A), a reflector (B), a resin (C) and a solvent (D), wherein the glittering property is (1) or (2) A method for producing a colored resin composition.
(1) The absolute value of the zeta potential (Aζ) is equal to or greater than the standard deviation (Aζ _σ ) of the zeta potential distribution, and the difference between the dispersion of the metal nanoparticles (A) and the reflector (B) is 70 mV or less. The dispersion, resin (C) and solvent (D) are mixed.
(2) The dispersion of the metal nanoparticles (A), the absolute value of the zeta potential (Aζ) is less than the standard deviation (Aζ _σ ) of the zeta potential distribution, and the difference is 20 mV or less, and the reflector (B) The dispersion, resin (C) and solvent (D) are mixed. A dispersion of metal nanoparticles (A) having a positive zeta potential (Aζ) and a dispersion of a reflector (B) having a positive zeta potential (Bζ);
Or
A dispersion of metal nanoparticles (A) having a negative zeta potential (Aζ) and a dispersion of a reflector (B) having a negative zeta potential (Bζ) are mixed;
A method for producing the glittering colored resin composition according to claim 8.