JP2009091411A - Glitter pigment-containing composition, print and coated article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glitter pigment-containing composition capable of forming a bright layer which inhibits its color from being tinged with yellow, has high luminance, takes on a silver white tone and has brightness like sprinkled diamonds, and to provide a print, a coated article or the like including the bright layer. <P>SOLUTION: The glitter pigment-containing composition comprises a glitter pigment (A), at least one silver-free metallic pigment selected from the group consisting of a glitter pigment (B) comprising scale-like aluminum and a scale-like glitter pigment (C) in which an inorganic substrate is coated with titanium dioxide, and a vehicle, wherein the glitter pigment (A) includes a scale-like inorganic substrate and a silver-based alloy film covering the inorganic substrate and comprising silver and at least one noble metal selected from the group consisting of gold, palladium and platinum, a content of the noble metal being 0.1-2 at.%, provided that the summation of at.% of the silver and at.% of the noble metal is 100 at.%. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a glittering pigment-containing composition, and a printed material and a coated article including a glittering layer formed using the glittering pigment-containing composition.

  As an example of a glitter pigment, a metallic pigment in which a flaky substrate is coated with a metal layer is known.

  The metallic pigment has a characteristic that its surface reflects light and glitters, and is used as a material for paints, inks and the like. These glitter pigments give a unique appearance that is rich in change and excellent in cosmetics, in combination with the color tone of the substrate, on a coated product obtained by applying a paint or a printed product using ink.

  Therefore, glitter pigments are used by adding to inks such as paints, various printed materials or writing utensils used for coating automobiles, motorcycles, OA equipment, mobile phones, home appliances, etc. ing.

  For example, Patent Document 1 discloses a glitter pigment in which a metal film having a thickness of 50 to 200 mm is formed on the surface of glass flakes by a sputtering method. The metal coating is made of Au, Ag, Cu, Al, or an alloy thereof. The thickness of the metal coating is 50 to 200 mm.

  Patent Document 2 discloses a silver metallic pigment in which a powdery base material such as glass flakes and mica is coated with a silver alloy. The silver alloy contains 0.5 to 10% by weight of one or more selected from the group consisting of Al, Cr, Ni, Ti, and Mg. The coating layer made of the silver alloy is formed by physical vapor deposition.

  In Patent Document 3, a powdery base material such as glass flakes and mica is a silver alloy containing one or more selected from the group consisting of Al, Cr, Ni, Ti, and Mg, and Sn. Coated glitter pigments are disclosed. The coating layer made of the silver alloy is formed by physical vapor deposition.

  Patent Document 4 discloses a glittering cosmetic material containing scaly glittering particles having a smooth metal surface. The metal that forms the metal surface is a single metal of silver, gold, nickel, or aluminum, or an alloy thereof, and the particle matrix is glass flake particles, inorganic particles such as mica-like iron (III) oxide particles, Resin film powder, multilayer film powder, and the like.

Patent Document 5 discloses a glittering cosmetic material in which a film containing silver or gold is formed on a layered substrate. The coating contains rhodium, and the rhodium content in the coating is about 2% by weight or less. Suitable materials for the layered substrate are, for example, mica, talc, glass, kaolin.
JP-A-9-188830 JP-A-10-158540 JP-A-10-158541 JP 2001-270805 A Special table 2003-509530 gazette

  By the way, silver has a very high visible light reflectance. Therefore, the brightness of the glitter pigment in which the flaky substrate is coated with a film made of simple silver is high. However, the light on the short wavelength side (500 nm or less) of visible light has a lower reflectivity for silver than the light on the long wavelength side (more than 500 nm and 700 nm or less) of visible light. For this reason, there has been a problem that the coloring of the bright pigment is yellowish.

  In the present invention, a composition containing a glittering pigment that is capable of forming a glittering layer that is suppressed from being yellowish with respect to color development, has a high brightness, has a silver-white color tone, and has a brightness as if diamond is scattered. And the coating or printed matter etc. containing the said brightness layer are provided.

  The glitter pigment-containing composition of the present invention comprises a glitter pigment (A), a glitter pigment (B) made of scaly aluminum, and a scaly glitter pigment (C) in which an inorganic substrate is coated with titanium dioxide. At least one silver-free metallic pigment selected from the group consisting of: and a vehicle, wherein the glitter pigment (A) covers the inorganic substrate in the form of a scale, gold, palladium, and platinum And a silver-based alloy coating containing at least one noble metal selected from the group consisting of silver and silver, and the content of the noble metal is 0.1 to 2 atomic%. However, the sum of the atomic percent of silver and the atomic percent of the noble metal is 100 atomic percent.

  The printed matter of the present invention includes a glitter layer formed using the glitter pigment-containing composition of the present invention.

  The coated article of the present invention includes a glitter layer formed using the glitter pigment-containing composition of the present invention.

  In the present invention, a composition containing a glittering pigment that is capable of forming a glittering layer that is suppressed from being yellowish with respect to color development, has a high brightness, has a silver-white color tone, and has a brightness as if diamond is scattered. In addition, it is possible to provide a painted product or a printed product including the glitter layer.

  The present inventor has studied to suppress silver reflected light from becoming yellowish and whiten the silver reflected light. When heat is applied to the crystal structure of silver, lattice defects are formed by the diffusion of atoms. In a high humidity environment where the humidity is, for example, 80% RH (relative humidity) or higher, the diffusion is promoted even when the heating temperature is, for example, about 80 to 200 ° C., so that silver atoms move to the grain boundary and crystal grains grow. It is known to go. Even in a high humidity environment, crystal grains grow even when the heating temperature is as high as 300 ° C. or higher. As the crystal grains grow, the reflected light of silver becomes whiter. However, if the crystal grains become too large, silver aggregation occurs and the smoothness of the surface of the silver coating is impaired. As a result, the reflectance is reduced and the metallic luster is impaired.

  The temperature is measured using a thermocouple thermometer, and the humidity is measured using a ceramic sensor type hygrometer.

  The present inventor has found that the growth of silver crystal grains can be controlled to an appropriate level by adding a predetermined amount of a predetermined noble metal to a silver matrix and replacing silver atoms with noble metal atoms. Further, it is possible to provide a glittering pigment in which yellowing of reflected light is suppressed and deterioration of metallic luster is suppressed by increasing the reflectance with respect to light on the short wavelength side (500 nm or less) of visible light. did.

  Then, as the glitter pigment (A), a silver-white Ag-free metallic pigment, a glitter pigment (B) made of scale-like aluminum, and a scale-like glitter pigment in which titanium dioxide is coated on an inorganic substrate ( By using a glittering pigment-containing composition containing at least one pigment selected from the group consisting of C), the glittering layer is suppressed from being yellowish with respect to color development, has high brightness, and exhibits a silver-white color tone Made possible. Since the brightness pigment (A) and the Ag-free metallic pigment have different brightness from each other, the brightness layer containing them strongly exhibits brightness as if diamonds were scattered.

  The present inventor presumes that silver atoms are substituted with noble metal atoms, and the presence of the substituted noble metal atoms suppresses movement of silver atoms, thereby suppressing excessive growth of silver crystal grains. However, the present invention is not limited by this estimation.

  Incidentally, the atomic radius of silver is 1.44Å, and the crystal structure is a face-centered cubic lattice. On the other hand, the atomic radius of gold, palladium, and platinum is 1.37 to 1.5 Å, which is close to the atomic radius of silver. The crystal structures of gold, palladium, and platinum are all face-centered cubic lattices that are the same as silver. Therefore, gold, palladium, platinum, and silver are heated at a relatively low temperature (for example, a temperature lower than the melting point of the metal having the lowest melting point among these metals), thereby causing a crystal structure. A substitutional solid solution can be obtained without changing.

  Whether or not it is a substitutional solid solution can be confirmed by X-ray photoelectron spectroscopy (XPS) analysis. Specifically, it can be confirmed based on the chemical shift of the binding energy specific to each element.

  The glittering pigment-containing composition of the present invention may be a composition in which the solvent in the vehicle described later is composed of an organic solvent, or may be a composition in which the solvent in the vehicle is composed of water. Moreover, the paste-form composition which further contains lubricants, such as a mineral spirit, may be sufficient, and an aqueous emulsion may be sufficient.

  Applications of the glitter pigment-containing composition of the present invention include paints and inks. The glitter pigments (A) to (C) described in detail below all exhibit a silvery white color. Therefore, if the glitter pigment-containing composition of the present invention further contains a dye, for example, red, Not only primary colors such as blue, green, and black, but also lustrous pigment-containing compositions such as pastel colors whose color tone is difficult to adjust can be realized.

(Illuminating pigment (A))
Next, the glitter pigment (A) and the production method thereof will be described.

  As shown in FIG. 1, the glitter pigment (A) 200 includes a scaly inorganic base 20 and a silver-based alloy coating 21 covering the inorganic base 20. The silver-based alloy coating 21 contains at least one noble metal selected from the group consisting of gold, palladium, and platinum and silver.

  When the glitter pigment-containing composition of the present invention is an ink, the average thickness of the glitter pigment (A) is 0.3 to 2 μm because the surface finish (smoothness) of printing is good. Preferably there is. For the same reason, the average particle diameter of the glitter pigment (A) is preferably 50 μm or less. When the ink is a gravure ink or an offset ink, printability such as plate fog becomes good, and therefore the average particle diameter of the glitter pigment (A) is preferably an average particle diameter of 1 μm to 30 μm. The plate fog is a phenomenon in which the doctor blade cannot sufficiently remove the ink on the plate at the time of printing, and the ink is transferred to the printing medium and causes the printed matter to be stained. The average particle size of the glitter pigment (B) and the glitter pigment (C) described below is also preferably within the above range for the same reason.

  When the glittering pigment-containing composition of the present invention is a paint, the preferred average thickness and preferred average particle diameter of the glittering pigment (A) are as follows.

  For example, paint is circulated in a painting process for an automobile outer plate or the like. A filter for removing foreign substances is provided in the middle of the circulation line for circulating the paint. When a pigment having a large particle size is contained in the paint, the pigment is collected in the filter, and as a result, an increase in pressure loss in coating and a content of the pigment in the paint are reduced, which adversely affects the coating quality. There is little adverse effect on the coating quality due to this filtration, or the pigment is neatly arranged in the coating film without causing the pigment to protrude from the surface of the coating film, and the finish quality of the coating film is improved. For the reason, the average particle diameter of the glitter pigment (A) contained in such a paint is preferably 5 to 50 μm, and the average thickness is preferably 0.3 to 3 μm. The average particle size of the glitter pigment (B) and the glitter pigment (C) described below is also preferably within the above range for the same reason.

  Here, the average particle diameter of the glitter pigments (A) to (C) is a particle diameter (D50) measured by a laser diffraction particle size meter and corresponding to 50% of the cumulative volume of the particle size distribution.

  The average thickness of the glitter pigments (A) to (C) is a value obtained by measuring the thickness at the end face of 60 glitter pigments using an electron microscope and averaging them.

(Scale-like inorganic substrate)
Examples of the material for the scale-like inorganic substrate 20 include at least one selected from the group consisting of glass, mica, synthetic mica, silica, and alumina. Of these, glass is preferable because a smooth surface can be easily obtained.

  The shape of the scale-like inorganic substrate 20 varies depending on the intended use and is not particularly limited. In general, the average particle diameter is preferably 1 μm to 50 μm, and the average thickness is preferably 0.1 μm to 3 μm. If the average particle size is too large, the scale-like inorganic substrate 20 may be crushed during the preparation of the paint containing the glitter pigment (A). On the other hand, if the average particle size is too small, the main surface of the glitter pigment (A) is directed in a random direction in the coating film, and the reflected light emitted by the individual particles is weakened. For this reason, a glittering feeling will be impaired. When the average particle diameter is 1 μm to 50 μm, the glitter pigment (A) is suppressed from being crushed during the blending process, and the glitter feeling can be enhanced.

  The average particle diameter of the inorganic substrate 20 is a particle diameter (D50) measured by a laser diffraction particle size meter and corresponding to a volume accumulation of 50% of the particle size distribution.

  The average thickness of the inorganic substrate 20 is a value obtained by measuring the thickness of 100 inorganic substrates and averaging them. The thickness of each inorganic substrate is determined by measuring the optical path difference between direct light (light not affected by the phase object) and light transmitted through the inorganic substrate using an interference microscope.

  Although the manufacturing method of the flaky glass substrate which is an example of the flaky inorganic substrate 20 is not particularly limited, for example, a blow method is preferable. In the blow method, first, the raw material cullet is melted. The molten glass is continuously discharged from the circular slit, and at the same time, a gas such as air is blown from a blow nozzle provided inside the circular slit. As a result, the molten glass is pulled into a balloon shape while being inflated. A flaky glass substrate can be obtained by pulverizing the balloon-like glass.

  The scaly glass substrate produced by the blow method has a smooth surface and therefore reflects light well. It is preferable to adjust the paint using an example of a glitter pigment using the glass flake substrate, since a glitter layer having a high glitter feeling can be obtained. As a commercial item of such a scaly glass substrate, for example, a micro glass (registered trademark) glass flake (registered trademark) series (RCF-160, REF-160, RCF-015, REF, manufactured by Nippon Sheet Glass Co., Ltd.) -015).

(Silver alloy coating)
The silver-based alloy coating 21 contains silver and at least one noble metal selected from the group consisting of gold, palladium, and platinum. The content of noble metal is 0.1 to 2 atomic%. However, the sum of the atomic percent of silver in the silver-based alloy coating 21 and the atomic percent of noble metal in the silver-based alloy coating 21 is 100 atomic percent. When the noble metal content is less than 0.1 atomic%, the silver crystal grains become too large, and the growth of crystal grains cannot be suppressed to an appropriate level. On the other hand, when the content of the noble metal exceeds 2 atomic%, it is affected by the color of the noble metal itself. For example, when the noble metal contains gold, the silver-based alloy coating is yellowish, when the noble metal contains palladium, the silver-based alloy coating is reddish, and when the noble metal contains platinum, the silver-based alloy coating Has a blue tint. The reflection color tone can be adjusted by changing the type and content of the noble metal. However, when the content of the noble metal is 0.2 to 1.5 atomic%, the silver-white color and the brightness are higher. A silver-based alloy coating is more preferable.

  The silver-based alloy coating 21 is preferably, for example, a silver-gold alloy, a silver-palladium alloy, a silver-platinum alloy, a silver-gold-palladium alloy, a silver-platinum-palladium alloy, or a silver-gold-platinum alloy.

  The film thickness of the silver-based alloy coating 21 is preferably 25 to 65 nm. If the film thickness of the silver-based alloy coating 21 is 25 to 65 nm, a sufficient amount of reflected light can be obtained.

  In addition, the average thickness (n = 10) of the silver-based alloy coating film was measured by a field emission scanning electron microscope FE-SEM (Field Emission Scanning Electron Microscope) (S-4800, manufactured by Hitachi High-Technologies Corporation). It can be measured from the cross section of the functional pigment.

  Next, a method for forming a silver alloy film will be described.

  After forming the first coating containing silver and the second coating containing the noble metal and silver in this order, the first coating and the second coating are heated at a predetermined temperature for a predetermined time. By this heating, the noble metal contained in the second coating is diffused by heat, reaches the first coating, and also diffuses into the first coating. The first film contains silver, but may be formed substantially of only silver, for example. The second film contains at least one kind of noble metal selected from the group consisting of gold, palladium, and platinum, and silver, but may be formed substantially only from the noble metal and silver, for example.

  By the heating, for example, the interface between the first film and the second film disappears, and the first film and the second film are integrated to form the silver-based alloy film 21. According to this method, for example, it is possible to easily increase the concentration of noble metal on the outer surface of the silver-based alloy coating 21 (the surface opposite to the surface on the inorganic substrate side) and in the vicinity thereof.

  The temperature of the atmosphere for heating is preferably 350 to 600 ° C., for example, from the viewpoint of enabling formation of a good substitutional solid solution and obtaining a bright pigment with high brightness. About heating time, what is necessary is just to determine suitably according to the temperature of the said atmosphere, but it is preferable in it being 0.1 to 10 hours normally.

  The formation method of a 1st film and a 2nd film is not specifically limited. Examples of methods for forming these films include sputtering, CVD, electroless (chemical) plating, and the like. Among these, electroless plating is preferable because uniform film formation is easy. .

  The thickness of the second coating is thinner than that of the first coating and is preferably 1 to 20 nm. Thus, when the thickness of the second coating is thin, a decrease in luminance due to aggregation of silver can be effectively suppressed by adding a small amount of a noble metal that is more expensive than silver. The thickness of the first coating is preferably determined so that the sum of the thickness of the first coating and the thickness of the second coating is, for example, 25 to 65 nm. If the sum of the thickness of the first coating and the thickness of the second coating is 25 to 65 nm, a sufficient amount of reflected light can be obtained.

In the electroless plating solution, examples of the metal raw material include the following compounds.
(1) Silver raw material: Silver nitrate (2) Gold raw material: Gold (I) sodium sulfite, Gold chloride (III) acid [Tetrachlorogold (III) acid tetrahydrate]
(3) Palladium raw material: diamino palladium nitrite, palladium (II) chloride, palladium nitrate (II), tetraammine palladium (II) dichloride (4) Platinum raw material: platinum chloride (IV) acid [hexachloroplatinum (IV) acid hexahydrate Japanese], dinitrodiammineplatinum (II), tetraamminedichloroplatinum (II)
In addition, it is preferable to avoid the use of a cyanide compound from the viewpoint of safety.

  The method for forming the silver-based alloy coating 21 is not limited to the above method. For example, after forming the single film A containing the noble metal and silver, the film is heated in a predetermined temperature atmosphere for a predetermined time, for example, in an atmosphere of 350 to 600 ° C. for 0.1 to 10 hours. By doing so, the silver-based alloy coating 21 may be formed. There is no restriction | limiting in particular also about the formation method of the film A, It may be the same as the formation method of a 1st film and a 2nd film.

  The noble metal does not necessarily need to be uniformly dispersed in the silver-based alloy coating 21, and for example, as the concentration of the noble metal approaches the outer surface of the silver-based alloy coating 21 (the surface opposite to the surface on the inorganic substrate side). The noble metal may be contained in the silver-based alloy coating 21 with a concentration distribution that increases. If the concentration of the noble metal increases as it approaches the outer surface of the silver-based alloy coating 21 (opposite the surface on the inorganic substrate side), the addition of a small amount of noble metal effectively reduces the luminance caused by the aggregation of silver. Can be suppressed.

(Bright pigment (B))
Next, the luster pigment (B) which consists of scale-like aluminum, and its manufacturing method are demonstrated.

  The glitter pigment (B) made of aluminum is usually produced by pulverizing aluminum powder (for example, atomized powder) with a pulverizer such as a ball mill, vibration mill, planetary mill, stamp mill, or attritor. In grinding aluminum powder, fatty acids such as oleic acid and stearic acid are usually used as grinding aids. The grinding aid works as a lubricant when grinding the aluminum powder, and adsorbs to the surface of each glitter pigment (B) to prevent secondary aggregation of particles. Further, the grinding aid contributes to the improvement of dispersibility, redispersibility, dispersion stability, etc. of the glitter pigment (B) in the vehicle.

  The average particle diameter of the glitter pigment (B) is not particularly limited, but it can effectively suppress aggregation of the glitter pigment (B) and is excellent in handleability in the production process. It is preferable that the thickness is 5 μm or more. In addition, the average particle diameter of the glitter pigment (B) is preferably 40 μm or less because the flatness of the coating film surface is enhanced when the glitter pigment-containing composition of the present invention is used as a paint. More preferably, it is 30 μm or less.

  The shape factor (referred to herein as “aspect ratio”) obtained by dividing the average particle diameter by the average thickness of the glitter pigment (B) is 5 or more from the viewpoint of securing a high glitter feeling. Preferably, it is more preferably 15 or more. The aspect ratio is preferably 1,000 or less and more preferably 500 or less from the viewpoint of enhancing the stability of the color tone by sufficiently securing the mechanical strength of the glitter pigment (B).

  The grinding aid may be attached to the surface of the glitter pigment (B). Examples of the grinding aid include unsaturated fatty acids, and examples of the unsaturated fatty acid include oleic acid, linoleic acid, linolenic acid, ricinoleic acid, elaidic acid, zomarinic acid, gadoleic acid, and erucic acid. It is done.

(Bright pigment (C))
The glitter pigment (C) comprises a scaly inorganic base and a titanium dioxide layer covering the inorganic base.

(Scale-like inorganic substrate)
The material of the scale-like inorganic substrate constituting the glitter pigment (C) may be the same as the scale-like inorganic substrate constituting the glitter pigment (A). For example, glass, mica, synthetic mica, silica And at least one selected from the group consisting of alumina. Of these, glass is preferable because a smooth surface can be easily obtained.

(Titanium dioxide layer)
The titanium dioxide layer may be substantially made of rutile titanium dioxide. Titanium dioxide has three crystal types, anatase type, brookite type, and rutile type. Among them, the anatase type and the rutile type are industrially produced. Anatase type titanium dioxide has a strong photocatalytic activity. On the other hand, rutile type titanium dioxide has a photocatalytic activity of about 1/10 compared with anatase type titanium dioxide. Therefore, rutile type titanium dioxide is more suitable as a pigment than anatase type titanium dioxide and brookite type titanium dioxide from the viewpoint of preventing discoloration and decomposition. In addition, rutile titanium dioxide has a higher refractive index than anatase titanium dioxide and can easily form a dense and uniform film. Therefore, when the titanium dioxide layer is made of rutile titanium dioxide, it has a higher brightness. Layers can be formed.

  As a method for producing rutile type titanium dioxide, as disclosed in JP 2001-31421 A, a rutile type is obtained by neutralization reaction from a titanium-containing solution under conditions of a temperature of 55 to 85 ° C. and a pH of 1.3 or less. A method for depositing titanium dioxide can be exemplified. When this method is used, heating for crystal transition is essentially unnecessary, and rutile titanium dioxide can be easily fixed to a substrate having low heat resistance.

  The average thickness of the titanium dioxide layer 20 is preferably 30 nm to 80 nm, for example, since a silver-white bright pigment (C) is obtained. The thickness of the titanium dioxide layer can be measured by the same method as the thickness of the silver alloy-containing coating constituting the glitter pigment (A).

  Commercially available products of the glitter pigment (C) include, for example, Metashine (registered trademark) RC series (MC5090RS, MC1080RS, MC1040RS, MC1030RS, MC1020RS) available from Nippon Sheet Glass.

  The glitter pigment-containing composition of the present invention comprises the glitter pigment (A), at least one silver-free metallic pigment selected from the group consisting of the glitter pigment (B) and the glitter pigment (C), The vehicle described later is obtained by stirring and mixing by a conventionally known method. Stirring and mixing can be performed using, for example, a mixing and dispersing machine.

  The total content of the glitter pigment (A) and the silver-free metallic pigment in the glitter pigment-containing composition of the present invention is the mass of solids in the vehicle (components other than volatile components in the vehicle), glitter When the total of the mass of the conductive pigment (A) and the mass of the silver free metallic pigment is 100, a bright layer having a high glitter feeling can be obtained without impairing the color tone of the substrate. %, Preferably 1 to 15% by mass.

  The ratio of the mass of the glitter pigment (A) to the mass of the silver-free metallic pigment (the mass of the glitter pigment (A) / the mass of the silver-free metallic pigment) increases the brightness and gives a stronger diamond shine. For reasons, it is preferably (1/9) to (7/3), and more preferably (2/8) to (5/5).

(Vehicle)
Resin and solvent are mentioned as a main component of the vehicle contained in the luster pigment containing composition of this invention.

  As the resin, for example, a resin having a carboxyl group (hereinafter also referred to as a carboxyl group-containing resin) is preferable. When the vehicle of the glittering pigment-containing composition of the present invention contains a carboxyl group-containing resin, it has high hardness, excellent wear resistance and chemical resistance, and good adhesion to an adherend. A bright layer can be formed.

  Examples of the carboxyl group-containing resin include acrylic resin (homopolymer), (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer, vinyl acetate- (meth) acrylic acid copolymer, Examples thereof include carboxyl group-containing acrylic polymers such as (meth) acrylic acid ester- (meth) acrylic acid copolymers and styrene- (meth) acrylic acid copolymers. Other examples include styrene-butadiene copolymers (for example, styrene / butadiene latexes having carboxyl groups introduced), styrene-maleic anhydride copolymers, carboxyl group-containing urethane resins, carboxyl group-containing polyester resins, carboxyls. Examples thereof include a group-containing alkyd resin and a carboxyl group-containing polyvinyl alcohol resin. Still other examples include natural resins such as carboxymethylcellulose. Two-component resins such as acrylic-modified polyester, acrylic-modified polyurethane, and acrylic-modified epoxy resin can also be used. Hereinafter, the carboxyl group-containing acrylic acid polymer and the acrylic-modified epoxy resin will be described in detail.

(Carboxyl group-containing acrylic acid polymer)
A carboxyl group-containing acrylic polymer is obtained, for example, by copolymerizing an acrylic ester with an aromatic vinyl or vinyl ester. The carboxyl group-containing acrylic acid polymer is, for example, 0.2 to 30% by mass of a structural unit derived from a monomer (a monomer having a carboxyl group (the monomer may be a salt)). It is preferably contained, and more preferably 1 to 20% by mass. The acid value of the carboxyl group-containing acrylic acid polymer is preferably 2 to 200 mg · KOH / g, and more preferably 10 to 100 mg · KOH / g.

  The weight average molecular weight of the carboxyl group-containing acrylic acid polymer is, for example, preferably from 1,000 to 1,000,000, more preferably from 3,000 to 500,000, and even more preferably from 5,000 to 100,000. Moreover, although the glass transition temperature of a carboxyl group-containing acrylic acid-type polymer changes according to the use of a resin composition, generally -60 degreeC-50 degreeC is preferable.

  When the use of the glitter pigment-containing composition of the present invention is a paint or a printing ink, the glitter pigment-containing composition is a carboxyl group-containing acrylic polymer having a glass transition temperature of -10 ° C to 50 ° C. It is preferable to include. When the use of the glitter pigment-containing composition of the present invention is an adhesive, the glitter pigment-containing composition contains a carboxyl group-containing acrylic acid polymer having a glass transition temperature of −20 ° C. to 30 ° C. preferable.

(Acrylic modified epoxy resin)
The acrylic-modified epoxy resin is obtained by introducing an acrylic vinyl copolymer into a main chain epoxy resin, and having a carboxyl group bonded to the vinyl copolymer.

  The acrylic-modified epoxy resin containing a carboxyl group can be obtained by esterifying a vinyl copolymer and an epoxy resin in a hydrophilic organic solvent in the presence of a basic compound. It does not specifically limit as an ethylenically unsaturated carboxylic acid monomer which is a raw material of a vinyl copolymer, For example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid etc. are mentioned. Two or more of these may be used. The method for polymerizing the monomer component is not particularly limited, and for example, polymerization may be performed using a normal radical polymerization initiator such as azobisisobutyronitrile or benzoyl peroxide.

  The epoxy resin is preferably one or more selected from the group consisting of bisphenol F type, bisphenol A type and hydrogenated bisphenol A type epoxy resin, and has an average of 1.1 to 2.0 epoxy groups in one molecule. And having a number average molecular weight of 900 or more is preferable.

  As a weight average molecular weight of an acrylic modified epoxy resin, 2000-100000 are preferable, for example. If the weight average molecular weight is 2000 to 100,000, the emulsion dispersibility is good, and gelation hardly occurs during the reaction between the acrylic vinyl copolymer and the epoxy resin.

  When the solvent contained in the vehicle is an organic solvent, examples of the organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, n-butanol, etc.), aliphatic hydrocarbons (eg, hexane, heptane, etc.). , Octane, etc.), alicyclic hydrocarbons (eg, cyclohexane, etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, etc.), esters (eg, ethyl acetate, n-butyl acetate, isobutyl acetate, N-butyl acetate, etc.), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ethers (eg, diethyl ether, dioxane, tetrahydrofuran, etc.), cellsolves (eg, methyl cellosolve (ethylene glycol monomethyl ether)) , Ethyl cell sol , Propylcellosolve, butylcellosolve, phenylcellosolve, benzylcellosolve, etc.), carbitols (eg, diethylene glycol monomethyl ether, carbitol (diethylene glycol monoethyl ether), diethylene glycol monopropyl ether, etc.), or a mixed solvent thereof Etc. can be used.

  When the solvent contained in the vehicle is water, the resin further dissolves in the water because the vehicle further contains an alkali. Examples of the alkali include organic bases such as aliphatic amines (for example, trimethylamine, triethylamine, and ethylenediamine); alkanolamines such as ethanolamine, diethanolamine, dimethylethanolamine, and triethanolamine; heterocyclic amines such as morpholine; ammonia; Examples include inorganic bases such as metal compounds (sodium hydroxide, potassium hydroxide, etc.). Of these alkalis, ammonia, diethanolamine, dimethylethanolamine, and triethanolamine are preferred.

  It is desirable that the acidic group (for example, carboxyl group) contained in the resin (for example, carboxyl group-containing acrylic acid polymer) is neutralized with a base to such an extent that the resin can be dispersed in water. The proportion of acidic groups to be neutralized is preferably about 50% of all acidic groups. For example, when the total number of moles of acidic groups contained in the resin is 1, neutralization is performed using an amine having a mole number of 0.4 to 2.0 times, preferably 0.6 to 1.4 times. Good.

  Aqueous emulsions can be prepared by conventional methods. For example, a method of dispersing the carboxyl group-containing acrylic acid polymer in water by neutralizing a part of the carboxyl group in the carboxyl group-containing acrylic acid polymer with a base can be mentioned. The aqueous emulsion may be prepared by an emulsion polymerization method. In the emulsion polymerization, a conventional emulsifier (for example, anionic surfactant, nonionic surfactant, protective colloid such as polyvinyl alcohol or water-soluble polymer) may be used. The pH of the aqueous emulsion may be adjusted using a pH adjuster.

  The concentration of the resin in the vehicle is not particularly limited. For example, the total amount of the glitter pigment-containing composition is preferably 10 to 70% by mass, and more preferably 25 to 50% by mass.

(Crosslinking curing agent)
The vehicle constituting the glittering pigment-containing composition of the present invention may further contain a crosslinking curing agent. An amino resin and / or a polyisocyanate compound can be used as the crosslinking curing agent. When the resin constituting the vehicle has a hydroxyl group, the hydroxyl group reacts with a crosslinking agent such as an amino resin or a polyisocyanate compound to cure the resin. The amino resin and / or polyisocyanate compound also undergoes a crosslinking reaction with a carbosyl group having an active hydrogen in addition to a hydroxyl group, an amino group, and the like.

  Examples of the amino resin as an example of the crosslinking curing agent include melamine resins such as alkyl etherified melamine resins, benzoguanamine resins such as alkyl etherified benzoguanamine resins, and urea resins such as alkyl etherified urea resins. Among these, melamine resin is preferable. Specific examples of the melamine resin include dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, and hexamethylol melamine. Further, as amino resins, alkyl ethers (methyl ether, ethyl ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether, etc.), urea-formamide condensates, urea-melamine condensates of these melamine resins may be used. Good. Two or more of these amino resins may be used in combination.

  The amino resin content is preferably set so that, for example, the mass ratio of the resin (solid content) and the amino resin (solid content) constituting the vehicle is 95/5 to 60/40. More preferably, it is set to be / 15 to 65/35. If it does in this way, high intensity | strength and high corrosion resistance will be obtained about the coating film formed by apply | coating a coating material.

  As a polyisocyanate compound which is an example of a crosslinking curing agent, for example, a blocked polyisocyanate compound having a structure in which an isocyanate group is masked with a blocking agent is suitable. Examples of the polyisocyanate compound include HDI (hexamethylene diisocyanate, etc.), TDI (tolylene diisocyanate, etc.), XDI (xylylene diisocyanate, etc.), MDI (diphenylmethane diisocyanate, etc.) and the like. Examples of the blocking agent include oxime and lactam.

  As the content of the polyisocyanate compound, when the polyisocyanate compound is a blocked polyisocyanate compound, the molar ratio of the hydroxyl group of the resin constituting the vehicle to the deblocked regenerated isocyanate group of the polyisocyanate compound ( The number of moles of hydroxyl groups / number of moles of regenerated isocyanate groups is preferably 100/20 to 100/150.

  In addition, the vehicle of the glittering pigment-containing composition of the present invention includes other thermoplastic resins (for example, acrylic resins not containing carboxyl groups, polyester resins, etc.), thermosetting resins (for example, urethane), depending on the application. Resins, amino resins, etc.), stabilizers such as antioxidants, UV absorbers, heat stabilizers, etc., viscosity modifiers such as plasticizers, antistatic agents, dispersants, anti-skinning agents, thickeners, flattening Additives such as additives, sagging inhibitors, antifungal agents, preservatives, fillers, dyes and pigments may be included.

(Painting method, printing method)
The glitter pigment-containing composition of the present invention is coated or printed on an object to be coated or printed, and then heated and dried as necessary to form a glitter layer.

  Although there is no restriction | limiting in particular as an application method, The usual method etc. which used spray coating, roll coating, knife coating, bar coater coating, dip coating, a brush, etc. are mentioned. Examples of the printing method include lithographic offset printing, stencil screen printing, intaglio flexographic printing, and gravure printing.

  The thickness of the bright layer varies depending on the type of the object to be coated or the object to be printed, but is preferably 0.5 μm to 100 μm, more preferably 1 μm to 50 μm, for example, 1 μm to 30 μm. Further preferred.

  Note that the average thickness of the bright layer is a value measured using a micrometer. Specifically, the average thickness of the glitter layer is the average thickness (n = 5) of the painted object or printed object in which the glitter layer is formed on the painted object or the printed object, and the average of the painted object or the printed object. It calculates | requires from the difference of average thickness (n = 5).

  The temperature of the atmosphere in which the bright pigment-containing composition is dried or cured is, for example, preferably 10 ° C to 200 ° C, more preferably 20 ° C to 150 ° C, and further preferably 50 ° C to 120 ° C. .

(Painted material)
As a specific example of the coated object of the present invention, as shown in FIG. 2, for example, an outer plate 1 that is an exterior of an automobile, a radiator grill 2, a side molding 3, a door mirror 4, a back panel 5, a bumper 9, an emblem 10, The tire wheel cover 13 etc. are mentioned.

  Next, an example of the coated product of the present invention will be described using an outer plate as an example.

  As shown in FIG. 3, the outer plate has an undercoat portion 15 and an overcoat portion 16 formed in this order on one main surface of a steel plate 14. The undercoat portion 15 includes a chemical conversion treatment layer 15a, a cationic electrodeposition layer 15b, and an intermediate coating layer 15c in this order from the steel plate 14 side. The top coat portion 16 includes a glitter layer 16a and a top clear layer 16b formed in this order from the steel plate 14 side using the glitter pigment-containing composition of the present invention.

  Since an example of the coated product of the present invention includes the glitter layer 16a formed using the glitter pigment-containing composition of the present invention, yellowing of the color development is suppressed, brightness is high, and silver white In addition, it has a shine like that of diamonds.

  In the present invention, the materials and forming methods for forming the chemical conversion treatment layer 15a, the cationic electrodeposition layer 15b, the intermediate coating layer 15c, and the top clear layer 16b are not particularly limited, and are the same as those conventionally known. For example, the following may be mentioned as examples.

  The chemical conversion treatment layer 15 a is provided to prevent corrosion of the steel plate 14. The chemical conversion treatment layer 15a is made of, for example, a zinc phosphate coating.

  The cationic electrodeposition layer 15b improves the corrosion resistance of the steel sheet 14, improves the stability of the layer formed above the cationic electrodeposition layer 15b, and is formed above the cationic electrodeposition layer 15b. Provided to facilitate layer formation. The cationic electrodeposition layer 15b is, for example, a cured coating film containing an acrylic / urethane resin.

  The intermediate coating layer 15c is provided in order to improve the adhesion between the lower layer and the upper layer than the intermediate coating layer 15c and to improve the chipping resistance of the layer above the intermediate coating layer 15c. The intermediate coating layer 15c is made of, for example, a cured coating film containing an acrylic / melamine resin.

  The top clear layer 16b is provided in order to give a glossy appearance and to improve the antifouling property. The top clear layer 16b is made of, for example, a cured coating film containing an acrylic / melamine resin.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples.

1. Preparation of pigments Pigments (1) to (8) were prepared as follows. The pigments (1) to (5) correspond to the glitter pigment (A), the pigment (7) corresponds to the glitter pigment (C), and the pigment (8) corresponds to the glitter pigment (B). . The pigment (6) is not any of the glitter pigments (A) to (C).

[Pigment (1)]
As in the example shown in FIG. 1, the pigment (1) has a structure in which a scaly glass base is covered with a silver-based alloy coating. The silver-based alloy coating is made of a silver-gold-palladium alloy. This pigment (1) was prepared as follows.

  <Preparation of scale-like glass substrate> A scale-like glass substrate having an average particle diameter of 20 μm and an average thickness of 1.3 μm was prepared. The glass flake substrate is a glass piece molded by the balloon method using molten glass as a material, pulverized with a pulverizer, and the pulverized glass substrate is classified with a vibration sieve, an ultrasonic sieve and an airflow classifier. I got it.

  <Pretreatment> Next, 0.7 g of stannous chloride is added to 1 L of pure water and dissolved, and further dilute hydrochloric acid is added, and a pretreatment solution for electroless plating having a pH of 2.0 to 2.2. Got. After adding 100 g of the glass flake substrate to the pretreatment liquid, the glass flake substrate was taken out and washed with water. By repeating this treatment several times, the scaly glass substrate was pretreated.

  <Formation of silver coating> Next, a silver coating (first coating) was formed on the pre-treated scaly glass substrate by the electroless plating method as follows. First, 100 g of 25% by mass ammonia water as a complexing agent, 10 g of sodium hydroxide as a pH adjusting agent, and 30 g of silver nitrate as a silver raw material are added to 2 L of pure water, and these are stirred while heating to 30 ° C. Liquid A was obtained. On the other hand, 30 g of glucose as a reducing agent was added to 1 L of pure water to obtain a butter sugar solution. A pre-treated scaly glass substrate was added to this solution and stirred to obtain a plating solution B.

  Next, the plating solution B was added to the plating solution A, and these were stirred for 20 minutes to deposit silver on the surface of the scaly glass substrate by an electroless plating reaction to form a silver coating. After the silver coating was formed, it was confirmed by ICP emission spectroscopic analysis that 25% of the charged silver remained in the mixed solution (plating solution) of the plating solution A and the plating solution B.

  <Formation of Silver-Gold-Palladium Alloy Film> Next, a silver-gold-palladium alloy film (second film) was formed on the silver film by the electroless plating method as described below.

  The plating solution containing the glass flake substrate coated with a silver coating is prepared by adding 2.5 g of a sodium gold sulfite aqueous solution (concentration 50 g / L) as a gold raw material and a diamino palladium nitrite aqueous solution (concentration 1.0 mass%) as a palladium raw material. ) 8.2 g was added, and 55 ml of a sodium L-ascorbate aqueous solution (concentration 3% by mass) was added as a reducing agent. Subsequently, these were stirred for 20 minutes while raising the temperature to 50 ° C. to form a silver-gold-palladium alloy film on the silver film.

  Subsequently, filtration was performed, and the scaly glass substrate covered with the silver coating and the silver-gold-palladium alloy coating was washed with water several times, and then dried at 180 ° C. (silver coating thickness: 40 nm, silver − Gold-palladium alloy film thickness: about 10 nm). Finally, the scaly glass substrate covered with the silver coating and the silver-gold-palladium alloy coating was subjected to heat treatment at 450 ° C. for 2 hours using an electric muffle furnace. A gold atom and a palladium atom were thermally diffused in the silver coating to obtain a pigment (1). The pigment (1) had an average particle diameter of 25 μm, an average thickness of 1.4 μm, and exhibited a silver-white metallic luster.

  The atomic% of each metal, converted from the results of analysis by ICP emission spectroscopy, was 99.5 atomic% for silver, 0.4 atomic% for gold, and 0.1 atomic% for palladium. As a result of secondary ion mass spectrometry, gold and palladium were uniformly distributed in the silver from the surface of the pigment to the surface of the scaly glass substrate.

[Pigment (2)]
As in the example shown in FIG. 1, the pigment (2) has a structure in which a scaly glass base is covered with a silver-based alloy coating. The silver alloy film is made of a silver-platinum alloy.

  Instead of the gold raw material and the palladium raw material, 15 g of hexachloroplatinic acid hexahydrate (concentration 1.0%) was used as the platinum raw material, and hydrazine (50 mass) was used instead of the sodium L-ascorbate aqueous solution (concentration 3 mass%). %) Was used as a reducing agent, except that Pigment (2) was prepared in the same manner as Pigment (1). The pigment (2) had an average particle diameter of 25 μm, an average thickness of 1.4 μm, and exhibited a silver-white metallic luster.

  The atomic% of each metal converted from the result of the analysis by ICP emission spectroscopy was 99.8 atomic% for silver and 0.2 atomic% for platinum. As a result of secondary ion mass spectrometry, platinum was uniformly distributed in the silver from the surface of the pigment (2) to the surface of the scaly glass substrate.

[Pigment (3)]
The pigment (3) has a structure in which a scaly glass substrate is coated with a silver-based alloy coating, as in the example shown in FIG. The silver-based alloy coating is made of a silver-gold alloy.

  Pigment (3) was produced by the same method as the production method of pigment (1) except that the palladium raw material was not added to the plating solution containing the scaly glass substrate coated with the silver coating. The pigment (3) had an average particle size of 35 μm, an average thickness of 1.3 μm, and exhibited a silver-white metallic luster.

  The atomic% of each metal, converted from the results of analysis by ICP emission spectroscopy, was 99.6 atomic% for silver and 0.4 atomic% for gold. As a result of secondary ion mass spectrometry, gold was uniformly distributed in the silver from the surface of the pigment (3) to the surface of the scaly glass substrate.

[Pigment (4)]
The pigment (4) has a structure in which a scaly glass substrate is covered with a silver-based alloy coating, as in the example shown in FIG. The silver-based alloy coating is made of a silver-gold-palladium alloy. The pigment (4) is the same as the pigment (1) except that the atomic percent of gold and palladium is different.

  The amount of sodium gold sulfite aqueous solution (concentration 50 g / L) used as a gold raw material was 7.5 g, and the amount of diamino palladium nitrite aqueous solution (concentration 1.0 mass%) used as a palladium raw material was 25 g. Pigment (4) was prepared in the same manner as in preparation of pigment (1) except that the amount of sodium L-ascorbate aqueous solution (concentration: 3% by mass) used as the agent was 165 ml. The pigment (4) had an average particle diameter of 35 μm, an average thickness of 1.3 μm, and exhibited a silver-white metallic luster.

  The atomic% of each metal, converted from the results of analysis by ICP emission spectroscopy, was 98.5 atomic% for silver, 1.2 atomic% for gold, and 0.3 atomic% for palladium. As a result of secondary ion mass spectrometry, gold was uniformly distributed in the silver from the surface of the pigment (4) to the surface of the scaly glass substrate.

[Pigment (5)]
The pigment (5) has a structure in which a scaly glass substrate is covered with a silver-based alloy coating, as in the example shown in FIG. The silver-based alloy coating is made of a silver-gold alloy. The pigment (5) is the same as the pigment (3) except that the atomic% of gold is different.

  Other than the addition amount of the sodium gold sulfite aqueous solution (concentration 50 g / L) used as the gold raw material was 1.3 g and the addition amount of the sodium L-ascorbate aqueous solution (concentration 3 mass%) used as the reducing agent was 28 ml. Prepared pigment (5) in the same manner as in preparation of pigment (3). The pigment (5) had an average particle diameter of 35 μm, an average thickness of 1.3 μm, and exhibited a silver-white metallic luster.

  The atomic% of each metal, converted from the result of analysis by ICP emission spectroscopy, was 99.8 atomic% for silver and 0.2 atomic% for gold. As a result of secondary ion mass spectrometry, gold was uniformly distributed in the silver from the surface of the pigment (5) to the surface of the scaly glass substrate.

[Pigment (6)]
The pigment (6) is Metashine (registered trademark) ME2025PS manufactured by Nippon Sheet Glass Co., Ltd., which is coated with silver and has a high brightness and a metallic luster. This pigment (6) has an average particle size of 23 μm, an average thickness of 1.4 μm, an adhesion amount of silver of about 24% by mass, and exhibits a high brightness metallic luster with yellowing.

[Pigment (7)]
As the pigment (7), Metashine (registered trademark) MC1020RS manufactured by Nippon Sheet Glass Co., Ltd. was used as the pigment (7) which is coated with rutile titanium dioxide and exhibits a white color. This pigment (7) has an average particle diameter of 20 μm, an average thickness of 1.6 μm, an adhesion amount of rutile titanium dioxide of about 7% by mass, and exhibits a white gloss with a complementary yellow color.

[Pigment (8)]
Pigment (8) was 153.8 g of aluminum flakes exhibiting metallic luster (Alpaste (registered trademark) 7675NS, Toyo Aluminum Co., Ltd., solid content 65 mass%, average thickness of aluminum flakes 0.3 μm)) (100 g as aluminum) Was washed with mineral spirits and filtered to obtain a paste containing aluminum flakes (solid content: 60% by mass). 167 g of the obtained paste and 600 g of mineral spirit were put into a 1 L separable flask, and these were stirred while introducing nitrogen gas, and the temperature in the system was raised to 80 ° C. Next, 0.4 g of acrylic acid, 8 g of epoxidized polybutadiene, 10 g of trimethylolpropane triacrylate, 3.6 g of divinylbenzene, and 0.75 g of azobisisobutyronitrile are placed in the separable flask, and these are placed at 80 ° C. For 6 hours. After completion of the reaction, the resulting slurry was filtered to obtain a paste containing aluminum flakes coated with a resin coating (solid content 60 mass%, flake average particle diameter 14 μm, flake average thickness 1.0 μm). The thickness of the resin film was 0.3 μm.

<Preparation of paint sample>
An appropriate amount of thinner is added to the following components a to c, and the mixture is mixed using a stirrer so that the viscosity becomes 13 Pa · s (Ford Cup No. 4/20 ° C. manufactured by Yasuda Seiki Seisakusho Co., Ltd.). A containing composition was obtained. This glittering paint is applied to a substrate (D-7, intermediate coating color N = 6.0, manufactured by Nippon Route Service Co., Ltd.) using a spray gun (W-100, manufactured by Anest Iwata Corporation). (Uncured) was formed.

(Component a) Acrylic resin 78% by mass,
(Product name “ACRYDEC A-322” manufactured by Dainippon Ink and Chemicals, Inc.)
(Component b) Butylated melamine resin 16% by mass,
(Product name "Super Becamine L-117-60" manufactured by Dainippon Ink & Chemicals, Inc.)
(Component c) 6% by mass of one or more pigments selected from pigments (1) to (8),

  Next, acrylic resin (product name “Acrydec A-345” (Dainippon Ink Chemical Co., Ltd.)) 72% by mass, butylated melamine resin (product name “Super Becamine L-117-60” (Dainippon Ink, Ltd.) Chemical Industry Co., Ltd.)) 28% by mass, thinner is added and mixed using a stirrer so that the viscosity becomes 24 Pa · s (Ford Cup No. 4/20 ° C. manufactured by Yasuda Seiki Co., Ltd.) A top clear coating composition was prepared. This top clear coating composition is applied to a plate to be coated on which a glitter layer (uncured) is formed using a spray gun (W-100 manufactured by Anest Iwata Co., Ltd.), and then fired (140 ° C., 30 minutes) ) To form a top clear layer (30 μm). The average thickness of the glitter layer (cured) after firing was 15 μm.

  The brightness of the painted sample, the degree of yellowing, and the degree of diamond-like shine were evaluated as follows. The results are shown in Table 1.

(Luminance)
The luminance (Intensity Value, hereinafter abbreviated as IV) was measured using a semiconductor laser type non-contact measuring device “ALCOPE LMR-200” manufactured by Kansai Paint Co., Ltd. A larger brightness (IV) value means higher glitter.

(Yellow Nigori)
As shown in FIG. 4, the observation light source 6 was disposed at a position where light can be incident at an angle of 45 ° with respect to the surface of the coated sample. And the color tone (shade color tone) of the reflected light in a direction shifted by 110 ° from the direction of regular reflection to the observation light source side with respect to the surface of the coating sample was measured by the detector 7. If the observation is performed at an angle of 110 ° from the direction of regular reflection, the influence of regular reflection is removed, and the color tone of scattered light (yellow mist) can be measured from the inside of the bright layer.

The shade color tone was measured using a multi-angle spectrocolorimeter (manufactured by Color Techno System Co., Ltd.). However, L ^* , a ^*, and b ^* were measured in the color system L ^* a ^* b ^* . Table 1 shows b ^* . When b ^* exceeds 6, yellow negligible that cannot be ignored is observed.

(Visual evaluation of appearance)
Using a D65 natural light source, the degree of shine as if diamonds were scattered was visually observed. Evaluation was performed in the following three stages.
1: No shine as if diamonds were scattered on the appearance.
2: Some shine like diamonds scattered on the appearance is recognized.
3: A strong shine as if diamonds were scattered on the appearance was recognized.

  As shown in Table 1, in Examples 1 to 5 in which the glitter layer contains the glitter pigment (A), the glitter pigment (B) and / or the glitter pigment (C), from Comparative Examples 1 to 3 In addition, it was confirmed that the yellowing of the color development was suppressed, the brightness was high, the color of silver white was exhibited, and the brightness was as if diamonds were scattered.

Schematic sectional view of the bright pigment (A) contained in the bright pigment-containing composition of the present invention Side view of an example of a vehicle provided with an example of a painted object of the present invention Schematic sectional view of an example of the painted product of the present invention Conceptual diagram explaining the measurement of b ^*

Explanation of symbols

200 Bright pigment (A)
20 Scale-like inorganic substrate 21 Silver alloy coating 1 Outer plate 2 Radiator grill 3 Side molding 4 Door mirror 5 Back panel 9 Bumper 10 Emblem 13 Tire wheel cover

Claims (10)

Glitter pigment (A),
At least one silver-free metallic pigment selected from the group consisting of a scaly glittering pigment (B) composed of scaly aluminum and a scaly glittering pigment (C) in which titanium dioxide is coated on an inorganic substrate;
Vehicle, and
The glitter pigment (A) includes a scale-like inorganic substrate, and a silver-based alloy coating that covers the inorganic substrate and contains at least one noble metal selected from the group consisting of gold, palladium, and platinum and silver. A glittering pigment-containing composition comprising: a noble metal content of 0.1 to 2 atomic%.
However, the sum of the atomic percent of silver and the atomic percent of the noble metal is 100 atomic percent.   The glittering pigment-containing composition according to claim 1, wherein in the silver-based alloy coating, atoms of the silver lattice points are substituted with atoms of the noble metal.   The silver-based alloy coating comprises a silver-gold alloy, a silver-palladium alloy, a silver-platinum alloy, a silver-gold-palladium alloy, a silver-platinum-palladium alloy, or a silver-gold-platinum alloy. A luster pigment-containing composition.   The glittering pigment-containing composition according to claim 1, wherein the noble metal is contained in the silver-based alloy coating in such a concentration distribution that the concentration of the noble metal increases as it approaches the outer surface of the silver-based alloy coating.   The bright pigment-containing composition according to claim 1, wherein the silver-based alloy coating has an average thickness of 25 nm to 65 nm.   The glitter pigment-containing composition according to claim 1, wherein the inorganic substrate constituting the glitter pigment (A) contains at least one selected from the group consisting of glass, mica, synthetic mica, silica, and alumina.   The total content of the glitter pigment (A) and the silver free metallic pigment is the sum of the mass of the solid content in the vehicle, the mass of the glitter pigment (A), and the mass of the silver free metallic pigment. The bright pigment-containing composition according to claim 1, wherein the content is 0.1 to 30% by mass.   The glitter pigment-containing composition according to claim 1, wherein the glitter pigment-containing composition is an ink or a paint.   A printed matter comprising a glitter layer formed using the glitter pigment-containing composition according to any one of claims 1 to 7.   A coated article comprising a glitter layer formed using the glitter pigment-containing composition according to any one of claims 1 to 7.

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