Metal Pigment Composition and Coloring Method

Abstract

To provide a metal pigment composition that has excellent dispersion stability of metal particles and can be suitably applied to produce a colored body having an excellent glossy feeling as well as excellent abrasion resistance; and to provide a coloring method that can be applied to produce a colored body having an excellent glossy feeling as well as excellent abrasion resistance.SOLUTION: A metal pigment composition of the present disclosure is a coloring composition or a composition to be used for preparation of the coloring composition and includes: a metal pigment; a polyoxyalkyleneamine compound; and a liquid medium component, wherein the metal pigment includes metal particles, the metal particles are surface-modified with a surface treatment agent, and the surface treatment agent is at least one selected from the group consisting of a compound represented by the following formula (1): (A-R-O)aP(O)(OH)3-a and a compound represented by the following formula (2): (A-R)aP(O)(OH)3-a.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a metal pigment composition and a coloring method.

Background Art

[0002] Conventionally, as methods for manufacturing ornaments exhibiting a glossy appearance, metal plating, foil stamping using a metal foil, heat transfer using a metal foil, etc. have been used. However, these methods have properties such that, for example, application to a curved surface part is difficult.

[0003] On the other hand, a composition containing a pigment or a dye is used as an inkjet ink applied to a recording medium by an inkjet method, or used as a paint. Such a method is excellent in that it can be suitably applied even to a curved surface part.

[0004] However, when simply attempting to apply metal particles instead of a pigment or a dye, there has been a problem that characteristics such as the glossiness inherent to the metal cannot be sufficiently exhibited.

[0005] For the purpose of solving the above problems, it has been proposed to use metal particles surface-treated with a fluorine-based compound (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] Although the gloss of the portion of the adherend to which the composition is attached and the dispersibility of the metal particles in the composition are improved to some extent, the adhesion between the object to be treated to which the composition is applied and the colored portion formed using the composition cannot be made sufficiently excellent, and there has been a problem that the abrasion resistance of the colored body formed using the composition is poor.

Means for Solving the Problems

[0008] The present invention has been made to solve the above problems and can be realized as the following application examples.

[0009] The metal pigment composition according to the application example of the present invention contains a metal pigment, a polyoxyalkyleneamine compound, and a liquid medium component. The metal pigment is composed of a plurality of metal particles. The metal particles are surface-modified with a surface treatment agent. The surface treatment agent is at least one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2). The metal particles are made of aluminum or an aluminum alloy, The polyoxyalkyleneamine compound is a compound represented by the following formula (3) or a salt thereof, The content of the polyoxyalkyleneamine compound is 1.0 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the metal particles, It is a solvent-based composition containing an organic solvent as the liquid medium component, The proportion of the organic solvent in the total liquid medium component constituting the metal pigment composition is 60% by mass or more, The organic solvent is one or more selected from glycol ethers and cyclic esters, The water content rate in the total liquid medium component is 1.0% by mass or less, A metal pigment composition which is a composition for coloring or a composition used for preparing a composition for coloring. (A-R-O) a P(O)(OH) 3-a (1) (A-R) a P(O)(OH) 3-a (2) (In the formula (1) and formula (2) wherein A is any one of a hydrogen atom, a carboxyl group, a hydroxyl group, an amino group, and an oxyalkylene-containing group, R is a divalent hydrocarbon group having 10 or more carbon atoms, and a is 1 or 2.) R1 -(O-R 2 ) x -NH 2 (3) (In formula (3), R 1 is a hydrogen atom or an alkyl group having 4 or less carbon atoms, R 2 is an alkylene group having 5 or less carbon atoms, X is an integer of 5 or more, and the polyoxyalkyleneamine compound may contain a plurality of types of alkylene groups having different R 2 conditions in the molecule.)

[0011] In addition, in the metal pigment composition according to another application example of the present invention, the polyoxyalkyleneamine compound is a compound represented by the following formula (4) or a salt thereof. R 1 -(OCH2CH2) m -(OCH2CH(CH3)) n -NH2(4) (In the formula, R 1 is a hydrogen atom or an alkyl group having 4 or less carbon atoms, n and m are each independently 0 or an integer of 1 or more, and m + n is an integer of 10 or more. The order of the oxyethylene unit and the oxypropylene unit in the molecule of the polyoxyalkyleneamine compound is not limited.)

[0012] In addition, in the metal pigment composition according to another application example of the present invention, the weight average molecular weight of the polyoxyalkyleneamine compound is 400 or more and 8000 or less.

[0013] In addition, in the metal pigment composition according to another application example of the present invention, the content of the polyoxyalkyleneamine compound is 2.0 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the metal particles.

[0014] In addition, in the metal pigment composition according to another application example of the present invention, the metal particles are made of aluminum by constituted.

[0015] In addition, in the metal pigment composition according to another application example of the present invention, the metal particles are in a flaky shape.

[0016] In addition, a metal pigment composition according to another application example of the present invention by is The organic solvent contains one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetraethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol n-butyl ether, tripropylene glycol dimethyl ether, triethylene glycol diethyl ether, 1,2-dimethoxyethane, bis(2-methoxyethyl) ether, γ-butyrolactone .

[0017] In addition, a metal pigment composition according to another application example of the present invention containing a resin as a binder .

[0018] In addition, in the metal pigment composition according to another application example of the present invention, the content of the surface treatment agent is 1.0 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the metal particles.

[0019] In addition, the metal pigment composition according to another application example of the present invention is the coloring composition.

[0020] In addition, the metal pigment composition according to another application example of the present invention is an inkjet ink.

[0021] In addition, the coloring method according to the application example of the present invention includes a step of attaching the metal pigment composition according to the application example of the present invention to an object to be treated.

BEST MODE FOR CARRYING OUT THE INVENTION

[0022] Hereinafter, preferred embodiments of the present invention will be described in detail. [1] Metal pigment composition First, the metal pigment composition of the present invention will be described.

[0023] By the way, conventionally, as a method for manufacturing a decorative article having a shiny appearance, metal plating, foil stamping using a metal foil, heat transfer using a metal foil, etc. have been used. However, these methods have properties such that, for example, it is difficult to apply them to curved surfaces.

[0024] On the other hand, a composition containing a pigment or a dye has been used as an inkjet ink applied to a recording medium by an inkjet method or as a paint. Such a method is excellent in that it can be suitably applied to curved surfaces.

[0025] However, when attempting to simply apply metal particles instead of pigments or dyes, there was a problem in that the characteristics such as the luster inherent to the metal could not be fully exhibited.

[0026] For the purpose of solving the above problems, it has been proposed to use metal particles surface-treated with a fluorine-based compound. As a result, although the luster of the portion to which the composition is adhered is improved to some extent, the adhesion between the object to be treated to which the composition is applied and the colored portion formed using the composition cannot be made sufficiently excellent, and there has been a problem that the abrasion resistance of the colored body formed using the composition is poor. In addition, in terms of a composition that is excellent in the dispersion stability of the composition in addition to luster and abrasion resistance, it was not sufficient.

[0027] Therefore, as a result of intensive research for the purpose of solving the above problems, the inventors have arrived at the present invention. That is, the metal pigment composition of the present invention contains a metal pigment, a polyoxyalkyleneamine compound, and a liquid medium component. The metal pigment is composed of a plurality of metal particles, and the metal particles are surface-modified with a surface treatment agent. The surface treatment agent is at least one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2), and is a composition for coloring or a composition used for preparing a composition for coloring. (A-R-O) a P(O)(OH) 3-a (1) (A-R) a P(O)(OH) 3-a (2) (In the formula, A is any one of a hydrogen atom, a carboxyl group, a hydroxyl group, an amino group, and an oxyalkylene-containing group, R is a divalent hydrocarbon group having 10 or more carbon atoms, and a is 1 or 2.)

[0028] Accordingly, it is possible to provide a metal pigment composition that is excellent in the dispersion stability of metal particles, has an excellent gloss, and is also excellent in abrasion resistance, and can be suitably applied to the production of a colored body. In particular, excellent effects as described above can be obtained regardless of whether it is applied to a solvent-based metal pigment composition or an aqueous metal pigment composition. Further, since it is not necessary to use a fluorine-based surface treatment agent, it is also advantageous from the viewpoint of environmental compatibility.

[0029] Further, when the metal pigment composition is an inkjet composition applied to ejection by an inkjet method, in addition to the above effects, it is possible to more suitably form a fine pattern, and benefits such as excellent on-demand properties can be enjoyed by applying the inkjet method. Further, the ejection stability of droplets and the like can be made excellent in a relatively short period after the production of the inkjet composition, and the ejection stability of droplets and the like can be made excellent even when the inkjet composition is stored for a long period or stored under harsh conditions.

[0030] On the other hand, when the above conditions are not satisfied, satisfactory results cannot be obtained. For example, if the metal pigment composition does not contain a polyoxyalkyleneamine compound, the following problems occur. That is, for example, even if the metal pigment is surface-modified with a surface treatment agent, if it does not contain a polyoxyalkyleneamine compound, aggregation of the metal pigment in the metal pigment composition is likely to occur, the dispersion stability of the metal particles decreases, and the gloss of the colored body produced using the metal pigment composition is significantly reduced. Further, when aggregation of the metal pigment occurs, unevenness due to aggregates of the metal pigment is likely to occur on the surface of the colored body produced using the metal pigment composition, and the abrasion resistance of the colored body is likely to decrease. Also, when the dispersion stability is poor, the ejection stability when ejected by the inkjet method is poor due to aggregates.

[0031] Further, even if the metallic pigment composition contains a polyoxyalkyleneamine compound, problems as described below occur when the metal particles are not surface-modified with a surface treatment agent, or when the metal particles are surface-modified with a surface treatment agent other than the compounds represented by the above formula (1) and the above formula (2). That is, at least one of the dispersion stability of the metal particles in the metallic pigment composition, the glossiness of the colored body produced using the metallic pigment composition, and the abrasion resistance of the colored body produced using the metallic pigment composition deteriorates. In particular, when a fluorine-based surface treatment agent is used instead of the compounds represented by the above formula (1) and the above formula (2), the abrasion resistance of the colored body produced using the metallic pigment composition tends to be particularly low. This is presumably because the fluorine-based surface treatment agent is excellent in leafing property, so that the metal pigment easily floats to the upper layer of the film formed using the metallic pigment composition.

[0032] In the following description, the surface treatment agent which is at least one selected from the group consisting of the compounds represented by the above formula (1) and the above formula (2) is also referred to as a "specific surface treatment agent".

[0033] Hereinafter, the constituent components of the metallic pigment composition of the present invention will be described. [1-1] Metallic pigment The metallic pigment composition of the present invention contains a metallic pigment composed of a plurality of metal particles. The metal particles constituting the metallic pigment are surface-modified with a specific surface treatment agent, which will be described in detail later. More specifically, it is considered that the OH groups on the surface of the metal particles react with the phosphorus-containing acid group portion of the specific surface treatment agent, and the metal particles and the specific surface treatment agent are bonded by a covalent bond or a hydrogen bond.

[0034] The metal particles are those in which at least a part of the visually recognizable part in appearance is made of a metal material, and usually, the vicinity of the outer surface is made of a metal material.

[0035] Metal particles are components that have a great influence on the appearance of a colored body produced using a metal pigment composition.

[0036] The metal particles only need to be those in which at least the region including the vicinity of the surface is composed of a metal material. For example, those entirely composed of a metal material may be used, or those having a base composed of a non-metal material and a film composed of a metal material covering the base may be used. Further, an oxide film or the like such as a passive film may be formed on the surface of the metal particles. Even such metal particles have had the problems described above in the past, and by applying the present invention, the excellent effects described above can be obtained.

[0037] As the metal material constituting the metal particles, metals as simple substances, various alloys, etc. can be used. For example, aluminum, silver, gold, platinum, nickel, chromium, tin, zinc, indium, titanium, iron, copper, etc. can be mentioned. Among these, the metal particles are preferably composed of aluminum or an aluminum alloy. The reason why aluminum or an aluminum alloy is preferable is that it has a lower specific gravity compared to iron or the like. Thereby, when particles composed of aluminum or an aluminum alloy are dispersed in a metal pigment composition, sedimentation proceeds very slowly, so that uneven concentration and the like can be effectively prevented, and the metal pigment composition can be stored for a longer period of time.

[0038] In addition, while suppressing an increase in the production cost of a colored body produced using a metal pigment composition, the gloss and high-class feeling of the colored body can be made particularly excellent. Aluminum and aluminum alloys inherently exhibit a particularly excellent gloss among various metal materials. However, when attempting to apply particles composed of these materials to a metal pigment composition, the inventor has found that the following problems occur. That is, the storage stability of the metal pigment composition becomes particularly low. In particular, when such a metal pigment composition is used as an inkjet composition, problems such as a decrease in ejection stability due to an increase in viscosity caused by gelation are particularly likely to occur. On the other hand, by using a polyoxyalkyleneamine compound and a specific surface treatment agent in combination with the metal pigment, even when particles composed of aluminum or an aluminum alloy are used, the occurrence of the above problems can be surely prevented. That is, since the metal particles are composed of aluminum or an aluminum alloy, the effects of the present invention are more remarkably exhibited.

[0039] The metal particles may have any shape such as spherical, spindle-shaped, needle-shaped, etc., but are preferably flaky.

[0040] Thereby, on the object to be treated to which the metal pigment composition is applied, the main surface of the metal particles can be arranged along the surface shape of the object to be treated. As a result, the gloss and the like inherent in the metal material constituting the metal particles can be more effectively exhibited also in the obtained colored body, and the gloss and high-class feeling of the colored body can be made particularly excellent, and the abrasion resistance of the colored body can be made particularly excellent. In addition, in a metal pigment composition in which a polyoxyalkyleneamine compound and a specific surface treatment agent are not used in combination, if the metal particles are flaky, the storage stability of the metal pigment composition tends to be particularly low, and when the metal pigment composition is used as an inkjet composition, the ejection stability of the inkjet composition tends to be particularly low. In addition, the excellent gloss and the like due to the flaky metal particles cannot be exhibited.

[0041] On the other hand, when the metal pigment composition uses a polyoxyalkyleneamine compound and a specific surface treatment agent in combination with metal particles, even if the metal particles are flaky, the occurrence of the above problems can be surely prevented. That is, when the metal particles are flaky, the effects according to the present invention are more significantly exhibited.

[0042] In the present invention, "flaky" means a shape such as a flat plate shape or a curved plate shape, and when observed from a predetermined angle, for example, the area when viewed in a plan view is larger than the area when observed from an angle orthogonal to the observation direction. In particular, when observed from the direction in which the projected area is the largest, that is, the area S1 [μm 2 and the area S0 [μm 2 observed from the direction in which the area is the largest among the directions orthogonal to the observation direction, the ratio S1 / S0 is preferably 2 or more, more preferably 5 or more, still more preferably 8 or more. Further, 10 or more is preferable, and 20 or more is more preferable. The upper limit of S1 / S0 is not particularly limited, but preferably 1000, more preferably 500, and still more preferably 100. As this value, for example, observations can be made on any 50 particles, and the average value of the calculated values for these particles can be adopted. The observations can be carried out using, for example, an electron microscope, an atomic force microscope, or the like.

[0043] Alternatively, using the volume average particle diameter (D50) and the average thickness described later, after unifying the units, the volume average particle diameter (D50) / average thickness may be used and set within the above range.

[0044] When the metal particles are flaky, the lower limit of the average thickness of the metal particles is not particularly limited, but is preferably 5 nm, more preferably 10 nm, and even more preferably 15 nm. Also, when the metal particles are flaky, the upper limit of the average thickness of the metal particles is not particularly limited, but is preferably 90 nm, more preferably 70 nm, even more preferably 50 nm, and most preferably 30 nm. Further, 20 nm or less is preferable. The average thickness can be measured using an atomic force microscope. Although not limited thereto, for example, it can be measured by an atomic force microscopy method using NanoNavi E-Sweep (manufactured by SII NanoTechnology Inc.). For example, measurement is performed on any 50 metal particles and the average value is taken.

[0045] Thereby, the effects due to the particles being flaky as described above are more remarkably exhibited.

[0046] The lower limit of the volume average particle diameter of the metal particles is not particularly limited, but is preferably 0.20 μm, more preferably 0.25 μm, and even more preferably 0.30 μm. Also, the upper limit of the volume average particle diameter of the metal particles is not particularly limited, but is preferably 1.00 μm, more preferably 0.90 μm, and even more preferably 0.80 μm.

[0047] Thereby, while making the storage stability, water resistance, etc. of the metal pigment composition more excellent, it is possible to more effectively prevent the occurrence of unintended color unevenness, etc. in the colored body manufactured using the metal pigment composition, and to make the glossiness and rubbing resistance of the colored body more excellent.

[0048] In the present invention, the volume average particle diameter refers to the median diameter of the volume distribution measured for the particle dispersion liquid using the laser diffraction / scattering method. When a large number of measurement results are expressed as the cumulative ratio of the abundance ratio for each size, it is the size of the particles that shows exactly 50% of the median value in the cumulative results. When the metal particles are in a flaky shape, the volume average particle diameter shall be determined based on the shape and size when the metal particles are converted into a spherical shape.

[0049] In addition, the upper limit of the particle diameter D90 at a volume cumulative distribution rate of 90% from the fine particle side of the metal particles contained in the metal pigment composition is preferably 1.50 μm, more preferably 1.20 μm, and even more preferably 0.95 μm.

[0050] Thereby, while making the storage stability, water resistance, etc. of the metal pigment composition more excellent, it is possible to more effectively prevent the occurrence of unintended color unevenness, etc. in the colored body manufactured using the metal pigment composition, and make the glossiness and rubbing resistance of the colored body more excellent.

[0051] The lower limit of the content rate of the metal particles in the metal pigment composition is not particularly limited, but is preferably 0.1% by mass, more preferably 0.2% by mass, and even more preferably 0.3% by mass. Also, the upper limit of the content rate of the metal particles in the metal pigment composition is not particularly limited, but is preferably 30% by mass, more preferably 20% by mass, even more preferably 15% by mass, and particularly preferably 10% by mass. Further, 5% by mass or less is preferable.

[0052] Thereby, while making the storage stability, water resistance, etc. of the metal pigment composition more excellent, it is possible to make the glossiness and rubbing resistance of the colored part formed using the metal pigment composition particularly excellent.

[0053] In particular, when the metal pigment composition is the ink itself ejected by the inkjet method, the lower limit of the content of metal particles in the ink is not particularly limited, but is preferably 0.1% by mass, more preferably 0.2% by mass, and even more preferably 0.3% by mass. Further, when the metal pigment composition is the ink itself ejected by the inkjet method, the upper limit of the content of metal particles in the ink is not particularly limited, but is preferably 2.4% by mass, more preferably 2.2% by mass, and even more preferably 1.8% by mass.

[0054] Further, when the metal pigment composition is the stock solution used for preparing inks, paints, etc. or is a paint, the lower limit of the content of metal particles in the metal pigment composition is not particularly limited, but is preferably 2.0% by mass, more preferably 2.5% by mass, and even more preferably 3.0% by mass. Further, when the metal pigment composition is the stock solution used for preparing the ink ejected by the inkjet method or is a paint, the upper limit of the content of metal particles in the metal pigment composition is not particularly limited, but is preferably 30% by mass, more preferably 20% by mass, even more preferably 15% by mass, and even more preferably 10% by mass.

[0055] The metal particles may be produced by any method, but when they are composed of Al, it is preferable that they are obtained by forming a film composed of Al by a vapor deposition method and then pulverizing the film. Thereby, in the colored part formed using the metal pigment composition of the present invention, the luster and the like originally possessed by Al can be more effectively expressed. Further, variations in characteristics between particles can be suppressed. Further, by using this method, even relatively thin metal particles can be suitably produced.

[0056] When manufacturing metal particles using such a method, for example, metal particles can be suitably manufactured by forming a film composed of Al on a substrate. As the substrate, for example, a plastic film such as polyethylene terephthalate can be used. Further, the substrate may have a release agent layer on the film-forming surface.

[0057] Further, the pulverization is preferably performed by applying ultrasonic vibration to the film in a liquid. Thereby, metal particles with a particle diameter as described later can be easily and surely obtained, and variations in size, shape, and characteristics among the metal particles can be suppressed.

[0058] When performing pulverization by the method as described above, as the liquid, alcohols, hydrocarbon-based compounds, ether-based compounds, and polar compounds such as propylene carbonate, γ-butyrolactone, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, cyclohexanone, and acetonitrile can be preferably used. By using such a liquid, while preventing unintended oxidation of the metal particles, the productivity of the metal particles can be made particularly excellent, and variations in size, shape, and characteristics among the particles can be made particularly small.

[0059] Examples of the alcohols include methanol, ethanol, propanol, butanol and the like. Examples of the hydrocarbon compounds include n-heptane, n-octane, decane, dodecane, tetradecane, toluene, xylene, cymene, durene, indene, dipentene, tetrahydronaphthalene, decahydronaphthalene, cyclohexylbenzene and the like. Examples of the ether compounds include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetraethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol n-butyl ether, tripropylene glycol dimethyl ether, triethylene glycol diethyl ether, 1,2-dimethoxyethane, bis(2-methoxyethyl) ether, p-dioxane, tetrahydrofuran and the like.

[0060] [1-2] Polyoxyalkyleneamine compound The metal pigment composition of the present invention contains a polyoxyalkyleneamine compound.

[0061] The polyoxyalkyleneamine compound may be any amine compound having a polyoxyalkylene structure in the molecule, but is preferably a compound represented by the following formula (3) or a salt thereof. R 1 -(O-R 2 ) x -NH2(3) (In the formula, R 1 is a hydrogen atom or an alkyl group having 4 or less carbon atoms, R 2 is an alkylene group having 5 or less carbon atoms, X is an integer of 5 or more, and the polyoxyalkyleneamine compound may contain a plurality of types of alkylene groups having different R 2 conditions in the molecule.)

[0062] As a result, the dispersion stability of metal particles in the metal pigment composition, the glossiness of the colored body produced using the metal pigment composition, and the abrasion resistance can be made more excellent. Further, when the metal pigment composition is an inkjet composition, the ejection stability of the inkjet composition, particularly the ejection stability when stored for a long period or stored under severe conditions, can be made more excellent.

[0063] As described above, the polyoxyalkyleneamine compound is preferably a compound represented by the above formula (3) or a salt thereof.

[0064] In formula (3), R 1 is preferably an alkyl group having 4 or less carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms. R 2 is preferably an alkylene group having 1 to 3 carbon atoms, and may be a linear alkylene group or a branched alkylene group.

[0065] Among the compounds represented by the above formula (3) or salts thereof, the polyoxyalkyleneamine compound is particularly preferably a compound represented by the following formula (4) or a salt thereof. R 1 -(OCH2CH2) m -(OCH2CH(CH3)) n -NH2(4) (In the formula, R 1 is a hydrogen atom or an alkyl group having 4 or less carbon atoms, n and m are each independently 0 or an integer of 1 or more, and m + n is an integer of 10 or more. The arrangement order of the oxyethylene unit and the oxypropylene unit in the molecule of the polyoxyalkyleneamine compound is not limited.) As a result, the above-described effects are more remarkably exhibited.

[0066] Also, the value of m / n, which is the ratio of m to n in the above formula (4), that is, the ratio of the amount of substance of oxyethylene units to the amount of substance of oxypropylene units in the polyoxyalkyleneamine compound, preferably has a lower limit of 0.05, more preferably 0.15, and even more preferably 0.70. Further, the upper limit of the value of m / n is preferably 10.0, more preferably 9.5, and even more preferably 9.0.

[0067] Thereby, the dispersion stability of metal particles in the metal pigment composition, the glossiness of the colored body produced using the metal pigment composition, and the abrasion resistance can be further improved. In addition, when the metal pigment composition is an inkjet composition, the ejection stability of the inkjet composition, particularly the ejection stability when stored for a long time or under harsh conditions, can be further improved.

[0068] As described above, the order of the oxyethylene units and the oxypropylene units in the above formula (4) is not limited. More specifically, in the above formula (4), an amino group is bonded to the end of consecutive oxyethylene units, and a methyl group is bonded to the end of consecutive oxypropylene units. However, an amino group may be bonded to the end of consecutive oxypropylene units, and a methyl group may be bonded to the end of consecutive oxyethylene units. Further, the compound represented by the above formula (4) may be a block copolymer or a random copolymer.

[0069] The lower limit of the weight average molecular weight of the polyoxyalkyleneamine compound is not particularly limited, but is preferably 400, more preferably 500, even more preferably 600, and most preferably 1000. Further, the upper limit of the weight average molecular weight of the polyoxyalkyleneamine compound is not particularly limited, but is preferably 8000, more preferably 5000, and even more preferably 3000.

[0070] As a result, the dispersion stability of metal particles in the metal pigment composition, the glossiness of the colored body produced using the metal pigment composition, and the rubbing resistance can be further improved. Further, when the metal pigment composition is an inkjet composition, the ejection stability of the inkjet composition, particularly the ejection stability when stored for a long period or stored under severe conditions, can be further improved.

[0071] The metal pigment composition of the present invention may contain a plurality of compounds as the polyoxyalkyleneamine compound.

[0072] The lower limit of the content of the polyoxyalkyleneamine compound in the metal pigment composition is not particularly limited, but 0.005% by mass is preferable, and 0.007% by mass is more preferable. Further, 0.01% by mass is preferably, 0.02% by mass is more preferably, and 0.03% by mass is even more preferably. Also, the upper limit of the content of the polyoxyalkyleneamine compound in the metal pigment composition is not particularly limited, but 5.0% by mass is preferable. Further, 3.0% by mass is preferably, 2.0% by mass is more preferably, and 1.5% by mass is even more preferably. It is also preferable that the upper and lower limits are within the ranges described later.

[0073] As a result, the dispersion stability of metal particles in the metal pigment composition, the glossiness of the colored body produced using the metal pigment composition, and the rubbing resistance can be further improved. Further, when the metal pigment composition is an inkjet composition, the ejection stability of the inkjet composition, particularly the ejection stability when stored for a long period or stored under severe conditions, can be further improved.

[0074] In particular, when the metal pigment composition is the ink itself ejected by the inkjet method, the lower limit of the content of the polyoxyalkyleneamine compound in the ink is not particularly limited, but 0.005% by mass is preferable, and 0.007% by mass is more preferable. Further, 0.01% by mass is preferable, 0.02% by mass is more preferable, and 0.03% by mass is even more preferable. Also, when the metal pigment composition is the stock solution used for preparing inks, paints, etc. or is a paint, the lower limit of the content of the polyoxyalkyleneamine compound in the metal pigment composition is not particularly limited, but 0.025% by mass is preferable, and 0.035% by mass is more preferable. Further, 0.05% by mass is preferable, 0.10% by mass is more preferable, and 0.20% by mass is even more preferable. Also, when the metal pigment composition is the stock solution used for preparing the ink ejected by the inkjet method or is a paint, the upper limit of the content of the polyoxyalkyleneamine compound in the metal pigment composition is not particularly limited, but 5.0% by mass is preferable, and 3.5% by mass is preferable. Further, 3.0% by mass is preferable, 2.0% by mass is more preferable, and 1.5% by mass is even more preferable.

[0075] In addition, when the metal pigment composition is the stock solution used for preparing inks, paints, etc. or is a paint, the lower limit of the content of the polyoxyalkyleneamine compound in the metal pigment composition is not particularly limited, but 0.025% by mass is preferable, and 0.035% by mass is more preferable. Further, 0.05% by mass is preferable, 0.10% by mass is more preferable, and 0.20% by mass is even more preferable. Also, when the metal pigment composition is the stock solution used for preparing the ink ejected by the inkjet method or is a paint, the upper limit of the content of the polyoxyalkyleneamine compound in the metal pigment composition is not particularly limited, but 5.0% by mass is preferable, and 3.5% by mass is preferable. Further, 3.0% by mass is preferable, 2.0% by mass is more preferable, and 1.5% by mass is even more preferable.

[0076] The lower limit of the content of the polyoxyalkyleneamine compound in the metal pigment composition is preferably 0.5 parts by mass, more preferably 0.7 parts by mass, based on 100 parts by mass of the metal particles. Further, it is preferably 1.0 parts by mass, more preferably 1.5 parts by mass, and even more preferably 2.0 parts by mass. Also, the upper limit of the content of the polyoxyalkyleneamine compound in the metal pigment composition is preferably 100 parts by mass, more preferably 70 parts by mass, based on 100 parts by mass of the metal particles. Further, it is preferably 50 parts by mass, even more preferably 40 parts by mass, more preferably 30 parts by mass, and even more preferably 20 parts by mass.

[0077] Thereby, the dispersion stability of the metal particles in the metal pigment composition, the glossiness of the colored body produced using the metal pigment composition, and the abrasion resistance can be made even more excellent. Also, in the case where the metal pigment composition is an inkjet composition, the ejection stability of the inkjet composition, particularly the ejection stability when stored for a long period or under severe conditions, can be made even more excellent.

[0078] [1-3] Liquid medium component The metal pigment composition of the present invention contains a liquid medium component. The liquid medium component is, by itself, a component that is in a liquid state, and in the metal pigment composition of the present invention, it mainly has a function as a dispersion medium for dispersing metal particles. Also, it can make the composition easier to adhere to the adherend.

[0079] Further, when the metal pigment composition contains a liquid medium component, in the case where the metal pigment composition is the ink itself ejected by the inkjet method, the ejection of the ink by inkjet becomes possible. Examples of the liquid medium component include water and various organic solvents.

[0080] When the metal pigment composition of the present invention is a solvent-based composition containing an organic solvent as a liquid medium component, the dispersion stability of metal particles in the metal pigment composition, the glossiness of a colored body produced using the metal pigment composition, and the abrasion resistance can be further improved.

[0081] In addition, when the metal pigment composition of the present invention is an aqueous composition containing water as a liquid medium component, while the dispersion stability of metal particles in the metal pigment composition, the glossiness of a colored body produced using the metal pigment composition, and the abrasion resistance are sufficiently excellent, the environmental load of the metal pigment composition can be made smaller.

[0082] Examples of the organic solvent contained in the metal pigment composition of the present invention include alcohols, hydrocarbon-based compounds, ether-based compounds, ketones, esters, and polar compounds such as propylene carbonate, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, cyclohexanone, and acetonitrile, which can be preferably used.

[0083] Examples of the alcohols include monohydric alcohols such as methanol, ethanol, propanol, isopropanol, and butanol; polyhydric alcohols such as ethylene glycol, propylene glycol, and 1,2 - hexanediol. Examples of the hydrocarbon compounds include n - heptane, n - octane, decane, dodecane, tetradecane, toluene, xylene, cymene, durene, indene, dipentene, tetrahydronaphthalene, decahydronaphthalene, cyclohexylbenzene, etc. Examples of the ether compounds include glycol ethers. Examples of the glycol ethers include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetraethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol n - butyl ether, tripropylene glycol dimethyl ether, triethylene glycol diethyl ether, 1,2 - dimethoxyethane, bis(2 - methoxyethyl) ether, etc. Other examples of the ethers include p - dioxane and tetrahydrofuran. Examples of the ketones include acetone, methyl ethyl ketone, diethyl ketone, etc. Examples of the esters include ethyl acetate, propyl acetate, butyl acetate, etc. The esters also include cyclic esters. Examples of the cyclic esters include lactones such as γ - butyrolactone.

[0084] When the metal pigment composition of the present invention is a solvent - based composition, the organic solvent preferably contains one or more selected from the group consisting of ethers, esters, ketones, and alcohols, and more preferably contains one or more selected from the group consisting of ethers and esters. In particular, one or more selected from glycol ethers and cyclic esters are preferred, and glycol ethers are particularly preferred. Particularly, it is more preferable to contain one or more selected from the group consisting of diethylene glycol diethyl ether, tetraethylene glycol monobutyl ether, and γ-butyrolactone.

[0085] Thereby, the dispersion stability of metal particles in the metal pigment composition, the glossiness and scratch resistance of the colored body produced using the metal pigment composition can be made more excellent. In addition, the moisture retention of the metal pigment composition can be improved. For example, when the metal pigment composition is an inkjet ink, it is possible to more effectively prevent the solid content of the metal pigment composition from being inadvertently deposited due to drying or the like at an inkjet head or the like. Further, the viscosity of the metal pigment composition can be adjusted more suitably.

[0086] Particularly, when the metal pigment composition of the present invention is a solvent-based composition containing an organic solvent as a main liquid medium component, the proportion of the organic solvent in all the liquid medium components constituting the metal pigment composition of the present invention is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The upper limit is 100% by mass or less. Thereby, the above-described effects are more significantly exhibited.

[0087] When the metal pigment composition of the present invention is an aqueous composition containing water as a main liquid medium component, as the liquid medium component, an organic solvent may be contained together with water.

[0088] When it is an aqueous composition, the proportion of the organic solvent in all the liquid medium components is preferably less than 50% by mass, more preferably 40% by mass or less, and even more preferably 30% by mass or less. The lower limit is 0% by mass or more, and may be 10% by mass or more. When it is an aqueous composition, the proportion of the organic solvent in all the liquid medium components is preferably less than 50% by mass, more preferably 40% by mass or less, and even more preferably 30% by mass or less. The lower limit is 0% by mass or more, and may be 10% by mass or more.

[0089] When the metal pigment composition of the present invention is an aqueous composition, as the organic solvent contained together with water, a liquid component showing solubility in water, that is, a water-soluble organic solvent, is preferable.

[0090] Thereby, the dispersion stability of the metal particles in the metal pigment composition, the glossiness and scratch resistance of the colored body produced using the metal pigment composition can be made more excellent. Further, the moisture retention of the metal pigment composition can be improved. For example, when the metal pigment composition is an inkjet ink, it is possible to more effectively prevent the solid content of the metal pigment composition from being inadvertently deposited due to drying at an inkjet head or the like. Further, the viscosity of the metal pigment composition can be adjusted more suitably.

[0091] The water-soluble organic solvent may be any water-soluble liquid component. For example, a liquid component having a solubility in water of 2 g / 100 g water or more at 25°C can be preferably used.

[0092] The boiling point of the water-soluble organic solvent under 1 atm is preferably 110°C or higher and 300°C or lower.

[0093] Thereby, the moisture retention of the metal pigment composition can be further improved. For example, when the metal pigment composition is an inkjet ink, it is possible to more effectively prevent the solid content of the metal pigment composition from being inadvertently deposited due to drying at an inkjet head or the like. From such a situation, the ejection stability of the metal pigment composition by the inkjet method can be made more excellent. Further, after ejecting the metal pigment composition, if necessary, it can be volatilized relatively easily, and it is possible to more effectively prevent the liquid medium component from remaining inadvertently in the colored body produced using the metal pigment composition.

[0094] When the metal pigment composition of the present invention is an aqueous composition, examples of the water-soluble organic solvent contained together with water include polyhydric alcohols having three or more valences such as glycerin; glycols; glycol monoethers; lactams; monohydric alcohols, etc. One or more selected from these can be used in combination.

[0095] Examples of glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,2-hexanediol, etc. Examples of glycol monoethers include triethylene glycol monobutyl ether, etc. Examples of lactams include 2-pyrrolidone, etc. Examples of monohydric alcohols include ethanol, methanol, propanol, isopropanol, butanol, phenoxyethanol, etc.

[0096] When the metal pigment composition of the present invention is an aqueous composition, the proportion of water in all the liquid medium components constituting the metal pigment composition of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, and even more preferably 55% by mass or more. When the metal pigment composition of the present invention is an aqueous composition, the upper limit of the proportion of water in all the liquid medium components constituting the metal pigment composition of the present invention is 100% by mass.

[0097] The lower limit of the content rate of the liquid medium component in the metal pigment composition of the present invention is not particularly limited, but is preferably 60.0% by mass, more preferably 70.0% by mass, and still more preferably 75.0% by mass. Also, the upper limit of the content rate of the liquid medium component in the metal pigment composition of the present invention is not particularly limited, but is preferably 99.7% by mass, more preferably 99.5% by mass, and still more preferably 99.0% by mass. Thereby, the viscosity of the metal pigment composition can be made more suitable.

[0098] [1-4] Specific surface treatment agent The above-mentioned metal particles are surface-modified with a specific surface treatment agent.

[0099] The specific surface treatment agent is at least one selected from the group consisting of the compound represented by the above formula (1) and the compound represented by the above formula (2).

[0100] In the formula, A is any one of a hydrogen atom, a carboxyl group, a hydroxyl group, an amino group, and an oxyalkylene-containing group; R is a divalent hydrocarbon group having 10 or more carbon atoms; and a is 1 or 2. Even when A is a hydrogen atom, R is a divalent hydrocarbon group, counting the part bonded to the hydrogen atom A as monovalent. One or more kinds of the specific surface treatment agent may be selected. When two or more kinds are selected, one or more kinds may be selected from the compounds represented by the formula (1) and one or more kinds may be selected from the compounds represented by the formula (2), and the above A, R, and a may be independent for each selected compound. A in the above formula (1) and the above formula (2) is any one of a hydrogen atom, a carboxyl group, a hydroxyl group, an amino group, and an oxyalkylene-containing group. However, when the metal pigment composition of the present invention is a solvent-based composition, it is preferably a hydrogen atom, and when the metal pigment composition of the present invention is an aqueous composition, it is preferably any one of a carboxyl group, a hydroxyl group, an amino group, and an oxyalkylene-containing group. That is, (A-R) is a hydrocarbon group substituted with any one of a carboxyl group, a hydroxyl group, an amino group, and an oxyalkylene-containing group, or an unsubstituted hydrocarbon group.

[0101] Thereby, the dispersion stability of the metal particles in the metal pigment composition, the glossiness and rubbing resistance of the colored body produced using the metal pigment composition can be made more excellent.

[0102] When A in the above formula (1) and the above formula (2) is an oxyalkylene-containing group, A is a group having an oxyalkylene structure. The oxyalkylene structure is also referred to as an alkylene oxide structure. The oxyalkylene-containing group has one or more alkylene oxide units, and may have two or more. In particular, it may have a structure in which a plurality of alkylene oxide units are repeated. When A has a repeating structure of alkylene oxide units, the number of alkylene oxide units in A, that is, the number of repetitions of alkylene oxide units, is preferably 10 or less, and more preferably 4 or less. The lower limit is 1 or more, preferably 2 or more, and more preferably 3 or more. The number of carbon atoms of the alkylene in the alkylene oxide unit is preferably 1 or more and 4 or less.

[0103] R in the above formula (1) and the above formula (2) is a divalent hydrocarbon group having 10 or more carbon atoms, preferably a divalent hydrocarbon group having 10 or more and 30 or less carbon atoms. Further, the hydrocarbon group preferably has 12 or more and 28 or less carbon atoms, more preferably 13 or more and 25 or less carbon atoms, still more preferably 14 or more and 25 or less carbon atoms, and particularly preferably 15 or more and 25 or less carbon atoms.

[0104] Thereby, the dispersion stability of the metal particles in the metal pigment composition can be made excellent. In addition, the lubricity of the specific surface treatment agent itself can be made more excellent. For such reasons, the rubbing resistance and glossiness of the colored body produced using the metal pigment composition can be made more excellent.

[0105] Examples of the divalent hydrocarbon group include an alkylene group, an alkenylene group, and an alkynylene group.

[0106] The metal pigment composition of the present invention may contain a plurality of types of compounds as the specific surface treatment agent. In such a case, the same metal particles may be surface-treated with a plurality of types of surface treatment agents. Further, the metal pigment composition of the present invention may contain metal particles surface-treated with different specific surface treatment agents.

[0107] Surface treatment of metal particles with a specific surface treatment agent may be performed, for example, as described above, by including the specific surface treatment agent in a liquid when forming metal particles by pulverizing a metal film formed by a vapor deposition method in the liquid.

[0108] When performing surface treatment of the same metal particles with a plurality of types of specific surface treatment agents, the surface treatment may be performed in a plurality of steps corresponding to each specific surface treatment agent, or the surface treatment with a plurality of types of specific surface treatment agents may be performed in the same step.

[0109] In addition, the surface treatment with a specific surface treatment agent may be performed in the same step as or in a different step from the treatment with a polyoxyalkyleneamine compound. The surface treatment with a specific surface treatment agent may be performed before or after the step of treatment with a polyoxyalkyleneamine compound.

[0110] When the content rate of the polyoxyalkyleneamine compound in the metal pigment composition is XA [mass%] and the content rate of the specific surface treatment agent in the metal pigment composition is XP [mass%], the lower limit of the value of XA / XP is preferably 0.02, more preferably 0.05, and even more preferably 0.07. Also, the upper limit of the value of XA / XP is preferably 10.0, more preferably 7.0, and even more preferably 5.0. Further, it is preferably 3.0, more preferably 2.0, and even more preferably 1.5.

[0111] Thereby, the dispersion stability of the metal particles in the metal pigment composition, the glossiness of the colored body produced using the metal pigment composition, and the abrasion resistance can be made further excellent.

[0112] The lower limit of the content of the specific surface treatment agent in the metal pigment composition is not particularly limited, but is preferably 0.01% by mass, more preferably 0.03% by mass, and even more preferably 0.05% by mass. Further, the upper limit of the content of the specific surface treatment agent in the metal pigment composition is not particularly limited, but is preferably 10% by mass, more preferably 7.0% by mass, and even more preferably 5.0% by mass.

[0113] Thereby, the dispersion stability of the metal particles in the metal pigment composition, the glossiness of the colored body produced using the metal pigment composition, and the scratch resistance can be further improved.

[0114] In particular, when the metal pigment composition is the ink itself ejected by the inkjet method, the lower limit of the content of the specific surface treatment agent in the ink is not particularly limited, but is preferably 0.01% by mass, more preferably 0.03% by mass, and even more preferably 0.05% by mass. Further, when the metal pigment composition is the ink itself ejected by the inkjet method, the upper limit of the content of the specific surface treatment agent in the ink is not particularly limited, but is preferably 1.5% by mass, more preferably 1.0% by mass, and even more preferably 0.8% by mass.

[0115] Also, when the metal pigment composition is the stock solution used for preparing ink or paint or is paint, the lower limit of the content of the specific surface treatment agent in the metal pigment composition is not particularly limited, but is preferably 0.50% by mass, more preferably 0.70% by mass, and even more preferably 1.0% by mass. Further, when the metal pigment composition is the stock solution used for preparing ink ejected by the inkjet method or is paint, the upper limit of the content of the specific surface treatment agent in the metal pigment composition is not particularly limited, but is preferably 10% by mass, more preferably 7.0% by mass, and even more preferably 5.0% by mass.

[0116] The content of the specific surface treatment agent in the metallic pigment composition is not particularly limited, but is preferably 1.0 part by mass or more and 50 parts by mass or less, more preferably 1.5 parts by mass or more and 40 parts by mass or less, and still more preferably 2.0 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the metal particles.

[0117] Thereby, the dispersion stability of the metal particles in the metallic pigment composition, the glossiness and scratch resistance of the colored body produced using the metallic pigment composition can be further improved. Further, when the metallic pigment composition is an inkjet composition, the ejection stability of the inkjet composition, particularly the ejection stability when stored for a long period or under harsh conditions, can be further improved.

[0118] [1-5] Other components The metallic pigment composition of the present invention may contain components other than those described above. Hereinafter, these components are also referred to as other components. Examples of such components include surface treatment agents other than the specific surface treatment agent, leveling agents, binders, polymerization accelerators, polymerization inhibitors, photopolymerization initiators, dispersants, surfactants, penetration accelerators, humectants, colorants, fixing agents, antifungal agents, preservatives, antioxidants, chelating agents, thickeners, sensitizers, and the like.

[0119] The binder may be a resin, and preferred examples include acrylic resins, ester resins, urethane resins, and cellulose resins.

[0120] Preferred examples of the surfactant include silicone surfactants and acetylene glycol surfactants.

[0121] However, the content rate of other components in the metallic pigment composition of the present invention is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and still more preferably 2.0% by mass or less.

[0122] [1-6] Others The metallic pigment composition of the present invention is a coloring composition or a composition used in the preparation of a coloring composition. The coloring composition is, for example, used as it is for forming a colored portion. That is, it is a composition that is attached to an object to be colored to color the object. That is, it is a composition that is used in the attachment step in the coloring method described below. In this case, examples of the coloring composition include inks, paints, etc. Examples of the ink include, but are not limited to, inkjet inks, etc. The composition used for preparing the coloring composition is not used in the adhesion step in the coloring method described below, but is used for preparing the coloring composition, and the obtained coloring composition is used in the coloring method. In other words, the composition is prepared by mixing with other components and adjusting the concentration, and then used for forming the colored portion. In this case, examples of the coloring composition include a pigment dispersion and a concentrate.

[0123] In particular, when the metallic pigment composition of the present invention is a coloring composition, the metallic pigment composition can be used as is for producing a colored body without adjusting the concentration by dilution or the like or adjusting the composition.

[0124] The coloring composition is a composition that is applied to a target object to color the target object. Examples of the coloring composition include inks, paints, etc. Examples of the ink include, but are not limited to, inkjet inks, etc.

[0125] In particular, the metal pigment composition is preferably an inkjet ink. Conventionally, when a metallic pigment composition is applied to an inkjet method, there has been a problem that the ejection stability by the inkjet method and the glossiness and abrasion resistance of the produced colored body are likely to decrease, but according to the present invention, the occurrence of such problems can be effectively prevented. In other words, when the metallic pigment composition is an inkjet ink, the effects of the present invention are more remarkable. An inkjet ink is an ink that is ejected from an inkjet head by an inkjet method and used for recording.

[0126] The object to be treated is an object to be colored, that is, a colored object, to which a coloring composition is attached. When the coloring composition is an ink, the object to be treated is usually a recording medium. The object to be treated is not particularly limited, and examples include, in addition to recording media, plates, walls, floors, walls, fences, automobiles, and other articles.

[0127] As the recording medium, either absorbent or non-absorbent can be used. For example, paper such as plain paper and dedicated paper for inkjet, plastic materials, metals, ceramics, wood, shells, cotton, natural fibers and synthetic fibers such as polyester and wool, non-woven fabrics, etc. can be used, but it is preferably a non-colored body. Also, the shape of the recording medium is not particularly limited and can be any shape such as a sheet. Examples of the recording medium made of a plastic material include a plastic film and a plastic sheet. Examples of the plastic include, but are not limited to, vinyl chloride, polyester, polyolefin, etc. Examples of the polyester include polyethylene terephthalate.

[0128] The composition used for preparing the coloring composition is a composition for obtaining the coloring composition by mixing the composition and other components necessary for the coloring composition. The composition used for preparing the coloring composition is also referred to as a pigment dispersion or a pigment dispersion used for preparing the coloring composition. Therefore, the content of the metal pigment in the composition used for preparing the coloring composition is higher than the content of the metal pigment in the coloring composition obtained by using the composition used for preparing the coloring composition.

[0129] The upper limit of the viscosity at 25°C of the metal pigment composition of the present invention, measured in accordance with JIS Z8809 using a rotational viscometer, is not particularly limited, but is preferably 25 mPa·s, and more preferably 15 mPa·s. Further, the lower limit of the viscosity at 25°C of the metal pigment composition of the present invention, measured in accordance with JIS Z8809 using a rotational viscometer, is not particularly limited, but is preferably 1.5 mPa·s.

[0130] Thereby, for example, when the metal pigment composition is an ink ejected by an inkjet method, the droplet ejection of the ink by the inkjet method can be performed more suitably.

[0131] [2] Coloring method Next, the coloring method of the present invention will be described.

[0132] The coloring method of the present invention includes a step of attaching the metal pigment composition of the present invention, which is a coloring composition, to a treatment object, which is an object to be colored (attachment step).

[0133] Thereby, it is possible to provide a coloring method that can be applied to the production of a colored body excellent in gloss and abrasion resistance.

[0134] The step of attaching the metal pigment composition of the present invention to the treatment object can be performed by various printing methods such as the inkjet method, or various coating methods using a bar coater, a spray, a roll coater, a brush, etc. When the coloring composition is an ink, the coloring method is also a recording method.

[0135] When the metal pigment composition is ejected by the inkjet method, as the inkjet method, a piezo method, a method of ejecting the ink by bubbles generated by heating the ink, etc. can be used, but from the viewpoint of the difficulty of altering the metal pigment composition, etc., the piezo method is preferable.

[0136] The ejection of the metal pigment composition by the inkjet method can be performed using a known droplet ejection device.

[0137] The colored part formed by the metal pigment composition may have, for example, a predetermined pattern or may be formed on the entire surface of the object to be treated.

[0138] [3] Colored body Next, the colored body according to the present invention will be described.

[0139] The colored body according to the present invention is manufactured by applying the metal pigment composition as described above to the object to be colored, which is the object to be treated.

[0140] Such a colored body has a colored part that is excellent in glossiness and abrasion resistance and in which the occurrence of defects is prevented.

[0141] The colored body according to the present invention may be for any use, and may be applied to, for example, recording materials, ornaments, or others. Specific examples of the colored body according to the present invention include vehicle interior parts such as console lids, switch bases, center clusters, interior panels, emblems, center consoles, and meter nameplates, operation parts of various electronic devices, decorative parts that exhibit decorativeness, and display items such as indicators and logos.

[0142] As described above, the present invention has been described based on preferred embodiments, but the present invention is not limited thereto.

Example

[0143] Next, specific examples of the present invention will be described. [4] Production of Metal Pigment Composition A (Example A1) First, a polyethylene terephthalate film with a surface roughness Ra of 0.02 μm or less and a smooth surface and a thickness of 20 μm was prepared.

[0144] Next, a release layer was formed by coating the entire one surface of this film with a release resin solubilized with acetone using a roll coater.

[0145] A polyethylene terephthalate film with a release layer formed thereon was conveyed into a vacuum evaporation apparatus at a speed of 5 m / s, and a 15-nm-thick film composed of Al was formed under reduced pressure.

[0146] Next, the polyethylene terephthalate film with the Al film formed thereon was immersed in tetrahydrofuran, and ultrasonic vibration at 40 kHz was applied to obtain a dispersion of a metal pigment, which is an aggregate of Al metal particles.

[0147] Next, tetrahydrofuran was removed with a centrifuge, and diethylene glycol diethyl ether was added to obtain a suspension with a metal pigment content of 5% by mass.

[0148] Next, this suspension was treated with a circulation-type high-power ultrasonic mill to grind the metal particles until they reached a predetermined size. In this treatment, ultrasonic waves at 20 kHz were applied.

[0149] Next, the polyoxyalkyleneamine compound represented by the above formula (4) was added to the suspension at a mass ratio to the metal particles that is the value in Table 1, and heat treatment was performed at 55 °C for 1 hour under ultrasonic irradiation at 40 kHz to disperse the metal particles in the state of primary particles by dissociating the aggregation of the metal particles. Here, as the polyoxyalkyleneamine compound, a block copolymer in which an amino group is bonded to the end of continuous oxyethylene units and a methyl group is bonded to the end of continuous oxypropylene units was used, satisfying the condition that m / n is 6.3 between m and n in the above formula (4) and having a weight average molecular weight of 1000.

[0150] Furthermore, a specific surface treatment agent, which is the compound represented by the above formula (1), was added thereto at a mass ratio to the metal particles that is the value in Table 1. In this example, as the specific surface treatment agent, a mixture of a compound in which A in the above formula (1) is a hydrogen atom, R is an n-decylene group, and a is 1 and a compound in which a is 2 was used.

[0151] Then, by performing heat treatment at 55 °C for 3 hours under 28 kHz ultrasonic irradiation, a specific surface treatment agent was reacted on the surface of the metal particles to obtain a dispersion of metal particles surface-modified with the specific surface treatment agent.

[0152] Subsequently, diethylene glycol diethyl ether, tetraethylene glycol monobutyl ether, and γ-butyrolactone were added to the obtained dispersion of metal particles, and a metal pigment composition, which is a pigment dispersion, was obtained as a composition used for preparing a coloring composition. Cellulose acetate butyrate was added to the obtained pigment dispersion to obtain a metal pigment composition, which is a coloring composition having the composition shown in Table 1. It was a solvent-based composition.

[0153] The volume average particle diameter of the metal particles contained in the metal pigment composition thus obtained was 0.50 μm, and the average thickness was 15 nm.

[0154] (Examples A2 - A17) The metal pigment was configured as shown in Tables 1 and 2, and by changing the types and ratios of the raw materials contained, a metal pigment composition was produced in the same manner as in Example A1 except that the composition shown in Table 1 was obtained. The average thickness of the metal particles was adjusted during the deposition of Al. The average particle diameter of the metal particles was adjusted by controlling the amount of pulverization during ultrasonic pulverization.

[0155] (Example A18) First, a polyethylene terephthalate film with a surface roughness Ra of 0.02 μm or less and a smooth surface and a thickness of 20 μm was prepared.

[0156] Next, a release layer was formed by coating the entire one surface of this film with a release resin solubilized with acetone using a roll coater.

[0157] The polyethylene terephthalate film with the release layer formed was conveyed into a vacuum deposition apparatus at a speed of 5 m / s, and a film with a thickness of 17.4 nm composed of Al was formed under reduced pressure.

[0158] Next, a polyethylene terephthalate film with an Al film formed thereon was immersed in tetrahydrofuran, and ultrasonic vibration at 40 kHz was applied to obtain a dispersion of a metal pigment which is an aggregate of Al metal particles.

[0159] Next, tetrahydrofuran was removed with a centrifuge, and diethylene glycol diethyl ether was added to obtain a suspension having a metal pigment content of 5% by mass.

[0160] Next, this suspension was treated with a circulation-type high-power ultrasonic mill to grind the metal particles until they reached a predetermined size. In this treatment, ultrasonic waves at 20 kHz were applied.

[0161] Next, the polyoxyalkyleneamine compound represented by the above formula (4) was added at a mass ratio to the metal particles such that the value in Table 2 was obtained, and heat treatment was performed at 55 °C for 1 hour under ultrasonic irradiation at 40 kHz to disperse the metal particles in a state of primary particles by dissociating the aggregation of the metal particles. Here, as the polyoxyalkyleneamine compound, a block copolymer in which an amino group is bonded to the end of a continuous oxyethylene unit and a methyl group is bonded to the end of a continuous oxypropylene unit was used, satisfying the condition of m / n = 6.3 between m and n in the above formula (4) and having a weight average molecular weight of 1000.

[0162] Furthermore, a specific surface treatment agent which is the compound represented by the above formula (2) was added thereto at a mass ratio to the metal particles such that the value in Table 2 was obtained. In this example, as the specific surface treatment agent, a compound in which A in the above formula (2) is a carboxyl group, R is an n-decylene group, and a is 1 was used.

[0163] Then, heat treatment was performed at 55 °C for 3 hours under ultrasonic irradiation at 28 kHz to react the specific surface treatment agent on the surface of the metal particles. Next, diethylene glycol diethyl ether was replaced with water. Thus, a metal pigment composition, which is a pigment dispersion, was obtained as a composition used for preparing a coloring composition containing 5% by mass of metal particles surface-modified with a specific surface treatment agent. Water, 1,2-hexanediol, propylene glycol, and a urethane resin (Resamin D1060 manufactured by Dainippon Ink and Chemicals, Inc.) were added to the obtained pigment dispersion to obtain a metal pigment composition, which is a coloring composition having the composition shown in Table 2. It was an aqueous composition.

[0164] The volume average particle diameter of the metal particles contained in the metal pigment composition thus obtained was 0.50 μm, and the average thickness was 15 nm.

[0165] (Examples A19 to A23) A metal pigment composition was produced in the same manner as in Example A18, except that the types of raw materials contained were changed to obtain the composition shown in Table 2.

[0166] (Comparative Examples A1 to A3) A metal pigment composition was produced in the same manner as in Example A1, except that the types of raw materials used for preparing the metal pigment composition were changed to obtain the composition shown in Table 1.

[0167] (Comparative Examples A4 to A6) A metal pigment composition was produced in the same manner as in Example A18, except that the types of raw materials used for preparing the metal pigment composition were changed to obtain the composition shown in Table 2.

[0168] For each of the above Examples and Comparative Examples, the constitution of the metal pigment contained in the metal pigment composition which is a coloring composition and the composition of the metal pigment composition which is a coloring composition are summarized in Tables 1 and 2. In the tables, a mixture of the compound of a = 1 and the compound of a = 2, which is the surface treatment agent represented by the above formula (1) and in which A in the formula (1) is a hydrogen atom, R is an n-decylene group, is designated as "(1)-1"; a mixture of the compound of a = 1 and the compound of a = 2, which is the surface treatment agent represented by the above formula (1) and in which A in the formula (1) is a hydrogen atom, R is an n-dodecylene group, is designated as "(1)-2"; a mixture of the compound of a = 1 and the compound of a = 2, which is the surface treatment agent represented by the above formula (1) and in which A in the formula (1) is a hydrogen atom, R is an n-octadecylene group, is designated as "(1)-3"; a mixture of the compound of a = 1 and the compound of a = 2, which is the surface treatment agent represented by the above formula (1) and in which A in the formula (1) is a hydrogen atom, R is an n-oleylene group, is designated as "(1)-4"; a mixture of the compound of a = 1 and the compound of a = 2, which is the surface treatment agent represented by the above formula (1) and in which A in the formula (1) is a hydrogen atom, R is an n-tetracosylene group, is designated as "(1)-5"; the compound of a = 1, which is the surface treatment agent represented by the above formula (2) and in which A in the formula (2) is a hydrogen atom, R is an n-dodecylene group, is designated as "(2)-1"; the compound of a = 1, which is the surface treatment agent represented by the above formula (2) and in which A in the formula (2) is a hydrogen atom, R is an n-octadecylene group, is designated as "(2)-2"; the compound of a = 1, which is the surface treatment agent represented by the above formula (2) and in which A in the formula (2) is a carboxyl group, R is an n-decylene group, is designated as "(2)-3"; the compound of a = 1, which is the surface treatment agent represented by the above formula (2) and in which A in the formula (2) is a hydroxyl group, R is an n-undecylene group, is designated as "(2)-4"; the compound of a = 1, which is the surface treatment agent represented by the above formula (2) and in which A in the formula (2) is an amino group, R is an n-undecylene group, is designated as "(2)-5"; the compound of a = 1, which is the surface treatment agent represented by the above formula (2) and in which A in the formula (2) is a 2-[2-(2-methoxyethoxy)ethoxy]ethoxy group, R is an n-undecylene group, is designated as "(2)-6"; the polyoxyalkyleneamine compound represented by the above formula (4), in which m / n is 9 between m and n...Those satisfying the condition of 0 and having a weight average molecular weight of 600 are designated as "POAA1", which is a polyoxyalkyleneamine compound represented by the above formula (4), satisfying the condition that m / n is 6.3 between m and n and having a weight average molecular weight of 1000 is designated as "POAA2", which is a polyoxyalkyleneamine compound represented by the above formula (4), satisfying the condition that m / n is 3.1 between m and n and having a weight average molecular weight of 2000 is designated as "POAA3", diethylene glycol diethyl ether is designated as "DEDG", tetraethylene glycol monobutyl ether is designated as "BTGH", γ-butyrolactone is designated as "γBL", 1,2-hexanediol is designated as "1,2HD", propylene glycol is designated as "PG", cellulose acetate butyrate is designated as "CAB", urethane resin (manufactured by Dainippon Ink and Chemicals, Inc., Resamin D1060) is designated as "D1060", octyl phosphate is designated as "OdHP", CF3(CF2)5(CH2)2P(O)-(OH)2 is designated as "FHP", and polyoxyethylene polyoxypropylene block polymer (PE68, manufactured by Sanyo Chemical Industries, Ltd.) is designated as "PE68". Also, in Tables 1 and 2, the unit of the content of each component is mass%. Note that POAA1 to POAA3 are all block copolymers in which an amino group is bonded to the terminal of a continuous oxyethylene unit and a methyl group is bonded to the terminal of a continuous oxypropylene unit. Also, regarding the metal pigments constituting the metal pigment compositions of the respective examples, observations were made on 50 arbitrary metal particles each. As a result, when observed from the direction in which the projected area is the largest, that is, when viewed in plan view, the area S1 [μm. 2 and the area S0 [μm when observed from the direction in which the area is the largest among the directions orthogonal to the observation direction 2 The ratio S1 / S0 with respect to was determined, and when the average values thereof were determined, the average values of S1 / S0 were all 19 or more. The volume average particle diameter D50 in the table was measured using Microtrac MT-3300 (manufactured by Microtrac Bell Corporation, laser diffraction / scattering particle size distribution measuring device). Also, using a rotational viscometer, the viscosities at 25°C of the metal pigment compositions of Examples A1 to A23 measured in accordance with JIS Z8809 were all values within the range of 1.5 mPa·s or more and 15 mPa·s or less.

[0169]

Table 1

[0170]

Table 2

[0171] [5] Evaluation A [5-1] Dispersion stability of metal particles The metal pigment compositions, which are the coloring compositions of the respective examples and comparative examples, were each filled into a predetermined ink pack, left standing in a thermostat at 55°C for 8 days, and then gradually cooled to room temperature.

[0172] Thereafter, for these metal pigment compositions, measurement was carried out using a particle size distribution meter (MT3300EXII manufactured by Microtrac), the volume average particle diameter D50 of the metal particles was determined, the increase rate from the volume average particle diameter D50 of the metal particles contained in the metal pigment composition before being put into the thermostat was determined, and evaluation was carried out according to the following criteria. It can be said that the smaller the increase rate of the volume average particle diameter D50, the better the dispersion stability of the metal particles. C or more was set as a good level.

[0173] A: The increase rate of the volume average particle diameter D50 is less than 2%. B: The increase rate of the volume average particle diameter D50 is 2% or more and less than 7%. C: The increase rate of the volume average particle diameter D50 is 7% or more and less than 13%. D: The increase rate of the volume average particle diameter D50 is 13% or more.

[0174] [5-2] Gloss of the colored body First, using the metal pigment compositions, which are the coloring compositions of the respective examples and comparative examples, colored bodies were produced as follows.

[0175] That is, first, the metal pigment composition is put into an inkjet device, and using the inkjet device, on a polyvinyl chloride film (manufactured by Mactac, Mactac 5829R) as a recording medium, 5 mg / inch 2 , with a recording resolution of 1440×1440 dpi, the metal pigment composition is ejected to form a printed portion, thereby obtaining a colored body. As the inkjet device, a modified machine of SC-S606850 manufactured by Seiko Epson Corporation was used. The inkjet device has a nozzle density of 360 npi in the nozzle row and 360 nozzles. Also, the recording medium temperature of the platen during the adhesion of the metal pigment composition was 45°C, and the recording medium temperature of the after-heater was 50°C.

[0176] Regarding the printed portions of the colored bodies according to the above-described respective examples and comparative examples, using a MINOLTA MULTI GLOSS 268, which is a gloss meter, the glossiness at a flaring angle of 60° was measured and evaluated according to the following criteria. It can be said that the larger this value is, the better the glossiness. A level of C or higher was regarded as a good level.

[0177] <Evaluation Criteria for Examples A1 to A17 and Comparative Examples A1 to A3> A: The glossiness is 460 or more. B: The glossiness is 440 or more and less than 460. C: The glossiness is 410 or more and less than 440. D: The glossiness is less than 410.

[0178] <Evaluation Criteria for Examples A18 to A23 and Comparative Examples A4 to A6> A: The glossiness is 360 or more. B: The glossiness is 310 or more and less than 360. C: The glossiness is 260 or more and less than 310. D: The glossiness is less than 260.

[0179] [5-3] Rub Resistance For each printed portion of each colored body obtained in the above [5-2], after rubbing back and forth 20 times with a 500 g load using a gold cloth, the printed portion was visually inspected, and the peeled portion of the printed portion was evaluated according to the following criteria. It can be said that the smaller this value is, the better the rubbing resistance. A level of C or higher was regarded as good.

[0180] A: The area ratio of the peeled portion of the printed portion is less than 10%. B: The area ratio of the peeled portion of the printed portion is 10% or more and less than 20%. C: The area ratio of the peeled portion of the printed portion is 20% or more and less than 30%. D: The area ratio of the peeled portion of the printed portion is 30% or more. These results are shown in Table 3.

[0181]

Table 3

[0182] As is clear from Table 3, all of the examples using the metal pigment composition of the present invention were suitable for producing colored bodies with excellent dispersion stability of metal particles, glossiness, and rubbing resistance. On the other hand, all of the comparative examples not using the metal pigment composition of the present invention were inferior in any of dispersion stability, glossiness, and rubbing resistance. In addition, although it was possible to discharge from the inkjet head in any of the examples, particularly, in the examples with a dispersion stability of C or higher, good discharge stability was possible, and the higher the dispersion stability, the fewer discharge defects such as flight deflection and non-discharge.

[0183] In addition, the same evaluations as in the above [5-2] and [5-3] were performed except that a polyethylene terephthalate film (manufactured by Lintec Corporation, E1000ZC) was used instead of the polyvinyl chloride film (manufactured by Mactac Corporation, Mactac5829R) as the recording medium, and the same results as above were obtained.

[0184] [6] Production of Metal Pigment Composition B (Example B1) First, a polyethylene terephthalate film with a surface roughness Ra of 0.02 μm or less and a smooth surface and a thickness of 20 μm was prepared.

[0185] Next, a release layer was formed by coating the entire one surface of this film with a release resin solubilized with acetone using a roll coater.

[0186] The polyethylene terephthalate film with the release layer formed thereon was conveyed into a vacuum deposition apparatus at a speed of 5 m / s, and a film with a thickness of 15 nm composed of Al was formed under reduced pressure.

[0187] Next, the polyethylene terephthalate film with the Al film formed thereon was immersed in tetrahydrofuran, and ultrasonic vibration of 40 kHz was applied thereto, whereby a dispersion of a metal pigment, which is an aggregate of Al metal particles, was obtained.

[0188] Next, tetrahydrofuran was removed with a centrifuge, and diethylene glycol diethyl ether was added to obtain a suspension having a metal pigment content of 5% by mass.

[0189] Next, this suspension was treated with a circulation type high-power ultrasonic crusher to grind the metal particles until they reached a predetermined size. In this treatment, ultrasonic waves of 20 kHz were applied.

[0190] Next, the polyoxyalkyleneamine compound represented by the above formula (4) was added to the suspension at a mass ratio to the metal particles such that the value in Table 4 was obtained, and heat treatment was performed at 55 °C for 1 hour under irradiation with ultrasonic waves of 40 kHz, whereby the aggregation of the metal particles was resolved and the metal particles were dispersed in the state of primary particles. Here, as the polyoxyalkyleneamine compound, a block copolymer in which an amino group is bonded to the terminal of a continuous oxyethylene unit and a methyl group is bonded to the terminal of a continuous oxypropylene unit was used, which satisfies the condition that m / n is 6.3 between m and n in the above formula (4) and has a weight average molecular weight of 1000.

[0191] Furthermore, a specific surface treatment agent, which is the compound represented by the above formula (1), was added thereto at a mass ratio to the metal particles such that the value was as shown in Table 4. In this example, as the specific surface treatment agent, a mixture of a compound in which A in the above formula (1) is a hydrogen atom, R is an n-octadecylene group, and a is 1 and a compound in which a is 2 was used.

[0192] Then, by performing heat treatment at 55 °C for 3 hours under irradiation with ultrasonic waves of more than 28 kHz, the specific surface treatment agent was reacted on the surface of the metal particles to obtain a dispersion of metal particles surface-modified with the specific surface treatment agent.

[0193] After that, diethylene glycol diethyl ether in the obtained dispersion of metal particles was volatilized, and the metal pigment was adjusted to 10% by mass, and a metal pigment composition B1, which is a pigment dispersion, was obtained as a composition used for preparing a coloring composition.

[0194] The volume average particle diameter of the metal particles contained in the metal pigment composition thus obtained was 0.50 μm, and the average thickness was 15 nm.

[0195] Diethylene glycol diethyl ether, tetraethylene glycol monobutyl ether, γ-butyrolactone, and cellulose acetate butyrate were added to the composition obtained as described above and used for preparing a coloring composition, and a metal pigment composition C1, which is an ink as a coloring composition having the composition shown in Table 5, was obtained.

[0196] The volume average particle diameter of the metal particles contained in the metal pigment composition thus obtained was 0.50 μm, and the average thickness was 15 nm.

[0197] (Example B2) First, a polyethylene terephthalate film having a surface roughness Ra of 0.02 μm or less and a smooth surface with a thickness of 20 μm was prepared.

[0198] Next, a release layer was formed by coating the entire one surface of this film with a release resin solubilized with acetone using a roll coater.

[0199] The polyethylene terephthalate film with the release layer formed was conveyed into a vacuum deposition apparatus at a speed of 5 m / s, and a 15-nm-thick film composed of Al was formed under reduced pressure.

[0200] Next, the polyethylene terephthalate film with the Al film formed was immersed in tetrahydrofuran, and ultrasonic vibration of 40 kHz was applied to obtain a dispersion of a metal pigment which is an aggregate of Al metal particles.

[0201] Next, tetrahydrofuran was removed with a centrifuge, and diethylene glycol diethyl ether was added to obtain a suspension having a metal pigment content of 5% by mass.

[0202] Next, this suspension was treated with a circulation-type high-power ultrasonic crusher to crush the metal particles until they reached a predetermined size. In this treatment, ultrasonic waves of 20 kHz were applied.

[0203] Next, the polyoxyalkyleneamine compound represented by the above formula (4) was added to the suspension at a mass ratio to the metal particles such that the value in Table 4 was obtained, and heat treatment was performed at 55 °C for 1 hour under ultrasonic irradiation of 40 kHz to disperse the metal particles in a state of primary particles by dissociating the aggregation of the metal particles. Here, as the polyoxyalkyleneamine compound, a block copolymer in which an amino group is bonded to the terminal of a continuous oxyethylene unit and a methyl group is bonded to the terminal of a continuous oxypropylene unit was used, which satisfies the condition of m / n = 6.3 between m and n in the above formula (4) and has a weight average molecular weight of 1000.

[0204] Furthermore, a specific surface treatment agent, which is the compound represented by the above formula (1), was added thereto at a mass ratio to the metal particles such that the value in Table 4 was obtained. In this example, as the specific surface treatment agent, a mixture of a compound in which A in the above formula (1) is a hydrogen atom, R is an n-octadecylene group, and a is 1 and a compound in which a is 2 was used.

[0205] Then, by performing heat treatment at 55°C for 3 hours under 28 kHz ultrasonic irradiation, the specific surface treatment agent was reacted on the surface of the metal particles to obtain a dispersion of metal particles surface-modified with the specific surface treatment agent.

[0206] Thereafter, diethylene glycol diethyl ether was volatilized from the obtained dispersion of metal particles, butyl acetate was added, and the metal pigment was adjusted to 10% by mass to obtain a metal pigment composition B2, which is a pigment dispersion, as a composition for use in the preparation of a coloring composition.

[0207] The volume average particle diameter of the metal particles contained in the metal pigment composition thus obtained was 0.50 μm, and the average thickness was 15 nm.

[0208] To the composition B2 for use in the preparation of a coloring composition, obtained as described above, methyl ethyl ketone, isopropyl alcohol, and a urethane resin (manufactured by DIC Corporation, Barnock 16-416) were added to obtain a metal pigment composition C2, which is a paint as a coloring composition having the composition shown in Table 5.

[0209] The volume average particle diameter of the metal particles contained in the metal pigment composition thus obtained was 0.50 μm, and the average thickness was 15 nm.

[0210] For Examples B1 and B2, the conditions of the metal pigment composition as the composition used for preparing the coloring composition are summarized in Table 4. For metal pigment compositions C1 and C2 as the coloring composition, the amounts of materials used in the preparation are summarized in Table 5. In the table, a mixture of the compound in which A in the formula (1) is a hydrogen atom, R is an n-octadecylene group, and a is 1 and the compound in which a is 2 among the surface treatment agents represented by the above formula (1) is denoted as "(1)-3", a polyoxyalkyleneamine compound represented by the above formula (4) that satisfies the condition of m / n = 6.3 between m and n and has a weight average molecular weight of 1000 is denoted as "POAA2", diethylene glycol diethyl ether is denoted as "DEDG", tetraethylene glycol monobutyl ether is denoted as "BTGH", γ-butyrolactone is denoted as "γBL", methyl ethyl ketone is denoted as "MEK", isopropyl alcohol is denoted as "IPA", and a urethane resin (manufactured by DIC Corporation, Barnock 16-416) is denoted as "16-416". In addition, in Table 4, the unit of the content of each component is mass%, and in Table 5, the unit of the amount of each raw material used is part by mass. Regarding the metal pigments constituting the metal pigment compositions of Examples B1 and B2, as a result of observing 50 arbitrary metal particles respectively, the S1 / S0 was determined, and when the average values thereof were determined, the average values of S1 / S0 were all 19 or more. The volume average particle diameter D50 in the table was measured using Microtrac MT-3300 (manufactured by Microtrac Bell Corporation, laser diffraction / scattering particle size distribution measuring device).

[0211]

Table 4

[0212]

Table 5

[0213] [7] Evaluation B [7-1] Dispersion stability of metal particles The metal pigment compositions, which are the coloring compositions of Examples C1 and C2, were respectively filled into predetermined ink packs, left in a thermostat at 55°C for 10 days, and then gradually cooled to room temperature.

[0214] Thereafter, for these metal pigment compositions, measurements were performed using a particle size distribution analyzer (MT3300EXII manufactured by Microtrac) to obtain the volume average particle diameter D50 of the metal particles, and the increase rate from the volume average particle diameter D50 of the metal particles contained in the metal pigment composition before being placed in the thermostat was determined and evaluated according to the following criteria. The smaller the increase rate of the volume average particle diameter D50, the better the dispersion stability of the metal particles. C or more was regarded as a good level.

[0215] A: The increase rate of the volume average particle diameter D50 is less than 2%. B: The increase rate of the volume average particle diameter D50 is 2% or more and less than 7%. C: The increase rate of the volume average particle diameter D50 is 7% or more and less than 13%. D: The increase rate of the volume average particle diameter D50 is 13% or more.

[0216] [7-2] Gloss of the Colored Body First, using the metal pigment compositions, which are the coloring compositions of Examples C1 and C2, colored bodies were produced as follows.

[0217] That is, a bar coater was used to apply the metal pigment composition onto a polyvinyl chloride film (Mactac 5829R manufactured by Mactac) as a recording medium to form a colored portion, thereby obtaining a colored body.

[0218] Regarding the colored portions of the colored bodies according to Examples B1 and B2 obtained as described above, the glossiness at a flaring angle of 60° was measured using a gloss meter, MINOLTA MULTI GLOSS 268, and evaluated according to the following criteria. The larger this value, the better the glossiness. C or more was regarded as a good level.

[0219] A: The glossiness is 460 or more. B: The glossiness is 440 or more and less than 460. C: The glossiness is 410 or more and less than 440. D: The glossiness is less than 410.

[0220] [7-3] Rub resistance For each colored part of each colored body obtained in [7-2] above, after rubbing back and forth 20 times with a 500 g load using a gold cloth, the printed part was visually confirmed, and for the peeled part of the printed part, evaluation was carried out according to the following criteria. The smaller this value is, the better the rub resistance can be said to be. C or more was set as a good level.

[0221] A: The area ratio of the peeled part of the printed part is less than 10%. B: The area ratio of the peeled part of the printed part is 10% or more and less than 20%. C: The area ratio of the peeled part of the printed part is 20% or more and less than 30%. D: The area ratio of the peeled part of the printed part is 30% or more. These results are shown in Table 6.

[0222]

Table 6

[0223] As is clear from Table 6, the metal pigment composition of the present invention is excellent in the dispersion stability of metal particles and can be suitably applied to the production of colored bodies excellent in glossiness and rub resistance.

[0224] In addition, except that a polyethylene terephthalate film (manufactured by Lintec Corporation, E1000ZC) was used instead of a polyvinyl chloride film (manufactured by Mactac, Mactac5829R) as the recording medium, the same evaluations as in [7-2] and [7-3] above were carried out, and the same results as above were obtained.

Claims

1. A metal pigment, a polyoxyalkyleneamine compound, and a liquid medium component are contained, The metal pigment is composed of a plurality of metal particles, The metal particles are surface-modified with a surface treatment agent, The surface treatment agent is at least one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2), The metal particles are made of aluminum or an aluminum alloy, The polyoxyalkyleneamine compound is a compound represented by the following formula (3) or a salt thereof, The content of the polyoxyalkyleneamine compound is 1.0 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the metal particles, It is a solvent-based composition containing an organic solvent as the liquid medium component, The ratio of the organic solvent in the total liquid medium component constituting the metal pigment composition is 60% by mass or more, The organic solvent is one or more selected from glycol ethers and cyclic esters, The water content rate in the total liquid medium component is 1.0% by mass or less, A metal pigment composition which is a coloring composition or a composition used for preparing a coloring composition. (A-R-O) ａ P(O)(OH) ３－ａ (1) (A-R) ａ P(O)(OH) ３－ａ (2) (In formula (1) and formula (2), A is any one of a hydrogen atom, a carboxyl group, a hydroxyl group, an amino group, and an oxyalkylene-containing group, R is a divalent hydrocarbon group having 10 or more carbon atoms, and a is 1 or 2.) R1-(O-R2)x-NH2 (3) (In formula (3), R1 is a hydrogen atom or an alkyl group having 4 or less carbon atoms, R2 is an alkylene group having 5 or less carbon atoms, X is an integer of 5 or more, and the polyoxyalkyleneamine compound may contain a plurality of types of alkylene groups having different conditions of R2 in the molecule.)

2. The metal pigment composition according to claim 1, wherein the polyoxyalkyleneamine compound is a compound represented by the following formula (4) or a salt thereof. R １ -(OCH ２ CH ２ ) ｍ -(OCH ２ CH(CH ３ )) ｎ -NH ２ (4) (wherein, R １ is a hydrogen atom or an alkyl group having 4 or less carbon atoms, n and m are each independently 0 or an integer of 1 or more, and m + n is an integer of 10 or more. The order of the oxyethylene unit and the oxypropylene unit in the molecule of the polyoxyalkyleneamine compound is not limited.)

3. The metal pigment composition according to claim 1 or 2, wherein the weight average molecular weight of the polyoxyalkyleneamine compound is 400 or more and 8000 or less.

4. The metal pigment composition according to any one of claims 1 to 3, wherein the content of the polyoxyalkyleneamine compound is 2.0 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the metal particles.

5. The metal pigment composition according to any one of claims 1 to 4, wherein the metal particles are made of aluminum.

6. The metal pigment composition according to any one of claims 1 to 5, wherein the metal particles are flaky.

7. The organic solvent contains one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetraethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol n-butyl ether, tripropylene glycol dimethyl ether, triethylene glycol diethyl ether, 1,2-dimethoxyethane, bis(2-methoxyethyl) ether, and γ-butyrolactone. The metal pigment composition according to any one of claims 1 to 6.

8. The metal pigment composition according to any one of claims 1 to 7, containing a resin as a binder.

9. The metal pigment composition according to any one of claims 1 to 8, wherein the content of the surface treatment agent is 1.0 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the metal particles.

10. The metal pigment composition according to any one of claims 1 to 9, wherein the metal pigment composition is the coloring composition.

11. The metal pigment composition according to any one of claims 1 to 10, wherein the metal pigment composition is an inkjet ink.

12. A coloring method comprising a step of attaching the metal pigment composition according to any one of claims 1 to 11, which is the coloring composition, to an object to be treated.

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