Water-based composition and coloring method

Abstract

To provide a water-based composition that is excellent in water resistance and dispersion stability of metal particles and can be suitably applied to the manufacture of a recorded material having excellent glossiness; and a coloring method that can be applied to the manufacture of a recorded material having excellent glossiness.SOLUTION: A water-based composition of the present disclosure contains a metal pigment, a polyoxyalkylene amine compound, and a water-based medium. The metal pigment is formed of a plurality of metal particles. The metal particles are surface-modified with a surface treatment agent. The content of the polyoxyalkylene amine compound is from 0.1 pt.mass to 50 pts.mass inclusive based on 100 pts.mass of the metal particles.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a water-based composition and a coloring method. [Background technology]

[0002] BACKGROUND ART Conventionally, metal plating, foil stamping using metal foil, thermal transfer using metal foil, and the like have been used as methods for manufacturing decorative articles with a glossy appearance. However, these methods have the problem that they are difficult to apply to curved surfaces.

[0003] On the other hand, compositions containing pigments or dyes are used as inkjet inks that are applied to recording media by inkjet printing, or as paints, which are advantageous in that they can be suitably applied to recording on curved surfaces.

[0004] In particular, in recent years, there has been a demand for the use of aqueous compositions for the above-mentioned compositions, taking into consideration the burden on the environment and the health of workers.

[0005] However, simply applying metal particles instead of pigments or dyes poses the problem that the inherent properties of metals, such as luster, cannot be fully exhibited.

[0006] In order to solve the above problems, it has been proposed to use metal particles whose surfaces have been treated with a fluorine-based compound (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-212018 Summary of the Invention [Problem to be solved by the invention]

[0008] Although this improves the dispersibility of the metal particles in the composition to some extent, the dispersion stability and the glossiness of the recording material produced using the composition are insufficient. In particular, in the case of aqueous compositions, the above-mentioned problems are significant, and there is also the problem that the metal particles react with water and tend to generate gas during storage, i.e., the water resistance is low. Therefore, there is a demand for further improvements in the dispersion stability of the metal particles, the water resistance of the aqueous composition, and the glossiness of the recording material produced. [Means for solving the problem]

[0009] The present invention has been made to solve the above-mentioned problems, and can be realized as the following application examples.

[0010] The aqueous composition according to an application example of the present invention contains a metal pigment, a polyoxyalkyleneamine compound, and an aqueous medium, The metal pigment is composed of a plurality of metal particles, the metal particles are surface-modified with a hydrophobic phosphorus-based surface treatment agent; The content of the polyoxyalkyleneamine compound is 0.1 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the metal particles. the law of nature, The polyoxyalkyleneamine compound is at least one of a compound represented by the following formula (2) and a salt thereof: . [ka] (In formula (2), R 1 is a hydrogen atom or an alkyl group having 4 or less carbon atoms, and R 2 is a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X is an integer of 10 or more. In addition, in formula (2), multiple types of oxyalkylene units having different conditions for R may be provided.

[0013] In another application example of the aqueous composition of the present invention, the metal particles are made of aluminum or an aluminum alloy.

[0014] In the aqueous composition according to another application example of the present invention, the metal particles have a volume average particle size of 0.20 μm or more and 1.00 μm or less.

[0015] In the aqueous composition according to another application example of the present invention, the metal particles are scaly.

[0016] In the aqueous composition according to another application example of the present invention, the metal particles have an average thickness of 10 nm or more and 90 nm or less.

[0017] In addition, in the aqueous composition according to another application example of the present invention, Hydrophobic phosphorus-based surface treatment agent teeth, The hydrophobic atomic group is either an alkyl group having 3 or more carbon atoms or an alkyl group in which at least some of the hydrogen atoms are substituted with fluorine atoms. .

[0018] In the aqueous composition according to another application example of the present invention, the weight average molecular weight of the polyoxyalkyleneamine compound is 400 or more and 8,000 or less.

[0019] In the aqueous composition according to another application example of the present invention, the content of the polyoxyalkyleneamine compound is 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the metal particles.

[0020] The aqueous composition according to another application example of the present invention is a coloring composition or a composition used for preparing a coloring composition.

[0021] Furthermore, a coloring method according to an application example of the present invention includes a step of applying the aqueous composition according to an application example of the present invention, which is a coloring composition, to an object to be colored. DETAILED DESCRIPTION OF THE INVENTION

[0022] Preferred embodiments of the present invention will be described in detail below. [1] Water-based composition First, the aqueous composition of the present invention will be described.

[0023] Conventionally, methods of manufacturing decorative articles with a glossy appearance have included metal plating, foil stamping using metal foil, and thermal transfer using metal foil. However, these methods have the problem that they are difficult to apply to curved surfaces.

[0024] On the other hand, compositions containing pigments or dyes are used as inkjet inks that are applied to recording media by inkjet printing, or as paints, which are advantageous in that they can be suitably applied to recording on curved surfaces.

[0025] In particular, in recent years, there has been a demand for the use of aqueous compositions for the above-mentioned compositions, taking into consideration the burden on the environment and the health of workers.

[0026] However, simply applying metal particles instead of pigments or dyes poses the problem that the inherent properties of metals, such as luster, cannot be fully exhibited.

[0027] In order to solve the above problems, it has been proposed to use metal particles whose surfaces are treated with a fluorine-based compound. Although this improves the dispersibility of the metal particles in the composition to a certain extent, the dispersion stability and the glossiness of the resulting recording material are insufficient. In particular, the above problems are significant in aqueous compositions, and there is also the problem that the metal particles react with water during storage and tend to generate gas, i.e., have low water resistance. Therefore, there is a need for further improvements in the dispersion stability of the metal particles, the water resistance of the aqueous composition, and the glossiness of the resulting recording material.

[0028] The inventors have therefore conducted extensive research to solve the above-mentioned problems, and as a result have arrived at the present invention. That is, the aqueous composition of the present invention contains a metal pigment, a polyoxyalkyleneamine compound, and an aqueous medium, the metal pigment consisting of a plurality of metal particles, the metal particles being surface-modified with a surface treatment agent, and the content of the polyoxyalkyleneamine compound is 0.1 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the metal particles.

[0029] This makes it possible to provide an aqueous composition that is excellent in dispersion stability and water resistance of metal particles and that can be suitably used for producing recorded matter with excellent gloss. In particular, even when the aqueous composition is stored for a long period of time or under harsh conditions, the dispersion stability of metal particles in the aqueous composition and the glossiness of recorded matter produced using the aqueous composition can be excellent.

[0030] Furthermore, when the aqueous composition is a composition for inkjet to be applied to ejection by the inkjet method, in addition to the effects described above, it is possible to enjoy the benefits of applying the inkjet method, such as the ability to more suitably form fine patterns, excellent on-demand properties, etc. Furthermore, it is possible to make the ejection stability of droplets, etc., excellent in a relatively short period after the production of the composition for inkjet, and it is also possible to make the ejection stability of droplets, etc., excellent even when the composition for inkjet is stored for a long period of time or under harsh conditions.

[0031] The reason why such excellent effects are obtained is believed to be as follows. That is, the polyoxyalkyleneamine compound can improve the dispersion stability of metal particles in the aqueous composition by interacting with the surface treatment agent that modifies the surface of the metal pigment, and can also prevent aggregation of the metal pigment and loosen the metal pigment, thereby allowing the surface treatment of the metal pigment by the surface treatment agent to proceed sufficiently.

[0032] On the other hand, if the above conditions are not met, satisfactory results will not be obtained. For example, if an aqueous composition does not contain a polyoxyalkyleneamine compound, the following problems arise. That is, even if a metal pigment is surface-modified with a surface treatment agent, if the polyoxyalkyleneamine compound is not contained, the dispersion stability of the metal particles in the aqueous composition may be excellent in the short term, but if the aqueous composition is stored for a long period of time or under harsh conditions, the dispersion state of the metal particles in the aqueous composition cannot be maintained in a good state. As a result, the gloss of recorded materials produced using the aqueous composition is significantly reduced. In particular, even if the metal pigment is surface-modified with a surface treatment agent, if the polyoxyalkyleneamine compound is not contained, the surface-modified metal particles have low surface free energy and become hydrophobic, which is thought to make the metal particles more likely to aggregate due to hydrophobic interactions. Alternatively, if the polyoxyalkyleneamine compound is not contained when the metal pigment is surface-modified with a surface treatment agent, the metal particles will aggregate when treated with a fluorine-based compound, and the surface treatment agent will not be sufficient.

[0033] Furthermore, even if the aqueous composition contains a polyoxyalkyleneamine compound, if the content of the polyoxyalkyleneamine compound is less than the above-mentioned lower limit, the following problems will occur. That is, the effects of containing the polyoxyalkyleneamine compound as described above will not be fully exhibited. As a result, when the aqueous composition is stored for a long period of time or under harsh conditions, the dispersion state of the metal particles in the aqueous composition will deteriorate, and the glossiness of the resulting recorded matter will not be satisfactory.

[0034] Furthermore, even if the aqueous composition contains a polyoxyalkyleneamine compound, if the content of the polyoxyalkyleneamine compound exceeds the upper limit, the initial gloss value of the recorded material decreases, and further, the storage stability when stored for a long period of time or under harsh conditions also deteriorates.Furthermore, the water resistance of the aqueous composition also decreases.

[0035] The content of the polyoxyalkyleneamine compound in the aqueous composition may be 0.1 to 50 parts by mass per 100 parts by mass of metal particles, but preferably satisfies the following condition: The lower limit of the content of the polyoxyalkyleneamine compound per 100 parts by mass of metal particles is preferably 0.5 parts by mass, more preferably 1.0 parts by mass, and even more preferably 2.0 parts by mass. The upper limit of the content of the polyoxyalkyleneamine compound per 100 parts by mass of metal particles is preferably 40 parts by mass, more preferably 30 parts by mass, and even more preferably 10 parts by mass. This makes the above-mentioned effects more pronounced.

[0036] The components of the aqueous composition of the present invention will be described below. [1-1] Metallic pigments The aqueous composition of the present invention contains a metallic pigment consisting of a plurality of metal particles. The metal particles constituting the metal pigment are surface-modified with a surface treatment agent, which will be described in detail later.

[0037] Metal particles are particles in which at least a portion of the visible portion is made of a metal material, and usually the vicinity of the outer surface is made of a metal material.

[0038] Metal particles are a component that has a significant effect on the appearance of printed matter produced using a water-based composition.

[0039] In the aqueous composition of the present invention, it is assumed that the metal particles generally have a polyoxyalkyleneamine compound, which will be described in detail later, attached to their surfaces.

[0040] The metal particles may be any metal particles as long as at least a region including the surface is made of a metal material. For example, the entire metal particle may be made of a metal material, or the metal particle may have a base made of a non-metallic material and a coating made of a metal material that covers the base. Furthermore, the metal particles may have an oxide coating, such as a passive film, formed on their surfaces. Even with such metal particles, the problems described above have occurred in the past, and by applying the present invention, the excellent effects described above can be obtained.

[0041] The metal material constituting the metal particles can be a simple metal or various alloys. Examples include aluminum, silver, gold, platinum, nickel, chromium, tin, zinc, indium, titanium, iron, and copper. Of these, the metal particles are preferably made of aluminum or an aluminum alloy. One reason why aluminum and aluminum alloys are preferred is that they have a lower specific gravity than iron and the like. This allows particles made of aluminum or an aluminum alloy to settle very slowly when dispersed in an aqueous composition, thereby enabling the aqueous composition to be stored for a longer period of time while effectively preventing uneven concentration and the like.

[0042] In addition, it is possible to suppress increases in the production costs of recorded materials while achieving particularly excellent gloss and a luxurious feel for recorded materials. Although aluminum and aluminum alloys inherently exhibit particularly excellent gloss among various metal materials, the present inventors have discovered that when particles composed of these materials are used in aqueous compositions, the following problems arise. Specifically, the present inventors have discovered that the storage stability of aqueous compositions is particularly low, and that, particularly when such aqueous compositions are used as inkjet compositions, problems such as decreased ejection stability due to increased viscosity caused by gelation are particularly likely to occur. In response to these problems, by incorporating a polyoxyalkyleneamine compound in a predetermined ratio together with a metal pigment, it is possible to reliably prevent the occurrence of such problems, even when particles composed of aluminum or an aluminum alloy are used. Specifically, when the metal particles are composed of aluminum or an aluminum alloy, the effects of the present invention are more pronounced.

[0043] The metal particles may be of any shape, such as spherical, spindle-shaped, or needle-shaped, but are preferably scale-shaped.

[0044] This allows the main surfaces of the metal particles to be arranged on the recording medium to which the aqueous composition is applied so as to conform to the surface shape of the recording medium.As a result, the glossiness and other properties inherent to the metal material constituting the metal particles can be more effectively exhibited in the resulting recorded matter, thereby making it possible to particularly improve the glossiness and luxurious feel of the printed portion formed, and to particularly improve the abrasion resistance of the recorded matter.Furthermore, in an aqueous composition that does not contain a polyoxyalkyleneamine compound, if the metal particles are scaly, the storage stability of the aqueous composition is likely to be particularly low, and when the aqueous composition is used as an inkjet composition, the ejection stability of the inkjet composition is likely to be particularly low.Furthermore, it is not possible to achieve the excellent glossiness and other properties that are due to the scaly metal particles.

[0045] In contrast, when the aqueous composition contains a polyoxyalkyleneamine compound in a predetermined ratio together with metal particles, the occurrence of the above-mentioned problems can be reliably prevented even if the metal particles are scaly. In other words, when the metal particles are scaly, the effects of the present invention are more pronounced.

[0046] In the present invention, the term "scale-like" refers to a shape such as a flat plate or curved plate, in which the area when viewed from a predetermined angle, for example, when viewed in a plan view, is larger than the area when viewed from an angle perpendicular to the viewing direction. In particular, when viewed from a direction in which the projected area is largest, i.e., the area S1 [μm 2 ] and the area S0 [μm 2 The ratio S1 / S0 to the particle diameter [μm] is preferably 2 or more, more preferably 5 or more, and even more preferably 8 or more. It is further preferably 10 or more, and more preferably 20 or more. There is no upper limit, but it is preferably 1000 or less, more preferably 500 or less, and even more preferably 100 or less. For this value, for example, 50 random particles are observed, and the average value of the values ​​calculated for these particles can be used. Observation can be carried out using, for example, an electron microscope, an atomic force microscope, or the like.

[0047] Alternatively, the volume average particle diameter (D50) and the average thickness described below may be used to align the units and determine the volume average particle diameter (D50) / average thickness, which may be used to set the above range.

[0048] When the metal particles are scaly, the lower limit of the average thickness of the metal particles is not particularly limited, but is preferably 10 nm, more preferably 15 nm, and 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.

[0049] This allows the effect of the above-mentioned scale-like particles to be more pronounced.

[0050] 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. 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.

[0051] This makes it possible to improve the storage stability, water resistance, etc. of the aqueous composition, while more effectively preventing the occurrence of undesired color unevenness in recorded matter produced using the aqueous composition.

[0052] In the present invention, the volume-average particle diameter refers to the median diameter of the volume distribution measured by a particle dispersion using a laser diffraction / scattering method, and is the particle size that is exactly 50% of the median when the results of multiple measurements are expressed as the cumulative abundance ratio of each size. When the metal particles are scaly, the volume-average particle diameter is determined based on the shape and size of the metal particles when converted to spherical particles.

[0053] The upper limit of the particle diameter D90 of the metal particles contained in the aqueous composition at a volume cumulative distribution rate of 90% from the fine particle side is preferably 1.50 μm, more preferably 1.20 μm, and even more preferably 0.95 μm.

[0054] This makes it possible to improve the storage stability, water resistance, etc. of the aqueous composition, while more effectively preventing the occurrence of undesired color unevenness in recorded matter produced using the aqueous composition.

[0055] The lower limit of the content of metal particles in the aqueous composition is not particularly limited, but is preferably 0.1 mass%, more preferably 0.2 mass%, and even more preferably 0.3 mass%, and the upper limit of the content of metal particles in the aqueous composition is not particularly limited, but is preferably 30 mass%, more preferably 20 mass%, even more preferably 15 mass%, and most preferably 10 mass%.

[0056] This allows the storage stability and water resistance of the aqueous composition to be improved, while also making it possible to provide a printed portion formed using the aqueous composition with particularly excellent gloss.

[0057] In particular, when the aqueous composition is ink itself to be ejected by an inkjet method, the lower limit of the content of metal particles in the ink is not particularly limited, but is preferably 0.1 mass%, more preferably 0.2 mass%, and even more preferably 0.3 mass%. Also, when the aqueous composition is ink itself to be ejected by an inkjet method, the upper limit of the content of metal particles in the ink is not particularly limited, but is preferably 2.4 mass%, more preferably 2.2 mass%, and even more preferably 1.8 mass%.

[0058] Furthermore, when the aqueous composition is a liquid concentrate used to prepare ink to be ejected by an inkjet method or a paint, the lower limit of the content of metal particles in the aqueous composition is not particularly limited, but is preferably 2.0 mass%, more preferably 2.5 mass%, and even more preferably 3.0 mass%. Furthermore, when the aqueous composition is a liquid concentrate used to prepare ink to be ejected by an inkjet method or a paint, the upper limit of the content of metal particles in the aqueous composition is not particularly limited, but is preferably 30 mass%, more preferably 20 mass%, even more preferably 15 mass%, and most preferably 10 mass%.

[0059] The metal particles may be produced by any method. However, when the metal particles are composed of Al, they are preferably obtained by forming an Al film by a vapor deposition method and then pulverizing the film. This allows the inherent glossiness of Al to be more effectively expressed in printed parts formed using the aqueous composition of the present invention. Furthermore, the variation in properties between particles can be suppressed. Furthermore, by using this method, even relatively thin metal particles can be suitably produced.

[0060] When producing metal particles using such a method, the metal particles can be suitably produced, for example, by forming a film composed of Al on a substrate. The substrate can be, for example, a plastic film such as polyethylene terephthalate. The substrate may also have a release agent layer on the film-forming surface.

[0061] Preferably, the pulverization is carried out by applying ultrasonic vibrations to the film in a liquid, which allows metal particles having a particle size as described below to be easily and reliably obtained, and also prevents variations in size, shape, and properties among the individual metal particles.

[0062] Furthermore, when milling is performed by the above-described method, the liquid that can be suitably used includes alcohols, hydrocarbon compounds, ether compounds, and polar compounds such as propylene carbonate, γ-butyrolactone, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, cyclohexanone, acetonitrile, etc. Use of such a liquid can prevent undesired oxidation of the metal particles, while achieving particularly high productivity of the metal particles and particularly small variations in size, shape, and properties among the individual particles.

[0063] Examples of alcohols include methanol, ethanol, propanol, and butanol. Examples of hydrocarbon compounds include n-heptane, n-octane, decane, dodecane, tetradecane, toluene, xylene, cymene, durene, indene, dipentene, tetrahydronaphthalene, decahydronaphthalene, and cyclohexylbenzene. Examples of ether compounds include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl 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, and tetrahydrofuran.

[0064] [1-2] Polyoxyalkyleneamine compounds The aqueous composition of the present invention contains a polyoxyalkyleneamine compound.

[0065] The polyoxyalkyleneamine compound may be any amine compound having a polyoxyalkylene structure in the molecule, but is preferably at least one of the compounds represented by the following formula (1) and salts thereof: (R 1 -(OR 2 ) X ) Y -NH (3-Y) ··· (1) (In formula (1), R 1 is a hydrogen atom or an alkyl group having 4 or less carbon atoms, and R 2 is an alkylene group having 5 or less carbon atoms, and X is an integer of 10 or more. 2 Y is an integer of 1 to 3. When Y is 2 or more, R 1 , R2 , the conditions of X are different (R 1 -(OR 2 ) X ) units may be included.

[0066] This can improve the storage stability, water resistance, etc. of the aqueous composition, and can improve the glossiness of recorded matter produced using the aqueous composition even when the aqueous composition is stored for a long period of time or under harsh conditions. Furthermore, when the aqueous composition is an inkjet composition, the ejection stability of the inkjet composition can be improved, particularly when the aqueous composition is stored for a long period of time or under harsh conditions.

[0067] As mentioned above, the polyoxyalkyleneamine compound is preferably at least one of the compounds represented by the above formula (1) and salts thereof.

[0068] Among the compounds represented by formula (1), Y is preferably 1. 1 Among these, R is preferably an alkyl group having 4 or less carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms. 2 is preferably a group having 1 to 3 carbon atoms, and may be a linear or branched alkylene group.

[0069] Among the compounds represented by formula (1), at least one of the compounds represented by the following formula (2) and salts thereof is particularly preferred.

[0070] [ka] (In formula (2), R 1 is a hydrogen atom or an alkyl group having 4 or less carbon atoms, and R 2 is a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X is an integer of 10 or more. In addition, in formula (2), multiple types of oxyalkylene units having different conditions for R may be provided.

[0071] This can further improve the storage stability, water resistance, etc. of the aqueous composition, and can further improve the glossiness of recorded matter produced using the aqueous composition when the aqueous composition is stored for a long period of time or under harsh conditions. Furthermore, when the aqueous composition is an inkjet composition, the ejection stability of the inkjet composition can be further improved, particularly when the aqueous composition is stored for a long period of time or under harsh conditions.

[0072] R in the above formula (1) and formula (2) 1 is a hydrogen atom or an alkyl group having 4 or less carbon atoms, preferably an alkyl group having 4 or less carbon atoms, and more preferably a methyl group.

[0073] This can improve the storage stability, water resistance, etc. of the aqueous composition, and can improve the glossiness of recorded matter produced using the aqueous composition even when the aqueous composition is stored for a long period of time or under harsh conditions. Furthermore, when the aqueous composition is an inkjet composition, the ejection stability of the inkjet composition can be improved, particularly when the aqueous composition is stored for a long period of time or under harsh conditions.

[0074] R in the above formula (2) 2 is a hydrogen atom or an alkyl group having 3 or less carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a compound represented by the following formula (3):

[0075] [ka] (In formula (3), x1 and x2 are independently an integer of 1 or more, and x1+x2 is an integer of 10 or more. In formula (3), the order of the oxyethylene unit and the oxypropylene unit does not matter.)

[0076] This can further improve the storage stability, water resistance, etc. of the aqueous composition, and can further improve the glossiness of recorded matter produced using the aqueous composition when the aqueous composition is stored for a long period of time or under harsh conditions. Furthermore, when the aqueous composition is an inkjet composition, the ejection stability of the inkjet composition can be further improved, particularly when the aqueous composition is stored for a long period of time or under harsh conditions.

[0077] The lower limit of the value of x1 / x2, which is the ratio of x1 to x2 in the above formula (3), i.e., the ratio of the amount of oxyethylene units to the amount of oxypropylene units in the molecule of the polyoxyalkyleneamine compound, is preferably 0.05, more preferably 0.15, and even more preferably 0.70.The upper limit of the value of x1 / x2 is preferably 10.00, more preferably 8.00, and even more preferably 6.00.

[0078] This can further improve the storage stability, water resistance, etc. of the aqueous composition, and can further improve the glossiness of recorded matter produced using the aqueous composition when the aqueous composition is stored for a long period of time or under harsh conditions. Furthermore, when the aqueous composition is an inkjet composition, the ejection stability of the inkjet composition can be further improved, particularly when the aqueous composition is stored for a long period of time or under harsh conditions.

[0079] As mentioned above, the order of the oxyethylene units and the oxypropylene units in the formula (3) does not matter. More specifically, in the formula (3), an amino group is bonded to the end of successive oxyethylene units, and a methyl group is bonded to the end of successive oxypropylene units. However, an amino group may be bonded to the end of successive oxypropylene units, and a methyl group may be bonded to the end of successive oxyethylene units. In addition, the compound represented by the formula (3) may be a block copolymer or a random copolymer.

[0080] In the above formula (1) or (2), when the oxyalkylene unit has an oxypropylene unit and an oxyethylene unit, it is preferable that the oxypropylene unit and the oxyethylene unit are the same as those described above. For example, it is preferable that the ratio of the oxypropylene unit to the oxyethylene unit is in the above range.

[0081] 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 800, and most preferably 1000. 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.

[0082] This can further improve the storage stability, water resistance, etc. of the aqueous composition, and can further improve the glossiness of recorded matter produced using the aqueous composition when the aqueous composition is stored for a long period of time or under harsh conditions. Furthermore, when the aqueous composition is an inkjet composition, the ejection stability of the inkjet composition can be further improved, particularly when the aqueous composition is stored for a long period of time or under harsh conditions.

[0083] The aqueous composition of the present invention may contain a plurality of types of compounds as the polyoxyalkyleneamine compound.

[0084] The lower limit of the content of the polyoxyalkyleneamine compound in the aqueous composition is not particularly limited, but is preferably 0.01% by mass, more preferably 0.02% by mass, and even more preferably 0.03% by mass. The upper limit of the content of the polyoxyalkyleneamine compound in the aqueous composition is not particularly limited, but is preferably 3.0% by mass, more preferably 2.0% by mass, and even more preferably 1.5% by mass.

[0085] This can further improve the storage stability, water resistance, etc. of the aqueous composition, and can further improve the glossiness of recorded matter produced using the aqueous composition when the aqueous composition is stored for a long period of time or under harsh conditions. Furthermore, when the aqueous composition is an inkjet composition, the ejection stability of the inkjet composition can be further improved, particularly when the aqueous composition is stored for a long period of time or under harsh conditions.

[0086] In particular, when the aqueous composition is the ink itself to be ejected by the inkjet method, the lower limit of the content of the polyoxyalkyleneamine compound in the ink is not particularly limited, but is preferably 0.01% by mass, more preferably 0.02% by mass, and even more preferably 0.03% by mass. Also, when the aqueous composition is the ink itself to be ejected by the inkjet method, the upper limit of the content of the polyoxyalkyleneamine compound in the ink is not particularly limited, but is preferably 1.0% by mass, more preferably 0.70% by mass, and even more preferably 0.50% by mass.

[0087] Furthermore, when the aqueous composition is a liquid concentrate used to prepare ink to be ejected by an inkjet method or a paint, the lower limit of the polyoxyalkyleneamine compound content in the aqueous composition is not particularly limited, but is preferably 0.05% by mass, more preferably 0.10% by mass, and even more preferably 0.20% by mass. Furthermore, when the aqueous composition is a liquid concentrate used to prepare ink to be ejected by an inkjet method or a paint, the upper limit of the polyoxyalkyleneamine compound content in the aqueous composition is not particularly limited, but is preferably 3.0% by mass, more preferably 2.0% by mass, and even more preferably 1.5% by mass.

[0088] The content of the polyoxyalkyleneamine compound in the aqueous composition is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 20 parts by mass or less, and even more preferably 1.0 parts by mass or more and 10 parts by mass or less, per 100 parts by mass of the metal particles.

[0089] This can further improve the storage stability, water resistance, etc. of the aqueous composition, and can further improve the glossiness of recorded matter produced using the aqueous composition when the aqueous composition is stored for a long period of time or under harsh conditions. Furthermore, when the aqueous composition is an inkjet composition, the ejection stability of the inkjet composition can be further improved, particularly when the aqueous composition is stored for a long period of time or under harsh conditions.

[0090] [1-3]Aqueous medium The aqueous composition of the present invention contains an aqueous medium. The aqueous medium contains at least water as a main component and may further contain a liquid component that is soluble in water, and is well mixed with water in the composition. In the aqueous composition of the present invention, the main function is to act as a dispersion medium for dispersing metal particles.

[0091] Furthermore, when the aqueous composition contains an aqueous medium, the ink can be ejected by inkjet printing when the aqueous composition is an ink itself to be ejected by an inkjet method. Furthermore, the moisture retention of the ink can be improved, and the unintended precipitation of solids in the ink due to drying in an inkjet head or the like can be more effectively prevented. Furthermore, the viscosity of the ink can be more suitably adjusted.

[0092] A liquid component that is soluble in water is a water-soluble liquid component, such as a water-soluble organic solvent. For example, a liquid component having a solubility in water of 2 g / 100 g water or more at 25°C can be suitably used. The aqueous medium may be water itself. In this case, the solubility of the aqueous medium in water is infinite.

[0093] The water content in the aqueous medium is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 55% by mass or more. The water content in the aqueous medium is 100% by mass or less. The content of water in the aqueous composition may be within the above range.

[0094] The aqueous medium preferably contains, in addition to water, a water-soluble organic solvent having a solubility in water of 100 g / 100 g water or more at 25° C. In this case, the boiling point of the water-soluble organic solvent at 1 atmosphere is preferably 110° C. or more and 300° C. or less.

[0095] This can further improve the moisture retention of the aqueous composition, and can more effectively prevent, for example, the unintended precipitation of solids in the inkjet composition as the aqueous composition due to drying in an inkjet head or the like. This can further improve the ejection stability of the aqueous composition when used in an inkjet method. Furthermore, after ejecting the aqueous composition, it can be relatively easily volatilized as needed, and can more effectively prevent the aqueous medium from unintendedly remaining in the resulting recorded matter.

[0096] Examples of such water-soluble organic solvents include alkyl monoalcohols; glycerin; glycols; glycol monoethers; lactams; alcohols, and one or more selected from these can be used in combination.

[0097] Examples of glycols include triethanolamine, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and 1,2-hexanediol. Examples of glycol monoethers include triethylene glycol monobutyl ether. Examples of lactams include 2-pyrrolidone.

[0098] Examples of alcohols include, but are not limited to, ethanol, methanol, propanol, butanol, and phenoxyethanol.

[0099] The lower limit of the content of the aqueous medium in the aqueous composition is not particularly limited, but is preferably 30% by mass, more preferably 40% by mass, and even more preferably 50% by mass. It is further preferably 60.0% by mass, more preferably 70.0% by mass, and even more preferably 75.0% by mass. The upper limit of the content of the aqueous medium in the aqueous composition is not particularly limited, but is preferably 99.7% by mass, more preferably 99.5% by mass, and even more preferably 99.0% by mass. This allows the viscosity of the aqueous composition to be more suitable.

[0100] Furthermore, when the content of water in the aqueous composition is XW [mass %] and the content of the water-soluble organic solvent in the aqueous composition is XH [mass %], XH / XW is preferably 0.15 or more and 1.20 or less, more preferably 0.20 or more and 0.90 or less, and even more preferably 0.30 or more and 0.60 or less.

[0101] This makes it possible to more suitably improve the moisturizing properties of the aqueous composition while making the viscosity of the aqueous composition more suitable.

[0102] [1-4] Surface treatment agent The metal particles are surface-modified with a surface treatment agent. The surface treatment agent may be any agent that can modify the surface of the metal particles, but it is preferable that the surface treatment agent contains at least one of a hydrophobic phosphorus-based surface treatment agent and a silicon-based surface treatment agent.

[0103] This makes it possible to improve the dispersion stability and water resistance of the metal particles in the composition for inkjet.

[0104] The hydrophobic phosphorus-based surface treatment agent may be any phosphorus-based surface treatment agent that, when attached to metal particles, has the function of increasing the hydrophobicity of the metal particles relative to metal particles to which the hydrophobic phosphorus-based surface treatment agent is not attached. The hydrophobic phosphorus-based surface treatment agent may be any phosphorus-based compound containing a phosphorus atom, and examples of such phosphoric acid derivatives, phosphonic acid derivatives, phosphinic acid derivatives, etc., may be used. Examples of derivatives include tautomers, esters, ethers, and derivatives in which hydrogen atoms in the structural formula are replaced with organic substituents. These hydrophobic phosphorus-based surface treatment agents may also be those used as surfactants, etc. The hydrophobic phosphorus-based surface treatment agent preferably has a hydrophobic atom or atomic group.

[0105] Examples of hydrophobic atoms or atomic groups include fluorine atoms, alkyl groups having 3 or more carbon atoms, and alkyl groups in which at least some of the hydrogen atoms are substituted with fluorine atoms. The number of carbon atoms in the alkyl group or alkyl group in which at least some of the hydrogen atoms are substituted with fluorine atoms is preferably 3 or more, more preferably 5 or more, and even more preferably 8 or more. The upper limit of the carbon number is not particularly limited, but is preferably 30, more preferably 25, and even more preferably 20. The alkyl group or alkyl group in which at least some of the hydrogen atoms are substituted with fluorine atoms is preferably bonded to the phosphorus atom of a phosphorus-based surface treatment agent, or a hydroxyl group bonded to the phosphorus atom of a phosphorus-based surface treatment agent that has been etherified with the alkyl group or alkyl group in which at least some of the hydrogen atoms are substituted with fluorine atoms. The alkyl group or alkyl group in which at least some of the hydrogen atoms are substituted with fluorine atoms may be linear or branched, but linear groups are preferred.

[0106] Examples of surface treatment agents include, but are not limited to, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, octylphosphonic acid, decylphosphonic acid, dodecylphosphonic acid, octadecylphosphonic acid, hexadecylphosphonic acid, undecylphosphonic acid, tridecylphosphonic acid, propyl phosphate, butyl phosphate, pentyl phosphate, octyl phosphate, decyl phosphate, dodecyl phosphate, octadecyl phosphate, hexadecyl phosphate, undecyl phosphate, and tridecyl phosphate.

[0107] Suitable hydrophobic phosphorus-based surface treatment agents include fluorine-based phosphorus compounds, which are phosphorus compounds having at least one fluorine atom in the molecule, and phosphorus compounds having at least one unsubstituted alkyl group in the molecule. In particular, phosphorus compounds in which the hydrogen atom bonded to the phosphorus atom of a phosphate ester or phosphonic acid is substituted are preferred.

[0108] This can further enhance the hydrophobicity of the metal particles in the state of being attached thereto, and can make the dispersion stability of the metal particles in the aqueous composition more excellent.In addition, the synergistic effect of using it in combination with the above-mentioned polyoxyalkyleneamine compound is more significantly exhibited, and the storage stability of the aqueous composition and the glossiness of the recorded matter produced using the aqueous composition can be further improved.In particular, in the recorded matter produced using the aqueous composition, the metal particles can be more suitably arranged near the outer surface of the printed part, and the properties such as glossiness that the metal material constituting the metal particles originally has can be more effectively exhibited.

[0109] When the hydrophobic phosphorus-based surface treatment agent is a fluorine-based phosphorus-based compound, the fluorine-based phosphorus-based compound preferably has a perfluoroalkyl structure.

[0110] This makes it possible to further improve the storage stability of the aqueous composition, and to further improve the glossiness and abrasion resistance of the printed portion of a recording material produced using the aqueous composition.

[0111] As the silicon-based surface treatment agent, for example, a surface treatment agent prepared by using tetraethoxysilane and aqueous ammonia can be used.

[0112] The aqueous composition of the present invention may contain multiple types of compounds as surface treatment agents. In such a case, the same metal particles may be surface-treated with multiple types of surface treatment agents. Furthermore, the aqueous composition may contain metal particles that have been surface-treated with different surface treatment agents.

[0113] The surface treatment of metal particles with a surface treatment agent may be carried out, for example, by including the surface treatment agent in a liquid when a metal film formed by a vapor phase deposition method is pulverized in the liquid to form metal particles, as described above.

[0114] When the same particles are surface-treated with multiple types of surface treatment agents, the surface treatment may be performed in multiple steps corresponding to the respective surface treatment agents, or the surface treatment may be performed with the multiple types of surface treatment agents in the same step.

[0115] The surface treatment with the surface treatment agent may be carried out in the same step as the treatment with the polyoxyalkyleneamine compound or in a different step, and may be carried out either before or after the treatment with the polyoxyalkyleneamine compound.

[0116] When the content of the polyoxyalkyleneamine compound in the aqueous composition is XA [% by mass] and the content of the surface treatment agent in the aqueous composition is XP [% by mass], the lower limit of the value of XA / XP is preferably 0.02, more preferably 0.05, and even more preferably 0.07, and the upper limit of the value of XA / XP is preferably 3.0, more preferably 2.0, and even more preferably 1.0.

[0117] This can further improve the storage stability, water resistance, etc. of the aqueous composition, and can further improve the glossiness of recorded matter produced using the aqueous composition.

[0118] The lower limit of the content of the surface treatment agent in the aqueous composition is not particularly limited, but is preferably 0.01 mass%, more preferably 0.05 mass%, and even more preferably 0.10 mass%, and the upper limit of the content of the surface treatment agent in the aqueous composition is not particularly limited, but is preferably 10 mass%, more preferably 7.0 mass%, and even more preferably 5.0 mass%.

[0119] This can further improve the storage stability, water resistance, etc. of the aqueous composition, and can further improve the glossiness of recorded matter produced using the aqueous composition when the aqueous composition is stored for a long period of time or under harsh conditions. Furthermore, when the aqueous composition is an inkjet composition, the ejection stability of the inkjet composition can be further improved, particularly when the aqueous composition is stored for a long period of time or under harsh conditions.

[0120] In particular, when the aqueous composition is the ink itself to be ejected by the inkjet method, the lower limit of the content of the surface treatment agent in the ink is not particularly limited, but is preferably 0.01% by mass, more preferably 0.05% by mass, and even more preferably 0.10% by mass. Also, when the aqueous composition is the ink itself to be ejected by the inkjet method, the upper limit of the content of the 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.

[0121] Furthermore, when the aqueous composition is a stock solution used to prepare ink to be ejected by an inkjet method or a paint, the lower limit of the content of the surface treatment agent in the aqueous 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. Furthermore, when the aqueous composition is a stock solution used to prepare ink to be ejected by an inkjet method or a paint, the upper limit of the content of the surface treatment agent in the aqueous 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.

[0122] The content of the surface treatment agent in the aqueous composition is preferably 5.0 parts by mass or more and 60 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less, and even more preferably 20 parts by mass or more and 40 parts by mass or less, per 100 parts by mass of the metal particles.

[0123] This can further improve the storage stability, water resistance, etc. of the aqueous composition, and can further improve the glossiness of recorded matter produced using the aqueous composition when the aqueous composition is stored for a long period of time or under harsh conditions. Furthermore, when the aqueous composition is an inkjet composition, the ejection stability of the inkjet composition can be further improved, particularly when the aqueous composition is stored for a long period of time or under harsh conditions.

[0124] [1-5] Other ingredients The aqueous composition of the present invention may contain components other than those described above, such as a leveling agent, a binder, a polymerization accelerator, a polymerization inhibitor, a photopolymerization initiator, a dispersant, a surfactant, a penetration accelerator, a moisturizer, a colorant, a fixing agent, an antifungal agent, a preservative, an antioxidant, a chelating agent, a thickener, and a sensitizer.

[0125] The binder may be any resin, preferably an acrylic resin, an ester resin, a urethane resin, etc., and more preferably an acrylic resin. When a binder is contained, the binder is preferably contained in an amount of 0.1% by mass or more, preferably 1% by mass or less, and more preferably 0.5% by mass or less in the composition.

[0126] Preferred surfactants include silicone surfactants, fluorine surfactants, acetylene glycol surfactants, etc., and silicone surfactants are particularly preferred. When a surfactant is contained, it is preferably contained in an amount of 0.1% by mass or more, preferably 1% by mass or less, and more preferably 0.5% by mass or less in the composition.

[0127] [1-6]Other The aqueous composition of the present invention may be used for any purpose, but examples of the uses of the aqueous composition include a coloring composition and a composition used for preparing a coloring composition.

[0128] The coloring composition is a composition for coloring an object by adhering the composition to the object. Examples thereof include inks and paints. Examples of inks include, but are not limited to, inkjet inks.

[0129] The object to be colored is an object to which the coloring composition is attached and colored. If the coloring composition is ink, it is a recording medium. The object to be colored includes, but is not limited to, a recording medium, as well as a board, a wall, a floor, a fence, a barrier, an automobile, and other articles.

[0130] The composition used to prepare a coloring composition is a composition used to obtain a coloring composition by mixing the composition with other components necessary for the coloring composition. It is also called a pigment dispersion or pigment dispersion used in the preparation (manufacturing) of a coloring composition. Therefore, the content of the metal pigment in the composition used to prepare a coloring composition is higher than the content of the metal pigment in a coloring composition obtained using the composition used to prepare a coloring composition.

[0131] The upper limit of the viscosity of the aqueous composition of the present invention at 25°C measured using a rotational viscometer in accordance with JIS Z8809 is not particularly limited, but is preferably 25 mPa s, and more preferably 15 mPa s. The lower limit of the viscosity of the aqueous composition of the present invention at 25°C measured using a rotational viscometer in accordance with JIS Z8809 is not particularly limited, but is more preferably 1.5 mPa s.

[0132] This allows, for example, when the water-based composition is an ink to be ejected by an inkjet method, the ink to be ejected in droplets by the inkjet method to be ejected more suitably.

[0133] [2] Coloring method Next, the coloring method of the present invention will be described.

[0134] The coloring method of the present invention comprises a step of applying the aqueous composition of the present invention, which is a coloring composition, to an object to be colored.

[0135] This makes it possible to provide a coloring method that can be applied to the production of printed matter with excellent gloss.

[0136] The step of attaching the aqueous composition of the present invention to an object to be colored can be carried out by, for example, various printing methods such as an inkjet method, or various coating methods using a bar coater, a spray, a roll coater, a brush, or the like. When the coloring composition is an ink, the coloring method is also a recording method.

[0137] The recording medium may be of any type, absorbent or non-absorbent, and may include, for example, plain paper, inkjet paper, and other paper, plastic materials, metals, ceramics, wood, shells, natural fibers and synthetic fibers such as cotton, polyester, and wool, nonwoven fabrics, etc., but is preferably non-colored. The shape of the recording medium is not particularly limited, and may be any type, such as a sheet.

[0138] When the water-based composition is ejected by an inkjet method, the inkjet method may be a piezoelectric method or a method in which ink is ejected by bubbles generated by heating the ink. However, the piezoelectric method is preferred from the viewpoint of preventing deterioration of the water-based composition.

[0139] The ejection of the water-based composition by the inkjet method can be carried out using a known droplet ejection device.

[0140] [3] Recorded material Next, the recorded matter according to the present invention will be described.

[0141] The recorded matter according to the present invention is produced by applying the above-mentioned aqueous composition onto a recording medium.

[0142] Such a recorded matter has a printed portion that is excellent in gloss and in which the occurrence of defects is prevented.

[0143] The recorded matter according to the present invention may be used for any purpose, for example, decorative items or other applications. Specific examples of the recorded matter 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, operating parts for various electronic devices, decorative parts that exhibit decorative properties, indicators, logos, and other displays.

[0144] Although the present invention has been described above based on the preferred embodiments, the present invention is not limited to these. [Example]

[0145] Next, specific examples of the present invention will be described. [4] Preparation of aqueous composition Example 1 First, a polyethylene terephthalate film having a thickness of 20 μm and a smooth surface with a surface roughness Ra of 0.02 μm or less was prepared.

[0146] Next, a release resin solubilized with acetone was coated on the entire surface of one side of the film using a roll coater to form a release layer.

[0147] The polyethylene terephthalate film on which the release layer was formed was transported into a vacuum deposition device at a speed of 5 m / s, and a 17.4 nm thick film made of Al was formed under reduced pressure.

[0148] Next, the polyethylene terephthalate film on which the Al film was formed was immersed in tetrahydrofuran and subjected to ultrasonic vibrations of 40 kHz, resulting in a dispersion of a metal pigment, which is an aggregate of Al metal particles.

[0149] Next, tetrahydrofuran was removed using a centrifuge, and diethylene glycol diethyl ether was added to obtain a suspension with a metal pigment content of 5% by mass.

[0150] Next, this suspension was treated in a high-power circulating ultrasonic crusher to crush the metal particles to a predetermined size by applying ultrasonic waves of 20 kHz.

[0151] Next, the polyoxyalkyleneamine compound represented by the above formula (3) was added to the suspension in a mass ratio to the metal particles that was the value shown in the table, and the suspension was subjected to heat treatment at 55°C for 1 hour under 40kHz ultrasonic irradiation to break up the agglomerates of the metal particles and disperse the metal particles in the form of primary particles. Here, the polyoxyalkyleneamine compound used was a block copolymer in which 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, and which satisfies the condition that x1 / x2 between x1 and x2 in the above formula (3) is 3.1 and has a weight average molecular weight of 2000.

[0152] Furthermore, FHP, a fluorine-based phosphorus compound serving as a hydrophobic phosphorus-based surface treatment agent, was added to the mixture at a mass ratio relative to the metal particles shown in the table. FHP is a compound represented by 2-(perfluorohexyl)ethylphosphonic acid: CF3(CF2)5(CH2)2P(O)-(OH)2. The mixture was then subjected to a heat treatment at 55°C for 3 hours under 28 kHz ultrasonic irradiation, causing the FHP to react with the surfaces of the metal particles, resulting in a dispersion of metal particles with extremely low surface free energy and high leafing ability.

[0153] The obtained dispersion of metal particles was subjected to a centrifugal separation process, and then the solvent was replaced with an aqueous medium to adjust the concentration to a metal particle content of 5% by mass. The mass ratio of the polyoxyalkyleneamine compound and the hydrophobic phosphorus-based surface treatment agent to the metal particles was adjusted to the values ​​shown in the table. In this way, an aqueous composition was obtained. The obtained aqueous composition was used as a composition for preparing a coloring composition. This is also referred to as a pigment dispersion. This pigment dispersion was mixed with the remaining components shown in the table and stirred thoroughly to prepare a coloring composition, and the coloring composition of Example 1 was obtained.

[0154] The metal particles contained in the aqueous composition thus obtained had a volume average particle size of 0.49 μm, and the particle size D90 of the metal particles contained in the aqueous composition at a volume cumulative distribution rate of 90% from the fine particle side was 0.80 μm.

[0155] Examples 2 to 20 Aqueous compositions were produced in the same manner as in Example 1, except that the metallic pigments were prepared as shown in Tables 1 and 2, and the types and ratios of the raw materials contained were changed to obtain the compositions shown in Tables 1 and 2.

[0156] (Comparative Examples 1 to 10) Aqueous compositions were produced in the same manner as in Example 1, except that the metallic pigments were configured as shown in Table 2 and the types and ratios of raw materials used in preparing the aqueous compositions were changed to obtain the compositions shown in Table 2.

[0157] In Examples 17 to 20 and Comparative Examples 9 and 10, when the solvent was replaced with an aqueous medium, pigment dispersions were obtained in which the metal particle content was adjusted to 10 mass %.

[0158] In Examples 17 and 19 and Comparative Examples 9 and 10, the resulting pigment dispersions were used to prepare coloring compositions in the same manner as in the other examples, thereby obtaining aqueous compositions that were coloring compositions.

[0159] In Examples 18 and 20, the process was completed to obtain a pigment dispersion, and an aqueous composition was obtained. The aqueous composition may be used to prepare a coloring composition, or may be used as a coloring composition as is.

[0160] The constitution of the metal pigment contained in the aqueous composition and the composition of the aqueous composition for each of the examples and comparative examples are summarized in Tables 1 and 2. In the tables, the polyoxyalkyleneamine compound represented by the above formula (3), which satisfies the condition that the ratio x1 / x2 between x1 and x2 is 3.1 and has a weight-average molecular weight of 2000, is designated "POAA1," the polyoxyalkyleneamine compound represented by the above formula (3), which satisfies the condition that the ratio x1 / x2 between x1 and x2 is 0.11 and has a weight-average molecular weight of 600, is designated "POAA2," the polyoxyalkyleneamine compound represented by the above formula (3), which satisfies the condition that the ratio x1 / x2 between x1 and x2 is 6.33 and has a weight-average molecular weight of 1000, is designated "POAA3," and the polyoxyalkyleneamine compound represented by the above formula (3), which satisfies the condition that the ratio x1 / x2 between x1 and x2 is 7.25 and has a weight-average molecular weight of 300, is designated "POAA4." The hydrophobic phosphorus surface treatment agent 2-(perfluorohexyl)ethylphosphonic acid is "FHP", the hydrophobic phosphorus surface treatment agent octadecylphosphonic acid is "C18", the hydrophobic phosphorus surface treatment agent dodecylphosphonic acid is "C12", the hydrophobic phosphorus surface treatment agent octylphosphonic acid is "C8", the surface treatment agent prepared using 0.2 parts by mass of 1 mol / L ammonia water for 1 part by mass of tetraethoxysilane is "SiO2", the dispersant Esleem AD-374M (manufactured by NOF Corporation) is "AD-374M", and the dispersant Esleem AD-3172M (manufactured by NOF Corporation) is "AD-3172M". POAA1 to POAA4 were all block copolymers in which an amino group was bonded to the end of consecutive oxyethylene units and a methyl group was bonded to the end of consecutive oxypropylene units. Furthermore, for the metallic pigments constituting the aqueous compositions of each of the above examples, observations were made on 50 randomly selected metallic particles. As a result, when observed from the direction in which the projected area was maximized, i.e., when viewed in plan, the area S1 [μm 2 ] and the area S0 [μm 2The ratio S1 / S0 to the total volume of the aqueous compositions in Examples 1 to 16 was calculated, and the average value of these values ​​was found to be 19 or greater. The volume average particle diameters D50 and D90 in the table were measured using a Microtrac MT-3300 (a laser diffraction / scattering particle size distribution analyzer manufactured by Microtrac-Bell). The viscosities at 25°C of the aqueous compositions in Examples 1 to 16, measured using a rotational viscometer in accordance with JIS Z8809, were all within the range of 1.5 mPa s to 15 mPa s.

[0161] [Table 1]

[0162] [Table 2]

[0163] [5] Evaluation [5-1] Dispersibility of metal particles In each of the above examples and comparative examples, in the manufacturing process of each aqueous composition, in the step of subjecting metal particles to heat treatment at 55°C for 1 hour under 40 kHz ultrasonic irradiation, the polyoxyalkyleneamine compound was not used, but instead Esreem AD-374M (manufactured by NOF Corporation) was used in a mass ratio of 5 mass% relative to 100 mass% of the metal particles, and the heat treatment was similarly performed.

[0164] In addition, Esreem AD-374M is a dispersant that exhibits good dispersibility in non-aqueous media.

[0165] After the heat treatment, the volume average particle diameter D50 of the metal particles contained in the resulting dispersion was measured as is. Using the volume average particle diameter D50 of the metal particles contained in this dispersion as a reference value, the volume average particle diameter D50 of the metal particles contained in the final aqueous composition obtained in each of the above Examples and Comparative Examples was also measured and compared.

[0166] The measurements were carried out using a Microtrac MT-3300 (a laser diffraction / scattering particle size distribution analyzer manufactured by Microtrac Bell).

[0167] The dispersibility of metal particles was evaluated according to the following criteria. The smaller the ratio of the volume average particle diameter D50 of the metal particles contained in the aqueous composition to the above-mentioned criteria, the better the dispersibility of the metal particles. A grade of B or higher was considered to be good.

[0168] A: The ratio of D50 of metal particles contained in the aqueous composition to the standard value is less than 110%. B: The ratio of D50 of metal particles contained in the aqueous composition to the standard value is 110% or more and less than 150%. C: The ratio of D50 of metal particles contained in the aqueous composition to the standard value is 150% or more and less than 200%. D: The ratio of D50 of metal particles contained in the aqueous composition to the standard value is 200% or more and less than 500%. E: The ratio of D50 of metal particles contained in the aqueous composition to the standard value is 500% or more.

[0169] [5-2]Water resistance The aqueous compositions of the above Examples and Comparative Examples were each sealed in a pack and left in a thermostatic chamber at 70°C for 6 days. The amount of gas generated per unit mass of the aqueous composition was determined, and water resistance was evaluated according to the following criteria. The smaller the amount of gas generated, the better the water resistance. A rating of B or higher was considered good.

[0170] A: The amount of gas generated is less than 0.2 mL / g. B: The amount of gas generated is 0.2 mL / g or more but less than 0.4 mL / g. C: The amount of gas generated is 0.4 mL / g or more but less than 1.0 mL / g. D: The amount of gas generated is 1.0 mL / g or more but less than 5.0 mL / g. E: The amount of gas generated is 5.0 mL / g or more.

[0171] [5-3] Gloss First, printed matter was produced using the aqueous compositions of the above-mentioned Examples and Comparative Examples in the following manner.

[0172] That is, for the aqueous compositions of Examples 1 to 16 and Comparative Examples 1 to 8, droplets were ejected using an inkjet printer (Seiko Epson Corporation, SC-S80650) to print on a 2 mm thick polycarbonate plate as a recording medium with a solid content of the aqueous composition of 8 mg / inch. 2 The water-based composition was applied so as to obtain a printed matter.

[0173] In addition, the aqueous compositions of Examples 17 to 20 and Comparative Examples 9 and 10 were coated on a 2 mm thick polycarbonate plate as a recording medium using a bar coater so that the amount of solid matter of the aqueous composition attached was 8 mg / inch. 2 The water-based composition was applied so as to obtain a printed matter.

[0174] The gloss of the printed portion of the recorded matter according to each of the Examples and Comparative Examples obtained as described above was measured at a tilt angle of 60° using a gloss meter, MINOLTA MULTI GLOSS 268, and evaluated according to the following criteria. The higher this value, the better the gloss. A grade of B or higher was considered to be good.

[0175] A: Glossiness of 400 or more. B: Glossiness is 350 or more and less than 400. C: Glossiness is 300 or more and less than 350. D: Glossiness is 250 or more and less than 300. E: Glossiness is less than 250.

[0176] [5-4] Discharge stability A droplet ejection device was installed in a thermal chamber, and droplets were ejected from all nozzles of a droplet ejection head with a nozzle hole size of 22 μm in diameter under an optimized piezoelectric element drive waveform at 25°C and 50% RH for each of the aqueous compositions of Examples 1 to 16 and Comparative Examples 1 to 8 while varying the piezoelectric element vibration frequency. The droplet ejection time at each frequency was 1 minute. The practically usable frequency was defined as the frequency at which the number of un-ejected nozzles after 1 minute of ejection was less than 0.5% of the total number of nozzles, and the number of nozzles exhibiting abnormalities such as delays or ejection deflection was less than 5% of the total number of nozzles. The practically usable frequency range was evaluated for ejection stability according to the following four-level scale. The higher this value, the better the frequency characteristics. A rating of B or higher was considered good.

[0177] A: 11kHz or more. B: 5kHz or higher and less than 11kHz. C: 3kHz or higher but less than 5kHz. D: Less than 3kHz. These results are shown in Tables 3 and 4.

[0178] [Table 3]

[0179] [Table 4]

[0180] As is clear from Tables 3 and 4, the aqueous compositions of the present invention are excellent in water resistance and dispersion stability of metal particles, and can be suitably used to produce printed matter with excellent gloss. In contrast, the comparative examples did not produce satisfactory results. The aqueous compositions of Examples 17 to 20 could be suitably used to prepare inkjet inks by diluting them with an aqueous medium.

Claims

1. A coating composition comprising a metal pigment, a polyoxyalkyleneamine compound, and an aqueous medium, The metal pigment is composed of a plurality of metal particles, the metal particles are surface-modified with a hydrophobic phosphorus-based surface treatment agent; the content of the polyoxyalkyleneamine compound is 0.1 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the metal particles, The aqueous composition, wherein the polyoxyalkyleneamine compound is at least one of a compound represented by the following formula (2) and a salt thereof: 【Chemistry 1】 (In formula (2), R 1 is a hydrogen atom or an alkyl group having 4 or less carbon atoms, R 2 is a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X is an integer of 10 or more. In addition, formula (2) may have multiple types of oxyalkylene units with different R conditions.)

2. 2. The aqueous composition of claim 1, wherein the metal particles are composed of aluminum or an aluminum alloy.

3. 3. The aqueous composition according to claim 1, wherein the metal particles have a volume average particle size of 0.20 μm or more and 1.00 μm or less.

4. 4. The aqueous composition according to claim 1, wherein the metal particles are scaly.

5. The aqueous composition according to claim 4, wherein the metal particles have an average thickness of 10 nm or more and 90 nm or less.

6. 6. The aqueous composition according to claim 1, wherein the hydrophobic phosphorus-based surface treatment agent has a hydrophobic atomic group, and the hydrophobic atomic group is either an alkyl group having 3 or more carbon atoms or an alkyl group in which at least a portion of hydrogen atoms has been substituted with fluorine atoms.

7. 7. The aqueous composition according to claim 1, wherein the polyoxyalkyleneamine compound has a weight average molecular weight of 400 or more and 8,000 or less.

8. 8. The aqueous composition according to claim 1, wherein the content of the polyoxyalkyleneamine compound is 0.1 parts by mass or more and 30 parts by mass or less per 100 parts by mass of the metal particles.

9. The aqueous composition according to claim 1 , which is a coloring composition or a composition used for preparing a coloring composition.

10. A coloring method comprising a step of applying the aqueous composition according to any one of claims 1 to 9, which is a coloring composition, to an object to be colored.

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