KR20230001525A - Packaging body of metallic pigment composition - Google Patents

Abstract

The present invention relates to a packaging body in which a packaging container is packed with a metal pigment composition including metal particles and composite particles having one or more coating layers on the surface thereof. Here, the packaging body satisfies the following (1) to (3): (1) the composite particles have a scale-like shape; (2) the composite particles have a volume standard (D_50) of 1 ㎛ or more and 30 ㎛ or less when the particle size distribution is measured with a laser diffraction particle size distribution meter; and (3) the packaging container has a base material at least partially containing metal, and in addition, at least one type of a protective layer selected from the following a), b) and c) is formed on a portion of the packaging container, which is in contact with the metal pigment composition, wherein a) a protective layer having a thickness of 1-200 ㎛, formed of a resin including at least one selected from the group consisting of a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin, a cyclic oxirane type epoxy resin, a novolac phenol resin, a resol type phenol resin, and an epoxy resin thermally cured with polyester resin and phenolic resin; b) a protective layer formed of a phosphoric acid metal salt and having a weight per unit area of 0.1-10 g/m^2; and a protective layer which is a thin chrome plating layer. According to the present invention, even when the metal pigment composition is stored and/or transported for a long time, aggregation of particles and the progression of changes in color tone can be suppressed.

Description

Package of metallic pigment composition {PACKAGING BODY OF METALLIC PIGMENT COMPOSITION}

The present invention relates to a package of a metallic pigment composition containing novel composite particles and a method for storing and transporting the package. More specifically, the present invention relates to a package of a metal pigment composition containing novel composite particles capable of maintaining excellent hiding power, color tone, etc. with low cohesiveness of individual particles even after long-term storage, and a method for storing and transporting the package It is about.

Conventionally, metallic pigments have been used for the purpose of obtaining a cosmetic effect emphasizing a metallic feel for metallic paints, printing inks, and plastic pastes.

In recent years, in the paint field, as a resource saving and pollution-free countermeasure, the necessity of switching to water-based paints with a small amount of organic solvents has increased. don't One reason for this is that metal pigments are easily corroded in water-based paints. When metal powder is present in water-based paint, corrosion by water occurs in any of acidic, neutral, and basic or a plurality of regions based on the properties of various metals, and hydrogen gas is generated. This is a very important safety issue in a paint or ink manufacturing process in a paint or ink manufacturer, or in a painting or printing process in an automobile, home appliance, or printing manufacturer. In addition, since corrosion causes loss of smoothness of the metal surface, aggregation of pigment particles, and deformation of pigment particles, color tone degradation is unavoidable.

Patent Document 1 (Japanese Unexamined Patent Publication No. 2003-147226) discloses an aluminum pigment having an inorganic molybdenum film and a film containing amorphous silica covering the film. Further, Patent Document 2 (Pamphlet of International Publication No. 2004/096921) discloses an aluminum pigment having an inorganic molybdenum film and a film containing amorphous silica covering the film and/or a film formed by a silane coupling agent. has been

However, any method described in these patent documents cannot avoid color change of the metallic pigment. In addition, in these methods, aggregation and color tone change of metal pigments progress while being stored and / or transported in a package for a long time in an environment that is not particularly managed (for example, under an environment such as high temperature or high humidity) There is a problem with becoming.

Patent Document 3 (Pamphlet of International Publication No. 2018/180936) includes a coating layer that is a metal particle and a silicon-containing compound layer for the purpose of providing a coating pigment (metal pigment composition) dispersed in a state in which aggregates are relatively small, 4 A coating pigment of composite particles in which the proportion of aggregates in which two or more particles are adhered to each other is small is disclosed.

However, in Patent Literature 3, no specific teaching can be found on how to obtain a target coating pigment with a small amount of agglomerates, other than that it is preferable to adjust the stirred Reynolds number within a predetermined range. In addition, even if it satisfies the range of the characteristic parameters stipulated in Patent Document 3, it is difficult to obtain sufficiently satisfactory hydrogen gas generation suppression performance, low cohesion, hiding power, and color tone only with that. In addition, even with the coating pigment, there is a problem that aggregation or color tone change progresses while being stored and/or transported in a package for a long time in an environment that is not controlled (for example, under an environment such as high temperature or high humidity) can't solve

Japanese Unexamined Patent Publication No. 2003-147226 International Publication No. 2004/096921 pamphlet International Publication No. 2018/180936 pamphlet

An object of the present invention is to provide a package of a metallic pigment composition comprising novel composite particles not found in the prior art, and a method for storing and transporting the package.

A further object of the present invention is to solve the problems of the prior art, that is, to have excellent storage stability, small individual particle aggregation, excellent hiding power, color tone, etc. It is to provide a novel technique capable of maintaining these characteristics even when stored and/or transported for a long period of time in a package.

As a result of the inventors of the present invention repeating intensive research to solve the above problems, in a package in which a metal pigment composition containing composite particles having metal particles and one or more coating layers on the surface thereof is packaged in a packaging container, the packaging container By forming a specific protective layer on a portion in contact with the metal pigment composition of the present invention, it was discovered that aggregation of the metal pigment composition in the package and advancing of color tone change could be suppressed, and the present invention was completed.

That is, various aspects of the present invention are as follows.

[One].

A package in which a metal pigment composition comprising metal particles and composite particles having one or more coating layers on the surface thereof is packed in a packaging container, and the package satisfies the following (1) to (3):

(1) The shape of the composite particle is scaly;

(2) The composite particles have a volume-based D ₅₀ of 1 μm or more and 30 μm or less when the particle size distribution is measured with a laser diffraction type particle size distribution meter;

(3) The packaging container is provided with a substrate at least partially made of metal, and at least one protective layer selected from the following a), b) and c) is formed on a portion of the packaging container in contact with the metal pigment composition. What has been:

a) glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, cyclic oxirane type epoxy resin, novolak phenol resin, resol type phenol resin, polyester resin and phenol resin A protective layer having a thickness of 1 to 200 μm formed of a resin containing at least one selected from the group consisting of thermosetting epoxy resins;

b) a protective layer formed of a metal phosphoric acid salt and having a weight per unit area of 0.1 g/m ² to 10 g/m ² ;

c) a protective layer which is thin chrome plating.

[2].

The package according to [1] above, wherein at least one type of protective layer selected from a) and b) is formed on a portion of the packing container in contact with the metal pigment composition.

[3].

The package according to [1] or [2] above, wherein the moisture contained in the metal pigment composition in the package is 0 to 1000 ppm with respect to the mass of the metal pigment composition.

[4].

The package according to any one of [1] to [3] above, wherein the composite particle has an average thickness of 20 to 400 nm.

[5].

The package according to any one of [1] to [4] above, wherein at least one layer of the coating layer is a silicon compound-containing layer.

[6].

The package according to any one of [1] to [5] above, wherein the metal particles are aluminum or an aluminum alloy.

[7].

The package according to any one of [1] to [6], wherein the pH of the metal pigment composition is in the range of 5 to 9.

[8].

The package according to any one of [1] to [7] above, wherein the residue of the metallic pigment composition after storage is 0.1% by weight or less when the sealed package is stored in an indoor warehouse at 20°C for one year.

[9].

The package according to any one of [1] to [8] above, wherein the residue of the metal pigment composition after storage is 0.05% by weight or less when the sealed package is stored in an indoor warehouse at 20°C for one year.

[10].

The package according to any one of [1] to [9] above, wherein the residue of the metal pigment composition after storage is 0.1% by weight or less when the sealed package is stored in a warming room at 60°C for 3 months.

[11].

The package according to any one of [1] to [10] above, wherein the residue of the metal pigment composition after storage is 0.05% by weight or less when the sealed package is stored in a warming room at 60°C for 3 months.

[12].

A storage method for storing the metal pigment composition at 0 to 50°C using the package according to any one of [1] to [11] above.

[13].

A delivery method for transporting a metal pigment composition at 0 to 50°C by the package according to any one of [1] to [11] above.

According to the present invention, even if a metal pigment composition comprising metal particles in a package and composite particles having one or more coating layers on the surface thereof is stored and/or transported for a long period of time, the aggregation of the particles and progress of color change can be suppressed. there is. In addition, the high-quality metal pigment composition in which the aggregation of particles or the progress of color change is suppressed in this way can be suitably used as a raw material for a water-based coating material.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail. In addition, this invention is not limited to the following embodiment, Within the scope of the summary, various modifications can be implemented.

<Package>

The package according to the present invention is a package in which a metal pigment composition containing metal particles and composite particles having one or more coating layers on the surface thereof is packaged in a packaging container, and at least the following (1) to (3) are satisfied: It is a package to do.

(1) The shape of the composite particle is scaly.

(2) The composite particles have a volume-based D ₅₀ of 1 μm or more and 30 μm or less when the particle size distribution is measured with a laser diffraction type particle size distribution analyzer.

(3) The packaging container is provided with a substrate at least partially made of metal, and at least one protective layer selected from the following a), b) and c) is formed on a portion of the packaging container in contact with the metal pigment composition. What has been:

a) glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, cyclic oxirane type epoxy resin, novolak phenol resin, resol type phenol resin, polyester resin and phenol resin A protective layer having a thickness of 1 to 200 μm formed of a resin containing at least one selected from the group consisting of thermosetting epoxy resins;

b) a protective layer formed of a metal phosphoric acid salt and having a weight per unit area of 0.1 g/m ² to 10 g/m ² ;

c) a protective layer which is thin chrome plating.

1. Composite Particles Included in Metallic Pigment Composition

The metal pigment composition according to the present invention includes metal particles and composite particles having one or more coating layers on the surface thereof.

In addition, when it is referred to as "the metal pigment composition according to the present invention" in the present specification (or when it is referred to as a similar expression), this metal pigment composition is intended to be placed in the packaging container according to the present invention .

In addition, in the present specification, the term "metal pigment composition" means that composite particles including metal particles and one or more coating layers on the surface thereof are dispersed in a solvent containing a hydrophilic solvent, or composite particles are a solvent containing a hydrophilic solvent. It refers to a composition that is accompanied by and may optionally contain other ingredients.

1) metal particles

The composite particle included in the metal pigment composition of the present invention contains a metal particle and one or more coating layers formed on the surface thereof.

The material of the metal particles constituting the composite particles is not particularly limited, and for example, known or commercially available metal pigments such as aluminum, aluminum alloy, zinc, iron, magnesium, nickel, copper, silver, tin, chromium, stainless steel, etc. Any of the metals used as may be used. In this specification, the metal of the metal particle constituting the composite particle includes not only a single metal but also an alloy and an intermetallic compound.

In this way, the metal particles may use a metal containing only one type of metal element alone, or may use a metal containing two or more types of metal elements.

The metal particle is preferably a metal containing an aluminum element as a main component, for example, it is preferably aluminum or an aluminum alloy, and more preferably aluminum.

It is preferable that the shape of a metal particle is scaly (flake shape). As a result of this, the composite particles included in the metal pigment composition of the present invention can also have a scaly shape, it becomes easy to obtain high hiding properties and the like more reliably. The aspect ratio (shape factor obtained by dividing the average particle diameter by the average thickness) of the scaly metal particles is preferably 20 or more and 400 or less. When the aspect ratio of the metal particles is 20 or more, a higher sense of brilliance can be obtained. In addition, when the aspect ratio of the metal particles is 400 or less, mechanical strength is maintained and stable color tone can be obtained. Here, the average thickness of the metal particles used in the present invention can be obtained by a known method, and can be obtained using, for example, a method of calculating from the surface diffusion area and density of the metal particles.

The average particle diameter of the metal particles is not particularly limited as long as it is an average particle diameter that can give D ₅₀ in the particle size distribution of the composite particles described later. That is, the composite particle has a D ₅₀ of 1 µm or more and 30 µm or less (the lower limit is preferably 2 µm or more, more preferably 3 µm or more, and the upper limit is preferably 3 µm or more) when the volume distribution is measured with a laser diffraction particle size distribution meter It is preferable to set the average particle diameter of the metal particles so that it is preferably 25 μm or less, more preferably 20 μm or less, or any combination of any of these upper limit values and these lower limit values).

The average particle size of the metal particles is the particle size of the raw material atomized metal powder in the process of grinding, sifting, and filtering the raw material atomized metal powder (eg aluminum powder) using a ball mill, etc. It can be controlled by appropriately adjusting the mass of each trituration ball in the case, the number of revolutions of the trituration device, the sieve powder, the degree of filter press, and the like.

In addition, the metal particles do not necessarily consist only of metal, and, for example, particles of synthetic resin, particles of inorganic particles such as mica, glass, etc. whose surfaces are coated with metal can also be used, as long as the effect of the present invention is not impaired. there is. In the present invention, particles formed of aluminum or aluminum alloy are preferable from the viewpoints of particularly high weather resistance, small specific gravity, ease of availability, and the like.

Aluminum flakes, which are commonly used as metallic pigments, are particularly suitable as metal particles constituting the composite particles. As aluminum flakes, those having surface properties, particle size, and shape required for metallic pigments, such as surface glossiness, whiteness, and brilliance, are suitable. Aluminum flakes are usually marketed in a paste state. Pasty aluminum flakes may contain ordinary scaly aluminum powder, mineral spirits (aliphatic hydrocarbons) used during pulverization, residual fatty acids, and organic solvents such as solvent naphtha and xylene. Pasty aluminum flakes may be used as they are, or may be used after removing fatty acids on the surface with an organic solvent or the like in advance.

In addition, the volume average particle diameter (D ₅₀ ) in the state of composite particles is 1 μm or more and 30 μm or less (the lower limit is preferably 2 μm or more, more preferably 3 μm or more, and the upper limit is preferably 25 μm or less, more It is preferably 20 μm or less, or may be any combination of any of the upper limit value and the lower limit thereof), and preferably has an average thickness of 20 nm or more and 400 nm or less (the lower limit is preferably 25 nm or more, more preferably It is preferably 30 nm or more, and the upper limit is preferably 350 nm or less, more preferably 300 nm or less, or any combination of any of these upper limit values and these lower limit values), so-called aluminum deposited foils can also be used Do.

2) metal pigment composition

The metal pigment composition according to the present invention is characterized by satisfying both of the following physical property requirements.

(1) The shape of the composite particle is scaly.

(2) D ₅₀ on a volume basis when the particle size distribution of the composite particles is measured with a laser diffraction type particle size distribution meter is 1 μm or more and 30 μm or less.

In addition, the metal pigment composition preferably further satisfies at least one of the following physical property requirements (namely, (a) or (b), or both (a) and (b)).

(a) The composite particle has an average thickness of 20 nm or more and 400 nm or less.

(b) The water content contained in the metal pigment composition in the package is 0 to 1000 ppm with respect to the mass of the metal pigment composition.

(1) Composite particles having a scaly shape

The shape of the composite particle of the metal pigment composition according to the present invention is scale-like (flake-like). Accordingly, a coating film formed using the metal pigment composition can exhibit high luminance, high flip-flop feeling, and high hiding properties. In this specification, the composite particle having a "scaly" (flaky) shape means that the composite particle has an average aspect ratio (shape factor obtained by dividing the average particle diameter by the average thickness) of 20 or more. It is preferable that the average aspect ratio of the scale-like composite particle|grains is 20 or more and 400 or less from a viewpoint of obtaining high brightness, flip-flop feeling, hiding property, etc. When the average aspect ratio is 20 or more, sufficient brilliance can be exhibited, while when the average aspect ratio is 400 or less, the mechanical strength of the flakes is maintained and stable color tone can be obtained. An aspect ratio of 25 or more is more preferable, and 30 or more is still more preferable. Moreover, it is more preferable that it is 350 or less, and it is still more preferable that it is 300 or less.

The "composite particle" in the present physical property requirement (1) refers to an aggregate (aggregate) of a plurality of composite particles in the case where they are aggregated and fixed.

Here, the average particle diameter for calculating the average aspect ratio of the composite particles is the volume-based D ₅₀ called the median diameter, and this point will be explained in detail in the description of requirement (2) to be described later. The average thickness for calculating the average aspect ratio of the composite particles will be explained in detail in the description of the preferred requirement (a) described later.

(2) D ₅₀ on a volume basis when the particle size distribution of composite particles is measured with a laser diffraction type particle size distribution meter is 1 μm or more and 30 μm or less

D ₅₀ on a volume basis when the particle size distribution of the composite particles is measured with a laser diffraction type particle size distribution analyzer is 1 μm or more and 30 μm or less. As a result, the coating film formed using the metal pigment composition exhibits high luminance, high flip-flop feeling, high hiding property, etc., and at the same time, the aggregation of individual particles constituting the metal pigment composition is suppressed, and its cohesiveness is reduced. can This volume-based D ₅₀ is also generally referred to as the median diameter.

From the viewpoint of obtaining such high luminance, high flip-flop feeling, high hiding property and small cohesiveness of individual particles, the volume-based D ₅₀ when the particle size distribution of composite particles is measured with a laser diffraction type particle size distribution meter is the lower limit. Is 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, and the upper limit is 30 μm or less, preferably 25 μm or less, more preferably 20 μm or less, or their upper limit and combinations of any of these lower limits may also be employed.

The "composite particle" in the present physical property requirement (2) refers to an aggregate (aggregate) of a plurality of composite particles when they are aggregated and fixed.

Here, D ₅₀ on a volume basis when the particle size distribution of composite particles is measured with a laser diffraction type particle size distribution analyzer indicates a particle size with a cumulative degree of 50% in the volume cumulative particle size distribution. Although it does not specifically limit as a laser diffraction-type particle size distribution analyzer, For example, "LA-300" (made by Horiba Seisakusho Co., Ltd.) can be used. Mineral spirits can be used as the measurement solvent. For example, the metal pigment composition containing the composite particles of the sample is ultrasonically dispersed for 2 minutes as a pretreatment, and then put into a dispersion tank to confirm that the metal pigment composition is properly dispersed, and then D ₅₀ can be measured.

The particle size of the composite particles in the resin composition obtained by adding the resin to the metal pigment composition cannot be measured by this method. Therefore, as an alternative method in this case, for example, by photographing the composite particles in the resin composition from the surface of the coating film with an optical microscope, laser microscope, etc., and obtaining distribution of equivalent circle diameters using commercially available image analysis software. A method of determining the particle size can be employed.

The volume-based D ₅₀ of the composite particles included in the metal pigment composition is determined by grinding and sifting the raw material atomized metal powder (eg, aluminum powder) using a ball mill or the like in the manufacturing method of the metal pigment composition described later.・In the step of filtering, by appropriately adjusting the particle size of the raw material atomized metal powder, the mass per ball of the grinding ball in the case of using a ball mill, the number of rotations of the grinding device, the sieves, the degree of filter press, etc. For example, in the step of coating the silicon compound-containing layer (and other coating layers as necessary), the type of organosilicon compound to be used and the coating step (if the organosilicon compound is hydrolyzed and used, that step is also included) It can be controlled by appropriately adjusting pH, concentration, stirring temperature, stirring time, type of stirring device, power/degree of stirring (type and diameter of stirring blade, number of rotations, presence or absence of external stirring, etc.).

(a) The average thickness of the composite particles is preferably 20 nm or more and 400 nm or less.

It is preferable that the average thickness of the metal particle and the composite particle having one or more coating layers on the surface contained in the metal pigment composition according to the present invention is 20 nm or more and 400 nm or less. Accordingly, in addition to satisfying the above requirements (1) and (2), a coating film formed using the metal pigment composition can exhibit high luminance, high flip-flop feeling, high hiding property, and the like.

From the above viewpoint, the average thickness of the composite particles is preferably 20 nm or more as a lower limit, more preferably 25 nm or more, still more preferably 30 nm or more. As a preferable upper limit, it is 400 nm or less, more preferably 350 nm or less, and even more preferably 300 nm or less. In addition, the average thickness of the composite particles may be within the range of any combination of these upper limit values and these lower limit values.

The average thickness of the "composite particle" in this desirable physical property requirement refers to the average thickness of the aggregate (aggregate) when a plurality of composite particles are aggregated and fixed.

The average thickness of the composite particles here can be calculated from the surface diffusion area and density of the composite particles. The water surface diffusion area refers to the area occupied by the dry composite particles per unit mass when the composite particles dried using the leafing phenomenon are uniformly spread on the surface of the water surface and covered without gaps. Measurement of the surface spreading area can be performed according to the rules of JIS K5906:1998.

However, in the case of the composite particle of the metal pigment composition according to the present invention, when the hydrophilicity of the surface is strong, it may be difficult to obtain the above water surface diffusion area. In this case, the average thickness of the composite particles may be measured according to the method described in the later examples. That is, a film (thin film) is formed using a metal pigment composition in which composite particles are dispersed in a mixture of an alcohol solvent such as methoxypropanol and water, and the thickness of the composite particles (100 or more) is measured by a scanning electron microscope (SEM). By observing, the average thickness of the composite particles can be obtained.

The average thickness of the composite particles included in the metal pigment composition is similar to D ₅₀ on a volume basis. In the process of trituration, sifting and filtration, by appropriately adjusting the particle size of the raw material atomized metal powder, the mass per ball of trituration when using a ball mill, the number of rotations of the trituration device, the degree of sifting and filter press, etc. And, for example, in the step of coating the silicon compound-containing layer (and other coating layers as necessary), the type of organosilicon compound used, and the coating step (in the case of hydrolyzing the organosilicon compound and using it, that step is also included) ) can be controlled by appropriately adjusting the pH, concentration, stirring temperature, stirring time, type of stirring device, power / degree of stirring (eg, type and diameter of stirring blades, number of rotations, presence or absence of external stirring), etc. can

(b) The moisture contained in the metal pigment composition in the package is preferably 0 to 1000 ppm with respect to the mass of the metal pigment composition

The moisture content contained in the metal pigment composition in the package of the present invention is preferably (on a mass basis) 1000 ppm or less (0 ppm or more) with respect to the metal pigment composition. By setting it as such a water content, aggregation of the composite particle of the metal pigment composition in a package and advancing of a color tone change can be further suppressed. The moisture content is more preferably 500 ppm or less, still more preferably 300 ppm or less, and particularly preferably 200 ppm or less. There is no lower limit on the moisture content, and the lower the better.

The method for making the metal pigment composition in the package such a moisture content will be described later in the item of the packaging container.

In addition, the water content in the metal pigment composition can be measured by the method described later in Examples.

3) coating layer

The metal pigment composition according to the present invention needs to have one or more coating layers formed on the surface of the metal particle serving as the core of the composite particle. As the coating layer, silicon compounds, metals (alkali metals; alkaline earth metals; metals such as manganese, iron, cobalt, nickel, copper, silver, etc.), metal oxides (titanium oxide, zirconium oxide, iron oxide, etc.), metal hydrates and resins ( synthetic resins such as acrylic resins, alkyd resins, polyester resins, polyurethane resins, polyvinyl acetate resins, nitrocellulose resins, and fluororesins); It is preferable to include a compound-containing layer, particularly a layer made of a structure containing a Si-O bond. As a result, gas generation in the water-based paint can be suppressed, good storage stability (namely, corrosion resistance) is obtained, and excellent water resistance when used as a coating film is obtained. The coating layer includes the case where two or more layers are formed, and also in this case, it is preferable that at least one layer is a silicon compound-containing layer.

The silicon compound-containing layer is preferably a layer composed of a compound containing a Si-O-bond (siloxane bond). Examples of such a layer include a layer containing at least one of polysiloxane, silane-based compound, and silicon oxide formed by hydrolysis/condensation of an organosilicon compound. Examples of such compounds include polysiloxanes as well as silane-based compounds [H ₃ SiO(H ₂ SiO) _n SiH ₃ ] (where n represents an arbitrary positive integer) as well as SiO ₂ and SiO ₂ nH ₂ O (however, n is arbitrary). represents an integer of the amount of phosphorus) and the like are exemplified. These silane-based compounds and silicon oxides may be either crystalline or amorphous, but are particularly preferably amorphous. Therefore, as a layer containing silicon oxide (silica etc.), for example, a layer containing amorphous silica is also suitably employable.

In addition, the layer composed of a compound containing a Si-O bond may be a layer formed using an organosilicon compound (including a silane coupling agent) as a starting material. In this case, the silicon compound-containing layer may contain an organosilicon compound or a component derived from it within a range that does not hinder the effects of the present invention. In a typical example, the layer composed of a compound containing a Si-O bond can be formed by hydrolyzing an organosilicon compound.

The silicon compound-containing layer may contain additives other than the silicon compound, impurities, and the like within a range not impairing the characteristics of the present invention.

The coating layer of the composite particles included in the metal pigment composition according to the present invention is particularly preferably hydrophilic. The composite particles usually form a metal pigment composition dispersed in an aqueous solvent (water or a mixed solvent containing water and an organic solvent), but when the coating layer has a hydrophilic surface, the composite particles are highly dispersed in such an aqueous solvent. can do. In addition, since compounds containing Si-O bonds (polysiloxane, amorphous silica, etc.) are very stable in aqueous solvents, it is possible to provide a metal pigment composition comprising composite particles that are highly stable in aqueous solvents. From this point of view, in the composite particles included in the metal pigment composition according to the present invention, it is preferable that at least the outermost layer is a silicon compound-containing layer (particularly a layer composed of a compound containing a Si-O bond). When the coating layer is composed of a plurality of layers, in addition to the outermost silicon compound-containing layer, a silicon compound-containing layer (particularly a Si-O-based coating layer) may be separately formed as a layer other than the outermost layer.

As described above, the thickness of the coating layer of each composite particle is usually about 10 to 80 nm, particularly 15 nm to 70 nm, and further within the range of 20 nm to 60 nm so that the average thickness of the composite particle is in the preferred range of 20 nm to 400 nm. It is desirable to do When the coating layer has a thickness of 10 nm or more, it is possible to obtain a coating film having sufficient water resistance and suppressing the occurrence of corrosion or discoloration of metal particles in the water-based coating material. On the other hand, when the coating layer has a thickness of about 80 nm or less, the brightness, clarity, and hiding properties of the coating film can be maintained at a high level.

In the case where the silicon compound-containing layer is included in the coating layer of each composite particle, its thickness is also usually in the range of 10 nm or more and 80 nm or less from the viewpoint of exhibiting the function of the layer so that the average thickness of the composite particle is in a preferable range of 20 nm or more and 400 nm or less. It should just be, and it is especially preferable that it is the range of 15 nm or more and 70 nm or less.

Specific examples of the organosilicon compound that can be used in the present invention are further described below, but the organosilicon compound is not limited to these specific examples.

The organosilicon compound is obtained from at least one organosilicon compound represented by the following formula (1), a silane coupling agent represented by any of the following formulas (2), (3) and (4), and partial condensates thereof You may contain at least 1 sort(s) chosen.

Si(OR ¹ ) ₄ ...(1)

(In the formula, R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and all of R ¹ may be the same, some may be the same, or all may be different.)

R ² _m Si(OR ³ ) _4-m ...(2)

(Wherein, R ² is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, optionally containing a halogen group, and R ³ is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. R ² and R ³ may be the same or different, and when there are two or more R ² or R ³ , all may be the same, some may be the same, or all may be different. 1≤m≤3)

R ⁴ _p R ⁵ _q Si(OR ⁶ ) _4-pq ...(3)

(Wherein, R ⁴ is a group containing a reactive group capable of chemically bonding with another functional group, R ⁵ is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, optionally containing a halogen group, and R ⁶ is It is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.When there are two or more R ⁴ , R ⁵ or R ⁶ , all may be the same, some may be the same, or all may be different. , and 0≤q≤2, and 1≤p+q≤3)

R ⁷ _r SiCl _4-r ...(4)

(In the formula, R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, which may optionally include a halogen group, and when there are two or more R ⁷ , even if all are the same, even if some are the same, all It can be different. 0≤r≤3)

Examples of the hydrocarbon group for R ¹ in Formula (1) include methyl, ethyl, propyl, butyl, hexyl, and octyl, which may be branched or linear. Among these hydrocarbon groups, methyl, ethyl, propyl and butyl are particularly preferred. In addition, all four R< ¹ > may be the same, some may be the same, or all may be different.

Preferred examples of the organosilicon compound of the formula (1) include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane and the like. Among these, tetraethoxysilane is particularly preferable.

Examples of the hydrocarbon group for R ² in formula (2) include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, oleyl, stearyl, cyclohexyl, phenyl, benzyl, naphthyl and the like. They may be branched or linear, and may contain halogen groups such as fluorine, chlorine, and bromine. Among these, a hydrocarbon group having 1 to 18 carbon atoms is particularly preferable. In addition, when there are two or more R ² , they may all be the same, some may be the same, or all may be different. The number of R ² in the molecule is m = 1 to 3, that is, 1 to 3 in formula (2), but m = 1 or 2 is more preferred.

Examples of the hydrocarbon group for R ³ in Formula (2) include methyl, ethyl, propyl, butyl, hexyl, and octyl, which may be branched or linear. Among these hydrocarbon groups, methyl, ethyl, propyl and butyl are particularly preferred. In addition, when there are two or more R ³ , they may all be the same, some may be the same, or all may be different.

Preferred examples of the organosilicon compound (silane coupling agent) of the formula (2) include methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and dimethyldibutoxysilane. , trimethylmethoxysilane, trimethylethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltributoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltribu Toxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dibutyldibutoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, dihexyldimethoxy Silane, dihexyldiethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dioctyldimethoxysilane, dioctyldiethoxysilane, dioctylethoxybutoxysilane, decyltrimethoxysilane, decyltriethoxy Silane, didecyldimethoxysilane, didecyldiethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, dioctadecyldimethoxysilane, dioctadecyldiethoxysilane, phenyltrimethoxysilane, phenyltri Ethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, trifluoropropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooc Tyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltributoxysilane, etc. are mentioned.

Examples of reactive groups capable of chemically bonding with other functional groups in R ⁴ of formula (3) include vinyl group, epoxy group, styryl group, methacryloxy group, acryloxy group, amino group, ureido group, mercapto group, polysulfide group, isocyanate group, etc. are mentioned.

In addition, when there are two or more R ⁴ , they may all be the same, some may be the same, or all may be different. In the formula (3), the number of R ⁴ in the molecule is p = 1 to 3, that is, 1 to 3, but p = 1 is more preferable.

Examples of the hydrocarbon group for R ⁵ in formula (3) include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, oleyl, stearyl, cyclohexyl, phenyl, benzyl, naphthyl, and the like, These may be branched or linear, and may contain halogen groups such as fluorine, chlorine, and bromine. Among these, a hydrocarbon group having 1 to 18 carbon atoms is particularly preferable. In addition, when there are two or more R ⁵ , they may all be the same, some may be the same, or all may be different.

Examples of the hydrocarbon group for R ⁶ in Formula (3) include methyl, ethyl, propyl, butyl, hexyl, and octyl, which may be branched or linear. Among these hydrocarbon groups, methyl, ethyl, propyl and butyl are particularly preferred. In addition, when there are two or more R ⁶ , they may all be the same, some may be the same, or all may be different.

Preferred examples of the organosilicon compound (silane coupling agent) of the formula (3) include vinyl trimethoxysilane, vinyltriethoxysilane, vinyl-tris(2-methoxyethoxy)silane, 2-(3,4- Epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxy Silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxy Propyltrimethoxysilane, N-methyl-3-aminopropyl-trimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-amino Propylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyl Trimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, 3 -Ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, bis(triethoxysilylpropyl)tetrasul A feed, 3-isocyanate propyltriethoxysilane, etc. are mentioned.

Examples of the hydrocarbon group for R ⁷ in formula (4) include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, oleyl, stearyl, cyclohexyl, phenyl, benzyl, naphthyl and the like. They may be branched or linear, and may contain halogen groups such as fluorine, chlorine, and bromine. Among these, a hydrocarbon group having 1 to 12 carbon atoms is particularly preferable. In addition, when there are two or more R ⁷ , they may all be the same, some may be the same, or all may be different. The number of R ⁷ in the molecule is r = 0 to 3, that is, 0 to 3 in Formula (4), but it is more preferable that r = 1 to 3.

Preferred examples of the organosilicon compound (silane coupling agent) of the formula (4) include methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, octyldimethylchlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, tetrachlorosilane, and the like. can be heard

The organosilicon compound represented by the said general formula (1) may be used individually by 1 type, and may be used in combination of 2 or more types. In addition, only 1 type of silane coupling agent represented by any of Formula (2), (3) and (4) may be used independently, and may be used in combination of 2 or more types. When using in combination of two or more, only the silane coupling agent represented by any of (2), (3) and (4) may be used in combination of two or more, and silanes represented by other two or more chemical formulas You may use it combining a coupling agent.

The hydrolyzate of an organosilicon compound and/or its condensation reaction product is obtained by stirring and mixing an organosilicon compound, the water of the quantity required for carrying out a hydrolysis reaction, and a hydrolysis catalyst. In that case, you may use a hydrophilic solvent as needed. Various conditions for the hydrolysis reaction (that is, the reaction for forming the silicon compound-containing layer) will be described later.

You may use the oligomer partially condensed previously as a raw material of the hydrolysis reaction for obtaining the hydrolyzate of an organosilicon compound and/or its condensation reaction product, and/or the condensation reaction.

The condensation reaction of the hydrolyzate of the organosilicon compound may be performed simultaneously with the hydrolysis reaction of the organosilicon compound, or may be carried out by dividing the process and changing the catalyst if necessary. In that case, you may warm as needed.

In the coating layer of the composite particle included in the metal pigment composition according to the present invention, it is preferable that at least one layer is a silicon compound-containing layer. Alternatively, it may be formed together with a silicon compound-containing layer.

Other coating layers include, for example, metals (alkali metals; alkaline earth metals; metals such as manganese, iron, cobalt, nickel, copper, and silver), metal oxides (titanium oxide, zirconium oxide, iron oxide, etc.), metal hydrates, and It may consist of at least 1 sort(s) of resin (synthetic resin, such as an acrylic resin, an alkyd resin, a polyester resin, a polyurethane resin, a polyvinyl acetate resin, a nitrocellulose resin, and a fluororesin). As other coating layers, for example, a molybdenum-containing film, a phosphoric acid compound film, or the like can be formed. By providing another coating layer, the corrosion resistance of a metal particle improves.

When other coating layers of composite particles are formed, they are preferably formed between the metal particles and the silicon compound-containing layer. Therefore, for example, a layer configuration of "metal particles/other coating layers/silicon compound-containing layers" can be suitably employed. Although not particularly limited, examples of molybdenum-containing coatings include those disclosed in Japanese Patent Laid-Open No. 2003-147226, International Laid-Open No. 2004/096921 pamphlet, Japanese Patent No. 5979788, and Japanese Unexamined Patent Publication No. 2019-151678. can As an example of the phosphoric acid compound film, the one disclosed in Japanese Patent No. 4633239 is mentioned. Preferred examples of the molybdenum-containing material constituting the molybdenum-containing film include the mixed coordination type heteropolyanion compound disclosed in Japanese Unexamined Patent Publication No. 2019-151678.

In another variant, another coating layer may be formed outside the layer containing the metal particles and the silicon compound. Further, in another modified form, constituents of the silicon compound-containing layer (such as a molybdenum-containing compound or a phosphoric acid compound) may be included together with the silicon compound in the silicon compound-containing layer.

The mixed coordination type heteropolyanion compound used in the form of forming a coating layer (a typical example is a molybdenum-containing film) other than the silicon compound-containing layer of the composite particles contained in the metal pigment composition according to the present invention is not particularly limited, but specifically: can be given as an example.

The mixed coordination type heteropolyanion of the mixed coordination type heteropolyanion compound that can be used is one having a structure in which several polyatoms of a heteropolyanion containing one element are substituted with another element, and each heteropolyanion It exhibits different physical properties from the mixture of

When represented by a chemical formula, when a mixed coordination type heteropolyanion is represented by [X _p M _q N _r O _s ] ^t , the heteropoly anion is [X _p M _q O _s ] ^t , and isopoly anion [M _q O _s ] is also distinguished from ^t . However, X as a heteroatom represents an element of Groups IIIB, IVB, and VB such as B, Si, Ge, P, and As, and among them, B, Si, and P are preferable. M and N, which are poly atoms, represent transition metals such as Ti, Zr, V, Nb, Ta, Mo, and W, and Ti, Zr, V, Nb, Mo, and W are preferable.

In addition, p, q, r, and s represent the number of atoms, and t represents the oxidation number.

Since heteropolyanion compounds have numerous structures, mixed coordination heteropolyanion compounds may have more structures, but representative and preferred mixed coordination heteropolyanion compounds include the following mixed coordination heteropolyacids: H ₃ PW _x Mo _12-x O ₄₀ nH ₂ O (phosphotungstomolybdic acid n hydrate), H _3+x PV _x Mo _12-x O ₄₀ nH ₂ O (phosphovanadomolybdic acid n hydrate), H ₄ SiW _x Mo _12-x O ₄₀ ·nH ₂ O (silicone domolybdic acid ·n hydrate), H _4+x SiV _x Mo _12-x O ₄₀ ·nH ₂ O (silicone domolybdic acid ·n hydrate), and the like are exemplified. (However, 1≤x≤11, n≥0)

Preferable specific examples among these heterovalent anion compounds are H ₃ PW ₃ Mo ₉ O ₄₀ nH ₂ O, H ₃ PW ₆ Mo ₆ O ₄₀ nH ₂ O, H ₃ PW ₉ Mo ₃ O ₄₀ nH ₂ O , H ₄ PV ₁ Mo ₁₁ O ₄₀ nH ₂ O, H ₆ PV ₃ Mo ₉ O ₄₀ nH ₂ O, H ₄ SiW ₃ Mo ₉ O ₄₀ nH ₂ O, H ₄ SiW ₆ Mo ₆ O ₄₀ nH ₂ O, H ₄ SiW ₉ Mo ₃ O ₄₀ nH ₂ O, H ₅ SiV ₁ Mo ₁₁ O ₄₀ nH ₂ O, H ₇ SiV ₃ Mo ₉ O ₄₀ nH ₂ O and the like mixed coordination heteropolyacids are exemplified. .(However, n≥0)

The mixed coordination type heteropolyanion compound may be used in the form of an acid (so-called mixed coordination type heteropolyacid), or may be used in the form of a (partial or complete) salt having a specific cation as a counter ion.

Examples of the counter cation source in the case of using a mixed coordination type heteropolyanion compound in the form of a salt having a specific cation as a counter ion include alkali metals such as lithium, sodium, potassium, rubidium, and cesium; Alkaline-earth metals, such as magnesium, calcium, strontium, and barium; metals such as manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, lead, and aluminum; inorganic components such as ammonia; and at least one selected from amine compounds, which are organic components, and the like. Among the inorganic components, salts of alkali metals, alkaline earth metals and ammonia are preferred.

In addition, when at least one selected from these alkali metals, alkaline earth metals, and ammonia is used as a counter cation source, H ₃ PW _x Mo _12-x O ₄₀ nH ₂ O (phosphotungstomolybdic acid n hydrate), H _{3 +x} PV _x Mo _12-x O ₄₀ nH ₂ O (invanadomolybdic acid n hydrate), H ₄ SiW _x Mo _12-x O ₄₀ nH ₂ O (silicotungstomolybdic acid n hydrate), H ₄ It is more preferable to use in the form of a salt with at least one selected from _+x SiV _x Mo _12-x O ₄₀ nH ₂ O (gyuvanadomolybdic acid n hydrate).

In addition, as a counter cation source of the mixed coordination type heteropolyanion compound, an amine compound which is an organic component is also preferably used, and as a specific example, those represented by the following formula (5) are preferable.

(R ⁸ -N(-R ¹⁰ )-) _n -R ⁹ ...(5)

(In the formula, R ⁸ , R ⁹ and R ¹⁰ may be the same or different, and may be a hydrogen atom or a monovalent group having 1 to 30 carbon atoms, optionally containing an ether bond, an ester bond, a hydroxyl group, a carbonyl group, or a thiol group; A divalent hydrocarbon group, optionally R ⁸ and R ⁹ combine to form a 5- or 6-membered cycloalkyl group, or a 5- or 6-membered ring that may additionally contain a nitrogen or oxygen atom as a bridging member. may be formed, or optionally R ⁸ , R ⁹ and R ¹⁰ may combine to form a multi-membered multi ^- ring which may contain one or more additional nitrogen atoms and/or oxygen atoms as a bridging member. , R ⁹ and R ¹⁰ do not become hydrogen atoms at the same time, n represents an integer of 1 to 2)

Examples of the amine compound as a counter cation source of the mixed coordination type heterovalent anion compound include, for example, linear or branched primary amines, linear or branched or asymmetric secondary amines, linear or branched or tertiary amines having a mixed hydrocarbon group, etc. , alicyclic primary amines, primary amines having an aromatic ring substituent, alicyclic secondary amines, secondary amines having an aromatic ring substituent, alicyclic secondary amines, alicyclic tertiary amines, tertiary amines having an aromatic ring substituent, ether bonds amines, alkanolamines, diamines, cyclic amines, aromatic amines, etc. or arbitrary mixtures thereof.

Preferred examples of these amine compounds include at least one selected from primary, secondary, or tertiary amines of straight-chain or branched alkyl having 4 to 20 carbon atoms, or alkanolamines. Specifically, for example, butylamine, hexylamine, cyclohexylamine, octylamine, tridecylamine, stearylamine, dihexylamine, di-2-ethylhexylamine, straight-chain or branched ditridecylamine, distea relamine, tributylamine, trioctylamine, straight-chain or branched tritridecylamine, tristearylamine, N,N-dimethylethanolamine, N-methyldiethanolamine, triethanolamine, morpholine and the like.

At least one selected from amine compounds represented by the general formula (5), H ₃ PW _x Mo _12-x O ₄₀ nH ₂ O (phosphotungstomolybdic acid n hydrate), H _3+x PV _x Mo _{12 -x} O ₄₀ nH ₂ O (phosphovanadomomolybdic acid n hydrate), H ₄ SiW _x Mo _12-x O ₄₀ nH ₂ O (silicotungstomolybdic acid n hydrate), H _4+x SiV _x Mo ₁₂ It is more preferable to use it in the form of a salt with at least 1 sort(s) chosen from _-x O ₄₀ *nH ₂ O (cubanadomolybdic acid n hydrate).

Among the above mixed coordination type heteropolyanion compounds, H ₃ PW _x Mo _12-x O ₄₀ nH ₂ O (phosphotungstomolybdic acid n hydrate), H _3+x PV _x Mo _12-x O ₄₀ nH ₂ Mixed coordination heteropolyacids of O (invanadomomolybdic acid n hydrate), H ₄ SiW _x Mo _12-x O ₄₀ nH ₂ O (silicotungstomolybdic acid n hydrate), or organic amine salts of these mixed coordination heteropolyacids this is most preferable

Other coating layers other than the silicon compound-containing layer of the composite particles included in the metal pigment composition according to the present invention (when formed) are used to further improve the corrosion resistance of the metal particles (preferably aluminum particles or aluminum alloy particles) serving as the core. For this purpose, any layer containing another corrosion inhibitor is sufficient. The corrosion inhibitor to be added is not particularly limited, and any known corrosion inhibitor can be used. The usage amount may be within a range that does not impair the desired effects of the present invention. Examples of such corrosion inhibitors include acidic phosphoric acid esters, dimer acids, organic phosphorus compounds, and metal salts of molybdic acid.

In the silicon compound-containing layer and/or other coating layers of the composite particles included in the metal pigment composition, or as a separate layer, from the viewpoint of adhesion when a coating film is formed and chemical resistance, an organic oligomer or polymer may be further contained. there is.

In addition, from the viewpoint of storage stability, in the silicon compound-containing layer and/or other coating layer of the composite particles or as a separate layer, from the group consisting of inorganic phosphoric acids and salts thereof, and acidic organic (phosphorous) phosphate esters and salts thereof. You may contain at least 1 sort(s) chosen.

Although these compounds are not specifically limited, For example, what is disclosed in Unexamined-Japanese-Patent No. 2019-151678 can be used.

2. Method for producing metal pigment composition

The metal pigment composition according to the present invention is made into scale-like metal particles by, for example, a method commonly used in the pigment industry, and after this step, through steps such as sieving (classification), filtration, washing, and mixing, to obtain metal particles It can be suitably produced by a production method including a step of preparing a coating layer under stirring using a solvent containing water and/or a hydrophilic solvent. More specifically, although the following methods are mentioned, it is not limited to this.

Hereafter, as a typical example, a case where at least one layer of the coating layer of the composite particles included in the metal pigment composition is a silicon compound-containing layer will be described.

The metal pigment composition according to the present invention includes, for example, (a) metal particles, (b) a silicon-containing raw material including at least one of organosilicon compounds, (c) a solvent (water and/or a hydrophilic solvent), and necessary In a liquid mixture containing other optional components according to the above, by a method including a step of forming a silicon compound-containing layer on the surface of metal particles by subjecting an organosilicon compound to hydrolysis/(partial) condensation reaction (silicon compound-containing layer forming step) can be suitably manufactured. This process can be carried out under normal stirring.

1) Grinding and sifting/filtration process

Here, the case where aluminum powder is used as a metal particle is taken as an example and demonstrated.

Aluminum powder is generally atomized aluminum powder and / or aluminum foil, using methods commonly used in the pigment industry such as dry ball milling, wet ball milling, attritor method, stamp milling, grinding aids and inert solvents It is pulverized in the presence of, so-called scaly, and further obtained through required steps such as sifting (classification), filtration, washing, and mixing after this step.

Examples of the grinding aid here include fatty acids, fatty amines, fatty amides, fatty alcohols and the like. In general, oleic acid, stearic acid, stearylamine and the like are preferred. In addition, examples of the inert solvent include those exhibiting hydrophobicity such as mineral spirits, solvent naphtha, LAWS, HAWS, toluene, and xylene, and these may be used alone or in combination. Grinding aids and inert solvents are not limited thereto.

As the pulverization step, pulverization by a wet ball mill method is preferable from the viewpoint of preventing dust explosion and securing safety.

When aluminum particles are employed as metal particles in the production of the metal pigment composition according to the present invention, commercially available pasty aluminum flakes obtained through such grinding, sieving and filtration can be used. The paste-like aluminum flakes may be used as they are, or may be used after removing fatty acids on the surface with an organic solvent or the like in advance.

In addition, as metal particles in the production of the metal pigment composition of the present invention, so-called vapor-deposited aluminum foil produced by peeling and pulverizing a metal layer deposited on a carrier material such as a resin film by physical vapor deposition (PVD) from the carrier material Pigments of can also be used.

2) Step of Forming Silicon Compound-Containing Layer

A liquid mixture containing the above-described (a) metal particles, (b) silicon-containing raw material containing at least one of organosilicon compounds and (c) solvent, and other optional components as necessary can be prepared by mixing these components. there is. The order of mixing is not particularly limited.

As the metal particles, the metal particles described above can be used, but aluminum or aluminum alloy particles can be particularly suitably used. Also, as described above, it is preferable to use scaly metal particles. As the metal particles, known or commercially available ones (typically pasty aluminum flakes) can be used.

The content (solid content) of the metal particles in the liquid mixture is not particularly limited, and can be appropriately set according to the type, particle size, etc. of the metal particles to be used.

As a silicon-containing raw material, an organosilicon compound is used. Although it is not limited as an organosilicon compound, The thing mentioned above can be used preferably.

At least one of the organosilicon compound represented by the formula (1) (tetraalkoxysilane as a typical example) and/or a condensate thereof, and a silane coupling agent represented by any of the formulas (2) to (4) is suitable can be used

Hereafter, the case where tetraalkoxysilane is used as an organosilicon compound represented by the formula (1) will be described as an example. In addition, below, tetraalkoxysilane and/or its condensate may simply be collectively called "tetraalkoxysilane".

When the tetraalkoxysilane represented by the above formula (1) and the silane coupling agent represented by any of the above formulas (2) to (4) are used together, a method of mixing and using both (referred to as "first method") can be employed. Alternatively, a method including a step of forming a first silicon compound-containing layer by performing one treatment on the metal particles and forming a second silicon compound-containing layer by performing treatment on the other (referred to as "the second method" ) may be employed.

In the first method, for example, the pH of a liquid mixture containing metal particles, tetraalkoxysilane represented by the above formula (1), and a silane coupling agent represented by any of the above formulas (2) to (4) is appropriately adjusted. By adjusting, the method including the process of carrying out the hydrolysis/condensation reaction of tetraalkoxysilane and a silane coupling agent, and forming a silicon compound containing layer is mentioned.

As a second method, for example, by appropriately adjusting the pH of a liquid mixture containing metal particles and tetraalkoxysilane represented by the above formula (1), tetraalkoxysilane is subjected to a hydrolysis/condensation reaction, and the first Step of forming a silicon compound-containing layer (for example, a silica film containing amorphous silica), and adjusting the pH of a liquid mixture containing metal particles and a silane coupling agent represented by any of the above formulas (2) to (4) A method including a step of subjecting a silane coupling agent to a hydrolysis/condensation reaction to form a second silicon compound-containing layer on the surface of the first silicon compound-containing layer is exemplified.

The amount of tetraalkoxysilane represented by the formula (1) or its condensate can be appropriately set according to the type of tetraalkoxysilane to be used. The amount used may be, for example, 2 to 200 parts by mass with respect to 100 parts by mass of the metal particles (solid content), and from the viewpoint of the coating treatment effect and the viewpoint of suppressing the aggregation of the metal particles or the decrease in brilliance, and 5 to 5 parts by mass. It is more preferable that it is 100 mass parts.

The amount of the silane coupling agent represented by any of the above formulas (2) to (4) is not particularly limited, but is usually about 0.1 to 20 parts by mass, particularly 1 to 10 parts by mass, based on 100 parts by mass of the metal particles (solid content). It is preferable to deny When this usage amount is about 0.1 to 20 parts by mass, desired coating treatment effects and desirable coating film properties can be obtained.

The solvent in the liquid mixture, that is, the solvent for the hydrolysis reaction and/or condensation reaction of the organosilicon compound, may be appropriately selected depending on the type of silicon-containing raw material to be used, but is usually water, a hydrophilic organic solvent, or a mixture thereof. solvents may be used. By using these solvents, the uniformity of the reaction and the obtained hydrolyzate and/or condensation reaction product can be improved. In the aspect in which the silicon compound-containing layer is directly formed on the metal particles, it is particularly preferable that the solvent of the liquid mixture contains a hydrophilic organic solvent from the viewpoint of avoiding rapid progress of the reaction between the metal particles and water. In the present invention, a mixed solvent of water and a hydrophilic organic solvent can be suitably used.

Although it does not specifically limit as a hydrophilic organic solvent, For example, Alcohol, such as methanol, ethanol, propanol, butanol, isopropanol, and octanol; Ether alcohols such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether; esters thereof; glycols of ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, polyoxyethylene glycol, polyoxypropylene glycol, and ethylene propylene glycol; Ethyl cellosolve, butyl cellosolve, acetone, methoxypropanol, ethoxypropanol, other alkoxy alcohols, etc. are mentioned. These can be used by 1 type or 2 or more types.

In the case of using a mixed solvent of water and a hydrophilic organic solvent as the solvent, the ratio between the two is not particularly limited. In the aspect in which the silicon compound-containing layer is directly formed on the metal particles, from the viewpoint of avoiding rapid progress of the reaction between the metal particles and water, before the silicon compound is introduced, the sum of both is set to 100% by mass, and the amount of water It is preferable to make content into 20 mass % or less. In this case, the lower limit of the water content is not limited.

The amount of the solvent used in the step of forming the silicon compound-containing layer (excluding the amount of the solvent for that purpose when the metal particles are pre-dispersed) is not limited, but is usually 100 to 10,000 per 100 parts by mass of the metal particles (solid content). It should just be about a mass part, and it is preferable that it is 200-1000 mass parts especially. When the amount of the solvent used is 100 parts by mass or more, an increase in the viscosity of the liquid mixture (slurry) is suppressed, and appropriate stirring is possible. In addition, when the amount of the solvent used is 10000 parts by mass or less, the cost of recovering and reproducing the treatment liquid can be prevented from increasing. In addition, the usage amount of the solvent here refers to the total amount of the solvent used for forming the first silicon compound-containing layer and the second silicon compound-containing layer in the case of the second method.

In the above liquid mixture, other additives may be blended as necessary within a range that does not impede the effects of the present invention. Examples include catalysts such as hydrolysis catalysts and dehydration condensation catalysts, as well as surfactants and metal corrosion inhibitors.

Among these, a hydrolysis catalyst can be used suitably. By blending the hydrolysis catalyst, the organosilicon compound can be efficiently hydrolyzed and dehydrated and condensed while adjusting the pH of the liquid mixture, and as a result, a silicon compound-containing layer can be efficiently and reliably formed on the surface of the metal particle. it becomes possible

A known or commercially available hydrolysis catalyst may be used, and is not particularly limited. As a hydrolysis catalyst, For example, Inorganic acids, such as hydrochloric acid, nitric acid, a sulfuric acid, phosphoric acid; organic acids such as benzoic acid, acetic acid, chloroacetic acid, salicylic acid, oxalic acid, picric acid, phthalic acid, and malonic acid; Phosphonic acids, such as vinylphosphonic acid, 2-carboxyethanephosphonic acid, 2-aminoethanephosphonic acid, and octanephosphonic acid, etc. can be used. These hydrolysis catalysts may be used individually by 1 type, or may be used in combination of 2 or more type.

Moreover, as a hydrolysis catalyst, For example, inorganic alkalis, such as ammonia, sodium hydroxide, and potassium hydroxide; Inorganic alkali salts, such as ammonium carbonate, ammonium hydrogencarbonate, sodium carbonate, and sodium hydrogencarbonate; monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, N,N-dimethylethanolamine, ethylenediamine, pyridine, aniline, choline, amines such as tetramethylammonium hydroxide and guanidine; Salts of organic acids such as ammonium formate, ammonium acetate, monomethylamine formate, dimethylamine acetate, pyridine lactate, guanidinoacetic acid, and aniline acetate can also be used. These hydrolysis catalysts can be used singly or in combination of two or more.

Although the addition amount of the hydrolysis catalyst is not particularly limited, it is usually 0.01 to 20 parts by mass, preferably 0.02 to 10 parts by mass, based on 100 parts by mass of the metal particles (solid content). When the addition amount is 0.01 parts by mass or more, the deposition amount of the silicon compound-containing layer can be sufficient. In addition, when the addition amount is 20 parts by mass or less, aggregation of the metal particles can be effectively suppressed.

In preparing the mixed solution, these components may be mixed uniformly in the mixed solution, and the mixing order is not particularly limited.

In the production of the metal pigment composition according to the present invention, it is preferable to prepare the liquid mixture under appropriate stirring.

The stirrer for stirring the mixture is not particularly limited, and a known stirrer capable of efficiently and uniformly stirring a mixture containing aluminum particles and an organosilicon compound can be used. Specific examples include kneaders, kneaders, rotary vessel agitators, agitated reaction vessels, V-shaped agitators, double cone agitators, screw mixers, sigma mixers, flash mixers, airflow agitators, ball mills, edge runners and the like. Additional description of the agitator will be given later.

The temperature of the liquid mixture at the time of stirring the liquid mixture containing the metal particles and the organosilicon compound may be usually about 10 to 80°C, and particularly preferably 20 to 70°C. When this temperature is 10 degreeC or more, the reaction time for obtaining sufficient treatment effect can be shortened. Moreover, when this temperature is 80 degrees C or less, control of reaction for obtaining a desired metal pigment composition becomes easier.

The stirring time of the liquid mixture is not particularly limited as long as it is sufficient for forming a desired silicon compound-containing layer. It is preferable to set this stirring time as 0.5 to 20 hours, for example, and it is more preferable to set it as 1 to 10 hours. When the stirring time is 0.5 hour or longer, a sufficient treatment effect can be obtained. Moreover, the increase in processing cost can be suppressed because stirring time is 20 hours or less.

In the liquid mixture, a silicon compound-containing layer is formed on the surface of the metal particles (or through another coating layer) by subjecting the silicon-containing raw material to a hydrolysis/condensation reaction. This hydrolysis/condensation reaction can be carried out by, for example, adjusting the pH of the liquid mixture.

When adjusting the pH, especially in the step where the silicon compound-containing layer is formed on the surface of the metal particle (or through another coating layer), the pH value of the mixed solution changes, so appropriately adjusted so that the pH value can be maintained within a certain range it is desirable In that case, it is preferable to adjust the pH value by adding a hydrolysis catalyst, but the pH value may be adjusted using other acidic or alkaline compounds as long as the properties of the metal pigment composition according to the present invention are not impaired.

When using a basic hydrolysis catalyst as a hydrolysis catalyst, it is preferable to set pH value to 7-11, and it is more preferable to set it as 7.5-10 especially. When the pH value is 7 or higher, the silicon compound-containing layer can be quickly formed. On the other hand, when the pH value is 11 or less, aggregation of metal particles and decrease in brilliance can be suppressed, and generation of hydrogen gas due to corrosion can be prevented.

When using an acidic hydrolysis catalyst as a hydrolysis catalyst, it is preferable to set pH value to 1.5-4, and it is more preferable to set it as 2-3 especially. When the pH value is 1.5 or more, the reaction is moderately controlled and it becomes easy to obtain a metal pigment composition containing desired composite particles. On the other hand, when the pH value is 4 or less, the deposition rate of the silicon compound-containing layer can be held high.

Even in the case of employing either of the first method and the second method, the hydrolyzate and/or condensate thereof of the organosilicon compound represented by the above formula (1) is based on 100 parts by mass of metal particles (solid content), It is preferable to add 0.01 to 50 parts by mass, more preferably 1 to 30 parts by mass, in terms of the state in which the hydrolysis and condensation reactions have been completed. In addition, the silane coupling agent represented by any of the above formulas (2) to (4), and / or hydrolyzates derived from their partial condensates and / or condensates thereof, relative to 100 parts by mass of metal particles (solid content) , In terms of the state in which the hydrolysis and condensation reactions have been completed, 0.01 to 0.8 parts by mass is added in total, and it is more preferable to add 0.01 to 0.7 parts by mass.

The addition amount of the hydrolyzate of the organosilicon compound represented by the general formula (1) and/or its condensate is based on the mass of the organosilicon compound represented by the general formula (1) used in the production of the metal pigment composition. It can be calculated by multiplying the mass ratio before and after the reaction in the case of hydrolysis and condensation reaction.

For example, when tetraethoxysilane (TEOS) is used as the organosilicon compound represented by formula (1), using the following mass ratio before and after the hydrolysis and condensation reaction, the hydrolyzate and/or The addition amount of its condensate can be calculated.

(hydrolysis)

Si(OC ₂ H ₅ ) ₄ (molecular weight: 208)+4H ₂ O → Si(OH) ₄ (molecular weight: 96)+(C ₂ H ₅ OH) ₄

(condensation)

Si(OH) ₄ (molecular weight: 96)+ Si(OH) ₄ (molecular weight: 96) → (SiO ₂ ) ₂ (molecular weight: 60×2)+4H ₂ O

Before and after the above hydrolysis and condensation reaction, the mass becomes 60/208 = 0.288 times, so for example, when 10 parts by mass of TEOS is used with respect to 100 parts by mass of metal particles (solid content), its hydrolyzate and / or its condensation The amount of water added is 0.288 times that, that is, 2.88 parts by mass.

Similarly, the addition amount of a hydrolyzate such as a silane coupling agent represented by any of formulas (2) to (4) and/or a condensate thereof is also any of formulas (2) to (4) used in the production of the metal pigment composition. It can be calculated by multiplying the mass ratio of the silane coupling agent and/or its partial condensate represented by the mass ratio before and after the reaction when all of the silane coupling agent and/or its partial condensate hydrolyzes and undergoes a condensation reaction.

For example, when methyltrimethoxysilane is used as the silane coupling agent represented by the general formula (2), the following mass ratios before and after the hydrolysis and condensation reactions are used, and the hydrolyzate of the silane coupling agent and/or its condensation The amount of water added can be calculated.

(hydrolysis)

CH ₃ Si(OCH ₃ ) ₃ (molecular weight: 136)+3H ₂ O → CH ₃ Si(OH) ₃ (molecular weight: 94)+(CH ₃ OH) ₃

(condensation)

CH ₃ Si(OH) ₃ (molecular weight: 94)+CH ₃ Si(OH) ₃ (molecular weight: 94) → (SiCH ₃ O _1.5 ) ₂ (molecular weight: 67×2)+3H ₂ O

Before and after the above hydrolysis/condensation reaction, the mass becomes 67/136 = 0.49 times, so for example, when 1.23 parts by mass of methyltrimethoxysilane is used with respect to 100 parts by mass of metal particles (solid content), its hydrolyzate and The addition amount of / or its condensate is 0.49 times that, ie, 0.60 parts by mass.

In addition, even in the case of adopting either of the first method and the second method, the metal particles are combined with the organosilicon compound as the source of the silicon compound (or, in the case of forming other coating layers, typically before they are combined with the molybdenum compound). ), water, a hydrophilic organic solvent, or a mixed solvent thereof is preferably sufficiently dispersed. In this pre-dispersion (initial dispersion), preferably a portion of the dispersion (for example, 0.5 to 30% by mass, preferably 1 to 20% by mass, more preferably 1 to 15% by mass of the entire dispersion per minute) The degree of dispersion can be further increased by performing external circulation in which %) is once drawn out to the outside of the dispersion tank and then returned to the dispersion tank again. Dispersibility can be further improved by performing ultrasonic treatment outside the dispersing tank in the middle of the external circulation passage.

Although the ultrasonic treatment is not particularly limited, it can be performed usually at 10 to 1000 W, preferably 50 to 800 W, and usually for 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes. The amount of the solvent used for this pre-dispersion may be usually about 100 to 10000 parts by mass, or 200 to 5000 parts by mass per 100 parts by mass of the metal particles (solid content), from the viewpoint of obtaining sufficient dispersion by appropriately adjusting the intensity of stirring. It is preferable that it is a mass part, and it is more preferable that it is 300-1000 mass parts.

The pre-dispersion of these metal particles can be usually carried out at 10 to 80°C, preferably 15 to 60°C, and most preferably around room temperature (about 20 to 40°C). In addition, the pre-dispersion of the metal particles can be performed for 5 minutes to 10 hours, preferably 10 minutes to 5 hours (including when ultrasonic treatment is performed).

3) Other Coating Layer Formation Steps

As described above, the other coating layer (if formed) is particularly preferably formed between the metal particle and the silicon compound-containing layer. Therefore, a layer configuration of "metal particles/other coating layer/silicon compound-containing layer" can be suitably adopted.

The other coating layer is not particularly limited, but may be a molybdenum-containing film, a phosphoric acid compound film, or the like. Preferred examples of the molybdenum-containing material constituting the molybdenum-containing film include the mixed coordination type heteropolyanion compound disclosed in Japanese Unexamined Patent Publication No. 2019-151678. Examples of constituent components of the coating layer including the mixed coordination type heteropolyanion compound are as described above.

Hereafter, an embodiment in which a molybdenum-containing film is formed as another coating layer between the metal particles and the silicon compound-containing layer will be described as an example.

In the case of forming a molybdenum-containing film as another coating layer between the metal particles and the silicon compound-containing layer, prior to formation of the silicon compound-containing layer, a liquid mixture containing the metal particles and a molybdenum compound (typically a mixed coordination type heteropolyanion compound) is prepared. By stirring, a molybdenum-containing film can be formed on the surface of the metal particle.

The method for forming the molybdenum-containing film on the surface of the metal particles is not particularly limited, and any method may be used as long as the mixed solution containing the metal particles and the molybdenum compound can be stirred uniformly in an aqueous solvent. For example, a molybdenum-containing film can be formed on the surfaces of metal particles by stirring or kneading a liquid mixture containing metal particles and a molybdenum compound in a slurry state or paste state. In the liquid mixture, the molybdenum compound may be dissolved or dispersed.

In addition, the stirrer for stirring the liquid mixture containing the metal particles and the molybdenum compound is not particularly limited, and a known stirrer capable of efficiently and uniformly stirring the liquid mixture containing the aluminum particles and the molybdenum compound can be used. Specific examples include a kneader, a kneader, a rotary vessel stirrer, a stirred reaction vessel, a V-type stirrer, a double-conical stirrer, a screw mixer, a sigma mixer, a flash mixer, an airflow stirrer, a ball mill, and an edge runner. Examples of the stirring blades of the stirrer are not particularly limited, but include anchor blades, paddle blades, propeller blades, and turbine blades.

In the case of forming a molybdenum-containing film as the other coating layer, the amount of the molybdenum compound used can be appropriately set according to the type of the molybdenum compound to be used. This amount of use is generally 0.02 to 20 parts by mass, preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the metal particles (solid content). When the said content is 0.02 mass part or more, sufficient treatment effect can be acquired. Moreover, when the said content is 20 mass parts or less, the luminance of the metal pigment composition obtained can be held highly.

As a solvent used for mixing the metal particles and the molybdenum compound, usually water, a hydrophilic organic solvent, or a mixed solvent thereof can be used.

Examples of the hydrophilic organic solvent include alcohols such as methanol, ethanol, propanol, butanol, isopropanol, and octanol; Ether alcohols such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether; esters thereof; glycols of ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, polyoxyethylene glycol, polyoxypropylene glycol, and ethylene propylene glycol; Ethyl cellosolve, butyl cellosolve, acetone, methoxypropanol, ethoxypropanol, other alkoxy alcohols, etc. are mentioned. These can use 1 type or 2 or more types.

The amount of the solvent used in the other coating layer formation steps (excluding the amount of the solvent for that purpose when the metal particles are previously dispersed) is not particularly limited, but is usually 50 to 50 parts per 100 parts by mass of the metal particles (solid content). It is preferable that it is 5000 mass parts, and it is more preferable that it is 100-2000 mass parts. When the amount of the solvent used is 50 parts by mass or more, uneven distribution of the molybdenum compound and aggregation of the metal particles can be suppressed. In addition, when the amount of the solvent used is 5000 parts by mass or less, a sufficient treatment effect with the molybdenum compound can be obtained with respect to the metal particles.

The temperature of the liquid mixture at the time of stirring the liquid mixture containing the metal particles and the molybdenum compound may be usually about 10 to 80°C, and particularly preferably 30 to 70°C. When this temperature is 10 degreeC or more, the reaction time for obtaining sufficient treatment effect can be shortened. Moreover, when this temperature is 80 degrees C or less, control of reaction for obtaining a desired metal pigment composition becomes easier.

The stirring time of the liquid mixture is not particularly limited as long as it is a time sufficient for forming a desired molybdenum-containing film. It is preferable to set this stirring time as 0.5 to 10 hours, for example, and it is more preferable to set it as 1 to 5 hours. When the stirring time is 0.5 hour or longer, a sufficient treatment effect can be obtained. Moreover, the increase in processing cost can be suppressed because stirring time is 10 hours or less.

After stirring of the liquid mixture containing the metal particles and the molybdenum compound is completed, the other coated particles can be recovered. In this case, well-known washing, solid-liquid separation, etc. can be appropriately performed as needed. For example, after washing the liquid mixture with a hydrophilic organic solvent, it is preferable to filter it using a filter or the like to remove water and unreacted substances from a cake containing metal particles having a molybdenum-containing film. In this way, a molybdenum-containing film, which is another coating layer, can be formed. In the case of forming other coating layers, it can also be carried out according to the above method.

In an embodiment in which a silicon compound-containing layer is formed following the other coating layer (molybdenum-containing film) on the metal particles, after stirring of the liquid mixture containing the metal particles and the molybdenum compound is completed, particles having other coating layers are not recovered, In the system, a silicon compound source (typically, an organosilicon compound represented by the above formula (1), for example, tetraalkoxysilane and/or a condensate thereof, and any of the above formulas (2) to (4) You may directly add and stir the dispersion liquid of water and/or a hydrophilic organic solvent of at least 1 sort(s) of the silane coupling agents represented. At this time, a dispersion of an organosilicon compound represented by the above formula (1), for example, tetraalkoxysilane and/or a condensate thereof, is added to the system containing the particles with other coating layers, and then, the above formulas (2) to You may add and stir the dispersion of at least 1 sort(s) of the silane coupling agent represented by any of (4) (refer the 2nd method in the above-mentioned "formation process of a silicon compound containing layer").

4) Agitation conditions

In the production of the metal pigment composition according to the present invention, it is necessary to carry out at least the step of forming the coating layer of the composite particles, typically the silicon compound-containing layer, while stirring. In the production of the metal pigment composition according to the present invention, it is preferable to carry out not only the silicon compound-containing layer formation process but also the other coating layer formation process under stirring. In the aspect of performing the prior dispersion of the metal particles described above, it is more preferable to carry out this also under stirring. Further, in the production of the metal pigment composition according to the present invention, it is more preferable to carry out the entire process including the pre-dispersion of the metal particles, the formation process of the other coating layer, and the formation process of the silicon compound-containing layer under stirring.

In the production of the metal pigment composition according to the present invention, the formation step of at least the coating layer of the composite particles, typically the silicon compound-containing layer, is carried out under appropriately controlled stirring, so that the composite particles adhere to each other via the silicon compound-containing layer, or It is possible to effectively suppress or prevent the phenomenon that each agglomerated particle containing a metal particle is coated with a silicon compound-containing layer. In addition, the entire process, including the pre-dispersion of the metal particles, the step of forming the other coating layer, and the step of forming the silicon compound-containing layer (until the time when all the layers to be formed on the surface of the metal particle are all formed), is carried out under stirring, It becomes possible to more easily obtain the metal pigment composition according to the present invention that satisfies all of the above physical property requirements.

Description of the stirring conditions described below can be applied to any process in the manufacture of the metal pigment composition according to the present invention.

Stirring can be performed with a known or commercially available stirring device. For example, at least one of a kneader, a kneader, a rotary vessel agitator, an agitated reactor, a V-type agitator, a double cone agitator, a screw mixer, a sigma mixer, a flash mixer, an air flow agitator, a ball mill, an edge runner, and the like can be used. .

Among these stirrers, it is preferable to use a stirring tank-type device that stirs with a stirring blade (impeller). As a result of exerting a pressure shearing action as well as a circulation action for fluidizing the entire reaction system including the liquid phase by the stirring blades, the formation of agglomeration of the composite particles can be more effectively suppressed.

The shape of the agitation blade is not particularly limited, and for example, an anchor type, a propeller type, a turbine type, an inclined turbine type, a fan turbine type, a paddle type, an inclined paddle type, or a gate type can be used. Max Blend Wings (manufactured by Sumitomo Jugaki Process Kiki Co., Ltd.) and Full Zone Wings (manufactured by Shinko Kankyo Solution Co., Ltd.) are also suitable. Moreover, it is also possible to combine the stirring blades of these shapes in multiple stages.

It is preferable that the stirring speed is stirred to such an extent that the stirring blades are not exposed by vortices (vortex) generated by stirring. In addition, in order to suppress the vortex generated by stirring, a cylindrical tank, a rectangular tank, or a tank provided with a baffle plate can be suitably used.

In the production of the metal pigment composition containing the composite particles according to the present invention, it is preferable to set the optimum stirring tank, stirring blade size, and stirring blade speed in relation to the amount of the mixed solution and physical properties (density, viscosity, etc.) Do. The size of the stirring vessel is preferably selected so that the maximum amount of the liquid mixture used in a series of steps is 20 to 80% of the stirring vessel. In the case of a cylindrical stirring vessel, the ratio of the height (L) and the inner diameter (D) of the stirring vessel is generally L/D in the range of 0.5 to 3.0, usually 1 to 2. In addition, as for the size of a stirring blade, it is common for the maximum diameter to be within the range of 0.2 to 0.9 of the inside diameter of the stirring vessel, and it is preferable to set it to about 0.4 to 0.6. The shape (including length) of the stirring blade is preferably selected appropriately according to the physical properties of the liquid mixture, and it is important that the entire stirring vessel is stirred throughout the process. In particular, it is preferable to combine an inclined paddle type, an inclined turbine type, and a propeller type that are prone to up and down flow in multiple stages, or use max blend blades or full zone blades to prevent the formation of unstirred retention areas near the liquid surface or the bottom of the stirring tank. Do. At this time, it is preferable that the distance between the stirring blades and the inner surface of the stirring tank (including the baffle plate) is 5 mm or more. By doing in this way, it becomes easy to suppress breakage and deformation of a metal particle.

The speed of the stirring blade is preferably 0.5 to 50 m/s at the tip, more preferably 1 to 20 m/s, still more preferably 2 to 10 m/s. When the speed of the tip of the stirring blade is in the range of 0.5 to 50 m/s, the dispersibility of the composite particles in the resulting metal pigment composition can be increased, and furthermore, the cohesiveness of individual particles is small, has excellent hiding power and color tone, It becomes easier to obtain a metal pigment composition with less occurrence. In addition, when the linear speed of stirring is within the above range, damage to metal particles (eg, scaly aluminum powder) is prevented, the rate of hydrolysis/condensation reaction is appropriately controlled, and aggregation of composite particles is effectively suppressed. It can be.

5) Recovery process of composite particles

After the process of forming the silicon compound-containing layer (and optionally other coating layers) on the metal particles is completed, the obtained composite particles can be recovered. In recovery, if necessary, known treatments such as washing and solid-liquid separation may be performed. For example, it is preferable to wash the dispersion liquid with an organic solvent and then filter it using a filter to remove water and unreacted substances from the cake containing the composite particles. In addition, after that, you may heat-process the cake containing composite particle|grains at the temperature of the range of 100-500 degreeC as needed. As will be described later, the composite particles recovered in this way can form a metal pigment composition accompanied by remaining solvents including a trace amount of water/hydrophilic solvent used in the usual manufacturing process.

3. Metallic Pigment Composition

The metal pigment composition of the present invention obtained as described above contains composite particles comprising metal particles and one or more coating layers on the surface thereof, and contains water used in the manufacturing process as a solid content (non-volatile content) residue. / It can be understood that a metal pigment composition containing a solvent such as a hydrophilic solvent is formed.

The metal pigment composition usually includes an organosilicon compound (for example, at least one organosilicon compound represented by the above formula (1) and a silane represented by any of the above formulas (2), (3) and (4). Coupling agent, and at least one selected from partial condensates thereof) hydrolyzate and/or a silicon compound that is a condensate thereof is 0.02 to 50 mass in terms of a state in which the hydrolysis/condensation reaction is completed, with respect to 100 parts by mass of metal particles. part may exist.

In the metal pigment composition, an optional other coating layer-forming compound (a molybdenum-containing compound, for example, a mixed coordination type heteropolyanion compound in an optional optional embodiment in which a molybdenum-containing film is formed as the other coating layer) is a metal 0.01 to 10 parts by mass may be present with respect to 100 parts by mass of the particles.

The metal pigment composition may contain 0.01 to 50 parts by mass of an organic oligomer or polymer of any choice based on 100 parts by mass of the metal particles.

In the metal pigment composition, 0.01 to 20 parts by mass of at least one selected from the group consisting of optional inorganic phosphoric acids and salts thereof, and acidic organic (sub)phosphate esters and salts thereof may be present in an amount of 0.01 to 20 parts by mass based on 100 parts by mass of metal particles. there is.

In the metal pigment composition, a solvent containing water/hydrophilic solvent used in the manufacturing process may be present as the remainder of the above components (non-volatile matter). The amount of the solvent containing water/hydrophilic solvent may be, for example, 0.5 to 95% by mass of the metal pigment composition. Alternatively, the amount of the solvent containing water/hydrophilic solvent may be 1 to 90% by mass, or 2 to 80% by mass, or 5 to 70% by mass of the metal pigment composition.

The metal pigment composition may optionally contain optional components other than those described above. Examples of the optional component include at least one of antioxidants, light stabilizers, polymerization inhibitors, and surfactants.

As antioxidants, those represented by phenol-based compounds, phosphorus-based compounds, and sulfur-based compounds can be used.

As the light stabilizer, those used as the above-mentioned antioxidants can also be used, but benzotriazole-based compounds, benzophenone-based compounds, salicylate-based compounds, cyanoacrylate-based compounds, oxalic acid derivatives, hindered amine-based compounds (HALS), hin What is represented by a dud phenol type compound can be used.

Examples of the surfactant include nonionic interfaces represented by polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenyl ethers, oxyalkylene alkylamino ethers, sorbitan fatty acid esters, polyalkylene glycol fatty acid esters, and glycerin fatty acid esters. active agents, including anionic surfactants represented by sulfuric acid ester salts, sulfonic acid salts, and phosphoric acid ester salts; and cationic surfactants represented by quaternary ammonium salts. Two or more types can be used. Among these, particularly preferable examples include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, or mixtures thereof.

4. Packing container

One). Composition of packing container

The packaging container of the present invention is one for wrapping a metal pigment composition, and at least one type of protective layer selected from a), b) and c) is formed on a portion in contact with the metal pigment composition:

a) glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, cyclic oxirane type epoxy resin, novolak phenol resin, resol type phenol resin, polyester resin and phenol resin A protective layer having a thickness of 1 to 200 μm formed of a resin containing at least one selected from the group consisting of thermosetting epoxy resins;

b) a protective layer formed of a metal phosphoric acid salt and having a weight per unit area of 0.1 g/m ² to 10 g/m ² ;

c) a protective layer which is thin chrome plating.

It is more preferable that the base material (substrate portion protected by the protective layer) of the packaging container of the present invention contains metal at least partially and is substantially formed of metal. If the base material of the packing container is metal, there are advantages in that it is resistant to impact, hardly receives leakage or contact with outside air during transportation, and the temperature change of the internal temperature during storage becomes gentle. In the packaging container of the present invention, a case in which a main constituent part such as a base material is made of metal, and a part such as a seal portion of a cover (substrate or accessory parts other than the protective layer thereof) is formed of a resin other than metal is also included. .

The metal constituting the substrate is preferably iron, stainless steel, or aluminum, more preferably iron or stainless steel, and still more preferably iron.

When the protective layer is thin chrome plating, it is preferable that the packaging container is subjected to a thin plating process of a chromium-containing compound on a base material composed at least partially of a steel plate. If at least a part of the base material of the packaging container (typically, substantially the entire base material) is made of steel plate, it is resistant to impact, hardly receives leakage or contact with outside air during transportation, and has the advantage that the temperature change of the internal temperature during storage becomes gentle. .

The thickness of the substrate is not particularly limited, but may be usually about 500 μm to 50 mm, more typically about 800 μm to 20 mm. It is preferable that the thickness of the substrate is substantially constant throughout, but may be thicker than other locations in the top portion, the bottom portion, or locations around them.

In the package of the present invention, if the protective layer as described above is formed on the portion of the packaging container in contact with the metal pigment composition, the aggregation of the composite particles contained in the metal pigment composition in the package and the progression of color tone change can be more prevented. can be further suppressed.

Although it does not specifically limit as an epoxy resin of a), For example, glycidyl ether type containing bisphenol A type, bisphenol F type, hydrogenated bisphenol A type, a phenol novolak type, etc., hexahydrophthalic-acid glycidyl ester, Glycidyl ester type including glycidyl methacrylate copolymer, etc., glycidyl amine type including tetraglycidyldiaminodiphenylmethane, 3,4-epoxycyclohexylmethyl 3,4-epoxy Cyclic oxirane types containing cyclohexane carboxylate etc. are mentioned. These may be used individually by 1 type, and may be used together 2 or more types. These epoxy resins are used as paints by generally known methods, such as room temperature curing by fatty acid modification, thermal curing using a curing agent such as melamine resin or amine, or powder coating or emulsifying to form a cationic electrodeposition type. do.

Although it does not specifically limit as a phenol resin of a), For example, a novolak phenol resin, a resol-type phenol resin, etc. are mentioned. These phenolic resins are used as paints by curing with an amine-based curing agent or curing by heat. These may be used individually by 1 type, and may be used together 2 or more types.

Although it does not specifically limit as resin containing the epoxy resin and phenol resin of a), For example, the resin thermosetted using the phenol resin as a hardening|curing agent of an epoxy resin is mentioned. The resin is used as a paint in its form as it is.

Although it does not specifically limit as a polyester resin, For example, polyethylene terephthalate resin, polyethylene isophthalate resin, polybutylene terephthalate resin, polytrimethylene terephthalate resin, and resin which copolymerized these are mentioned. These polyester resins may be used in the form of being laminated to a metal as a film, or may be used as a powder coating material. These may be used individually by 1 type, and may be used together 2 or more types.

Further, the resin for a) more preferably contains an epoxy resin, and more preferably contains a phenol resin.

The layer of resin in a) has a coating film thickness of 1 μm to 200 μm. When the thickness of the coating film of the resin is 1 μm or more, defects in the coating are easily prevented, and the effect of preventing coloration tends to be more favorably expressed. When the coating film thickness of the said resin is 100 micrometers or less, it is preferable from a viewpoint of cost and productivity. The coating film thickness of the resin is more preferably 2 μm to 50 μm, still more preferably 3 μm to 40 μm.

In addition, the film thickness here refers to the average value of the thickness of five arbitrary places including slight fluctuations resulting from an actual application process, for example.

The metal phosphate salt of b) is preferably iron phosphate or zinc phosphate.

The layer formed of the metal phosphate salt of b) has an area weight of 0.1 g/m ² to 10 g/m ² . When the coating amount of the metal phosphate salt is 0.1 g/m ² or more, defects in the coating are easily prevented, and the effect of preventing discoloration tends to be more suitably expressed. When the coating amount of the metal phosphate salt is 10 g/m ² or less, it is preferable from the viewpoints of cost and productivity. The coating amount of the metal phosphate salt is more preferably 0.2 to 7 g/m ² , and still more preferably 0.3 to 5 g/m ² .

As a protective layer, you may use a) and b) in combination. When these are combined, it is preferable that b) is in contact with the base material (typically made of metal) of the packaging container, and the resin layer of a) is formed thereon.

The resin layer of a) is formed by, for example, applying various solvent-based resin coating agents to a metal plate, drying, and baking at a predetermined temperature and time (for example, at 210° C. for 10 minutes in the case of epoxyphenol resin). can In the case of employing a pail can as the packaging container, a pail can can be obtained by molding a metal plate on which a layer of the resin described above is formed.

A steel sheet substrate provided with thin chrome plating of c) as a protective layer is also generally referred to as tin-free (non-tin-containing) steel. The thin chrome plating is typically produced from an aqueous solution of chromic acid by an electrolysis method, and the film structure thereof may be a two-layer film of a metal chromium layer and a hydrated chromium oxide layer on a substrate (preferably a steel sheet). The amount of metal chromium in the film in this embodiment may be about 50 to 150 mg/m ² , the amount of chromium oxide may be about 5 to 35 mg/m ² , and the thickness of both films may be about 20 to 50 nm. In addition, the thickness of the thin chrome plating film here refers to the average value of the thickness at five arbitrary places including slight fluctuations resulting from the actual application process, for example.

In the material of such a packaging container, when the low moisture content of the metal pigment composition is engaged, the aggregation of the composite particles contained in the metal pigment composition in the package and the progression of color tone change can be further suppressed.

When the foil chrome plating of c) is used as the protective layer, a protective layer containing a resin may be additionally formed on the foil chrome plating in a portion of the packaging container that is in contact with the metal pigment composition. The presence of an additional protective layer containing a resin can further suppress aggregation of the composite particles included in the metal pigment composition in the package and progression of color tone change. This additional protective layer may be the above a) and/or b), or may be formed of other resins.

When the thin chrome plating of c) is used as the protective layer, the resin constituting the additional protective layer is not particularly limited, but glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin , a resin containing at least one selected from the group consisting of cyclic oxirane-type epoxy resins, novolac phenol resins, resol-type phenol resins, polyester resins, polyethylene resins, and epoxy resins heat-cured with phenol resins.

The epoxy resin for the additional protective layer of c) is not particularly limited, but examples include bisphenol A type, bisphenol F type, hydrogenated bisphenol A type, glycidyl ether type including phenol novolak type, hexahydrophthalic acid, etc. Glycidyl ester type including glycidyl ester and glycidyl methacrylate copolymer, glycidyl amine type including tetraglycidyldiaminodiphenylmethane, 3,4-epoxycyclohexylmethyl and cyclic oxirane types including 3,4-epoxy cyclohexane carboxylate and the like. These may be used individually by 1 type, and may be used together 2 or more types. These epoxy resins are used as paints in generally known methods, such as room temperature curing by fatty acid modification, thermal curing using a curing agent such as melamine resin or amine, or powder coating or emulsifying to form a cationic electrodeposition type. .

The phenolic resin for the additional protective layer of c) is not particularly limited, but examples thereof include novolac phenolic resins and resol-type phenolic resins. These phenolic resins are used as paints by curing with an amine-based curing agent or curing by heat. These may be used individually by 1 type, and may be used together 2 or more types. Although it does not specifically limit as resin containing an epoxy resin and a phenol resin, For example, the resin thermosetted using the phenol resin as a hardening|curing agent of an epoxy resin is mentioned. The resin is used as a paint in its form as it is.

Further, the resin for the additional protective layer of c) more preferably includes an epoxy resin and more preferably includes a phenol resin.

Moreover, it is one of the more preferable aspects that the said resin contains a polyester resin. Although it does not specifically limit as a polyester resin, For example, polyethylene terephthalate resin, polyethylene isophthalate resin, polybutylene terephthalate resin, polytrimethylene terephthalate resin, and resin which copolymerized these are mentioned. A typical example is a polyester resin whose main component is a skeleton containing terephthalic acid, ethylene glycol or 1,4-butanediol. These polyester resins may be used in the form of being laminated to a metal as a film, or may be used as a powder coating material. These may be used individually by 1 type, and may be used together 2 or more types.

The layer of resin as an additional protective layer in c) preferably has a coating film thickness of 1 μm to 200 μm. When the thickness of the coating film of the resin is 1 μm or more, defects in the coating are easily prevented, and the effect of preventing coloration tends to be more favorably expressed. When the coating film thickness of the said resin is 150 micrometers or less, it is preferable from a viewpoint of cost and productivity. The coating film thickness of the resin is more preferably 2 μm to 100 μm, still more preferably 3 μm to 60 μm.

In addition, the film thickness here refers to the average value of the thickness of five arbitrary places including slight fluctuations resulting from an actual application process, for example.

As for the package of this invention, it is preferable that the said packing container can seal. If the packaging container can be hermetically sealed, the aggregation of the metal pigment in the package and the advancement of color tone change can be further suppressed. Usually, the package is sealed when storing the metal pigment composition over a long period of time, for example, 1 hour or longer or 1 day or longer, or when transporting.

The shape of the packing container of the present invention is not particularly limited, but may be, for example, a substantially rectangular column shape or a substantially columnar shape, preferably a substantially columnar shape. It is preferable that the packing container be called a pail can or a drum among substantially cylindrical shapes. If the packaging container is a pail can or a drum container, it is a general container and has the characteristics of saving space during logistics or storage, convenient for entering and exiting a warehouse, and stably storing contents.

2). Moisture rate

The moisture content contained in the metal pigment composition in the package of the present invention may be usually (on a mass basis) 2000 ppm or less (0 ppm or more) with respect to the metal pigment composition, and preferably 1000 ppm or less. By setting it as such a water content, aggregation of the composite particle of the metal pigment composition in a package and advancing of a color tone change can be further suppressed. The water content is more preferably 500 ppm or less, still more preferably 300 ppm or less, and particularly preferably 200 ppm or less. There is no lower limit on the moisture content, and the lower the better.

In order to achieve such a water content, in the process of producing a metal pigment composition, after the process of forming a silicon compound-containing layer (and/or optionally other coating layers) on metal particles is completed, washing, solid-liquid separation, etc. are known. The treatment is performed, and at this time, the dispersion is washed with an organic solvent having a water content of, for example, 2000 ppm or less, and then filtered using a filter. In some cases, this operation is repeated a plurality of times to obtain a composition containing composite particles. It is preferable to remove water and unreacted materials. After that, if necessary, the cake containing the composite particles may be heated and dehydrated at a temperature in the range of, for example, 100 to 500°C in a gas atmosphere such as nitrogen having a low moisture content. As described above, the composite particles recovered in this way can constitute a metal pigment composition accompanied by remaining solvents including a small amount of water/hydrophilic solvent used in the usual manufacturing process.

Further, also when adjusting the solid content ratio of the composition, it is preferable to use an organic solvent (for example, the above-mentioned hydrophilic solvent) having a moisture content of usually 2000 ppm or less, preferably 1000 ppm or less.

The water content of the organic solvent used for washing or adjusting the solid content is more preferably 500 ppm or less, still more preferably 300 ppm or less, and particularly preferably 200 ppm or less.

In addition, moisture may also be contained in the gaseous phase part in a package. Moisture in the gaseous portion of the package originates from moisture contained in the metal pigment composition wrapped in the packaging container, and originates from moisture in the air in portions other than the metal pigment composition within the volume of the packaging container. When there is much water in the gaseous phase, the metal pigment composition absorbs this water and the moisture content increases. For this reason, when putting a metal pigment composition into a packing container, it is preferable to use dry air. It is also a preferred method to replace the vapor phase with dry air prior to covering the packing container. Dry air is used when putting the metallic pigment composition into the packing container, or when the gas phase part is substituted with dry air before covering the packing container, and the packing container is sealed at the same time, the moisture content in the package is substantially equal to the moisture content in the metal pigment composition. , there is no case where the moisture content in the metal pigment composition increases significantly during storage. The water content in the metal pigment composition can be measured by the method described later in Examples.

3). pH

It is preferable that the pH of the metal pigment composition in the package of this invention is the range of 5-9. By setting the pH within this range, the aggregation of the composite particles of the metal pigment composition in the package and the progression of color tone change can be further suppressed. The pH of the metal pigment composition is more preferably in the range of 6 to 8, and more preferably in the range of 6.5 to 7.5.

In order to adjust the pH of such a metal pigment composition, for example, after the step of forming a silicon compound-containing layer (and/or optionally other coating layers) on metal particles is completed, washing with a sufficient amount of an organic solvent, solid-liquid separation, etc. It is preferable to repeatedly perform known treatments to sufficiently wash and remove polar compounds such as catalysts used when forming the coating layer.

5. How to store and transport

One). residue

When the package of the present invention is stored in an airtight indoor warehouse at 20°C for 1 year, the residue of the metal pigment composition after storage is preferably 0.1% by weight or less (based on the total weight of the metal pigment composition at that time). . The amount of the residue in the present invention is determined by dispersing 50 g of the metal pigment composition taken out of the package after storage under the above conditions in 1000 ml of mineral spirits with a spatula, and then filtering with a 200 mesh nylon net (manufactured by NBC Co.) After thoroughly washing the residue with acetone and drying it at 105° C. for 10 minutes, the mass was measured and the ratio thereof was determined as the mass of the residue (method employed in Examples described later). In addition, even when the package of the present invention is stored for one year in an indoor warehouse at 20 ± 10 ° C., preferably 20 ± 20 ° C. in a sealed state (that is, in an indoor warehouse at a constant temperature within this temperature range, or this It is more preferable that the residue of the metal pigment composition after storage is 0.1% by weight or less (even when stored for one year in an indoor warehouse at a temperature that is manually adjusted or naturally fluctuated within the temperature range). It becomes easy to obtain the coating material which can form a favorable coating film without protrusion by setting it as the residual amount of such a metal pigment composition. Since the residual amount of the metal pigment composition is affected by the coating state of the metal particles in the composite particle, the moisture content in the metal pigment composition, etc., the coating that satisfies the predetermined requirements as described above, the moisture content within the predetermined range in the package By doing so, it becomes easy to control the residual amount as described above. The amount of residue is more preferably 0.05% by weight or less, and still more preferably 0.01% by weight or less.

In particular, in the case where one or more types of protective layers selected from the above a) and b) are formed on the portion of the packaging container in contact with the metal pigment composition, the package of the present invention is sealed indoors at 20 ° C. When stored for one year in a warehouse, it is preferable that the residue of the metal pigment composition after storage is 0.05% by weight or less (based on the total weight of the metal pigment composition at that time). In the above case, even when the package of the present invention is stored for one year in an indoor warehouse at 20 ± 10 ° C., preferably 20 ± 20 ° C. in a sealed state (that is, at a constant temperature within this temperature range) It is preferable that the residue of the metal pigment composition after storage is 0.05% by weight or less. As for this residue amount, it is more preferable that it is 0.02 weight% or less, and it is still more preferable that it is 0.01 weight% or less. The advantage in this case is also the same as the above.

In addition, when the package of the present invention is stored in a sealed state in a heated room at 60°C for 3 months, it is preferable that the residue of the metal pigment composition after storage is 0.1% by weight or less. In addition, even when the package of the present invention is stored in a sealed state in a heated room at 60 ° C. ± 10 ° C. for 3 months (that is, in a warmed room at a constant temperature within this temperature range or manually within this temperature range) It is preferable that the residue of the metal pigment composition after storage is 0.1% by weight or less even when stored for 3 months in a heated room at an appropriately varied temperature. It becomes easy to obtain the coating material which can form a favorable coating film without protrusion by setting it as the residual amount of such a metal pigment composition. Since the residual amount of the metal pigment composition is affected by the coating state of the metal particles in the composite particle, the moisture content in the metal pigment composition, etc., the coating that satisfies the predetermined requirements as described above, the moisture content within the predetermined range in the package By doing so, it becomes easy to control the residual amount as described above. The amount of residue is more preferably 0.05% by weight or less, and still more preferably 0.01% by weight or less.

In particular, in the case where one or more types of protective layers selected from a) and b) are formed on the portion of the packaging container in contact with the metal pigment composition, the package of the present invention is sealed. When stored for 3 months in a warming room at 60°C, it is preferable that the residue of the metal pigment composition after storage is 0.05% by weight or less. In the above case, even when the package of the present invention is stored in a heated room at 60 ° C ± 10 ° C. for 3 months in a closed state (that is, in a heated room at a constant temperature within this temperature range Alternatively, even when stored for 3 months in a heated room at a temperature suitably fluctuated manually within this temperature range), it is preferable that the residue of the metal pigment composition after storage is 0.05% by weight or less. As for this residue amount, it is more preferable that it is 0.02 weight% or less, and it is still more preferable that it is 0.01 weight% or less. The advantage in this case is also the same as the above.

2). How to store and transport

The storage method of the present invention is a method of storing the metal pigment composition by the above-mentioned package.

In the storage method of the present invention, the temperature in the packaging container when storing the metal pigment composition is preferably 0 to 50°C, more preferably 10 to 40°C, and still more preferably 15 to 25°C.

In the storage method of one embodiment, the storage period of the metal pigment composition is preferably 5 years or less, more preferably 2 years or less, and still more preferably 1 year or less.

In the storage method of one embodiment, the storage warehouse is preferably a warehouse that can be controlled in the range of 0 to 50 ° C. or 10 to 40 ° C., and is a constant temperature warehouse that can be controlled in the range of 15 to 25 ° C. more preferable It is desirable that the temperature of the warehouse can be controlled to a constant temperature throughout the storage period.

The conveying method of the present invention is a method of conveying the metal pigment composition by the above-mentioned package.

In the delivery method of one embodiment, the temperature in the packaging container when transporting the metal pigment composition is preferably 0 to 50 ° C, more preferably 10 to 40 ° C, and still more preferably 15 to 25 ° C. .

In the transport method of one embodiment, it is preferable that the container or cargo area to be transported can be controlled within the range of 0 to 50°C or 10 to 40°C, and the constant temperature container or cargo area can be controlled within the range of 15 to 25°C. is more preferable. Preferably, the temperature of the warehouse can be controlled to a constant temperature throughout the transport period.

In addition, it is preferable that direct rays of the sun do not reach the package in any case of storage and transportation. It is for preventing that the possibility that the temperature of a part of a package rises increases when direct rays of the sun hits.

[Example]

Next, the present invention will be specifically described by way of Examples and Comparative Examples.

The following examples are described to illustrate the present invention, and do not limit the scope of the present invention at all.

One). Production example of metal pigment composition

[Production Example 1]

A commercially available aluminum paste (manufactured by Asahi Kasei Co., Ltd., trade name "GX ^- 3100 (average particle size: 11 μm, volatile content: 74%)) ]) 230 kg of methoxypropanol (hereinafter abbreviated as "PM") was added to 67 kg, the mixture was stirred with a stirring blade at 100 rpm, and a 10 L/min dispersion liquid extracted from the bottom was returned to the reaction tank from the top of the reaction tank While performing external circulation, the aluminum paste was uniformly dispersed in the PM.

Subsequently, a solution obtained by dissolving 0.5 kg of phosphotungstomolybdic acid (H ₃ PW ₆ Mo ₆ O ₄₀ ) hydrate in 2.5 kg of methoxypropanol was gradually added, and the slurry was stirred for 1 hour while maintaining the temperature at 40°C.

Thereafter, 5 kg of tetraethoxysilane was added as an organosilicon compound, and then 5 kg of 25% ammonia water and 100 kg of purified water were added over 3 hours. After that, 0.7 kg of methyltrimethoxysilane was further added as a silane coupling agent, and the mixture was stirred for 2 hours. After completion of the reaction, after cooling, the slurry was filtered.

The filtered slurry was washed 5 times (i.e. sufficiently) with PM having a moisture content of 200 ppm to lower the moisture content, and after sufficiently removing raw materials and catalysts used for forming the coating layer, pressure filtration was performed again, and an aluminum pigment composition having a non-volatile content of 60% was obtained. got it Here, dry air having a dew point of -40°C was used when handling slurry such as pressure filtration.

[Production Example 2]

It carried out similarly to manufacture example 1 except having changed to aluminum paste (made by Asahi Kasei Co., Ltd., brand name "FD-5090 (average particle diameter 9 micrometers, volatile content 7%)"), and the aluminum pigment composition of 60% of non-volatile content was obtained.

2). Formation examples of a) a protective layer formed of a specific resin or b) a protective layer formed of a metal phosphate salt and a comparative example therefor

[Example 1]

As a packaging container for packing the metal pigment composition, a steel pail can (20 liter straight pail can, manufactured by Shinpo Kogyo Co., Ltd.) having an inner weight of 20 liters was prepared. A layer of epoxy phenol resin (Dytoron #5301, manufactured by Dainippon Paint Co., Ltd.) having an average thickness of 7 μm was formed on the portion of the packaging container in contact with the metal pigment composition. In addition, the epoxyphenol resin was applied as a coating agent in which 20% by mass of an epoxy resin, 30% by mass of a phenolic resin, and 50% of a solvent were mixed, and after volatilizing the solvent at room temperature, it was baked at 210°C for 10 minutes to obtain a resin layer. . 15 kg of the metal pigment composition prepared in Production Example 1 was put into the packaging container, and it was sealed to obtain a package. At this time, the gas phase part of the pail can was filled with the same dry air (dew point: -40 ° C.) as used in the preparation example. Note that the "average thickness" of the protective layer here refers to the average of the thicknesses at five arbitrary locations.

[Comparative Example 1]

A package was obtained in the same manner as in Example 1 except that an untreated steel pail can in which a layer containing a resin was not formed on a portion in contact with the metal pigment composition was used as a packaging container for packing the metal pigment composition.

[Example 2]

A package was obtained in the same manner as in Example 1 except for using the metal pigment composition prepared in Production Example 2.

[Comparative Example 2]

A package was obtained in the same manner as in Comparative Example 1 except for using the metal pigment composition prepared in Production Example 2.

[Example 3]

A package was obtained in the same manner as in Example 1 except that a packing container having an epoxy phenol resin layer having an average thickness of 50 µm was used.

[Example 4]

A package was obtained in the same manner as in Example 1 except that a packing container having an average thickness of the epoxyphenol resin layer of 3 µm was used.

[Example 5]

A package was obtained in the same manner as in Example 1 except that PM having a water content of 2000 ppm was used for washing the filtered slurry.

[Example 6]

A package was obtained in the same manner as in Example 1 except that the number of washings of the filtered slurry was reduced to once.

[Comparative Example 3]

A package was obtained in the same manner as in Example 5 except that an untreated steel pail can in which a layer containing a resin was not formed on a portion in contact with the metal pigment composition was used as a packaging container for packing the metal pigment composition.

[Example 7]

A package was obtained in the same manner as in Example 1 except that a steel pail can (special pail can PS-20, manufactured by Shinpo Kogyo Co., Ltd.) having an inner weight of 20 liters and having a polyethylene resin layer having an average thickness of 100 μm was used. Further, the layer of polyethylene resin was formed by blow molding and heat-sealed to the inner surface of the metal can.

[Example 8]

Using a steel pail can (13L white pail, manufactured by Takamura Shokai Co., Ltd.) having a net weight of 13 liters on which a layer of epoxy resin having an average thickness of 7 μm is formed, 10 kg of the metal pigment composition was added, and Example 1 and A package was obtained in the same manner.

[Comparative Example 4]

A package was obtained in the same manner as in Example 5, except that a steel pail can having an epoxy phenol resin layer having an average thickness of 0.5 μm was formed on a portion in contact with the metal pigment composition as a packaging container for packing the metal pigment composition.

[Example 9]

A package was obtained in the same manner as in Example 1 except that 150 kg of the metal pigment composition was loaded into a 200 liter steel drum (open head drum, manufactured by JFE Container) in which a layer of 3 g/m ² iron phosphate was formed.

[Example 10]

A package was obtained in the same manner as in Example 1 except that 150 kg of the metal pigment composition was loaded into a steel drum (manufactured by JFE Container) in which a layer of 3 g/m ² zinc phosphate was formed.

3). c) Example of use of a steel sheet having a thin chrome plating protective layer and comparative example thereof

[Example 12]

As a packaging container for packing the metal pigment composition, a pail can (20 L of pail can, manufactured by Shinpo Kogyo Co., Ltd.) made of foil chrome-plated steel sheet having an internal weight of 20 liters was prepared. 15 kg of the metal pigment composition prepared in Production Example 1 was put into the packaging container, and it was sealed to obtain a package. At this time, the gas phase part of the pail can was filled with the same dry air (dew point: -40 ° C.) as used in the preparation example.

[Comparative Example 5]

As a packing container for packing the metal pigment composition, an untreated steel pail can (corresponding to the structure except for the foil chrome plating portion of the foil chrome plated steel pail can used in Example 12) not subjected to the foil chrome plating treatment was used. Except for that, it carried out similarly to Example 12, and obtained the package.

[Example 13]

A package was obtained in the same manner as in Example 12 except for using the metal pigment composition prepared in Production Example 2.

[Comparative Example 6]

A package was obtained in the same manner as in Comparative Example 5 except for using the metal pigment composition prepared in Production Example 2.

[Example 14]

A package was obtained in the same manner as in Example 12, except that PM having a water content of 500 ppm was used for washing the filtered slurry.

[Example 15]

A package was obtained in the same manner as in Example 12, except that the number of washings of the filtered slurry was reduced to once.

[Example 16]

A package was obtained in the same manner as in Example 12 except for using a thin chrome-plated steel pail can (laminated pail can, manufactured by Nippon Tekan Co., Ltd.) having a net weight of 20 liters and having a polyethylene layer having an average thickness of 100 μm. In addition, the "average thickness" of the polyethylene layer here points out the average of the thickness of 5 arbitrary places.

[Example 17]

The portion in contact with the metal pigment composition is a foil chrome-plated steel pail can (manufactured by Shinpo Kogyo Co., Ltd.) in which a layer of epoxy phenol resin (Ditoron #5301, manufactured by Dainippon Paint Co., Ltd.) having an average thickness of 7 μm is formed. A package was obtained in the same manner as in Example 12 except for using.

In addition, the epoxyphenol resin was applied as a coating agent in which 20% by mass of an epoxy resin, 30% by mass of a phenolic resin, and 50% of a solvent were mixed, and after volatilizing the solvent at room temperature, it was baked at 210°C for 10 minutes to obtain a resin layer. . The "average thickness" of the epoxy phenol resin layer here refers to the average of the thicknesses at five arbitrary locations.

[Reference Example 1]

A package was obtained in the same manner as in Example 16, except that PM having a water content of 2000 ppm was used for washing the filtered slurry.

4). Evaluation of metallic pigment compositions

(Average particle diameter: D ₅₀ )

The average particle diameter (D ₅₀ ) of the composite particles in the metal pigment composition was measured using a laser diffraction/scattering type particle size distribution analyzer (LA-300/manufactured by Horiba Seisakusho Co., Ltd.).

Isopropanol was used as the measurement solvent.

The measurement was carried out according to the instrument instruction manual, but as a precaution, the composite particles to be samples were ultrasonically dispersed for 2 minutes as a pretreatment, and then put into a dispersion tank to confirm that they were dispersed at an appropriate concentration, and then the measurement was started. After completion of the measurement, D ₅₀ was calculated by the software of the instrument and displayed automatically.

(moisture content)

The water content in the metal pigment composition was measured by the Karl Fischer method according to JIS K 0068.

(pH)

The pH of the metal pigment composition was measured at a temperature of 25°C using a glass electrode type pH measuring device (PH METER F-15 type, manufactured by Horiba Seisakusho).

(Residual ratio of metal pigment composition after package storage)

Metal taken out from the package after storing the package of the metal pigment composition obtained in each of the above Examples / Comparative Example in a storage for 1 year at 20 ± 10 ° C. (under a temperature naturally fluctuated by the influence of the atmosphere around the storage) After dispersing 50 g of the pigment composition in 1000 ml of mineral spirits with a spatula, filtering with a 200 mesh nylon net (manufactured by NBC), washing the residue sufficiently with acetone, drying at 105 ° C. for 10 minutes, and measuring the mass. and the ratio thereof was obtained as the mass of the residue.

(Evaluation of coating film obtained from metal pigment composition before and after package storage)

Before storage of the package of the metal pigment composition obtained in each of the above examples and comparative examples, and after storing the package at 20 ± 10 ° C. (under a temperature that naturally fluctuates due to the atmospheric influence around the storage) for one year, Gon Using the metal pigment composition taken out from the body, an aqueous metallic paint was prepared with the following composition, and the paint and the coating film obtained therefrom were respectively evaluated by the following method.

<Composition of water-based metallic paint>

・Metal pigment composition: 12.0 g as non-volatile matter

・Methoxypropanol: 18.0g

- Polyoxyethylene lauryl ether (nonionic surfactant, manufactured by Matsumoto Yushi Seiyaku Co., Ltd., trade name "Mapon L5"): 6.0 g

・Purified water: 12.0g

・Water-soluble acrylic resin (※1): 110.0g

・Melamine resin (※2): 18.0g

※1: Manufactured by Mitsui Chemical Co., Ltd., Almatex WA911

※2: Cymel 350, manufactured by Cytec Industries, Ltd., Japan

After mixing the above components, the pH was adjusted to 7.7 to 7.8 with dimethylethanolamine, and the viscosity was adjusted to 650 to 750 mPa s with a carboxylic acid-based thickener and purified water (Type B viscometer, No.3 rotor, 60 rotations, 2°C). adjusted to

(Evaluation of coating film)

The water-based metallic paint prepared in the above formulation was applied by air spraying to a dry film thickness of 6 μm on a 12 cm × 6 cm steel plate (manufactured by Miki Coating Co., Ltd.), pre-dried at 90 ° C. for 10 minutes, and then After dispersing the organic solvent-type top coat paint of the composition for 3 minutes with a spatula, the paint viscosity was adjusted to 20.0 seconds with Ford Cup No. 4, and air spray coating was applied to a dry film thickness of 20 μm, followed by 30 minutes at 140 ° C. It was made to dry, the painted board was produced, and it used for the following evaluation.

(Composition of organic solvent-type top coat paint)

・Acridic 44-179 (manufactured by DIC, acrylic clear resin) 141g

・Super Beckamine J-820 (manufactured by DIC, melamine resin) 35.3g

・Toluene 123.5g

(Coating projection)

The number of projections on the entire surface of the topcoat coating film of the obtained coated board was measured and evaluated according to the following index.

○: Projections could not be recognized.

(triangle|delta): The number of projections was 10 or less.

x: There were more than 10 projections.

(luminance)

About the obtained painted board, it evaluated using Kansai Paint Co., Ltd. laser-type metallic feeling measuring device Alcop LMR-200. Optical conditions include a laser light source with an incident angle of 45 degrees and a light receiver with light receiving angles of 0 degrees and -35 degrees. As the measured value, the IV value was determined at -35 degrees at the receiving angle at which the maximum light intensity was obtained, excluding the light in the specular reflection region reflected from the surface of the coating film among the reflected light of the laser. The IV value is a parameter proportional to the intensity of regular reflected light from the coating film, and indicates the magnitude of the luminance.

From the obtained IV value, it was evaluated based on the following criteria.

◎: The range of decrease from the standard (before storage) was less than 20.

○: The range of decrease from the standard (before storage) was 20 or more and less than 40.

Δ: The range of decrease from the standard (before storage) was 40 or more and less than 60.

×: The range of decrease from the standard (before storage) was 60 or more.

(concealment)

The prepared water-based metallic paint was applied on a polyethylene terephthalate production sheet (PET sheet) with a 2-mil applicator to a dry film thickness of 15 μm, and the coating film dried at 140° C. for 30 minutes was visually evaluated.

○: Slightly lower than the standard (before storage).

Δ: lower than the standard (before storage).

x: Significantly lower than the standard (before storage).

(average thickness of composite particles, average thickness of coating layer)

In order to facilitate measurement of particle thickness, etc., the amount of the metal pigment composition in the formulation of the paint used for the above "coating film evaluation" produced using the metal pigment composition taken out from the package before storage was 1/10 The above water-based metallic paint was prepared under the same conditions except for the above, and a painted board was produced under the conditions described in the above "coating film evaluation".

The above painted board was cut into 1 cm squares using a shearing machine.

The resulting coating film cross section was set to allow ion beam irradiation to a portion 20 μm away from the coating film cross section using an ion milling device (manufactured by Nihon Electric Co., Ltd./IB-09010CP), and a precision polished cross section sample was produced by ion milling treatment. .

The thickness of the composite particle was evaluated by observing the obtained coating film cross section (coated board) with FE-SEM (S-4700 manufactured by Hitachi).

As conditions for FE-SEM observation and acquisition, the setting of the accelerating voltage was adjusted to 5.0 kV, and the image magnification was measured at a magnification of 10,000.

From the obtained FE-SEM image (10,000 times), using image analysis software Win Roof version 5.5 (manufactured by Mitani Corporation), the thickness of 100 arbitrary particles in the cross section of the composite particle was measured, and the average thickness was calculated. In addition, the thickness uniformity of the composite particles is high, and the thickness difference due to the cutting part of the particles is small. Therefore, the effect of the difference in the cut area of the particles on the average thickness measurement can be ignored.

For the coated plate prepared for the above-mentioned FE-SEM image acquisition, using HR-STEM (high-resolution scanning transmission electron microscope, manufactured by Hitachi/S-5500), the setting of the accelerating voltage was adjusted to 30 kV, and the magnification was 20 An image was obtained at 10,000 magnifications, and the thickness of the coating layer of the composite particles was measured. When there are irregularities on the surface of the coating layer, the area of the coating layer was measured using image analysis software Win Roof version 5.5 and divided by the circumferential length of the coated particles to determine the thickness of the coating layer. In addition, when the particle is large, it is not necessarily necessary to measure the entire area of the coating layer, and the thickness of the coating layer can be obtained with sufficient accuracy by measuring the area of the coating layer in a region of about 1 μm along the particle surface and dividing it by the particle surface length. lose In addition, since the thickness of the coating layer is almost uniform regardless of the number of particles, an average value was obtained for 10 particles.

[Example 11]

After storing the package of the metal pigment composition obtained in Example 1 in a storage (heating room) at 60 ° C. (substantially constant temperature including temporary fluctuations within ± 10 ° C.) for 3 months, the package was taken out The same evaluation as in Example 1 was performed except for the storage conditions using the metal pigment composition.

Table 1 shows the evaluation results of Examples 1 to 11 and Comparative Examples 1 to 4. It was found that in the packages according to the present invention that satisfy all the requirements of the above items (1) to (3) obtained in each example, the aggregation of the metal pigment composition in the package and the progress of coloring can be suppressed.

[Example 18]

After storing the package of the metal pigment composition obtained in Example 12 in a storage (heating room) at 60 ° C. (under a substantially constant temperature including temporary fluctuations within ± 10 ° C.) for 3 months, the package was taken out The same evaluation as in Example 12 was performed except for the storage conditions using the metal pigment composition.

Table 2 shows the evaluation results of Examples 12 to 18, Comparative Examples 5 to 6, and Reference Example 1. It has been found that in the packages of the present invention which satisfy all of the above items (1) to (3) requirements obtained in each Example, the aggregation of the metal pigment composition in the package and the progression of coloring can be suppressed.

The package according to the present invention, the metal pigment composition contained in the package after being stored and transported by the storage and transportation method of the present invention, and the coating film obtained using them, have low VOC, storage stability when used for water-based paints, etc. , the excellent properties of the coating film, such as suppression of projections, design, and concealment, etc., are combined at a high level exceeding the limits of the prior art. Therefore, these metal pigment compositions and coating films are used for various applications in which metal pigments have conventionally been used, such as paints, inks, resin pastes, etc., more specifically, automobile bodies, automobile repair materials, automobile parts, home appliances, etc., plastic parts, PCM It can be suitably used in application paints, highly weather resistant paints, heat resistant paints, anticorrosive paints, ship bottom paints, offset printing inks, gravure printing inks, screen printing inks, and the like. Alternatively, these metal pigment compositions and coating films have high applicability in various industries such as transport machinery industry such as automobiles, electrical and electronic industries such as home appliances, paint industry, and printing industry.

Claims (14)

A package in which a metal pigment composition comprising metal particles and composite particles having one or more coating layers on the surface thereof is packed in a packaging container, and the package satisfies the following (1) to (3):
(1) The shape of the composite particle is scaly;
(2) The composite particles have a volume-based D ₅₀ of 1 μm or more and 30 μm or less when the particle size distribution is measured with a laser diffraction type particle size distribution meter;
(3) The packaging container is provided with a substrate at least partially made of metal, and at least one protective layer selected from the following a), b) and c) is formed on a portion of the packaging container in contact with the metal pigment composition. What has been:
a) glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, cyclic oxirane type epoxy resin, novolak phenol resin, resol type phenol resin, polyester resin and phenol resin A protective layer having a thickness of 1 to 200 μm formed of a resin containing at least one selected from the group consisting of thermosetting epoxy resins;
b) a protective layer formed of a metal phosphoric acid salt and having a weight per unit area of 0.1 g/m ² to 10 g/m ² ;
c) a protective layer which is thin chrome plating. The package according to claim 1, wherein at least one type of protective layer selected from a) and b) is formed on a portion of the packing container in contact with the metal pigment composition. The package according to claim 1, wherein the amount of moisture contained in the metal pigment composition in the package is 0 to 1000 ppm with respect to the mass of the metal pigment composition. The package according to claim 2, wherein the moisture contained in the metal pigment composition in the package is 0 to 1000 ppm with respect to the mass of the metal pigment composition. The package according to claim 1 or 3, wherein the composite particles have an average thickness of 20 to 400 nm. The package according to claim 1 or 3, wherein at least one layer of the coating layer is a silicon compound-containing layer. The package according to claim 1 or 3, wherein the metal particles are aluminum or an aluminum alloy. The package according to claim 1 or 3, wherein the pH of the metal pigment composition is in the range of 5 to 9. The package according to claim 1 or 3, wherein the residue of the metal pigment composition after storage is 0.1% by weight or less when the sealed package is stored in an indoor warehouse at 20°C for one year. The package according to claim 2, wherein the residue of the metal pigment composition after storage is 0.05% by weight or less when the sealed package is stored in an indoor warehouse at 20°C for one year. The package according to claim 1 or 3, wherein the residue of the metal pigment composition after storage is 0.1% by weight or less when the sealed package is stored in a heated room at 60°C for 3 months. The package according to claim 2, wherein when the sealed package is stored in a heated room at 60°C for 3 months, the residue of the metal pigment composition after storage is 0.05% by weight or less. A storage method for storing the metal pigment composition at 0 to 50°C by the package according to claim 1 or 3. A method for conveying a metal pigment composition at 0 to 50°C by the package according to claim 1 or 3.