JP2012162638A - Metal pigment composition, and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal pigment composition wherein in the case of using the composition for an aqueous coating material, an aqueous ink and the like, the amount of hydrogen gas generated during storage is small providing excellent storage stability, and the brightness and the hiding property and the flip-flop feeling of the coating film are excellent.SOLUTION: The metal pigment composition contains: a phosphorus-containing metal compound obtained by reacting one or two or more metal oxide-based compounds selected from the group consisting of metal oxides, alkaline metal salts of metal oxides, and ammonium salts of metal oxides, with one or two or more phosphorus compounds; and a metal pigment.

Description

  The present invention relates to a metal pigment composition blended in water-based paints, water-based inks and the like used for plastic coating, automobile body coating, and the like, and a method for producing the same.

  In recent years, in order to eliminate pollution and improve the working environment, high solid type paints that do not use organic solvents as much as possible and water-based paints that use water as a solvent have been increasingly used in the painting field. In addition, due to the advancement of technical improvement of water-based paints, high-quality coating films that have been obtained only with solvent-type paints can be realized with water-based paints.

  However, in metallic coatings containing metal pigments such as aluminum, there are currently few practical water-based paints. The main reason why there are few practical water-based metallic paints is that metal pigments such as aluminum react with water in the water-based paint to generate hydrogen gas. When the amount of generated hydrogen gas is large, there is a concern about safety during the production of the paint and during the painting work using the paint, and the storage container swells due to the hydrogen gas generated by the reaction during the storage of the paint. There was a problem that it was deformed (poor storage stability).

  Therefore, the following techniques have been proposed as solutions that can solve such problems. That is, Patent Document 1 describes that a metal powder such as aluminum is surface-treated with an organophosphate compound and the organophosphate compound is adsorbed on the surface of the metal powder. Patent Document 2 describes a metal pigment composition containing at least one amine molybdate and a metal pigment.

Japanese Patent Publication No. 60-8057 JP 2008-120933 A

  However, the above-described conventional technology has a problem that it is difficult to sufficiently suppress the generation of hydrogen gas, and excellent water resistance cannot be obtained.

  The present invention has been made in view of such a technical background. For example, when used in water-based paints and water-based inks, the amount of hydrogen gas generated during storage is small and storage stability (storage stability) is improved. An object of the present invention is to provide a metal pigment composition that is excellent and has excellent luster, concealment, and flip-flop feeling of a coating film, and a method for producing the same.

  In order to achieve the above object, the present invention provides the following means.

[1] One or more metal oxide compounds selected from the group consisting of metal oxides, alkali metal salts of metal oxides, and ammonium salts of metal oxides, and one or more phosphorus compounds A phosphorus-containing metal compound obtained by reacting with
A metal pigment composition comprising a metal pigment.

  [2] The metal oxide compound is one or more metal oxide compounds selected from the group consisting of metal oxides containing at least a transition metal element as a constituent metal, alkali metal salts thereof, and ammonium salts thereof 2. The metal pigment composition according to item 1 above.

  [3] The metal oxide compound is one or more selected from the group consisting of molybdic acid, alkali metal molybdate, ammonium molybdate, vanadic acid, alkali metal vanadate, and ammonium vanadate. 2. The metal pigment composition according to item 1, which is a metal oxide compound.

  [4] The phosphorus compound is selected from the group consisting of an organic phosphate ester, an organic phosphate ester salt, an organic phosphite ester, an organic phosphite ester salt, an organic phosphonic acid, an organic phosphonate, and an inorganic phosphate amine salt. 4. The metal pigment composition according to any one of items 1 to 3, which is one or two or more selected phosphorus compounds.

  [5] The metal pigment composition according to any one of items 1 to 4, which contains 1 to 20 parts by mass of the phosphorus-containing metal compound with respect to 100 parts by mass of the metal content of the metal pigment.

  [6] The metal pigment composition according to any one of items 1 to 5, which contains an amine.

  [7] The metal pigment composition according to item 6 above, wherein the amine is one or more amines selected from the group consisting of primary amines, secondary amines and tertiary amines.

  [8] The metal pigment composition according to item 6 or 7, wherein the amine is contained in an amount of 0.5 to 15 parts by mass with respect to 100 parts by mass of the metal content of the metal pigment.

  [9] The metal pigment composition according to any one of items 1 to 8, wherein the metal component of the metal pigment is aluminum.

  [10] A paint containing the metal pigment composition according to any one of items 1 to 9.

  [11] An ink comprising the metal pigment composition according to any one of items 1 to 9.

[12] A phosphorus-containing metal compound obtained by reacting one or more metal oxide compounds selected from the group consisting of a metal oxide and an alkali metal salt thereof with one or more phosphorus compounds And mixing a metal pigment to obtain a mixed composition;
A water mixing step of mixing the mixed composition and water;
And a heat treatment step of heat-treating the mixed composition mixed with water at 40 ° C. to 200 ° C.

  [13] The metal pigment composition according to item 12, wherein in the water mixing step, 0.1 to 5 parts by mass of the water is mixed with 100 parts by mass of the metal content of the metal pigment in the mixture composition. Production method.

  [14] The method for producing a metal pigment composition according to item 12 or 13, wherein in the heat treatment step, heat treatment is performed until the water content in the mixed composition is 0.5% by mass or less.

  In the invention of [1], one or more metal oxide compounds selected from the group consisting of metal oxides, alkali metal salts of metal oxides and ammonium salts of metal oxides, and one or two kinds of metal oxide compounds. Since it contains a phosphorus-containing metal compound obtained by reacting with the above phosphorus compounds, for example, when used in water-based paints, water-based inks, etc., the amount of hydrogen gas generated during storage is small and storage stability (storage stability) In addition, the coating film has excellent luster, concealment and flip-flop feeling.

  In the invention of [2], as the metal oxide compound, one or more metal oxides selected from the group consisting of a metal oxide containing at least a transition metal element as a constituent metal, an alkali metal salt thereof, and an ammonium salt thereof Since a physical compound is used, the amount of hydrogen gas generated during storage can be further reduced, and the storage stability can be further improved.

  In the invention of [3], the metal oxide compound is selected from the group consisting of molybdic acid, alkali metal molybdate, ammonium molybdate, vanadic acid, alkali metal vanadate, and ammonium vanadate. Since two or more kinds of metal oxide compounds are used, the amount of hydrogen gas generated during storage can be further reduced, and the storage stability can be further improved.

  In the invention of [4], as the phosphorus compound, from an organic phosphate, an organic phosphate, an organic phosphite, an organic phosphite, an organic phosphonic acid, an organic phosphonate, and an inorganic phosphate amine salt Since one or two or more types of phosphorus compounds selected from the group consisting of these are used, the amount of hydrogen gas generated during storage can be further reduced, and the storage stability can be further improved.

  In the invention of [5], since the phosphorous metal compound is contained in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the metal content of the metal pigment, the amount of hydrogen gas generated during storage can be further reduced.

  Since the invention of [6] further contains an amine, the amount of hydrogen gas generated during storage can be further reduced.

  In the invention of [7], since one or more amines selected from the group consisting of primary amines, secondary amines and tertiary amines are used as amines, the amount of hydrogen gas generated during storage is further increased. Can be reduced.

  In the invention of [8], since the amine content is 0.5 to 15 parts by mass with respect to 100 parts by mass of the metal content of the metal pigment, the amount of hydrogen gas generated during storage can be further reduced.

  In the invention of [9], the metal component of the metal pigment is aluminum, and this aluminum reacts with water to generate a large amount of hydrogen gas. According to the present invention, the metal is thus aluminum. Even in this case, hydrogen gas generation can be sufficiently suppressed, so that excellent storage stability can be secured.

  In the invention of [10], a paint having excellent glossiness, concealment and flip-flop feeling of the coating film and excellent storage stability (storage stability) is provided.

  In the invention of [11], an ink excellent in the glossiness, concealability and flip-flop feeling of the coating film and in storage stability (storage stability) is provided.

  The metal pigment composition obtained by the production method according to the invention of [12] is one or two or more metal oxide compounds selected from the group consisting of metal oxides and alkali metal salts thereof, and one or more Since it contains a phosphorus-containing metal compound obtained by reacting two or more phosphorus compounds and a metal pigment, for example, when used in water-based paints and water-based inks, the amount of hydrogen gas generated during storage is small. In addition to excellent storage stability (storage stability), the coating film has excellent luster, concealment and flip-flop feeling. Furthermore, in this manufacturing method, since it has the heat processing process which heat-processes the mixed composition (containing phosphorus containing metal compound and a metal pigment) mixed with water at 40 to 200 degreeC, the metal which improved the storage stability more A pigment composition can be produced.

  In the invention of [13], in the water mixing step, 0.1 to 5 parts by mass of water is mixed with 100 parts by mass of the metal content of the metal pigment in the mixed composition, so that the storage stability is further improved. A metal pigment composition can be produced.

  In the invention of [14], in the heat treatment step, heat treatment is performed until the water content in the mixed composition is 0.5% by mass or less, so that almost no water remains in the obtained metal pigment composition. The metal pigment composition has an effect that the pigment stability during storage is further improved.

The FT-IR spectrum before reaction of the C6-C10 mixed phosphate ester of the reaction raw material used in Production Example 1 is shown. The FT-IR spectrum of the dark blue substance (reaction product) obtained in Production Example 1 is shown.

The metal pigment composition according to the present invention comprises:
Metal pigments,
A phosphorus-containing metal compound obtained by reacting the following compound (X) with compound (Y);
It is characterized by containing.
(X) One or more metal oxide compounds (Y) selected from the group consisting of metal oxides, metal oxide alkali metal salts, and metal oxide ammonium salts (Y) one or two or more phosphorus compounds.

  In the metal pigment composition according to the above configuration, it is estimated that there is a high possibility that the surface of the metal pigment is covered with a phosphorus-containing metal compound, but the details are not clear. In any case, since the metal pigment composition contains the phosphorus-containing metal compound together with the metal pigment, for example, when used in water-based paints and water-based inks, the amount of hydrogen gas generated during storage is small and storage stability is maintained. While being excellent in (storage stability), the formed coating film is excellent in glitter, concealment and flip-flop feeling.

Examples of the metal pigment include base metal particles (powder) such as aluminum, zinc, iron and copper, and particles (powder) of alloys of these base metals. Among these, aluminum particles (powder) frequently used as metallic pigments are particularly suitable. As the shape of the aluminum particles, a scaly shape (flakes) excellent in metallic luster is preferable. The scaly aluminum particles have an average particle diameter (D ₅₀ ) of 2 μm to 80 μm and an average thickness of 0.03 μm to 3 μm in that a metallic coating film having excellent brightness and denseness can be formed. Is preferably used. The metal pigment may have a structure in which the surface of metal particles is coated with a resin or the like. Incidentally, the average particle diameter D ₅₀ refers to the particle diameter D ₅₀ which cumulative volume of particles of 50% by volume.

  The phosphorus-containing metal compound is one or more metal oxide compounds selected from the group consisting of metal oxides, metal oxide alkali metal salts, and metal oxide ammonium salts, and one or two or more metal oxide compounds. It is a reaction product obtained by reacting with a phosphorus compound.

  The method for producing the phosphorus-containing metal compound is not particularly limited. For example, the metal oxide compound and the phosphorus compound may be mixed and reacted as they are, or the metal oxide compound. May be dispersed or dissolved in water, and a phosphorus compound may be added thereto to react at the oil-water interface. In general, the reaction temperature between the metal oxide compound and the phosphorus compound is suitably 40 ° C to 150 ° C. The reaction time is preferably 10 minutes to 10 hours, and more preferably 30 minutes to 5 hours. Note that this reaction does not require a catalyst, but the reaction may be performed using a catalyst.

  Although it does not specifically limit as said metal oxide type compound, For example, the metal oxide which contains at least a transition metal element as a constituent metal, its alkali metal salt, its ammonium salt, etc. are mentioned. Specific examples include molybdenum trioxide, molybdic acid, alkali metal molybdate, ammonium molybdate, vanadic acid, alkali metal vanadate, ammonium vanadate, and the like. The alkali metal is not particularly limited, and examples thereof include sodium and potassium.

  Among these, the metal oxide compound is one or more selected from the group consisting of molybdic acid, alkali metal molybdate, ammonium molybdate, vanadic acid, alkali metal vanadate, and ammonium vanadate. These metal oxide compounds are preferably used.

The phosphorus compound is not particularly limited.
i) Butyl Acid Phosphate, Octyl Acid Phosphate, Lauryl Acid Phosphate, Tridecyl Acid Phosphate, Stearyl Acid Phosphate, Nonyl Phenyl Acid Phosphate, Phenyl Acid Phosphate, Polyoxyethylene Alkyl Ether Acid Phosphate, Polyoxyethylene Alkyl Phenyl Ether Acid Phosphate, Acid Organophosphates such as phosphooxypolyoxypropylene glycol monomethacrylate
ii) Triphenyl phosphite, trisnonylphenyl phosphite, tricresyl phosphite, triethyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite, trio Rail phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl mono (tridecyl) phosphite, diethyl hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, etc. Organic phosphites
iii) Organic phosphonic acids such as octylphosphonic acid monoesters and diesters of the compounds exemplified above
iv) Amine salt of each phosphorous compound exemplified above v) Inorganic phosphate amine salt and the like. These may contain unsubstituted inorganic phosphoric acid and / or triesters that do not exhibit acidity.

  Examples of the phosphorus compound include organic phosphoric acid esters, organic phosphoric acid ester salts (such as organic phosphoric acid ester amine salts), organic phosphorous acid esters, organic phosphorous acid ester salts (such as organic phosphorous acid ester amine salts), and organic compounds. It is preferable to use one or more phosphorus compounds selected from the group consisting of phosphonic acids, organic phosphonates and inorganic phosphate amine salts. Among these, it is more preferable to use octyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, acid phosphooxypolyoxypropylene glycol monomethacrylate, dilauryl hydrogen phosphate monoester, diester or a mixture thereof. preferable. Further, orthophosphoric monoesters derived from aliphatic alcohols having 4 to 24 carbon atoms (including both monohydric alcohols and polyhydric alcohols) and aliphatic alcohols having 4 to 24 carbon atoms (monohydric alcohols and polyhydric alcohols). It is particularly preferable to use one or two or more organic phosphates selected from the group consisting of orthophosphoric diesters derived from those.

The chemical structure (general formula) of orthophosphoric monoester derived from aliphatic alcohol and the chemical structure (general formula) of orthophosphoric diester derived from aliphatic alcohol are:
Orthophosphoric monoester: R—O—PO (OH) ₂
Orthophosphoric acid diester: (R—O) ₂ PO (OH)
As described above (in the above chemical structure, “R” represents an organic group).

  In the metal pigment composition of the present invention, it is preferable to contain 0.01 to 40 parts by mass of the phosphorus-containing metal compound (reaction product) with respect to 100 parts by mass of the metal content of the metal pigment. When the amount is 0.01 parts by mass or more, the amount of hydrogen gas generated during storage can be sufficiently reduced, and when it is 40 parts by mass or less, a metallic pigment composition excellent in glitter, concealment and flip-flop feeling is obtained. be able to. Especially, it is more preferable to contain 0.1-30 mass parts of the said phosphorus containing metal compound with respect to 100 mass parts of metal parts of the said metal pigment, and it is much more preferable to contain 1-20 mass parts. .

  The metal pigment composition of the present invention preferably contains an amine in addition to the phosphorus-containing metal compound and the metal pigment.

The amine is not particularly limited.
a) linear primary amines such as ethylamine, propylamine, butylamine, hexylamine, octylamine, laurylamine, tridecylamine, stearylamine,
b) Branched primary amines such as isopropylamine, isobutylamine, 2-ethylhexylamine, branched tridecylamine,
c) linear secondary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, dihexylamine, dioctylamine, dilaurylamine, ditridecylamine, distearylamine,
d) Branched secondary amines such as diisopropylamine, diisobutylamine, di (2-ethylhexyl) amine, branched ditridecylamine,
e) Asymmetric secondary amines such as methyl butylamine, ethyl butylamine, ethyl hexylamine, ethyl laurylamine, ethyl stearylamine, isopropyl octylamine, isobutyl 2-ethylhexylamine,
f) linear tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, trioctylamine, trilaurylamine, tritridecylamine, tristearylamine,
g) Branched tertiary amines such as triisopropylamine, triisobutylamine, tri-2-ethylhexylamine, branched tritridecylamine,
h) A tertiary amine having a mixed hydrocarbon group such as dimethyloctylamine, dimethyllaurylamine, dimethylstearylamine, diethyllaurylamine,
i) amines having an alkenyl group such as allylamine, diallylamine, triallylamine, N, N-dimethylallylamine,
j) Alicyclic primary amines such as cyclohexylamine and 2-methylcyclohexylamine,
k) a primary amine having an aromatic ring substituent such as benzylamine and 4-methylbenzylamine;
l) Alicyclic secondary amines such as dicyclohexylamine and di-2-methylcyclohexylamine,
m) secondary amines having aromatic ring substituents such as dibenzylamine and di-4-methylbenzylamine;
n) Asymmetric secondary amines such as cyclohexyl 2-ethylhexylamine, cyclohexyl benzylamine, stearyl benzylamine, 2-ethylhexyl benzylamine,
o) Alicyclic tertiary amines such as dimethylbenzylamine, dimethylcyclohexylamine, and tricyclohexylamine;
p) a tertiary amine having an aromatic ring substituent such as tribenzylamine or tri-4-methylbenzylamine;
q) Morpholine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-butoxypropylamine, 3-decyloxypropylamine, 3-lauryloxypropylamine, monoethanolamine, diethanolamine, monoisopropanolamine, monopropanolamine, Butanolamine, triethanolamine, N, N-dimethylethanolamine, N-methylethanolamine, N-methyldiethanolamine, N-ethylethanolamine, N-propylethanolamine, N-isopropylethanolamine, N-butylethanolamine, N-cyclohexyl-N-methylaminoethanol, N-benzyl-N-propylaminoethanol, N-hydroxyethylpyrrolidine, N-hydroxyethylpiperazine N-hydroxyethylmorpholine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N-cyclohexyl-1,3-propanediamine, N-decyl- 1,3-propanediamine, N-isotridecyl-1,3-propanediamine, N, N-dimethylpiperazine, N-methoxyphenylpiperazine, N-methylpiperidine, N-ethylpiperidine, quinuclidine, diazabicyclo [2,2,2 ] Octane, 1,8-diazabicyclo [5,4,0] -7-undecene,
Etc. You may use 1 type, or 2 or more types of these in combination.

  Among these, as the amine, one or two or more amines selected from the group consisting of primary amines, secondary amines, and tertiary amines are used because hydrogen gas generation during storage can be further reduced. ,preferable. Among these, it is particularly preferable to use a tertiary amine in that the amount of hydrogen gas generated during storage can be further reduced.

  In the metal pigment composition of the present invention, it is preferable to contain 0.01 to 40 parts by mass of the amine with respect to 100 parts by mass of the metal content of the metal pigment. When it is 0.01 part by mass or more, the effect of reducing the amount of hydrogen gas generated during storage can be sufficiently secured, and when it is 40 parts by mass or less, the glitter, concealment, and flip-flop feeling can be sufficiently secured. Especially, it is more preferable to contain 0.1-20 mass parts of the said amine with respect to 100 mass parts of metal parts of the said metal pigment, and it is still more preferable to contain 0.5-15 mass parts.

  In the metal pigment composition of the present invention, the phosphorus-containing metal compound (reaction product) may be mixed in a slurry state in which a solvent is added to the metal pigment, or a metal pigment-containing paste state in which the amount of the solvent is reduced May be mixed (kneaded). Considering the raw material cost and the number of steps, it is preferable to knead into a paste. On the other hand, the phosphorus-containing metal compound may be added as it is to the metal pigment, or may be added to the metal pigment in a state where the phosphorus-containing metal compound is diluted in a solvent or the like. In order to obtain it, it is preferable to add a phosphorus-containing metal compound diluted with a solvent, mineral oil or the like to a metal pigment (slurry state or paste state).

  Examples of the solvent (solvent added to the metal pigment, solvent for diluting the phosphorus-containing metal compound, etc.) are not particularly limited. For example, alcohols such as methanol and isopropanol, cellosolves such as propylene glycol monomethyl ether, Hydrocarbon solvents such as hexane, octane, isooctane, benzene, toluene, xylene, tetralin and decalin, industrial gasoline such as mineral spirit and solvent naphtha, esters such as ethyl acetate and butyl acetate, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone Ketones, mineral oils and the like.

  The solvent used in the preparation of the metal pigment composition of the present invention may be a hydrophilic solvent or a hydrophobic solvent. The hydrophilic solvent is not particularly limited, for example, alcohols such as methanol, ethanol, propanol, butanol, isopropanol, octanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, Glycol ethers such as diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether, and esters thereof, glycols such as propylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, and ethylene propylene glycol And the like. The hydrophobic solvent is not particularly limited, and examples thereof include mineral spirit, solvent naphtha, low aromatic white spirit (LAWS), high aromatic white spirit (HAWS), toluene, xylene and the like. It is done. Furthermore, esters such as ethyl acetate and butyl acetate, and ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone can also be used. These can be used alone or in combination.

  When preparing the metal pigment composition of this invention in a slurry state, it is preferable to set the metal content concentration of the metal pigment in the slurry to 1% by mass to 50% by mass, and to 10% by mass to 30% by mass. It is more preferable to set. Moreover, when preparing the metal pigment composition of this invention in a paste state, it is preferable to set the density | concentration of the metal content of the metal pigment in a paste to 50 mass%-95 mass%, and 60 mass%-85 mass%. It is more preferable to set to%.

  In addition, you may make it obtain the metal pigment composition of this invention by heat-processing the said phosphorus containing metal compound, the said metal pigment, and the composition (it may contain amine further) containing water. The method for heat treatment with water is not particularly limited. For example, water is added to a composition containing a phosphorus-containing metal compound and a metal pigment (which may further contain an amine or the like). The method of mixing in a heating state etc. are mentioned. It is preferable to add water while mixing the composition in a heated state and mix in the heated state. By performing the operation of bringing the metal pigment surface into contact with water in a heated state in this way, the amount of hydrogen gas generated during storage when the metal pigment composition is used in water-based paints, water-based inks, etc. can be further reduced. (It is clear from comparison between Example 5 and Example 6 described later).

  The temperature of the heat treatment (temperature in the heated state) is preferably set to 40 ° C. to 200 ° C., and particularly preferably set to 50 ° C. to 120 ° C. Moreover, it is preferable to set heat processing time to 5 minutes-3 hours, and it is especially preferable to set to 10 minutes-2 hours.

  The water is preferably mixed in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the metal content of the metal pigment. When it is 0.1 part by mass or more, it is possible to sufficiently ensure the effect of reducing the amount of hydrogen gas generated during storage, and when it is 5 parts by mass or less, it is possible to prevent the occurrence of blisters and the color tone of the coating film. Especially, it is especially preferable to mix 0.5-3 mass parts of water with respect to 100 mass parts of metal parts of the said metal pigment.

  The metal pigment composition of the present invention may be obtained by placing it in an airtight container and performing a heat treatment at 40 ° C to 80 ° C.

  The metal pigment composition of the present invention includes, for example, pigments (excluding metal pigments), dyes, wetting agents, dispersants, anti-coloring agents, leveling agents, slip agents, silane coupling agents, titanium coupling agents, and organic phosphorus. Acid salts, organic phosphites, heteropolyanions, phosphosilicates, nitroparaffins, organometallic amine salts and the like may be added.

  The metal pigment composition of the present invention can be applied to water-based paints in combination with a resin for water-based paints. The resin for water-based paints means a water-soluble resin, a water-dispersible resin, an aqueous emulsion resin, and the like, and generally includes acrylic-based, acrylic-melamine-based, polyester-based, polyurethane-based resin for water-based paints. The metal pigment composition of the present invention can also be applied to water-based inks.

  Next, specific examples of the present invention will be described, but the present invention is not particularly limited to these examples.

[Production Example 1 (Production of phosphorus-containing metal compound A)]
A 300 mL glass beaker was charged with 100 g of an aqueous sulfuric acid solution having a concentration of 10% by mass, and 10 g of molybdic acid was further added, followed by sufficient stirring. Next, 100 g of C6 to C10 (6 to 10 carbon atoms) mixed phosphate ester (organophosphate ester; normal phosphate mono- and diesters derived from saturated aliphatic monohydric alcohol having 6 to 10 carbon atoms) and mineral spirits After further adding 50 g, the temperature was raised to 60 to 70 ° C. while stirring, and stirring was continued at 60 to 70 ° C. for 10 hours. Then, after cooling to room temperature with stirring and stopping stirring, oil and water were separated, so after removing the lower layer (aqueous layer), the upper layer (oil layer) was filtered and further desolvated under reduced pressure, A dark blue oily liquid (containing a phosphorus-containing metal compound A obtained by reacting molybdic acid with a C6-C10 mixed phosphate ester) was obtained. In addition, when the FT-IR analysis of the dark blue substance after reaction was conducted, it was 1208 cm < ^-1 > recognized by the FT-IR analysis spectrum (FIG. 1) before the reaction of C6-C10 mixed phosphate ester which is a reaction raw material. Peaks (peaks identified as HO—P═O bonds) are hardly seen, while new FT-IR analysis spectra (FIG. 2) of the dark blue substance after the reaction did not appear in the reaction raw material before the reaction. Since the peaks (920 cm ⁻¹ , 805 cm ⁻¹ ) were observed, it was confirmed that the molybdic acid and the C6-C10 mixed phosphate ester had reacted.

[Production Example 2 (Production of phosphorus-containing metal compound B)]
Production Example, except that 100 g of octyl acid phosphate (organophosphate ester; normal phosphate mono- and diester derived from saturated aliphatic monohydric alcohol having 8 carbon atoms) was used instead of 100 g of C6-C10 mixed phosphate ester In the same manner as in No. 1, a dark blue oily liquid (containing phosphorus-containing metal compound B obtained by reacting molybdic acid and octyl acid phosphate) was obtained. In addition, it was confirmed that the molybdic acid and the octyl acid phosphate were reacting by performing FT-IR analysis of the reaction raw material and the dark blue substance after the reaction in the same manner as described above.

[Production Example 3 (Production of phosphorus-containing metal compound C)]
A light yellow oily liquid (molybdic acid and octylphosphonate was reacted in the same manner as in Production Example 1 except that 100 g of octylphosphonate (organic phosphonic acid) was used instead of 100 g of the C6-C10 mixed phosphate ester. Obtained phosphorus-containing metal compound C). In addition, it confirmed that the molybdic acid and the octyl phosphonate were reacting by performing FT-IR analysis of the reaction raw material and the pale yellow substance after reaction similarly to the above.

[Production Example 4 (Production of phosphorus-containing metal compound D)]
A brown oily liquid (phosphorus-containing obtained by reacting sodium vanadate and a C6-C10 mixed phosphate ester in the same manner as in Production Example 1 except that 10 g of sodium vanadate was used instead of 10 g of molybdic acid. Containing metal compound D). In addition, it confirmed that sodium vanadate and C6-C10 mixed phosphate ester were reacting by performing the FT-IR analysis of the reaction raw material and the brown material after reaction similarly to the above.

<Example 1>
Aluminum pigment paste (made by Showa Aluminum Powder Co., Ltd., trade name “SAP CS430”, paste containing aluminum flakes and mineral spirits, average particle diameter D ₅₀ of aluminum flakes 9 μm, non-volatile content 70% by mass) 143 g of mineral spirits 500 g The solution dispersed in was filtered with a Buchner funnel to obtain an adjusted aluminum pigment paste adjusted to have an aluminum content of 75% by mass. To this adjusted aluminum pigment paste was added the oily liquid obtained in Production Example 1 (containing phosphorus-containing metal compound A obtained by reacting molybdic acid and a C6-C10 mixed phosphate ester) and oleylamine, and After adding the solvent naphtha, the mixture was kneaded at 70 ° C. for 12 hours to obtain a metal pigment composition. In addition, with respect to 100 parts by mass of aluminum in the adjusted aluminum pigment paste, phosphorus-containing metal compound A was added so that 5.0 parts by mass and oleylamine would be 3.0 parts by mass, respectively, in the metal pigment composition Solvent naphtha was added so that the aluminum content was 65% by mass.

<Example 2>
Aluminum pigment paste (made by Showa Aluminum Powder Co., Ltd., trade name “SAP CS450”, paste containing aluminum flakes and mineral spirits, average particle diameter D ₅₀ of aluminum flakes is 11 μm, non-volatile content 70% by mass) 143 g of mineral spirits 500 g The solution dispersed in was filtered with a Buchner funnel to obtain an adjusted aluminum pigment paste adjusted to have an aluminum content of 75% by mass. To this adjusted aluminum pigment paste, the oily liquid obtained in Production Example 1 (containing phosphorus-containing metal compound A obtained by reacting molybdic acid and a C6-C10 mixed phosphate ester) was added, and solvent naphtha was further added. Then, kneading was carried out at 70 ° C. for 12 hours to obtain a metal pigment composition. In addition, it adds so that phosphorus containing metal compound A may be 5.0 mass parts with respect to 100 mass parts of aluminum in the said adjustment aluminum pigment paste, and the aluminum content rate in a metal pigment composition is 65 mass%. Solvent naphtha was added.

<Example 3>
152 g of aluminum pigment paste (made by Showa Aluminum Powder Co., Ltd., trade name “SAP 561PS”, paste containing aluminum flakes and mineral spirits, average particle diameter D ₅₀ of aluminum flakes 16 μm, non-volatile content 66 mass%) 152 g of mineral spirits The solution dispersed in was filtered with a Buchner funnel to obtain an adjusted aluminum pigment paste adjusted to have an aluminum content of 75% by mass. To this adjusted aluminum pigment paste, the oily liquid obtained in Production Example 2 (containing phosphorus-containing metal compound B obtained by reacting molybdic acid and octyl acid phosphate) and di (2-ethylhexyl) amine were added. Further, after adding solvent naphtha, the mixture was kneaded at 80 ° C. for 8 hours to obtain a metal pigment composition. In addition, with respect to 100 parts by mass of aluminum in the adjusted aluminum pigment paste, the phosphorus-containing metal compound B is added in an amount of 7.0 parts by mass, and di (2-ethylhexyl) amine is 3.0 parts by mass, Solvent naphtha was added so that the aluminum content in the metal pigment composition was 65% by mass.

<Example 4>
Instead of the oily liquid obtained in Production Example 2 (containing phosphorus-containing metal compound B), the oily liquid obtained in Production Example 3 (phosphorus-containing metal compound C obtained by reacting molybdic acid and octylphosphonate) A metal pigment composition was obtained in the same manner as in Example 3, except that (containing) was used.

<Example 5>
152 g of aluminum pigment paste (made by Showa Aluminum Powder Co., Ltd., trade name “SAP FM4010”, paste containing aluminum flakes and mineral spirits, average particle diameter D ₅₀ of aluminum flakes 11 μm, non-volatile content 66% by mass) The solution dispersed in was filtered with a Buchner funnel to obtain an adjusted aluminum pigment paste adjusted to have an aluminum content of 75% by mass. To this adjusted aluminum pigment paste, the oily liquid obtained in Production Example 4 (containing phosphorus-containing metal compound D obtained by reacting sodium vanadate and a C6-C10 mixed phosphate ester) and ethanolamine are added. Further, after adding solvent naphtha, the mixture was kneaded at 100 ° C. for 4 hours to obtain a metal pigment composition. In addition, in the metal pigment composition, phosphorous-containing metal compound D was added to 7.0 parts by mass and ethanolamine to 3.0 parts by mass with respect to 100 parts by mass of aluminum in the adjusted aluminum pigment paste. Solvent naphtha was added so that the content of aluminum in was 65% by mass.

<Example 6>
After further adding water to the metal pigment composition obtained in Example 5 (adding 1.0 part by mass of water to 100 parts by mass of aluminum in the metal pigment composition), kneading is performed at 100 ° C. for 2 hours. As a result, a metal pigment composition (water content of 0.5% by mass or less) heat-treated in the presence of water was obtained.

<Example 7>
152 g of aluminum pigment paste (made by Showa Aluminum Powder Co., Ltd., trade name “SAP FM4010”, paste containing aluminum flakes and mineral spirits, average particle diameter D ₅₀ of aluminum flakes 11 μm, non-volatile content 66% by mass) The solution dispersed in was filtered with a Buchner funnel to obtain an adjusted aluminum pigment paste adjusted to have an aluminum content of 75% by mass. To this adjusted aluminum pigment paste, the oily liquid obtained in Production Example 4 (containing phosphorus-containing metal compound D obtained by reacting sodium vanadate and a C6-C10 mixed phosphate ester) and triethanolamine were added. Further, after adding solvent naphtha, kneading was performed at 100 ° C. for 4 hours to obtain a metal pigment composition. In addition, with respect to 100 parts by mass of aluminum in the adjusted aluminum pigment paste, a metal pigment composition was added so that phosphorus-containing metal compound D was 10.0 parts by mass and triethanolamine was 5.0 parts by mass. Solvent naphtha was added so that the content of aluminum in the mixture was 65% by mass.

<Comparative Example 1>
Aluminum pigment paste (made by Showa Aluminum Powder Co., Ltd., trade name “SAP CS430”, paste containing aluminum flakes and mineral spirits, average particle diameter D ₅₀ of aluminum flakes 9 μm, nonvolatile content 70% by mass) 143 g of mineral spirits 500 g The liquid dispersed in was filtered with a Buchner funnel, and then a solvent naphtha was added so that the aluminum content in the aluminum pigment paste was 65% by mass, thereby obtaining a metal pigment composition.

<Comparative example 2>
152 g of aluminum pigment paste (made by Showa Aluminum Powder Co., Ltd., trade name “SAP 561PS”, paste containing aluminum flakes and mineral spirits, average particle diameter D ₅₀ of aluminum flakes 16 μm, non-volatile content 66 mass%) 152 g of mineral spirits The solution dispersed in was filtered with a Buchner funnel to obtain an adjusted aluminum pigment paste adjusted to have an aluminum content of 75% by mass. To this adjusted aluminum pigment paste, octyl acid phosphate and di (2-ethylhexyl) amine were added, and solvent naphtha was added, followed by kneading at 80 ° C. for 8 hours to obtain a metal pigment composition. The metal pigment was added so that octyl acid phosphate was 7.0 parts by mass and di (2-ethylhexyl) amine was 3.0 parts by mass with respect to 100 parts by mass of aluminum in the adjusted aluminum pigment paste. Solvent naphtha was added so that the aluminum content in the composition was 65% by mass.

<Comparative Example 3>
152 g of aluminum pigment paste (made by Showa Aluminum Powder Co., Ltd., trade name “SAP 561PS”, paste containing aluminum flakes and mineral spirits, average particle diameter D ₅₀ of aluminum flakes 16 μm, non-volatile content 66 mass%) 152 g of mineral spirits The solution dispersed in was filtered with a Buchner funnel to obtain an adjusted aluminum pigment paste adjusted to have an aluminum content of 75% by mass. To this adjusted aluminum pigment paste, molybdic acid and di (2-ethylhexyl) amine were added, and further solvent naphtha was added, followed by kneading at 80 ° C. for 8 hours to obtain a metal pigment composition. The metal pigment composition was added such that molybdic acid was 7.0 parts by mass and di (2-ethylhexyl) amine was 3.0 parts by mass with respect to 100 parts by mass of aluminum in the adjusted aluminum pigment paste. Solvent naphtha was added so that the aluminum content in the product was 65% by mass.

<Comparative example 4>
152 g of aluminum pigment paste (made by Showa Aluminum Powder Co., Ltd., trade name “SAP FM4010”, paste containing aluminum flakes and mineral spirits, average particle diameter D ₅₀ of aluminum flakes 16 μm, non-volatile content 66 mass%) 152 g of mineral spirits The solution dispersed in was filtered with a Buchner funnel to obtain an adjusted aluminum pigment paste adjusted to have an aluminum content of 75% by mass. To this adjusted aluminum pigment paste, a C6-C10 mixed phosphate ester and ethanolamine were added, and solvent naphtha was further added, followed by kneading at 100 ° C. for 4 hours to obtain a metal pigment composition. In addition, with respect to 100 parts by mass of aluminum in the adjusted aluminum pigment paste, C6 to C10 mixed phosphate ester was added so that 7.0 parts by mass and ethanolamine would be 3.0 parts by mass, respectively, and a metal pigment composition Solvent naphtha was added so that the aluminum content in the product was 65% by mass. Water was further added to the obtained composition (1.0 part by mass of water with respect to 100 parts by mass of aluminum in the composition), and then kneaded at 100 ° C. for 2 hours, whereby heat treatment was performed in the presence of water. A metal pigment composition was obtained.

  The storage stability of the paint prepared using the metal pigment composition obtained as described above and the surface state of the coating film formed from the paint were evaluated based on the following evaluation methods. These evaluation results are shown in Table 1.

<Storage stability evaluation method>
An aqueous metallic paint (coating for storage stability evaluation) having the following composition was prepared using the metal pigment composition of each example and each comparative example. That is, 2.8 g of a metal pigment composition (as an aluminum component), 7.5 g of dipropylene glycol-n-butyl ether, 6.5 g of butyl cellosolve, 25 g of pure water, an aqueous emulsion (trade name “Polysol AP-7010N”, Showa Denko Co., Ltd. A water-based metallic paint was prepared by mixing 50.0 g. 40 g of the above-mentioned aqueous metallic paint is put in a test tube, and a gas collection tube is attached to the test tube, and this is set in a constant temperature water bath at 50 ° C., and the hydrogen gas accumulated generation amount after 336 hours (mL / paint 40 g (aluminum Minute 1.2 g)) was measured. The storage stability of the paint was evaluated based on the following criteria.
(Criteria)
“◎”: less than 1.0 (mL / aluminum content: 1.2 g) of hydrogen gas cumulative generation amount “◯”: hydrogen gas cumulative generation amount: 1.0 (mL / aluminum content: 1.2 g) to 3.0 ( Less than mL / aluminum content 1.2 g) “△”: Hydrogen gas cumulative generation amount is 3.0 (mL / aluminum content 1.2 g) or more and less than 5.0 (mL / aluminum content 1.2 g) “×” ... hydrogen Cumulative gas generation amount is 5.0 (mL / aluminum content 1.2 g) or more.

<Method for evaluating surface condition of coating film>
A metallic paint (coating for coating surface condition evaluation) having the following composition was prepared using the metal pigment composition of each example and each comparative example. That is, 4.1 g of metal pigment composition (as aluminum component), thinner (trade name “Planet Thinner # 175”, manufactured by Origin Electric Co., Ltd.) 80.0 g, acrylic lacquer clear (trade name “Planet SV Clear”, Origin Electric) Metallic paint was prepared by mixing 50.0 g. The metallic paint was spray-applied on an ABS resin plate so as to have a dry film thickness of about 15 μm, and then dried in an oven at 60 ° C. for 20 minutes to form a coating film. The surface state of the coating film was evaluated based on the following criteria.
(Criteria)
“◯”: No flaws are observed in the coating film “Δ”: Slight fuzziness is observed in the coating film, but there is no practical problem “×”: Many coatings are recognized or coated There are bumps on the entire surface of the film.

  As is clear from Table 1, the paints produced using the metal pigment compositions of Examples 1 to 7 of the present invention had very little hydrogen gas generation and were excellent in storage stability. Moreover, the coating film formed with the coating material containing the metal pigment composition of Examples 1 to 7 of the present invention exhibited an excellent surface state free from lumps.

  On the other hand, the paint produced using the metal pigment composition of Comparative Examples 1 to 4 that does not contain a phosphorus-containing metal compound (a phosphorus-containing metal compound obtained by reacting a metal oxide compound and a phosphorus compound) The storage stability was inferior.

  The metal pigment composition according to the present invention is suitably used as a metallic luster imparting component for water-based paints and water-based inks, but is not particularly limited to such applications. Moreover, since the coating film containing the metal pigment composition of the present invention is excellent in glitter, concealment and flip-flop feeling, the metal pigment composition of the present invention is used for automobile paints and home appliance paints. It is particularly suitable as a pigment composition.

Claims (14)

Reaction of one or more metal oxide compounds selected from the group consisting of metal oxides, alkali metal salts of metal oxides, and ammonium salts of metal oxides with one or more phosphorus compounds A phosphorus-containing metal compound obtained by
A metal pigment composition comprising a metal pigment.   The metal oxide compound is one or more metal oxide compounds selected from the group consisting of a metal oxide containing at least a transition metal element as a constituent metal, an alkali metal salt thereof, and an ammonium salt thereof. Item 2. The metal pigment composition according to Item 1.   The metal oxide compound is one or more metal oxides selected from the group consisting of molybdic acid, alkali metal molybdate, ammonium molybdate, vanadic acid, alkali metal vanadate, and ammonium vanadate. The metal pigment composition according to claim 1, which is a physical compound.   The phosphorus compound is selected from the group consisting of an organic phosphate ester, an organic phosphate ester salt, an organic phosphite ester, an organic phosphite ester salt, an organic phosphonic acid, an organic phosphonate, and an inorganic phosphate amine salt. It is a seed | species or 2 or more types of phosphorus compounds, The metal pigment composition of any one of Claims 1-3.   The metal pigment composition according to any one of claims 1 to 4, wherein the phosphorus-containing metal compound is contained in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the metal content of the metal pigment.   The metal pigment composition according to any one of claims 1 to 5, comprising an amine.   The metal pigment composition according to claim 6, wherein the amine is one or more amines selected from the group consisting of primary amines, secondary amines, and tertiary amines.   The metal pigment composition according to claim 6 or 7, which contains 0.5 to 15 parts by mass of the amine with respect to 100 parts by mass of the metal content of the metal pigment.   The metal pigment composition according to any one of claims 1 to 8, wherein the metal component of the metal pigment is aluminum.   The coating material containing the metal pigment composition of any one of Claims 1-9.   The ink containing the metal pigment composition of any one of Claims 1-9. A phosphorus-containing metal compound obtained by reacting one or more metal oxide compounds selected from the group consisting of a metal oxide and an alkali metal salt thereof with one or more phosphorus compounds, and a metal A step of mixing a pigment to obtain a mixed composition;
A water mixing step of mixing the mixed composition and water;
And a heat treatment step of heat-treating the mixed composition mixed with water at 40 ° C. to 200 ° C.   The said water mixing process WHEREIN: The manufacturing method of the metal pigment composition of Claim 12 which mixes the said water 0.1 mass part-5 mass parts with respect to 100 mass parts of metal parts of the metal pigment in the said mixed composition. .   The method for producing a metal pigment composition according to claim 12 or 13, wherein, in the heat treatment step, heat treatment is performed until a water content in the mixed composition is 0.5 mass% or less.

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