JPH01129070A - Novel metal powder pigment - Google Patents

Abstract

PURPOSE:To obtain the title pigment excellent in shelf stability and suitable as a pigment component of a water-based metallic paint which can give a paint film excellent in adhesion, (hot) water resistance and chemical resistance, by coating the surface of a metal powder with a surface-coating layer comprising an adsorption layer containing a specified adsorbed substance and a resin coating layer with which said adsorption layer is coated. CONSTITUTION:A malleable metal powder such as aluminum, copper, zinc or brass, 0.1-50wt.% substance which inhibits H2 gas formation, such as orthophosphoric acid or an organophosphorus compound (e.g., tridecyl phosphate), and grinding acid such as stearic acid are fed to, e.g., a ball mill, and an adsorption layer comprising the H2 gas formation inhibitor on the surface of the metal powder is formed by grinding. A resin coating layer is formed by copolymerizing a monomer having at least two radical-polymerizable double bonds in the molecule with a radical-polymerizable unsaturated carboxylic acid and/or a phosphoric ester monomer having at least one radical- polymerizable double bond in the molecule and, optionally, radical-polymerizable unsaturated monomers copolymerizable therewith so that the adsorption layer may by coated with the resin coating layer. In this way, the metal powder having a surface coating layer comprising said adsorption layer and the resin coating layer can be obtained.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a novel metal powder pigment, particularly a novel metal powder useful as a pigment component of water-based metallic paints used for the exterior of automobiles, home appliances, etc. It relates to pigments, and more specifically, it has extremely excellent storage stability as a metal powder itself and as a paint, as well as extremely excellent adhesion, water resistance,
The present invention relates to a novel metal powder pigment that is extremely suitable as a pigment component of a water-based metallic paint that can provide a coating film having hot water resistance and chemical resistance.

[Conventional technology]

In recent years, in the field of paints, water-based paints that contain very little or no organic solvent have been increasingly used as a resource-saving and pollution-free measure. In addition, due to remarkable technological advances in resins for water-based paints, water-based paints have been developed that can surpass the high-quality finish that could previously only be achieved with solvent-based paints, and from this point of view, there is a growing trend towards water-based paints. It's getting stronger.

Conventionally, metal powder pigments used in water-based paints have been produced using saturated or unsaturated fatty acids such as stearic acid and oleic acid, or their derivatives as a surface treatment agent, and a surfactant added to this to give water dispersibility. Powder compositions have been used.

However, these water-dispersible metal powder pigments have the disadvantage of low storage stability, especially in water-based paints, which may reduce the degree of pigment dispersion or generate a large amount of gas during storage. As a result, the properties of the paint were significantly impaired.

Thereafter, as methods for improving the storage stability of metal powder pigments, methods using wetting agents such as polyamides, aliphatic amides, fluorine, silicones, etc., as described in US Pat. No. 3,839,254, and US Pat. No. 926.874, a method using a perfluorinated alkyl wetting agent; US Pat. No. 4,138,270, a method using a fatty acid or an alkanolamide of a fatty acid and a nonionic wetting agent, etc. are disclosed. However, none of them showed a sufficient improvement effect on storage stability, and there was a problem in that the metal $J pigment had poor wettability with water. Furthermore, JP-A No. 81-29607 discloses a method of using a phosphoric acid ester of caprolactone for the purpose of suppressing the reaction between metal powder pigments and water and improving storage stability. JP-A-61-47771 describes a method using octylphenyl dihydrogen phosphate and a diethylamine adduct of bis(octylphenyl hydrogen phosphate) for the same purpose.
A method using a reaction product of orthophosphoric acid or phosphoric acid monoester and an epoxy compound is further described in JP-A-61-2916.
Publication No. 6 discloses a method using a reaction product of a styrene-allylic alcohol copolymer, p-tert-amylphenol, and orthophosphoric acid or phosphorus pentoxide, but neither method achieves the desired improvement effect. Even if it is insufficient or relatively improved, when used as a water-based paint, the performance of the resulting paint film, such as adhesion, water resistance, hot water resistance, and chemical resistance. etc., and it cannot be put to practical use.

On the other hand, in Japanese Patent Publication No. 60-8057, the present applicant disclosed an extremely effective method for suppressing the reaction between metal powder and water by using a specific organic phosphoric acid ester, but in subsequent studies, When this metal powder is applied as a pigment in water-based paints, the properties of the resulting paint films, such as adhesion, water resistance, and hot water resistance, are no longer necessarily satisfactory. The reason for this is that as the uses of water-based paints expand, the demands from users have become even more demanding. Also, behind this expansion of applications, as mentioned above, is the fact that it is becoming possible with water-based paints to achieve a finish that is comparable to or better than that of solvent-based paints, which was previously impossible to achieve, and also due to solvent regulations and resource conservation. Water-based paints are the closest to meeting these social needs for two reasons. In particular, automobiles that require a high-quality finish and have extremely high solvent content in the paint.
There is a strong demand for water-based solvent-based metallic paints used for the exterior of home appliances and the like.

(Problems to be Solved by the Invention) As mentioned above, many technologies have been disclosed regarding metal powder pigments intended for use in water-based paints, but the storage stability of pigments and water-based paints using the pigments is not clear. No metal powder pigment has been found that satisfies both aspects of coating film performance, which greatly influences properties and finish feel.

An object of the present invention is to provide a novel metal powder pigment that eliminates the drawbacks of the prior art.

Another object of the present invention is to provide a novel metal powder pigment that has excellent storage stability and excellent coating film performance, such as adhesion, water resistance, hot water resistance, and chemical resistance.

[Means for solving problems]

The above object is a metal powder consisting of particles having a surface coating layer, and the surface coating layer is composed of an adsorption layer in which a substance that suppresses a hydrogen gas production reaction is adsorbed, and a resin coating layer surrounding the adsorption layer. This is achieved by the novel metal powder pigment of the present invention, which is characterized by:

The present invention will be explained below.

The adsorption layer is located on the surface of the metal powder pigment, and suppresses the reaction between the water and the metal powder pigment that exists intentionally or unavoidably, thereby preventing the metal powder pigment itself or the metal powder pigment from being present. It plays a role in improving the storage stability of the paint containing it.

On the other hand, the resin coating layer that surrounds this adsorption layer plays the role of protecting the adsorption layer from mechanical shear, and also increases the affinity with the resin contained in the water-based paint, reducing metal powder in the paint and ultimately in the paint film. It also plays a role in improving the dispersibility of pigments. This improvement in dispersibility makes it possible to obtain a uniform coating film with extremely few structural defects, and in addition, the coating film is coated with dispersants, wetting agents, etc. that were conventionally added to metal powder pigments and paints for the purpose of imparting this dispersibility. Since additives that adversely affect performance can be reduced, coating performance such as adhesion, water resistance, and hot water resistance is significantly improved.

The metal powder used in the present invention is one type or a mixture of two or more types of malleable metals, such as aluminum, copper, zinc, brass, etc., and alloys thereof.

In order to obtain the metal powder pigment of the present invention, the metal powder described above is used as a starting material, and an adsorption layer made of a grinding aid and a substance that suppresses the hydrogen gas production reaction is formed on the surface of the metal powder, and the adsorption layer is wrapped. It is obtained by forming a resin coating layer. However, if the substance that suppresses the hydrogen gas production reaction also serves as a grinding aid, the use of the grinding aid may be omitted.

The method for forming the adsorption layer and the resin coating layer is not particularly limited, but generally, to form the adsorption layer,
It is preferable to use a known pulverization method.

For example, wet and dry pulverization methods such as ball milling, roller milling, high-speed rotary pulverization, media agitation milling, and air pulverization are used.

Of the substances that form the adsorption layer, that is, the grinding aid and the substance that suppresses the hydrogen gas production reaction, at least the grinding aid should be added in the grinding process, but the substance that suppresses the hydrogen gas production reaction It may be added in the pulverizing step, or it may be added in a step after the pulverizing step, or it may be added in multiple steps if necessary. Here, the steps after the pulverization step differ depending on the pulverization method, but for example, when a wet ball mill method is used, the steps following the pulverization step include a classification step, a filtration step, a mixing step, etc. Further, in the present invention, the method for forming the resin coating layer surrounding the adsorption layer is not particularly limited, but for example, known polymerization methods (solution polymerization method, suspension polymerization method, emulsion polymerization method) legal, etc.) is preferable.

The metal powder pigment according to the present invention is mainly intended for use in water-based paints, but if volatile matter is allowed to exist in the metal powder pigment, this volatile matter may be oil-based even if it is water-based. For example, even if the pigment is oil-based, it can be dispersed into an aqueous paint using a known dispersion technique, and solution polymerization is advantageous for obtaining such a metal powder pigment.

On the other hand, when the volatile matter is aqueous, it is advantageous to use emulsion polymerization or suspension polymerization, and an appropriate polymerization method may be selected depending on the purpose. However, in the metal powder pigment according to the present invention, the presence or absence of volatile matter is not necessarily an essential condition.

The grinding aid used in the present invention may be any commonly used grinding aid and is not particularly limited, but for example,
One or a mixture of two or more of saturated or unsaturated fatty acids such as stearic acid and oleic acid and their derivatives are preferred.

These grinding aids are used, for example, alone or in combination with a substance that suppresses the hydrogen gas production reaction in the grinding process, but the substance that suppresses the hydrogen gas production reaction is used as the intended grinding aid. If it can fulfill its role satisfactorily, it may not be used at all.

In addition, the substance that suppresses the hydrogen gas production reaction used in the present invention is not particularly limited as long as it can suppress the reaction between the metal powder used and water, or a compound that is structurally equivalent to such a group. compounds and organic phosphoric acid ester compounds are preferred. As a compound structurally equivalent to a group in the molecule,
Examples include orthophosphoric acid and phosphorus pentoxide.

As the organic phosphoric acid ester compound, the following general formula (1) is used.
Examples include compounds represented by and salts thereof, phosphoric acid ester compounds having a group induced in the molecule, and the like.

Here, R represents an alkyl group having 6 to 24 carbon atoms, an alkenyl group, or an alkyl group containing one or more alkyl substituents or alkenyl substituents having 6 to 24 carbon atoms, and A is an alkyl group having 2 to 24 carbon atoms. ~4 alkylene group, m is 0 to 20, R5 and RL may be the same or different, and represent hydrogen, an alkyl group, an alkenyl group, an aryl group, or R-(OA)% ( Here, R, A and m represent those shown above.

Examples of the alkyl group or alkenyl group in R5R1,1% include octyl, decyl, tridecyl, lauryl, cetyl, stearyl, oleyl, hexadecyl,
Octadecyl and the like are preferred. Further, as the aryl group in R, R, and the island, for example, octylphenyl, nonylphenyl, dodecylphenyl, dinonylphenyl, etc. are preferable, and as A, ethylene, propylene, etc. are preferable.

As specific compounds, the above-mentioned alkyl, alkenyl, or aryl esters of phosphoric acid, or esters obtained by adding ethylene oxide to alkyl, alkenyl, or aryl groups are preferable.The phosphoric acid esters may be mono-, di-, or triesters. , may be a mixture of these,
Alternatively, it may be a mixture of different types of phosphoric esters. Furthermore, since these organic phosphoric acid ester compounds exhibit acidity in an aqueous solution, ammonium, sodium hydroxide, potassium hydroxide, diptylamine, diethylamine, triethylamine, monoethanolamine, jetanolamine, triethanolamine, and morpholine are added to these compounds. It can be used after being neutralized with inorganic and organic basic substances such as.

The phosphoric acid ester substances derived by reacting include the reaction product of orthophosphoric acid or its monoester compound and a compound containing at least one epoxide group, or the reaction product of orthophosphoric acid or its monoester compound and a functional hydroxyl group. and/or reaction products with monohydric alcohols or monohydric phenols.

The organic phosphoric acid ester compound is 0.1 to 50% by weight, preferably 0.5 to 40% by weight, based on the pure metal powder content in the metal powder pigment.
It is used in a range of 1 to 25% by weight, more preferably 1 to 25% by weight. Here, the amount of the organic phosphoric acid ester compound used is 0.
If it is less than 1% by weight, the effect of suppressing the hydrogen gas production reaction is poor, and if it is more than 50% by weight, it is not preferable because it reduces the performance of the coating film obtained from the aqueous paint containing the metal powder pigment.

The resin coating layer in the present invention is formed to surround the adsorption layer, and protects the substance that suppresses the hydrogen gas production reaction present in the adsorption layer from mechanical shearing, and also protects the resin used in the water-based paint. Any material that has the effect of improving the performance of the resulting coating film, such as adhesion, water resistance, hot water resistance, and chemical resistance by improving affinity, is suitable, and is not particularly limited. However, for example, the resin coating layer may contain a monomer (a) having two or more radically polymerizable double bonds in one molecule and a radically polymerizable unsaturated carboxylic acid (b) and/or at least one radically polymerizable double bond in one molecule. a phosphoric acid ester monomer (c) having radically polymerizable double bonds;
Furthermore, a polymer [(a) +'(b), (a ) + (c), (a
) + (b> + (c), (a) + (b) + (
d), (a) + (0) + (d), (21) +
(b) + (c) + (dl polymer) is preferred.

Examples of the monomer (a) having two or more radically polymerizable double bonds in one molecule used in the present invention include trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, Trimethylolpropane trimethacrylate, tetramethylolmethane diacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane dimethacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethanetetraacrylate, tetramethylolmethanetetramethacrylate, etc., and one type thereof Or a mixture of two or more is used. The amount used is preferably between 2 parts by weight and 50 parts by weight per 100 parts by weight of the metal powder pigment.
If the amount is less than 2 parts by weight, the effects of the present invention, that is, the protection of the adsorption layer and the improvement of coating film performance, will not be sufficient, and if it exceeds 50 parts by weight, no increase in the above effects is expected, and on the contrary, the appearance of the coating film will be reduced. decreases.

Radically polymerizable unsaturated carboxylic acid (b) in the present invention
Examples of the acid include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, etc., and one type or a mixture of two or more thereof is used. The amount used varies depending on the type and characteristics of the metal in the metal powder pigment referred to in the present invention, especially the surface area, but generally from 0.01 parts by weight to 1 part by weight per 100 parts by weight of metal powder.
The amount is preferably between 0 parts by weight. If it is less than 0.01 parts by weight, the effects of the present invention, that is, the protection of the adsorption layer and the improvement of the coating film performance, are insufficient, and if it exceeds 10 parts by weight, the coating film is The water resistance and hot water resistance of the product will decrease.

In the present invention, the phosphoric acid ester monomer (c) having at least one radically polymerizable double bond in one molecule is:
For example, 2-methacryloyloxyethyl phosphate,
Di-2-methacryloyloxyethyl phosphate, tri-2-methacryloyloxyethyl phosphate, 2-acryloyloxyethyl phosphate, di-2-acryloyloxyethyl phosphate, tri-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyl Roxyethyl phosphate, diphenyl-2-acryloyloxyethyl phosphate, dibutyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxyethyl phosphate, dioctyl-2-methacryloyloxyethyl phosphate, dioctyl-2
-acryloyloxyethyl phosphate, 2-methacryloyloxymethyl phosphate, bis(2-chloroethyl)vinylphosphonate, diallyldibutylphosphonosuccinate, etc., and it is preferable to use one type or a mixture of two or more thereof. Among them, phosphoric acid monoester is preferable, because the presence of two OH groups in one molecule of the phosphoric acid group causes stronger adsorption on the surface of the metal powder pigment, creating a stable adsorption state. Presumed.

Preferred phosphoric acid monoesters include monoesters containing a methacroyloxy group and an acrylyloxy group, such as 2-methacryloxymethyl phosphate and 2-acryloyloxyethyl phosphate.

When using a phosphoric acid ester monomer (0) having at least one radically polymerizable double bond in one molecule, the amount used varies depending on the type and characteristics of the all-metal powder pigment, especially the surface area, but in general, For 100 parts by weight of powder pigment,
Preferably between 0.01 parts by weight and 30 parts by weight, 0.
If the amount is less than 0.01 parts by weight, the effects of the present invention, that is, the protection of the adsorption layer and the improvement of coating film performance, will not be sufficient; Even if the amount is exceeded, an increase in the above effects cannot be expected.

The radically polymerizable unsaturated carboxylic acid (C) and the phosphoric acid ester monomer (c) having at least one radically polymerizable double bond in one molecule may be used alone or as a mixture.

In the present invention, two radically polymerizable double bonds are contained in one molecule.
monomer (a) having at least one radically polymerizable double bond (a), a radically polymerizable unsaturated carboxylic acid pseudo) and/or a phosphoric acid ester monomer (c) having at least one radically polymerizable double bond in one molecule
The radically polymerizable unsaturated monomer (d) copolymerizable with one or more of the following is, for example, acrylic esters such as styrene, α-methylstyrene, and methyl acrylate;
Methacrylic acid esters such as methyl methacrylate, acrylonitrile, methacrylateril, vinyl acetate, vinyl propionate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate Examples include acrylate and divinylbenzene, and one or more of these may be used. The amount used is preferably in the range of 0 to 10 parts by weight per 100 parts by weight of the metal powder.

When the amount used exceeds 10 parts by weight, the effects of the present invention, i.e.,
This is not preferable because the performance of the aqueous metallic coating film using the metal powder pigment in the present invention deteriorates.

The metal powder pigment of the present invention has an adsorption layer on the surface of the metal powder that has an excellent effect of suppressing the reaction that reacts with water to generate hydrogen, and protects this adsorption layer from mechanical shear. When used as a commercial pigment, it is characterized by having a resin coating layer for improving the dispersibility of the metal powder pigment in the paint and eventually in the coating film by increasing the affinity with the resin in the paint.

The above-mentioned mechanical shear is that which is received from mixers, agitators, pumps, pipe wall surfaces, etc. during the production of metal powder pigments, the production of paints containing the metal powder pigments, or during liquid transfer. .

Furthermore, as mentioned above, the resin coating layer has the effect of greatly improving the dispersibility of metal powder pigments in water-based paints or in coating films obtained from the paints, and therefore, conventionally, the resin coating layer has been used for the purpose of improving dispersibility. The amount of surfactants such as dispersants and wetting agents used in conventional coatings can be reduced, and as a result, the properties of the resulting coating film, such as adhesion, water resistance, and hot water resistance, are significantly improved. This is presumed to be due to the synergistic effect of the uniform dispersion effect of the metal powder pigment and the reduction effect of dispersants, wetting agents, etc. that can adversely affect coating performance.

In addition, as a method of further actively reducing the amount of the dispersant, wetting agent, etc., it is preferable to make the resin coating layer more hydrophilic in nature. In this specific method, as the copolymerizable radically polymerizable unsaturated monomer of the present invention, for example, a monomer containing a highly hydrophilic hydroxyl group such as hydroxyethyl acrylate or 2-hydroxyethyl methacrylate is used. You may also use In addition to these, monomers having a functional group capable of imparting hydrophilicity, such as a carboxyl group or a sulfonic acid group, may also be used. However, it is necessary to limit the amount used so as not to impair the effects of the present invention.

The water-based metallic paint containing the metal powder pigment in the present invention is a paint made by a paint-forming technology normally employed in the field, and the metal powder pigment and the resin for water-based paint in the present invention are It is an essential component, and can be obtained with or without addition of various additives and organic or inorganic pigments other than the above-mentioned metal powder pigments depending on the purpose and use.

Here, the water-based paint resin refers to a water-soluble resin or a water-dispersible resin, which may be used alone or as a mixture.The types vary widely depending on the purpose and use, and are not particularly limited. Generally, acrylic, acrylic-melamine, polyester, polyurethane, etc. are mentioned, although the acrylic-melamine type is the most commonly used.

Examples of the various additives mentioned above include dispersants, iM agents, leveling agents, thixotropic agents, thickeners, anti-sagging agents, anti-mold agents, ultraviolet absorbers, film-forming aids, and other organic solvents. may be added as long as it can be commonly used in the field and does not impair the effects of the present invention.

In addition, examples of the above-mentioned inorganic or organic pigments include titanium white, zinc white, navy blue, red iron, calcium carbonate, cadmium yellow, cadmium red, barium sulfate, lead sulfate, calcium silicate, ultramarine blue, cobalt violet, manganese purple, burr mica, etc. Inorganic pigments such as Pearl Essence, vat dyes, isoindolinones, quinacridones, condensed azos, insoluble azo pigments, copper phthalocyanine, lake for basic dyeing, lake for acidic dyeing, mordant dye lake It is preferable to select organic pigments from among such organic pigments according to the purpose and use. However, in this case, it is necessary to appropriately select the type and amount so as not to impair the effects of the present invention.

〔Example〕

In carrying out the present invention, there are countless possible combinations of the embodiments, and some typical combinations will be described below with reference to examples.

First, the test method and measurement method used will be described.

■Amount of resin to be coated per 100 parts by weight of metal inspection Disperse 10 g of the paste containing the resin-coated metal powder pigment of the present invention in 100 ml of chloroform (reagent) and extract the soluble content. Next, extract the resin-coated metal powder from the extraction residue. Pigment at 80℃
Vacuum dry for an hour to powder, take 1.0g, 6N-H
CI (reagent) Melt the metal powder portion little by little with 200ml. The remaining insoluble resin content is filtered, and after vacuum drying at 80° C. for 14 hours, the weight is measured, and the resin content relative to 100 parts by weight of the metal content is calculated.

Regarding the obtained water-dispersible metal powder paste, water dispersibility, water stability, and long-term storage stability were investigated as metal powder paste properties, and the paint and coating properties when used in water-based paint were also investigated. The test method used was as follows.

■Properties of metal powder paste (1) Water dispersibility Collect 3 g of a sample into a 50 ml Nessler tube and add warm water for preliminary dispersion. Then add water up to 50m 1 mark,
Good (determined visually from the state of dispersion of metal powder particles after 5 minutes of shaking and mixing).

(2) Water stability 20 g of metal powder paste (heated residue: 65%) is taken into a 200 ml Erlenmeyer flask, 100 ml of pure water is added, and the sample is dispersed by shaking vigorously. Attach a graduated pipette with a rubber stopper and immerse it in a constant temperature bath at 60°C, and observe the state of gas generation after leaving it for 24 hours.

(3) Storage stability The metal powder paste was placed in a 500+nl glass container and its properties were examined after storage for 6 months at room temperature.

■Paint and paint film properties A water-soluble acrylic melamine resin paint was created using the following formulation, and the test metal powder paste was tested for (1) gas generation, (2) paint film appearance, (3) adhesion, and (4) hot water resistance. was evaluated.

Test metal powder paste (heating residue: 65%) 13.0 Part by weight Water-soluble acrylic resin (heating residue: 50%) 370.0
Part by weight Water-soluble melamine resin (heated residue 50%) 100.0
Parts by weight / 490.8 Total 973.8 Parts by weight + 1) Paint gas generation Put 100ml of the sample paint into a 200ml Erlenmeyer flask, attach a graduated pipette with a rubber stopper, and heat at 50°C for 20 minutes.
Observe the state of gas generation after leaving it for some time.

(2) Appearance of paint film Comparative observation is made between a paint film that was painted immediately after blending the paint and a paint film that was painted using a paint that was left at room temperature for three months.

(3) Adhesive After immersing the coated plate in warm water at 80° C. for 1 hour and leaving it to dry at room temperature for 8 hours, a cellophane tape peeling test with a loss cut was performed to compare and observe the peeling state of the paint film.

(4) Warm water resistance After immersing the coated plate in 40°C hot water for 10 days, the appearance and metallic feel of the coating film were compared and observed.

Example 1 Granular aluminum powder 1.0 Kg Mineral spirit 2.51! Stearylamine 5
0.0 g was ground in a ball mill for 8 hours. After grinding, wash the slurry with mineral spirit 101,
Passed through a 325 mesh screen. Thereafter, the mixture was filtered using a filter press to obtain a filter cake (1) having a metal content of 80% by weight. This filter cake (I
) A predetermined amount of a predetermined hydrogen gas generation inhibitor as shown in Table 1 was added to 125 parts by weight, and the mixture was mixed at 60° C. for 1 hour to obtain a paste (U).

Next, 100 parts by weight of metal and 400 parts by weight of mineral spirit were placed into a three-bottle flask, and the paste (II) was stirred while introducing nitrogen gas, and the temperature in the system was raised to 80°C. did. Then acrylic acid (reagent)
0.5 part by weight of was added, and stirring was continued at 80°C for 30 minutes.

Thereafter, trimethylolpropane trimethacrylate (reagent) and azobisisobutyronitrile (reagent) were added in predetermined amounts shown in Table 1, and polymerized at 80° C. for 5 hours.

After the polymerization is completed, the slurry is allowed to cool to room temperature and filtered.
Resin coated aluminum pigment filter cake (III)
I got it. The amount of coating resin per 100 parts by weight of aluminum metal in this filter cake (m) is shown in Table 1.

For 100 parts by weight of this filter cake (m),
As shown in Table 1, a predetermined amount of a predetermined nonionic surfactant was added, and after adding pure water so that the heating residue was 65%,
A water-dispersible aluminum paste was prepared by kneading.

The resulting water-dispersible aluminum paste was examined for its water-dispersibility, water stability, and long-term storage stability as paste properties, as well as the gas generation of the paint when used in water-based paints and the appearance of the paint film. , adhesion and hot water resistance were investigated, and the results are shown in Table 1.

Example 2 A water-dispersible aluminum paste was prepared in the same manner as in Example 1 except that trimethylolpropane trimethacrylate was replaced with trimethylolpropane triacrylate. The paste properties and the physical properties of the paint and coating film of the obtained aluminum paste were examined in the same manner as in Example 1.

The results are shown in Table 1.

Comparative Example 1 The filter cake (1) obtained by pulverization in Example 1 was used and kneaded with the following composition to obtain a water-dispersible aluminum paste.

Filter cake (I) 100 parts by weight Polyoxyethylene lauryl ether 4 〃25〃 Total 129〃 Comparative example 3 Paste obtained in Example 1, sample No. 4 (II
) and kneaded with the following composition to obtain a water-dispersible aluminum paste.

Paste (II) 100 parts by weight Polyoxyethylene lauryl ether 4 〃27〃 Total 131〃 Comparative example 2 Filter cake obtained by pulverization in Example 1 (I)
125 parts by weight and 400 parts by weight of mineral spirit were put into a three-bottle flask, stirred while introducing nitrogen gas, and the temperature in the system was raised to 80°C.

Next, 0.5 parts by weight of acrylic acid (reagent) was added, and 8 parts by weight of acrylic acid (reagent) was added.
Stirring was continued for 30 minutes at 0°C. Next, 5.0 parts by weight of trimethylolpropane trimethacrylate (reagent) and 0.5 parts by weight of azobisisobutyronitrile (reagent) were added and polymerized at 80°C for 5 hours. After the completion of the zero polymerization, the slurry was allowed to cool to room temperature and filtered to obtain a resin-coated aluminum pigment filter cake (III). Non-volatile content of this filter press cake (according to JIS K-5910)
was 70% by weight. The amount of coating resin was 5.6 parts by weight based on 100 parts by weight of aluminum metal.

This resin coated aluminum pigment filter cake (ml
) and kneaded for 30 minutes with the following composition to obtain a water-dispersible aluminum pigment paste.

Resin coated aluminum pigment filter cake (m) 10
0 parts by weight Polyoxyethylene lauryl ether 4 〃9 〃 Total 1) 3〃 Example 3 Filter cake (I) obtained after pulverization in Example 1
A predetermined amount of a predetermined hydrogen gas generation inhibitor shown in Table 2 was added to 125 parts by weight, and the mixture was mixed at 60° C. for 1 hour to obtain a paste (n).

Next, 100 parts by weight of this paste (n) and 400 parts by weight of Mineral Spirit 7) were placed in a three-bottle flask, stirred while introducing nitrogen gas, and the temperature in the system was brought to 80°C. The temperature rose. Next, 0.5 parts by weight of methacryloyloxyethyl phosphate (trial) was added, and 80
Stirring was continued for 30 minutes at °C. After that, predetermined amounts of trimethylolpropane trimethacrylate (reagent) and azobisisobutyronitrile (reagent) were added as shown in Table 2.
Polymerization was carried out at 0°C for 5 hours.

After the polymerization is completed, the slurry is allowed to cool to room temperature and filtered.
A resin coated aluminum pigment filter cake (DI) was obtained. The amount of coating resin per 100 parts by weight of the aluminum metal content of this filter cake (I[[) is shown in Table 2.

To 100 parts by weight of this filter cake (III), a predetermined amount of a predetermined nonionic surfactant as shown in Table 2 was added, and water was added so that the heating residue was 65%.
A water-dispersible aluminum paste was prepared by kneading.

The resulting water-dispersible aluminum paste was examined for its water-dispersibility, water stability, and long-term storage stability as paste properties, as well as the gas generation of the paint when used in water-based paints and the appearance of the paint film. , adhesion, and hot water resistance.
The results are shown in Table 2.

Example 4 Granular aluminum powder 1.0 Kg Mineral spirit 2.51 Oleic acid
50.0 g was ground in a ball mill for 8 hours. After grinding, add 10I of mineral spirit to the slurry.
! It was washed out and passed through a 325 mesh screen.

Thereafter, the mixture was filtered using a filter press to obtain a filter cake (I) having a metal content of 77% by weight.

To 130 parts by weight of this filter cake (I), 8 parts by weight of tridecyl phosphate was added and mixed at 60°C for 1 hour to obtain a paste (II).

Next, 100 parts by weight of metal and 400 parts by weight of mineral spirit were placed into a three-bottle flask, and the paste (If) was stirred while introducing nitrogen gas, and the temperature in the system was raised to 80°C. 0 then acrylic acid (reagent)
0.5 part by weight of was added, and stirring was continued at 80°C for 30 minutes.

Then trimethylolpropane trimethacrylate (
Reagent) 5 parts by weight and azobisisobutyronitrile (reagent)
0.5 part by weight was added and polymerized at 80°C for 5 hours.

After the polymerization is completed, the slurry is allowed to cool to room temperature and filtered.
A resin-coated aluminum pigment cake (Iff) was obtained. Aluminum metal content of this filter cake (III) 1
The amount of coating resin was 5.7 parts by weight based on 00 parts by weight.

To 100 parts by weight of this filter cake (I[[), add a predetermined amount of a specified nonionic surfactant as shown in Table 3, add water so that the heating residue becomes 65%, and then knead. A water-dispersible aluminum paste was prepared.

The resulting water-dispersible aluminum paste was examined for its water-dispersibility, water stability, and long-term storage stability as paste properties, as well as the gas generation of the paint when used in water-based paints and the appearance of the paint film. , adhesion, and hot water resistance.
The results are shown in Table 3.

Comparative Example 4 A water-dispersible aluminum paste as shown in Table 3 was prepared in the same manner as in Example 4 except that the step of adding tridecyl phosphate to the filter cake (I) to form a paste (n) was performed. Prepared.

Example 5 Granular aluminum powder 1.0Kg, mineral spirit)
2. ! A predetermined amount of M and a predetermined grinding aid shown in Table 4 was put into a ball mill, and the mixture was ground for 8 hours. After the grinding was completed, the slurry was washed out with Mineral Spirit 101 and passed through a 325 mesh screen. Thereafter, it was filtered using a filter press to obtain a filter cake (1).

Next, this filter cake (1) has a metal content of 10
0 parts by weight and 400M parts of mineral spirit were placed in a three-necked flask, stirred while introducing nitrogen gas,
The temperature inside the system was raised to 80°C.

Next, 0.5 parts by weight of acrylic acid (reagent) was added, and 8
Stirring was continued for 30 minutes at 0°C. Then, predetermined amounts of trimethylolpropane trimethacrylate (reagent) and azobisisobutyronitrile (reagent) were added as shown in Table 4.
Polymerization was carried out at 0°C for 5 hours.

After the polymerization is completed, the slurry is allowed to cool to room temperature and filtered.
Resin coated aluminum pigment filter cake (III)
I got it. Table 4 shows the amount of resin coated with respect to 100 parts by weight of the aluminum metal content of this filter cake (II[).

To 100 parts by weight of this filter cake (I [I), add a predetermined amount of a predetermined nonionic surfactant as shown in Table 4, add water so that the heating residue becomes 65%, and then knead. A water-dispersible aluminum paste was prepared.

The resulting water-dispersible aluminum paste was examined for its water-dispersibility, water stability, and long-term storage stability as paste properties, as well as the gas generation of the paint when used in water-based paints and the appearance of the paint film. , adhesion, and hot water resistance.
The results are shown in Table 4.

Comparative Example 5 To 100 parts by weight of the filter cake (I) obtained by crushing Sample No. 23 in Example 5, a predetermined amount of a predetermined nonionic surfactant as shown in Table 4 was added, and the heated residue was Water was added to the mixture to give a content of 65%, and the mixture was kneaded to prepare a water-dispersible aluminum paste.

Example 6, Comparative Example 6 Granular copper powder 1.0 Kg Mineral spirit 1.21 Tridecyl phosphate
) 50.0 g were ground in a ball mill for 8 hours. After grinding, add 10% mineral spirit to the slurry.
1 and passed through a 325 mesh screen.

Thereafter, the mixture was filtered using a filter press to obtain a filter cake (1) having a metal content of 85% by weight.

Next, this filter cake (1) has a metal content of 100
Parts by weight and 400 parts by weight of mineral spirit were placed in a three-bottle flask, stirred while introducing nitrogen gas, and the temperature in the system was raised to 80°C.Next, 0.5 parts by weight of acrylic acid (reagent) was added. part was added and stirring was continued for 30 minutes at 80°C. Thereafter, predetermined amounts of trimethylolpropane trimethacrylate (reagent) and azobisisobutyronitrile (reagent) shown in Table 5 were added, and polymerization was carried out at 80° C. for 5 hours.

After the polymerization is completed, the slurry is allowed to cool to room temperature and filtered.
A resin-coated copper pigment filter cake (Ill) was obtained. Table 4 shows the amount of resin coated with respect to 100 parts by weight of the metal content of this filter cake (I[[).

To 100 parts by weight of the filter cake (I [ A water-dispersible copper paste was prepared.

The resulting water-dispersible copper paste was examined for its paste properties, such as water dispersibility, water stability, and long-term storage stability, as well as the gas generation of the paint when used in water-based paints and the appearance of the paint film. , adhesion, and hot water resistance, and the results were used in the fourth
Shown in the table.

For comparison with the present invention, as sample No. 28,
A predetermined amount of nonionic surfactant is added to the filter cake (I) obtained by grinding with tridecyl phosphate, water is added so that the heating residue becomes 65%, and the mixture is kneaded to obtain water-dispersible copper. A paste was prepared, and further, as sample No. 29, the same operation as in Example 6 was performed except that oleic acid was used instead of tridecyl phosphate, to prepare a water-dispersible copper paste with a heating residue of 65%. did.

Example 7, Comparative Example 7 Granular zinc powder 1.0 Kg Mineral spirit 1.27! 50.0 g of tridecyl phosphate was ground in a ball mill for 8 hours. After grinding, mix the slurry with mineral spirit 1)
It was washed out and passed through a 325 mesh screen. After that, it was filtered with a filter press and the metal content was 90% by weight.
A filter cake (I) consisting of the following was obtained.

Next, this filter cake (I) has a metal content of 100
Parts by weight and 400 parts by weight of mineral spirit were placed in a three-bottle flask, and while nitrogen gas was introduced, the mixture was stirred and the temperature in the system was raised to 80°C. Next, 0.5 parts by weight of acrylic acid reagent) was added, and stirring was continued at 80°C for 30 minutes. Then, add trimethylolpropane trimethacrylate (reagent) and azobisisobutyronitrile (reagent).
A predetermined amount shown in Table 4 was added and polymerized at 80°C for 5 hours.

After the polymerization is completed, the slurry is allowed to cool to room temperature and filtered.
A resin-coated zinc pigment filter cake (I[I) was obtained.

Table 4 shows the amount of resin coated with respect to 100 parts by weight of the metal content of this filter cake (III).

To 100 parts by weight of this filter cake (I[[), add a predetermined amount of a predetermined nonionic surfactant as shown in Table 4, add water so that the heating residue becomes 65%, and then knead. A water-dispersible zinc paste was prepared.

The resulting water-dispersible zinc paste was examined for its paste properties, such as water dispersibility, water stability, and long-term storage stability, as well as the gas generation of the paint when used in water-based paints and the appearance of the paint film. , adhesion, and hot water resistance were investigated, and the results are shown in Table 4.

For comparison with the present invention, a predetermined amount of nonionic surfactant was added to the filter cake (1) obtained by grinding with tridecyl phosphate as sample No. 31, and the heating residue was adjusted to 65%. After adding water to and kneading, a water-dispersible zinc paste was prepared. Furthermore, as sample No. 32, the operation was exactly the same as in Example 6 except that oleic acid was used instead of tridecyl phosphate. 6 left after heating
A 5% water-dispersible zinc paste was prepared.

〔Effect of the invention〕

The metal powder pigment of the present invention has excellent storage stability itself,
It is a pigment that provides paints containing it with excellent storage stability and extremely excellent adhesion, water resistance, hot water resistance, and chemical resistance, and coating films obtained from it, and its industrial value is great. .

Claims (4)

[Claims] (1) A metal powder consisting of particles having a surface coating layer,
A novel metal powder pigment characterized in that the surface coating layer comprises an adsorption layer to which a substance that suppresses a hydrogen gas production reaction is adsorbed, and a resin coating layer surrounding the adsorption layer. (2) The novel metal powder pigment according to claim 1, wherein the metal powder is a powder of aluminum, copper, zinc, brass, other malleable metals, or alloys thereof. (3) The novel metal powder pigment according to claim 1, wherein the substance that suppresses the hydrogen gas production reaction is orthophosphoric acid or an organic phosphoric acid compound. (4) The resin coating layer contains a monomer (a) having two or more radically polymerizable double bonds in one molecule and a radically polymerizable unsaturated carboxylic acid (b) and/or at least one radically polymerizable double bond in one molecule.
a phosphoric acid ester monomer (c) having 3 radically polymerizable double bonds, and a radically polymerizable unsaturated monomer ( d) [(a) + (b), (a) + (c), (
a)+(b)+(c),(a)+(b)+(d),(a
) + (c) + (d), (a) + (b) + (c) + (d)
The novel metal powder pigment according to claim 1, which is a coating layer of a polymer of