JP6233458B2 - paint - Google Patents

Description

The present invention relates to a paint .

Conventionally, metal plating, foil press printing using a metal foil, thermal transfer using a metal foil, and the like have been used as a method for producing a decorative product exhibiting a glossy appearance.
However, these methods have a problem that it is difficult to form a fine pattern or to apply to a curved surface portion.
On the other hand, paints containing metal powder are also widely used (see, for example, Patent Document 1). Although such a paint can solve or alleviate the above-mentioned problems, there is a problem that the glossiness and high-class feeling inherent in the metal material cannot be sufficiently exhibited. This is considered to be because the metal material is easily affected by oxidation or the like by including it in a powder state having a large specific surface area.

JP 2001-192618 A

The objective of this invention is providing the coating material containing the metal powder which exhibits the outstanding glossiness stably over a long period of time.

Such an object is achieved by the present invention described below.
The paint of the present invention is a metal powder whose surface is composed of a metal material and whose surface is treated with a fluorine-based phosphate compound,
Look containing a thermosetting resin powder,
The fluorine phosphoric acid compound is one having a chemical structure represented by the following formula (1), _{or, CF 3 (CF 2) 5} (CH 2) 2 O (P) (OH) (OCH 2 CH 3) It is characterized by being.
POR _n (OH) _3-n (1)
(In the formula (1), _{R, CF 3 (CF 2) m} -, CF 3 (CF 2) m (CH 2) l -, CF 3 (CF 2) m (CH 2 O) l -, CF 3 (CF ₂ ) _m (CH ₂ CH ₂ O) ₁ —, CF ₃ (CF ₂ ) _m O—, or CF ₃ (CF ₂ ) _m (CH ₂ ) ₁ O—, and n is 1 or more and 3 or less. M is an integer of 4 or more and 5 or less, and l is an integer of 1 or more and 12 or less.)
Thereby, the coating material containing the metal powder which exhibits the glossiness stably excellent over a long period of time can be provided. Further, the durability of the metal powder can be made particularly excellent. Further, the viscosity of the paint can be made lower, and the coatability of the paint can be made particularly excellent.
In the paint of the present invention, it is preferable that the mother particles have a surface mainly composed of Al.
Al originally exhibits a particularly excellent gloss feeling among various metal materials, but when it is made into a powder, the glossiness inherent in it is not fully exhibited, and the glossiness is caused by corrosion. There were problems such as significant deterioration over time. On the other hand, in this invention, even if it is a case where the surface uses the powder comprised by Al, generation | occurrence | production of the above problems can be prevented reliably. That is, the effect of the present invention is particularly remarkably exhibited because the mother particles constituting the metal powder are at least the surface of which is mainly composed of Al.

In the paint of the present invention, it is preferable that the metal powder has a scaly shape.
Thereby, when a recorded matter is manufactured using a paint, the glossiness and high-quality feeling of the recorded matter can be made particularly excellent .

In the paint of the present invention, the fluorine-based phosphate compound preferably has a perfluoroalkyl structure.
Thereby, the glossiness of the metal powder can be made particularly excellent. Further, the durability of the metal powder can be made particularly excellent. Further , the viscosity of the paint can be made lower, and the coatability of the paint can be made particularly excellent.

In the coating material of the present invention, the metal powder preferably has an average particle size of 500 nm or more and 3.0 μm or less.
Thereby, the glossiness of the metal powder can be made particularly excellent. Further, the durability of the metal powder can be made particularly excellent. In addition , the coating property of the paint can be made particularly excellent.
In coating of the present invention, the average thickness of the metal powder is preferably not 10nm 20 nm or more or less.
Thus, in the case of forming a coating film using a coating material, can be provided with particularly excellent smoothness of the coating film can be made particularly excellent gloss of the coating film. In addition, the metal powder can be produced with high productivity, and the unintentional deformation of the metal powder during the production of a paste or paint can be more suitably prevented.
In the paint of the present invention, it is preferable that the average particle diameter of the thermosetting resin powder is 5 μm or more and 100 μm or less.
Thereby, when performing powder coating, uniform dusting can be performed more suitably, the smoothness of the coating film can be improved, and the aesthetic appearance (aesthetics) of the coating film can be improved. It can be excellent.
In the coating material of this invention, it is preferable that content of the said metal powder with respect to 100 mass parts of said thermosetting resin powders is 1 mass part or more and 30 mass parts or less.
Thereby, glossiness (metallic feeling and brightness feeling) can be made more excellent, and the thickness of the coating film for concealing the substrate can be made smaller. Moreover, the smoothness of a coating film can be made more excellent, and the aesthetic appearance (aesthetics) of a coating film can be made more excellent.

Hereinafter, preferred embodiments of the present invention will be described in detail.
《Metal powder》
The metal powder of the present invention described in detail below may be handled as a powder in a dry state, but is usually dispersed in a dispersion medium from the viewpoint of safety, ease of distribution, etc. It is handled in the liquid state. Such a dispersion may be used as it is as a paste, paint, etc., which will be described in detail later, or by diluting with another dispersion medium component or replacing the dispersion medium component. It may be used as a paint or the like.

  The metal powder of the present invention is obtained by surface-treating mother particles whose surfaces are made of a metal material with a fluorine-based phosphate compound. With such a configuration, the metal powder exhibits an excellent gloss feeling stably over a long period of time. Further, with such a configuration, when the metal powder is applied to the paint, the viscosity of the paint can be made lower, and the coatability of the paint can be made particularly excellent. it can.

(Mother particles)
First, mother particles (particles subjected to surface treatment with a fluorine-based phosphoric acid compound) constituting metal particles will be described.
The mother particles constituting the metal powder need only have at least a region including the vicinity of the surface made of a metal material. For example, the whole may be made of a metal material or a non-metal material. And a base made of a metal material covering the base.

  Moreover, as a metal material which comprises a mother particle, the metal as a simple substance, various alloys, etc. can be used. In particular, even if it is not composed of a noble metal material with high chemical stability such as Pt, the glossiness and durability of the metal powder as a whole (excellent glossiness retention performance over a long period of time) is sufficient. It can be excellent. Thereby, the range of material selection is widened, and it is possible to express various color tones with excellent gloss.

  In particular, in the present invention, it is preferable that the mother particles are mainly composed of Al at least near the surface. Al originally exhibits a particularly excellent gloss feeling among various metal materials, but when it is made into a powder, the glossiness inherent in it is not fully exhibited, and the glossiness is caused by corrosion. There were problems such as significant deterioration over time. On the other hand, in this invention, even if it is a case where the surface uses the powder comprised by Al, generation | occurrence | production of the above problems can be prevented reliably. In addition, when the powder composed of Al is mixed with other components to form a paint, the viscosity of the paint is likely to be high, and the viscosity is likely to increase over time. However, in the present invention, even when a powder whose surface is composed of Al is used, it is possible to reliably prevent the occurrence of the above problems. That is, the effect of the present invention is particularly remarkably exhibited because the mother particles constituting the metal powder are at least the surface of which is mainly composed of Al.

  Further, the mother particles may be produced by any method, but when they are made of Al, a film made of Al is formed by a vapor deposition method, and then It is preferably obtained by pulverizing the membrane. Thereby, the glossiness etc. which Al originally has can be expressed more effectively. Moreover, the dispersion | variation in the characteristic between each particle | grain can be suppressed. Moreover, even if it is a comparatively thin metal powder, it can manufacture suitably by using the said method.

When producing mother particles using such a method, for example, the mother particles can be suitably produced by forming a film made of Al (film formation) on a substrate. As the substrate, for example, a plastic film such as polyethylene terephthalate can be used. Further, the substrate may have a release agent layer on the film forming surface.
Moreover, it is preferable that the said grinding | pulverization is performed by providing an ultrasonic vibration to the said film | membrane in a liquid. This makes it possible to easily and surely obtain mother particles having the above-described particle diameter, and to suppress the variation in size, shape, and characteristics among the particles.

  When the pulverization is performed by the above method, the liquid includes alcohols such as methanol, ethanol, propanol, and butanol, n-heptane, n-octane, decane, dodecane, tetradecane, toluene, xylene, and cymene. , Durene, indene, dipentene, tetrahydronaphthalene, decahydronaphthalene, cyclohexylbenzene and other hydrocarbon compounds, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether , Diethylene glycol monobutyl ether acetate, diethylene glycol n-butyl ether, triplicate Ether compounds such as pyrene glycol dimethyl ether, triethylene glycol diethyl ether, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, p-dioxane, propylene carbonate, γ-butyrolactone, N-methyl-2-pyrrolidone , N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), dimethyl sulfoxide, cyclohexanone, acetonitrile and the like can be preferably used. By using such a liquid, the productivity of the mother particles and metal powder is made particularly excellent while preventing unintentional oxidation of the mother particles, and the size, shape, and characteristics between each particle Can be made particularly small.

(Fluorine phosphate compound)
As described above, the metal powder according to the present invention is surface-treated with a fluorine-based phosphate compound.
As the fluorine-based phosphate compound, a phosphate compound having at least one fluorine atom in the molecule can be used.
In particular, the fluorine-based phosphoric acid compound preferably has a chemical structure represented by the following formula (1).

POR _n (OH) _3-n (1)
(In the formula (1), _{R, CF 3 (CF 2) m} -, CF 3 (CF 2) m (CH 2) l -, CF 3 (CF 2) m (CH 2 O) l -, CF 3 (CF ₂ ) _m (CH ₂ CH ₂ O) ₁ —, CF ₃ (CF ₂ ) _m O—, or CF ₃ (CF ₂ ) _m (CH ₂ ) ₁ O—, and n is 1 or more and 3 or less. M is an integer from 5 to 17, and l is an integer from 1 to 12.)

Thereby, the glossiness of the metal powder can be made particularly excellent. Further, the durability of the metal powder can be made particularly excellent. Moreover, when a metal powder is applied to a coating material, the viscosity of the coating material can be made lower, and the coating property of the coating material can be made particularly excellent.
In formula (1), m is preferably an integer of 5 to 17, but more preferably an integer of 4 to 12. Thereby, the effects as described above are more remarkably exhibited.
In formula (1), l is preferably an integer of 1 to 12, but more preferably an integer of 1 to 10. Thereby, the effects as described above are more remarkably exhibited.

In addition, the fluorine-based phosphoric acid compound is CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (P) (OH) ₂ and / or CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (P) (OH). ) (OCH ₂ CH ₃ ). Thereby, the glossiness of the metal powder can be made particularly excellent. Further, the durability of the metal powder can be made particularly excellent. Moreover, when a metal powder is applied to a coating material, the viscosity of the coating material can be made lower, and the coating property of the coating material can be made particularly excellent.

Further, fluorine-based phosphate compound is preferably one having a perfluoroalkyl structure _{(C n F 2n + 1)} . Thereby, the glossiness of the metal powder can be made particularly excellent. Further, the durability of the metal powder can be made particularly excellent. Moreover, when a metal powder is applied to a coating material, the viscosity of the coating material can be made lower, and the coating property of the coating material can be made particularly excellent.

The fluorine-based phosphoric acid compound as described above may be processed directly on the mother particle. However, after the mother particle is treated with an acid or a base, the mother particle is treated with fluorine-based phosphoric acid. Treatment with a compound is preferred. Thereby, the modification | change by the chemical bond by a fluorine-type phosphoric acid compound can be more reliably performed to the mother particle surface, and the effect by this invention as mentioned above can be exhibited more effectively. In addition, even when an oxide film is formed on the surface of the particles to be the mother particles before the surface treatment with the fluorine-based phosphate compound, the oxide film can be reliably removed, and the oxide film Since the surface treatment with the fluorine-based phosphoric acid compound can be performed in a state in which is removed, the glossiness of the manufactured metal powder can be made particularly excellent. Examples of the acid include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, boric acid, acetic acid, carbonic acid, formic acid, benzoic acid, chlorous acid, hypochlorous acid, sulfurous acid, hyposulfite, nitrous acid, hyponitrous acid, phosphorous acid. Protic acids such as acids and hypophosphorous acid can be used. Of these, hydrochloric acid, phosphoric acid, and acetic acid are preferable. On the other hand, as the base, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide or the like can be used. Of these, sodium hydroxide and potassium hydroxide are preferred.
The metal powder may have any shape such as a spherical shape, a spindle shape, or a needle shape, but preferably has a scaly shape. As a result, when the recorded matter is manufactured using metal powder (including the case where a coating containing metal powder is used in addition to the case where the metal powder is used alone), the glossiness and high-class feeling of the recorded matter are particularly high. It can be excellent.

In the present invention, the scale shape is an area when the area when observed from a predetermined angle (when viewed in plan) is observed from an angle orthogonal to the observation direction, such as a flat plate shape or a curved plate shape. In particular, the area S ₁ [μm ² ] when observed from the direction in which the projected area is maximum (when viewed in plan) and the direction orthogonal to the observation direction are observed. The ratio (S ₁ / S ₀ ) with respect to the area S ₀ [μm ² ] when observed from the direction in which the area of the area becomes maximum is preferably 2 or more, more preferably 5 or more, and still more preferably 8 or more. It is. As this value, for example, it is possible to observe an arbitrary 10 particles and adopt an average value of values calculated for these particles.

  The average particle size of the metal powder is preferably 500 nm or more and 3.0 μm or less, and more preferably 800 nm or more and 1.8 μm or less. Thereby, the glossiness of the metal powder can be made particularly excellent. Further, the durability of the metal powder can be made particularly excellent. Moreover, when a metal powder is applied to a paint, the coating property of the paint can be made particularly excellent.

The average thickness of the metal powder is preferably 10 nm or more and 70 nm or less. Thereby, when a coating film is formed using the coating material containing the metal powder, the smoothness of the coating film can be made particularly excellent, and the glossiness of the coating film can be made particularly excellent. it can. In addition, the metal powder can be produced with high productivity, and the unintentional deformation of the metal powder during the production of a paste or paint can be more suitably prevented. On the other hand, if the average thickness of the metal powder is less than the lower limit, unintentional deformation of the metal powder is likely to occur during the manufacture of pastes and paints. Further, if the average thickness of the metal powder exceeds the upper limit, in the production of the metal powder, the energy required for pulverization increases, and it becomes difficult to make the metal powder productivity sufficiently excellent. From the viewpoint of energy saving, it is not preferable. In addition, when the average thickness of the metal powder exceeds the upper limit, it is difficult to sufficiently improve the smoothness of the coating film when the coating film is formed using the coating material containing the metal powder. Accordingly, it becomes difficult to make the glossiness of the coating film sufficiently excellent.
Although the metal powder of the present invention as described above may be used for any purpose, for example, it can be used for various paints such as pastes for preparing paints and inks, powder paints and the like.

Hereinafter, these will be described in detail.
"paste"
The metal powder of the present invention described above can be used for preparing a paste.
The paste can be used, for example, for preparing a paint / ink.
The paste can be obtained, for example, by concentrating a slurry obtained by mixing the metal powder of the present invention as described above and an organic solvent.

As the organic solvent, for example, hydrocarbon solvents such as mineral spirit, solvent naphtha, toluene, and low viscosity solvents such as alcohols, ethers, ketones, esters and glycols can be used. Use of mineral spirits is preferred from the viewpoint of safety.
The paste may contain a grinding aid, a lubricant, or a modified product thereof. Examples of the grinding aid include higher fatty acids such as oleic acid and stearic acid, higher aliphatic amines such as stearylamine, higher aliphatic alcohols, and the like.
When the aluminum content is adjusted to 15% by weight or less, handling is easy.

  The above-described concentration treatment is performed using, for example, a device that continuously performs filtration while peeling the cake on the filter cloth (eg, drum filter, belt filter, disk filter), a centrifugal sedimentator, or the like. It can be carried out. A centrifugal settling machine is an apparatus that centrifugally settles aluminum pigment particles in a slurry by rotating a non-porous rotating bowl at a high speed. Examples of the centrifugal settling machine include a separation plate type centrifugal settling machine and a decanter type centrifugal settling machine.

"paint"
Moreover, the metal powder of this invention mentioned above can be used for preparation of a coating material.
Examples of the paint include powder paint, solvent-type paint (paint containing solvent), and water-based paint (paint containing water).
The paint according to the present invention may contain, for example, a binder in addition to the metal powder of the present invention as described above. Thereby, especially the intensity | strength of a coating film and the adhesiveness with respect to a to-be-adhered body can be made excellent.
As the binder, for example, an acrylic resin, a polyester resin, an alkyd resin, an epoxy resin, a fluororesin, a lacquer that cures by natural drying, a two-component polyurethane resin, a silicone resin, or the like can be used.

  When the paint according to the present invention contains a solvent (when it is a solvent-type paint), examples of the solvent include aliphatic hydrocarbon solvents such as hexane, heptane, cyclohexane, and octane, benzene, toluene, Aromatic hydrocarbon solvents such as xylene, mixed solvents of aliphatic hydrocarbons and aromatic hydrocarbons such as mineral spirits, halogenated hydrocarbon solvents such as chlorobenzene, trichlorobenzene, perchlorethylene, trichloroethylene, methanol Alcohols such as ethanol, n-propyl alcohol and n-butanol, ketones such as n-propanone and 2-butanone, esters such as ethyl acetate and propyl acetate, ethers such as tetrahydrofuran, diethyl ether and ethylpropyl ether Etc. can be used.

In addition to the metal powder of the present invention, the paint according to the present invention may contain other pigments. Thereby, various color tones that cannot be obtained by metal powder alone can be expressed.
Examples of the pigment include phthalocyanine, halogenated phthalocyanine, quinacridone, diketopyrrolopyrrole, isoindolinone, azomethine metal complex, indanthrone, perylene, perinone, anthraquinone, dioxazine, benzimidazolone, condensed azo, triphenylmethane Quinophthalone, anthrapyrimidine, titanium oxide, iron oxide, zinc white (zinc oxide), cobalt blue, ultramarine blue, yellow lead, carbon black, pearl mica and the like.

Further, the paint according to the present invention may contain other components. Examples of such components include dispersants, curing agents, ultraviolet absorbers, static eliminating agents, thickeners, coupling agents, plasticizers, antioxidants, polishes, synthetic preservatives, lubricants, fillers. , Dyes, sagging inhibitors, viscoelasticity improvers, and the like.
In addition, when the paint according to the present invention is a powder paint, in addition to the metal powder of the present invention described above, the paint includes powder composed of a thermoplastic resin (thermoplastic resin powder) and thermosetting. A powder composed of a resin (thermosetting resin powder) is included. Among these, from the viewpoint of hardness, durability, and appearance of a coating film formed using a coating material, it is preferable to include a thermosetting resin powder.

As a thermosetting resin powder, the powder of the composition (resin composition) containing thermosetting resins, such as an acrylic resin and a polyester resin, can be used, for example. In addition, the thermosetting resin powder used for the powder coating may contain a curing agent, a dispersing agent, and the like as necessary.
Examples of the curing agent include amines, polyamides, dicyandiamides, imidazoles, carboxylic acid dihydrazides, acid anhydrides, polysulfides, boron trifluoride, amino resins, triglycidyl isocyanate, primides, epoxy resins, and other dibasic acids. Examples include imidazolines, hydrazides, isocyanate compounds, and the like. Furthermore, these hardening | curing agents can also be used together with a hardening accelerator as needed.

Examples of the dispersant include surfactants such as phosphate esters, amines, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, and the like.
Furthermore, in addition to the above, the thermosetting resin powder includes various fillers such as calcium carbonate, barium sulfate, and talc, various fluidity modifiers such as silica, alumina, and aluminum hydroxide, and oxidation. Various colorants such as titanium, carbon black, iron oxide, copper phthalocyanine, azo pigments, condensed polycyclic pigments, various flow agents such as acrylic oligomers and silicones, various antifoaming agents such as benzoin, and waxes, Various additives such as coupling agents, antioxidants, magnetic powder and the like and various functional materials may be added.

  The average particle size of the thermosetting resin powder is not particularly limited, but is preferably 5 μm or more and 100 μm or less, and more preferably 15 μm or more and 60 μm or less. When the average particle size is less than the lower limit, uniform powdering becomes difficult when powder coating is performed, and the lump of resin adheres to the coating plate, and the smoothness of the coating film is sufficiently high. It can be difficult. Moreover, when an average particle diameter exceeds an upper limit, the smoothness of a coating film will fall and the aesthetic appearance (aesthetics) of a coating film may fall.

  In the powder coating, the content of the metal powder of the present invention is preferably 1 part by mass or more and 30 parts by mass or less, particularly 2 parts by mass or more and 20 parts by mass with respect to 100 parts by mass of the thermosetting resin powder. It is more preferable that the amount is not more than part by mass. If the content of the metal powder is less than the lower limit, the glossiness (metallic feeling and brightness feeling) tends to decrease, and the coating thickness tends to increase in order to conceal the substrate. . Moreover, when content of a metal powder exceeds the said upper limit, the smoothness of a coating film will fall and the aesthetic appearance (aesthetics) of a coating film may fall.

As a method of applying the powder coating according to the present invention, a method is adopted in which the coating surface is subjected to a known treatment such as a chemical conversion treatment after blasting the coating surface in advance, and then the powder coating is adhered and then heat-cured. Is preferred.
Although it does not restrict | limit especially as a to-be-coated material (base material), The thing which does not generate | occur | produce a deformation | transformation, a quality change, etc. by baking is preferable. For example, known simple metals such as iron, copper, aluminum and titanium, various alloys, and the like are preferable. As a specific form, for example, as a method of adhering the powder coating according to the present invention used for a vehicle body, office supplies, household goods, sports equipment, building materials, electrical products, etc. to the substrate surface, fluid immersion The electrostatic powder coating method can be applied, but the electrostatic powder coating method is more preferable because of its excellent coating efficiency. As a method for electrostatic powder coating, methods such as a corona discharge method and a friction charging method can be used.

Although heating temperature can be suitably set according to the kind of thermosetting resin powder to be used, it is preferable that it is 120 degreeC or more, and it is more preferable that it is 150-230 degreeC. The heating time is preferably 1 minute or longer, more preferably 5 minutes or longer and 30 minutes or shorter. The coating film formed by heating is preferably 20 μm or more and 100 μm or less.
As mentioned above, although this invention was demonstrated based on suitable embodiment, this invention is not limited to these.

Next, specific examples of the present invention will be described.
[1-1] Production of metal powder (pasty dispersion) (Example A1)
First, a film made of polyethylene terephthalate having a smooth surface (surface roughness Ra of 0.02 μm or less) was prepared.

Next, silicone oil was applied to the entire one surface of the film.
Next, a film made of Al was formed on the side coated with silicone oil by vapor deposition.
Next, a polyethylene terephthalate film (base material) on which an Al film was formed was placed in a liquid composed of diethylene glycol diethyl ether, and ultrasonic vibration was applied. As a result, a dispersion (dispersion) of scaly Al particles (particles to be mother particles) was obtained. The content of Al particles in the dispersion was 3.7% by mass.

Next, for the dispersion containing Al particles obtained as described above, 5 parts by mass of CF ₃ (CF ₂ ) ₅ as a fluorine-based phosphate compound with respect to 100 parts by weight of Al particles: Mixture of (CH ₂ ) ₂ O (P) (OH) ₂ and CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (P) (OH) (OCH ₂ CH ₃ ) (mass ratio 5:95) And the surface temperature was reacted while applying ultrasonic vibration at a liquid temperature of 55 ° C. for 3 hours. After completion of the reaction, the surface-treated Al particles (metal powder) are spun down in a centrifuge (6000 rpm × 30 minutes), the supernatant is discarded, and then diethylene glycol diethyl ether is added. Furthermore, by applying ultrasonic vibration, the metal powder was redispersed to obtain a dispersion liquid (redispersion liquid) having a metal powder content of 3.7% by mass. This re-dispersed liquid was concentrated with an evaporator to obtain a paste-like dispersion liquid (dispersion medium: diethylene glycol diethyl ether) having a metal powder content of 10% by mass. The metal powder thus obtained had an average particle size of 0.8 μm and an average thickness of 20 nm.

(Example A2 to Example A11)
A metal powder was produced in the same manner as in Example A1, except that the composition of the mother particles and the type of compound (fluorine phosphate compound) used for the surface treatment were as shown in Table 1.

(Comparative Example A1)
A metal powder was produced in the same manner as in Example A1, except that the surface treatment step was omitted and the Al particles were used as they were as the metal powder.
(Comparative Example A2)
A spherical Al powder was produced using the atomizing method. The Al powder was directly used as a metal powder without any surface treatment.

(Comparative Example A3)
First, in the same manner as in Example 1, a dispersion in which diethylene glycol diethyl ether is used as a dispersion medium and scaly Al particles (particles to be mother particles; those that have not been surface-treated) are used as a dispersoid. (Dispersion) was obtained.
Next, in a centrifuge (6000 rpm × 30 minutes), particles made of Al (particles to be mother particles) are spun down, the supernatant is discarded, and then a surface treatment that is not a fluorinated phosphate compound 10% by mass aqueous solution of Palcoat 3796 (manufactured by Nihon Parkerizing Co., Ltd., mainly composed of zircon hydrofluoric acid), and further kept at 80 ° C. for 10 minutes while applying ultrasonic vibration, Processed.

Thereafter, in a centrifuge (6000 rpm × 30 minutes), the surface-treated Al particles (metal powder) are spun down, the supernatant portion is discarded, and then pure water is added. The process of redispersing the metal powder by applying ultrasonic vibration was repeated twice.
Thereafter, the metal powder is centrifuged and settled in a centrifuge (6000 rpm × 30 minutes), and the supernatant is discarded. Next, diethylene glycol diethyl ether is added, and further ultrasonic vibration is applied to the metal powder. Redispersion was performed to obtain a dispersion (redispersion) having a metal powder content of 3.7% by mass. This re-dispersed liquid was concentrated with an evaporator to obtain a paste-like dispersion liquid (dispersion medium: diethylene glycol diethyl ether) having a metal powder content of 10% by mass.

Table 1 shows the composition of the metal powder for each of the above Examples and Comparative Examples. In the table, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (P) (OH) ₂ and CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (P) (OH) (OCH ₂ CH ₃ ) And a mixture (mass ratio 5:95) is “S1”, CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ O—PO (OH) ₂ is “S2”, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (P) (OH) ₂ for “S3”, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (P) (OH) (OCH ₂ CH ₃ ) for “S4”, CF ₃ (CF ₂ ) ₁ (CH ₂ ) ₃ P (O) (OCH ₂ CH ₃ ) is “S5”, and CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O—PO (OH) (OC ₂ H ₅ ) is “S6”. _{", CF 3 (CF 2) 14} (CH 2) 4 P (O) (OH) (OCH 2 CH 3) the" S7 ", Jirukonfu' Kamizu The basic acid is indicated by “S′1”. Moreover, about Example A9 in the table | surface, the composition of the constituent material of a mother particle showed the content rate of each element by weight ratio. In addition, the observation is performed for each arbitrary 10 metal particles contained in each metal powder, and the area S ₁ [μm ² ] when observed from the direction in which the projected area is maximized (when viewed in plan), The ratio (S ₁ / S ₀ ) to the area S ₀ [μm ² ] when observed from the direction in which the area when observed is the maximum among the directions orthogonal to the observation direction was determined. It was shown together.

[1-2] Appearance evaluation The paste-like dispersion (metal powder content: 10% by mass) containing the metal powder produced in each of the above Examples and Comparative Examples was applied to the surface of a glass plate (10 cm square) ( (Coating amount: 30 g / cm ² ) to form a coating film. The coating film was visually observed and evaluated according to the following seven-stage criteria.

A: It has high brightness and has an extremely excellent appearance.
B: It has high luminance and has a very excellent appearance.
C: High brightness and excellent appearance.
D: High brightness and good appearance.
E: Inferior in luminance and slightly poor in appearance.
F: Inferior in luminance and poor appearance.
G: Inferior in brightness and gloss, and very poor in appearance.

[1-3] Durability Evaluation Using the paste-like dispersion liquid (metal powder content: 10% by mass) containing the metal powder produced in each of the above Examples and Comparative Examples, a salt water corrosion experiment was performed as follows. The corrosion resistance was evaluated.
First, a paste-like dispersion containing metal powder (metal powder content: 10% by mass): 10 g of 10% by mass of saline is added to 100 g, and the mixture is stirred and allowed to stand at 50 ° C. for 24 hours. did.

Thereafter, the treatment was performed as follows for the purpose of washing (removing salt). That is, solid-liquid separation was performed by centrifugation, and 110 g of pure water was added to the separated solid content, and then a series of treatments in which ultrasonic vibration was further applied and redispersed were repeated twice.
Thereafter, solid-liquid separation is performed by centrifugal separation, and the separated solid is redispersed in diethylene glycol to obtain a paste-like dispersion having a metal powder content of 10% by mass. A coating film was formed by applying a spatula (coating amount: 30 g / cm ² ) to the surface of 10 cm square. The coating film was visually observed and evaluated according to the following two-stage criteria.
A: No change in appearance is observed.
E: Discoloration (whitening) due to corrosion (oxidation) is observed.
These results are shown in Table 2.

  As is apparent from Table 2, the metal powder of the present invention is excellent in gloss and has a high-grade appearance, and also has excellent durability and excellent gloss and aesthetic appearance over a long period of time. It was something that could be held. On the other hand, in the comparative example, a satisfactory result was not obtained.

[2-1] Production of paint (Example B1)
Paste dispersion containing metal powder prepared in Example A1 in [1-1] above: 3.7 parts by weight, Acrydic A160 (acrylic resin, manufactured by DIC): 35 parts by weight, ethyl acetate: A paint (powder paint) was produced by mixing 18 parts by weight, cyclohexane: 18 parts by weight, butyl cellosolve: 11 parts by weight, methyl cellosolve: 5 parts by weight, and isopropyl alcohol: 9.3 parts by weight.

(Example B2 to Example B11)
A paint (powder paint) was produced in the same manner as in Example B1, except that the metal powder used in Example A2 to Example A11 was used instead of the one produced in Example A1. .
(Comparative Example B1 to Comparative Example B3)
A coating material (powder coating material) was manufactured in the same manner as in Example B1, except that the metal powder used in Comparative Example A1 to Comparative Example A3 was used instead of the one manufactured in Example A1. .

[2-2] Sedimentability evaluation The degree of sedimentation of the metal powder when the 80 cc coating material produced in each of the above Examples and Comparative Examples was placed in a 110 cc glass bottle and allowed to stand for 30 days at room temperature (20 ° C.) Evaluation was performed according to the criteria of
A: Sedimentation does not occur and solid-liquid separation hardly occurs.
B: Sedimentation has occurred to some extent, but when stirred with a brush, it returns to its original state and there is no problem in use.
C: Sedimentation has occurred and it is difficult to use although it returns to its original state by stirring with a brush.
D: Sedimentation has occurred, stirring with a brush does not return to the original state, and is in an unusable state. If ultrasonic dispersion is performed, the original state is restored.
E: It is the state solidified by sedimentation solidification or some kind of reaction.
F: The color of the paint has changed.

[2-3] Evaluation of coating properties The paints produced in the above Examples and Comparative Examples were applied to the surface of a plate made of SUS314 as a material to be coated (base material) by brush painting. The coatability at this time was evaluated according to the following criteria.
A: Coating property is extremely excellent.
B: Coating property is excellent.
C: Coating property is good.
D: The coatability is slightly poor.
E: Coating property is poor.

[2-4] Manufacture of recorded material Using the coating materials manufactured in the above Examples and Comparative Examples, a plate material made of polyethylene terephthalate as a recording medium (Epanepet, in a temperature: 25 ° C., humidity: 55% RH environment) Air spray coating was performed on a spray pressure of 5 kg / cm ^{2 on} a ZAPP product (thickness: 3 mm). The coating amount was adjusted so that the thickness of the finally obtained coating film was 20 μm.
After standing for 24 hours in an environment of temperature: 25 ° C. and humidity: 55% RH, a heat treatment was performed at 50 ° C. for 30 minutes to obtain a recorded matter in which a dried coating film was provided on the recording medium.

[2-5] Appearance Evaluation The recorded matter according to each of the above Examples and Comparative Examples manufactured in [2-4] above was visually observed and evaluated according to the following seven-stage criteria.
A: It has a glossy feeling rich in luxury and has an extremely excellent appearance.
B: It has a glossy feeling full of luxury and has a very excellent appearance.
C: It has a glossiness with a high-class feeling and has an excellent appearance.
D: Glossy with a high-class feeling and a good appearance.
E: Inferior gloss and appearance is slightly poor.
F: Inferior glossiness and poor appearance.
G: Inferior glossiness and extremely poor appearance.

[2-6] Glossiness About the pattern formation part of the recorded matter according to each of the examples and comparative examples manufactured in the above [2-4], a glossiness meter (MINOLTA MULTI GLOSS 268) was used, and the turning angle was 60 °. The glossiness was measured and evaluated according to the following criteria.
A: Glossiness is 450 or more.
B: Glossiness is 300 or more and less than 450.
C: Glossiness is 200 or more and less than 300.
D: Glossiness is less than 200.

[2-7] Durability evaluation [2-7-1] Evaluation 1
The recorded matter according to each of the above Examples and Comparative Examples produced in the above [2-4] was allowed to stand for 160 hours in an environment of temperature: 80 ° C. and humidity: 80% RH.
Thereafter, the same evaluation items as in the above [2-6] were evaluated according to the same criteria as described above.

[2-7-2] Evaluation 2
The recorded matter before and after the durability evaluation in [2-7-1] was measured using a spectrophotometer (MCPD3000, manufactured by Otsuka Electronics Co., Ltd.). From the results, the color difference before and after the durability evaluation in [2-7-1] (color difference ΔE in the Lab display system) was obtained and evaluated according to the following four criteria.
A: ΔE is less than 3.
B: ΔE is 3 or more and less than 6.
C: ΔE is 6 or more and less than 12.
D: ΔE is 12 or more.

[2-8] Evaluation of Storage Stability of Paint The paint produced in each of the above Examples and Comparative Examples was allowed to stand for 10 days in an environment at a temperature of 50 ° C.
Thereafter, a recorded matter was produced using the coating material under the same conditions as in [2-4] above.
The recorded items thus obtained were evaluated on the same evaluation items as in the above [2-5] and [2-6] based on the same criteria as described above.
These results are shown in Table 3.

  As is apparent from Table 3, the coating material according to the present invention is excellent in glossiness, has a high-grade appearance, is excellent in durability, and can retain excellent glossiness and aesthetic appearance over a long period of time. It can be used suitably for manufacture of this. In addition, the paint according to the present invention has a relatively low viscosity and excellent coating properties. In addition, the paint according to the present invention was excellent in storage stability. On the other hand, in the comparative example, a satisfactory result was not obtained.

Claims (8)

A metal particle whose surface is composed of a metal material, a metal powder whose surface is treated with a fluorine-based phosphate compound,
Look containing a thermosetting resin powder,
The fluorine phosphoric acid compound is one having a chemical structure represented by the following formula (1), _{or, CF 3 (CF 2) 5} (CH 2) 2 O (P) (OH) (OCH 2 CH 3) The paint characterized by being.
POR _n (OH) _3-n (1)
(In the formula (1), _{R, CF 3 (CF 2) m} -, CF 3 (CF 2) m (CH 2) l -, CF 3 (CF 2) m (CH 2 O) l -, CF 3 (CF ₂ ) _m (CH ₂ CH ₂ O) ₁ —, CF ₃ (CF ₂ ) _m O—, or CF ₃ (CF ₂ ) _m (CH ₂ ) ₁ O— , and n is 1 or more and 3 or less. M is an integer of 4 or more and 5 or less , and l is an integer of 1 or more and 12 or less.)   The coating material according to claim 1, wherein the mother particle has a surface mainly composed of Al.   The paint according to claim 1 or 2, wherein the metal powder has a scaly shape. The paint according to any one of claims 1 to 3 , wherein the fluorine-based phosphoric acid compound has a perfluoroalkyl structure. The paint according to any one of claims 1 to 4 , wherein an average particle size of the metal powder is 500 nm or more and 3.0 µm or less. The paint according to any one of claims 1 to 5 , wherein an average thickness of the metal powder is 10 nm or more and 20 nm or less. The paint according to any one of claims 1 to 6 , wherein the average particle diameter of the thermosetting resin powder is 5 µm or more and 100 µm or less. The coating material according to any one of claims 1 to 7 , wherein a content of the metal powder with respect to 100 parts by mass of the thermosetting resin powder is 1 part by mass or more and 30 parts by mass or less.