JP2002363771A - Black bright material and production method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black bright material which has a satisfactory black coating color, and also has high brightness. SOLUTION: In the black bright material 20, a black nickel layer 12 has been formed on at least one side of a base material 10. A reducing agent and the base material 10 are charged to a nickel plating bath, and nickel plating is applied to the surface of the base material 10. Next, the surface of the nickel plated layer is subjected to etching with a chlorine based chemical, so that the nickel plated layer is blackened. Thus, the black nickel layer 12 is formed on the base material 10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a black glittering material and a method for producing the same, and more particularly to a black glittering material using an electroless nickel plating method or an electroless nickel alloy plating method and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, scaly (flake-like) aluminum powder, mica flake particles (mica pigment) or graphite flake particles coated with metal oxides such as titanium dioxide or iron oxide have been used as metallic pigments as brilliant materials. , Α-
Iron oxide particles mainly composed of iron oxide crystal particles are known. These metallic pigments receive incident light from the outside on the surface of the pigment, and shine brilliantly by the reflected light, and have brilliancy such as a metallic feeling and a pearly feeling. If the paint contains such a metallic pigment, the painted surface coated with the paint, and if the ink contains the paint, the drawn line or printed surface used is a resin composition further containing the pigment. If present, the surface of the resin molded product presents a variety of beautiful and excellent appearances in combination with various colors. Therefore, the above-mentioned metallic pigments are widely used for automobiles, motorcycles, OA equipment, mobile phones, household appliances, various printed materials, writing instruments, and the like according to their respective applications.

[0003] On the other hand, the black coating color is mainly colored by carbon black. In order to give this conventional black paint color a brilliant feeling, conventionally, a brilliant pigment such as the above-described aluminum pigment has been mixed and used.

[0004] However, the above-mentioned brilliant pigment aluminum powder (aluminum pigment) has its own color such as silver and mica pigment has a milky white color, and these colors themselves are pale. Therefore, when the above-mentioned aluminum pigment or the like is mixed with the carbon black pigment, the blackness decreases and the black color approaches a gray color, although the glitter is obtained. Therefore, when giving priority to glitter, the amount of the glitter pigment added increases, and it has been difficult to obtain a desired black coating color.

[0005] Therefore, recently, a black or dark pigment having glitter has been proposed. For example, JP-A-7-31
As shown in FIG. 7, a carbon black layer 44 is formed on a flaky substrate 42 made of mica or a metal oxide, as shown in FIG. Therefore, a coating layer 46 of a metal oxide and / or metal oxyhydrate such as titanium dioxide or titanium oxyhydrate is further formed on the carbon black layer 44, and the coating layer 46 is formed of an inert gas. A pigment 40 has been proposed in which the coating layer 46 is made darker by bringing it into contact with a reducing component such as an alkaline earth metal in an atmosphere and causing a reduction reaction at 700 to 1000 ° C.

Japanese Patent Application Laid-Open No. H10-330657 discloses a method of forming a metallic paint and a plurality thereof, as shown in FIG. A black-coated metallic pigment 50 in which a mixture of a normal coating resin and carbon black is uniformly coated to form a mixed layer 54 of carbon black and resin has been proposed.

[0007]

However, in the pigment 40 shown in FIG. 7, since the carbon black layer 44 has no glitter, a coating layer 46 made of a metal oxide or the like as the outermost layer is essential. Therefore, there is a limit in reducing the thickness of the pigment 40. For this reason, for example, when painting with a paint containing the pigment 40 in an automobile, a certain thickness is required so that the pigment does not protrude from the painted surface. . Therefore, when using the pigment 40,
Painting specifications could be limited. Further, in order to make the dark color deeper, it is necessary to cause the coating layer 46 to undergo a reduction reaction at a high temperature, and in such a case, the manufacturing process becomes complicated and the material of the base material 42 must be There was a problem of being limited.

The metallic pigment 50 shown in FIG.
Mixed layer containing carbon black diluted with resin 5
4, the base material 42 is covered. Therefore, the more the metallic pigment 50 is left, the more the luster is left.
Since the underlying color of the silver color of the aluminum lake is strong, the black color decreases as in the conventional case, and the color approaches a gray color. For this reason, with the metallic pigment 50, a brilliant feeling can be obtained, but it was difficult to obtain a desired black coating color.

[0009] On the other hand, glass flakes coated with nickel, which are more excellent in brilliancy than the above-mentioned metallic pigments, are described in Japanese Patent Application Laid-Open No. 5-1248, "Metallic paint and coating method". ing. This nickel-coated glass flake has a longitudinal dimension of 5
～40Myuemu, its thickness is preferably in the range of the longitudinal direction of 1 / 5-1 / 20, a main component SiO _2, ZnO and B ₂ O
₃ and may contain a small amount of other components, the material for coating the glass surface is preferably pure plating, the coating thickness is 0.01μm ~ 0.3μm,
Particularly, it is described that 0.05 μm to 0.2 μm is preferable.

However, the nickel-coated glass flake of the metallic pigment has a glossy white gray to glossy gray color, which is insufficient for applications requiring a jet-black color appearance. As a pigment having a black tone while exhibiting the above, there was a feeling of one step in response to recent demands.

Accordingly, the present invention has been made in view of the above problems, and an object of the present invention is to improve the metallic feeling and pearly feeling of black, especially jet-black paint color, reduce the thickness of the pigment, and further manufacture the pigment. An object of the present invention is to provide a black glittering material which simplifies the process and a method for manufacturing the same.

[0012]

Means for Solving the Problems To achieve the above object, the black glittering material of the present invention and the method for producing the same have the following features.

(1) A black glittering material having a black nickel layer formed on at least one surface of a substrate.

The black nickel layer has a higher rigidity than a conventional carbon black layer for a black coating color, and thus has durability even with stirring when the black glittering material is dispersed in a paint. Therefore, the black nickel layer can be made thinner than a conventional carbon black layer.
Further, since the black nickel itself has glitter, it is not necessary to form a glitter layer on the carbon black layer as in the related art. As a result, the thickness of the black glittering material can be reduced. Thereby, the coating film thickness of the paint containing the black glittering material can be made thinner than before, and the coating specification can be set in a wide range,
Versatile.

(2) The black glittering material according to the above (1), wherein at least one surface of the outermost layer is a metal glittering layer.

By having a metal oxide layer on the outermost layer, a black glittering material having a strong interference color can be obtained.

(3) A nickel plating layer forming step of forming a nickel plating layer on at least one surface of the substrate by electroless nickel plating, and a blackening step of etching the surface of the nickel plating layer with a chlorine-based chemical to blacken the surface. And a method for producing a black glittering material.

In electroless nickel plating, the thickness of the nickel plating layer can be made uniform and the film can be made denser than in electrolytic nickel plating. By blackening the surface of the nickel plating layer, which is a dense film, it is possible to obtain a black glittering material exhibiting a desired black coating color even if the film thickness is small. As a result, the coating specification of the paint using the black glittering material is wide and is versatile.

(4) The method for producing a black glittering material according to the above (3), further comprising a metal oxide layer forming step of forming a metal oxide layer as at least one surface of an outermost layer. Is the way.

By having a metal oxide layer as the outermost layer, a black glittering material having a strong interference color can be obtained.

(5) A black glittering material having a black appearance in which at least one surface of a substrate is coated with a nickel alloy, wherein the black glittering material has a visible light reflectance of 5% to 25%.

Visible light (for example, 550 nm) of a black glittering material
If the reflectance is within the above range, a jet-black black glittering material having a desired glitter can be obtained without excessive metallic luster.

(6) The black glittering material according to (5), wherein the nickel alloy has a coating thickness of 10 nm to 20 nm.
nm.

With the above-mentioned nickel alloy coating thickness,
A jet-black black glittering material having a desired glittering feeling can be obtained without excessive metallic luster.

(7) In the black glittering material according to the above (5) or (6), the nickel alloy is a nickel-phosphorus alloy.

The nickel-phosphorus alloy plating film becomes more glossy and more blackish as the phosphorus content increases, and can provide a jet-black black glittering material.

(8) Any one of the above (5) to (7)
In the black glittering material described in (1), the base material is a flaky powder.

A scaly (flake-like) substrate has a flat surface that reflects light as compared with a massive substrate, and thus it is easier to develop a brilliant feeling.

(9) In the black glittering material according to (8), the average thickness of the substrate is 0.01 μm to 7 μm.
The average particle size of the substrate is from 5 μm to 600 μm
It is.

When the average thickness is within the above range, the protrusion of the glittering material from the surface of the coating film can be suppressed, and the surface of the coating film can be smoothed. Further, when the average particle diameter is within the above range, it is possible to suppress the protrusion from the coating film surface while having a desired glitter, and to smooth the coating film surface.

(10) In the black glittering material according to any one of (5) to (9), an outermost layer is further provided on the nickel alloy film.

For example, when the outermost layer is formed of a metal oxide layer, an interference color can be developed in a black glittering material. When the outermost layer is made of another composition, the outermost layer functions as a surface treatment layer for improving characteristics such as durability of the black glittering material.

(11) A pretreatment step of sensitizing the surface of the base material and further depositing and activating palladium on the base material surface, and immersing the pretreated base material in an electroless nickel alloy plating solution to And an electroless plating step of depositing a nickel alloy on the surface of the material.

In electroless nickel alloy plating, the thickness of the nickel alloy plating layer can be made uniform and the film can be made denser than in electrolytic nickel alloy plating. Thereby, even if the plating film thickness is small, it is possible to obtain a black glittering material while having glittering properties.

(12) The method for producing a black glittering material according to (11), further comprising an outermost layer forming step of forming an outermost layer on the nickel alloy plating layer. It is.

For example, when the outermost layer is formed of a metal oxide layer, an interference color can be developed in a black glittering material. When the outermost layer is made of another composition, the outermost layer can function as a surface treatment layer for improving properties such as durability of the black glittering material.

[0037]

Preferred embodiments of the present invention will be described below.

Embodiment 1 In the method for producing a black glittering material according to the present embodiment, a black nickel layer is formed on at least one surface of a substrate. FIG. 1 shows an example of a manufacturing method according to the present embodiment, in which a black nickel layer 12 is formed on the entire surface of a base material 10.

[Substrate] The substrate 10 may be, for example, silica powder, mica, mica, titanium oxide pieces, aluminum pieces, water glass (ie, sodium silicate), a glass substrate,
Although it is made of other transparent resin substrates, etc., a highly transparent flaky glass substrate is most preferable in order to express the jet-black feeling of the black glittering material. In the case of a substrate such as mica, since the substrate has a multilayer structure, there is a case where light scattering occurs and a turbidity may be exhibited. Therefore, it is preferable to select a substrate according to a black color tone. Further, the chemical composition of the above-mentioned glass substrate may be any chemical composition as long as it is transparent, but usually comprises silicon dioxide as a main component, and is composed of metal oxides such as aluminum oxide, calcium oxide and sodium oxide. . Examples of the glass type of the glass substrate include, for example, E glass and C glass, which are currently frequently used, alkali-resistant glass, high-strength glass, quartz glass, and the like.
A glass and the like.

[Shape of Substrate] The shape of the base material may be any of, for example, crushed particles produced by pulverizing a lump or scaly particles called frates, and is particularly limited. Not something. In addition, it is preferable to select the shape and size according to the use used as a metallic pigment. The average thickness of the substrate 10 is 0.0
1 μm to 7 μm, more preferably 0.01 μm to 2 μm
It is. When the average thickness of the base material 10 is less than 0.01 μm, the shape of the glittering material cannot be maintained due to the circulation because the strength of the glittering material is low. On the other hand, if the average thickness of the base material 10 exceeds 7 μm, the thickness of the glittering material itself becomes too thick, for example, the glittering material existing non-parallel to the painted surface of the car body projects from the painted surface, and the desired finish is obtained. The appearance cannot be secured. The average particle size of the substrate 10 is 5 μm to 600 μm, more preferably 10 μm to
It is about 100 μm, more preferably about 10 to 20 μm. When the average particle size of the base material 10 is less than 5 μm, the glitter becomes weak, and when the average particle size of the base material 10 exceeds 600 μm, the smoothness of the coating film is impaired as described above.

The black nickel layer 12 is formed as shown in FIG. First, a reducing agent and a base material 1 were placed in a nickel plating bath.
0 is entered (S100). By putting the reducing agent into the bath, nickel precipitates in the bath, and the substrate 10 is plated with nickel. At this time, the bath temperature is preferably from room temperature (25 ° C.) to about 90 ° C. The higher the temperature, the faster the deposition rate, but at most about 20 μm / hour. Next, the surface of the nickel plating layer is blackened by etching with a chlorine-based chemical (S102). Thereby, as shown in FIG. 3, a black glittering material 20 having the black nickel layer 12 formed on the surface of the base material 10 is obtained.

The above-described electroless nickel plating method has a uniform film thickness and a denser film than the electrolytic nickel plating method. Further, since the nickel plating can be performed at a low temperature of from about room temperature to about 90 ° C., the material of the base material 10 is not limited as in the related art.

As the reducing agent, any agent can be used as long as it is used for the reduction reaction. Further, as the chlorine-based agent, any of a gas, a liquid, and a solid containing a chlorine atom can be used.

The thickness of the black nickel layer 12 may be such that the substrate 10 exhibits a desired black color.
In order to obtain an ultra-thin black glittering material 20, 0.01 to 0.
Preferably it is 5 μm.

Embodiment 2 In the method for manufacturing a black glittering material according to the present embodiment, a black nickel layer is formed on at least one surface of a substrate, and at least one surface of an outermost layer is formed of a metal oxide layer. The same components as those in the first embodiment are denoted by the same reference numerals, and description thereof will be omitted.

The black glittering material 20 of the first embodiment is
As shown in FIG. 1, a black nickel layer 12
Is formed, and the black glittering material 30 of the present embodiment is formed.
As shown in FIGS. 4 and 5, a metal oxide layer 14 is further formed on at least one surface of the above-described black nickel layer 12, for example, on the entire surface of the black nickel layer 12.

With the metal oxide layer 14, the black glittering material 30 exhibits an interference color. The metal oxide layer 14 preferably has a higher refractive index than the substrate 10 and the black nickel layer 12, for example, 1.5 or more. As such a metal oxide, for example, titanium oxide (Ti
O ₂ ), aluminum oxide (Al ₂ O ₃ ) or the like can be used alone or in combination, but titanium oxide is preferred. Further, the thickness of the metal oxide layer 14 is preferably as thin as possible in order to give a brilliant feeling, for example, 0.01 to 0.05 μm. If an interference color is desired, it is preferable that the film thickness is set according to the desired interference color. For example, when titanium oxide is used as the metal oxide, 0.04 to 0.06 μm is required to produce a silver color as an interference color, and 0.1 to 0.06 μm to produce a yellow color.
06-0.08 μm, 0.08 when red color is desired
0.1 to 0.1 μm, and 0.1 to 0.1 when blue color is desired.
3 μm, 0.13 to 0.16 μm when green color is desired
The metal oxide layer 14 having a thickness of m may be formed.

As the method of forming the metal oxide layer 14, any of the existing coating methods may be used as long as it can be formed to the above-mentioned thickness, but methods such as sputtering, wet coating, and chemical vapor deposition are used. Is preferred.

Embodiment 3 Next, a black glittering material according to another embodiment will be described below. Note that the same components as in Embodiment 1 (for example, the base material and the shape of the base material)
Are denoted by the same reference numerals, and the description thereof is omitted.

[Nickel Alloy Composition] The nickel alloy coating the base material is preferably, for example, a nickel-phosphorus alloy. In the case of a nickel-phosphorus alloy, the constituent weight ratio: P / Ni is 0.1 to 0.2. High corrosion resistant nickel alloys are more preferred. In general, a nickel-phosphorus alloy plating film has a higher brilliancy and a higher blackness as the phosphorus content increases. Therefore, in order to obtain a jet-black appearance, the weight ratio of phosphorus to nickel is preferably 0.1 or more. On the other hand, when the weight ratio of phosphorus to nickel is larger than 0.2, the plating film becomes hard and easily peels off from the substrate.
The nickel alloy film may be formed on at least one surface of the substrate, but is preferably formed on the entire surface of the substrate.

[Thickness of Nickel Alloy and Its Reflectivity] Reflection with respect to visible light is black, so it does not change much at any wavelength. However, when the reflectance is 550 nm as a general value, the reflectance is Desirably, it is 5 to 25%. When the reflectance is less than 5%, the transmittance increases, and a black appearance is not exhibited. On the other hand, if the reflectivity exceeds 25%, black color is exhibited, but metallic luster is increased and jet-blackness is reduced. It is preferable that the thickness of a nickel-phosphorus alloy that achieves this reflectance, for example, be 10 nm to 20 nm.
When the film thickness is as thin as less than 10 nm, the light transmittance is increased and no black appearance is exhibited. On the other hand, when the film thickness is more than 20 nm, the color is black, but the metallic luster is increased and the jet-black feeling is reduced.

Embodiment 4 FIG. Next, a method for manufacturing the black glittering material of the third embodiment will be described.

[Plating Method] In the present embodiment, an electroless plating method can be used as a method for coating the base material with the nickel alloy. With reference to FIG. 6, a process of forming a nickel-phosphorus alloy plating layer on the glass powder using the glass powder as the base material will be described below.

<Pretreatment Step> The surface of the glass powder as the base material is immersed in an aqueous solution of stannous chloride to sensitize the surface (S200). Next, the glass powder subjected to the sensitization treatment is collected, and excess stannous chloride remaining on the surface is removed by washing with water. Next, an activation treatment for depositing palladium on the surface of the glass powder is performed by immersing the glass powder subjected to the sensitization treatment in an aqueous solution of palladium dichloride (S202). The treatment of the surface with stannous chloride described above is for the purpose of susceptibility to easily cause the precipitation of palladium in the subsequent treatment.

<Electroless Plating Step> The pretreated glass powder is immersed in an electroless nickel-phosphorous plating solution to deposit a nickel-phosphorus alloy on the surface of the glass powder (S204). Deposition thickness is 0.01 μm to 0.04
By setting it to μm, a black metallic appearance coating can be formed. As a nickel ion supply source of the electroless plating solution, for example, nickel sulfate, nickel chloride,
Nickel salts such as nickel acetate are exemplified. Examples of the chelating agent for nickel ions in the electroless plating solution include carboxylic acids such as monocarboxylic acids and polyvalent carboxylic acids, and one or more selected from these can be used. It is desirable to select the chelating agent that is most stable in the type of coexisting reducing agent and the pH of the plating solution. Specific examples of chelating agents include acids such as malic acid, citric acid, tartaric acid, gluconic acid, acetic acid, propionic acid, and alkali metal salts and ammonium salts thereof. Examples of the reducing agent used for the plating solution include hypophosphites such as sodium hypophosphite. Further, a known metal stabilizer can be added to the plating solution as needed. Examples of the metal stabilizer include a lead ion, a zinc ion, a cadmium ion, a bismuth ion, an antimony ion and the like, and preferably a lead ion and a zinc ion. Further, the metal stabilizer can be added as a salt such as a nitrate and an ammonium salt.

Further, an outermost layer may be formed on at least one surface of the above-mentioned black nickel-phosphorus alloy layer, for example, on the entire surface of the black nickel-phosphorus alloy layer. For example, when the outermost layer is formed of a metal oxide layer, an interference color can be exhibited in a black glittering material. When the outermost layer is made of another composition, the outermost layer can function as a surface treatment layer for improving properties such as durability of the black glittering material.

As described above, the application of the black glittering material of the present embodiment is not limited to the above-mentioned paint for automobile bodies, but may be any application as long as it is used as a glittering material. Paints, inks and the like.

[0058]

Next, the present invention will be described in detail with reference to examples and comparative examples.

(A) Production example of black glittering material: Mica pieces and a reducing agent were placed in a nickel plating bath, and plating was performed at room temperature (25 ° C.). Then, when nickel plating of a desired thickness has been applied to the mica piece, the electroless nickel plating step is terminated, and thereafter, the surface of the nickel plating layer is etched using a chlorine-based chemical, and the surface is etched as desired. When the color became black, the blackening process was terminated. Next, a metal oxide layer was formed on the entire outermost layer of the glittering material by titanium oxide (refractive index: 2.6) by chemical vapor deposition with a thickness shown in Table 1 below to obtain a black glittering material.

In the comparative example, a glitter material having a titanium oxide metal oxide layer formed on mica pieces without forming a black nickel layer was used.

(B) Production and coating of paint containing black glittering material: 5% by weight of the black glittering material obtained by the above-mentioned production method and 5% by weight of the glittering material for comparative example, and 1% by weight of carbon black were added to the acrylic melamine paint. Was added and mixed to obtain base paints. Next, the base paint was applied at a thickness of about 15 μm on the intermediate-coated steel sheet without baking, and then an acrylic melamine-based clear paint was applied at a thickness of about 30 μm and baked at about 140 ° C. for 30 minutes. .

(C) Evaluation method and items: The coated steel sheet obtained in the above (b) was visually observed to have brilliancy,
The degree of design due to black paint color and interference color was determined. In addition, regarding the above items, “に は” indicates that the overall is good, “△” indicates that the overall is slightly good, and “×” indicates that the overall is poor, and the results are shown in Table 1. Show.

[0063]

[Table 1]

A specific example of another black glittering material having a nickel alloy layer formed thereon will be described below.

Example 4 Flaky glass powder (hereinafter referred to as “glass flake” (manufactured by Nippon Sheet Glass Co., Ltd.)), micro glass fine flake (RCFFX-1040 (9507) (registered trademark) C glass composition, average 1.2 kg (1.3 μm in thickness, average particle size of 38 μm) was added to 4 liters of ion-exchanged water, and stirred with a stirrer to form a slurry. After stirring for 5 minutes, the glass flakes were collected by vacuum filtration and washed with ion-exchanged water.
This glass flake is suspended in 4 liters of pure water to obtain a slurry liquid. Palladium (II) chloride is added to this slurry liquid.
Add 0.01 liter of 2% by weight aqueous solution at room temperature,
Stir for 5 minutes. The glass flakes are collected by vacuum filtration,
It was washed with pure water.

20 L of a plating solution having the following composition was heated to 70 ° C. while stirring. 1.2 kg of pretreated glass flakes were suspended in the plating solution and stirred for 20 minutes. The product was collected by filtration under reduced pressure, washed with pure water, and dried in vacuum at 150 ° C. Aperture 100μm
Of stainless steel wire mesh. The obtained pigment had a deep black color and a soft metallic luster.

[0067]

[Table 2]

The metallic pigment obtained by the above means was mixed with an acrylic resin (Nippon Paint Co., Ltd .; Acrylic Auto Clear Super (registered trademark)).
It was applied on a glass plate having a thickness of 1.1 mm using an applicator of a mill (228.6 μm) to form a coating film. This mixed liquid was obtained by sufficiently stirring and mixing 5 g of a color pigment with 45 g (weight of solid content) of an acrylic resin using a paint shaker. The glass plate coated with the metallic pigment was measured for reflectance using an integrating sphere with a U-3210 type self-recording spectrophotometer manufactured by Hitachi, Ltd., and the result was 550.
The reflectivity at nm was 18%. Further, the fracture surface of the metallic pigment obtained by breaking the resin in which the metallic pigment was embedded in the resin was observed with a scanning electron microscope, and the plating thickness of the pigment was measured to be 10 nm.

Further, 5% by weight of the metallic pigment obtained by the above method was added to the acrylic melamine paint and mixed to obtain a base paint. Next, the base paint is applied to a thickness of about 15 μm on a steel sheet which has been subjected to intermediate coating, and then is not baked.
m and baked at about 140 ° C. for 30 minutes.

When the resulting coated steel sheet was visually observed, it was a black coating having a deep black color and having a soft brilliant feeling.

(Example 5) In the same manner as in Example 4, except that the pretreated glass flakes were immersed in a plating solution having the composition shown in Table 2 and stirred for 25 minutes, plating was performed in the same manner as in Example 4. A coating was formed. The resulting metallic pigment had a deep black color and a soft metallic luster. Further, the metallic pigment obtained on a glass plate was applied in the same manner as in Example 4 to form a coating film, and the reflectance at 550 nm was measured.
Met. Further, when the fracture surface of the pigment obtained by breaking the metallic pigment embedded in a resin was observed by a scanning electron microscope, the plating thickness of the pigment was 20 nm.

To the acrylic melamine paint, 5% by weight of the metallic pigment obtained by the above method was added and mixed to obtain a base paint. Next, after coating the base paint at about 15 μm on the steel plate with the intermediate coating, it was not baked,
Next, an acrylic melamine-based clear paint was applied to a thickness of about 30 μm and baked at about 140 ° C. for 30 minutes.

When the obtained coated steel sheet was visually observed, it was found to be a black coating which had a deep black color and also had a soft glitter.

Comparative Example 3 The same procedure as in Example 4 was repeated except that the pretreated glass flakes were immersed in a plating solution having the composition shown in Table 2 and stirred for 30 minutes. A coating was formed. The obtained metallic pigment had a black metallic appearance but a strong metallic luster. Further, the metallic pigment obtained on the glass plate was applied by the same method as in Example 4 to form a coating film.
The measured reflectance at 50 nm was 32%. Further, when the metallic pigment was embedded in a resin and the resin was broken, the cross section of the pigment obtained was observed with a scanning electron microscope, and the plating thickness of the pigment was measured to be 22 nm.

To the acrylic melamine paint, 5% by weight of the metallic pigment obtained by the above method was added and mixed to obtain a base paint. Next, after coating the base paint at about 15 μm on the steel plate with the intermediate coating, it was not baked,
Next, an acrylic melamine-based clear paint was applied to a thickness of about 30 μm and baked at about 140 ° C. for 30 minutes.

When the resulting coated steel sheet was visually observed, the coated steel sheet was black, but had a strong metallic luster and was a black paint that appeared to glow white.

From the above, it has been found that by using the black glittering material of the present invention, it is possible to obtain a coated steel sheet having a high glitter, a good black paint color and, if necessary, an interference color with a very high designability. did.

[0078]

As described above, according to the present invention, it is possible to obtain a thinner black glittering material having a high glitter, a good black coating color. Furthermore, the number of stacked layers can be reduced as compared with the related art, the manufacturing process can be simplified, and the manufacturing cost can be reduced.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating a process of a method for manufacturing a black glittering material according to a first embodiment of the present invention.

FIG. 2 is a diagram illustrating a step of black nickel plating according to the embodiment of the present invention.

FIG. 3 is a cross-sectional view showing an example of the configuration of the black glittering material shown in Embodiment 1 of the present invention.

FIG. 4 is a diagram illustrating a process of a method for manufacturing a black glittering material according to a second embodiment of the present invention.

FIG. 5 is a cross-sectional view illustrating an example of a configuration of a black glittering material according to Embodiment 2 of the present invention.

FIG. 6 is a view illustrating a step of another method for manufacturing a black glittering material according to the fourth embodiment of the present invention.

FIG. 7 is a cross-sectional view showing a structure of a conventional dark pigment.

FIG. 8 is a cross-sectional view showing the structure of a conventional black-coated metallic pigment.

[Explanation of symbols]

Reference Signs List 10 base material, 12 black nickel layer, 14 metal oxide layer, 20, 30 black glittering material.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C23F 1/00 C23F 1/00 A (72) Inventor Shigeru Yanagase 4-28 Kitahama, Chuo-ku, Osaka City, Osaka Japan Inside Sheet Glass Co., Ltd. AA35 AA41 BA14 BA16 BA32 CA06 CA28 DA01 DB29 EA04 4K044 AA06 AA12 AA16 AB01 BA06 BA12 BB02 BB16 BC09 CA04 CA15 4K057 WA09 WB03 WE30

Claims (12)

[Claims] 1. A black glittering material wherein a black nickel layer is formed on at least one surface of a substrate. 2. The black glittering material according to claim 1, wherein at least one surface of the outermost layer is made of a metal oxide layer. 3. A nickel plating layer forming step of forming a nickel plating layer on at least one surface of the substrate by electroless nickel plating, and a blackening step of etching the nickel plating layer surface with a chlorine-based chemical to blacken the surface. A method for producing a black glittering material, comprising: 4. The method for producing a black glittering material according to claim 3, further comprising a metal oxide layer forming step of forming a metal oxide layer as at least one surface of an outermost layer. Material production method. 5. A black glittering material having a black appearance in which at least one surface of a substrate is coated with a nickel alloy, wherein the black glittering material has a visible light reflectance of 5% to 25%. Bright materials. 6. The black glittering material according to claim 5, wherein the coating thickness of the nickel alloy is 10 nm to 20 nm. 7. The black glittering material according to claim 5, wherein the nickel alloy is a nickel-phosphorus alloy. 8. The black glittering material according to claim 5, wherein the base material is a flaky powder. 9. The black glittering material according to claim 8, wherein the base material has an average thickness of 0.01 μm to 7 μm, and the base material has an average particle size of 5 μm to 600 μm. Black glittering material. 10. The black glittering material according to claim 5, wherein an outermost layer is further provided on the nickel alloy film. 11. A pretreatment step of sensitizing the surface of a base material, further precipitating and activating palladium on the surface of the base material, and immersing the pretreated base material in an electroless nickel alloy plating solution. An electroless plating step of depositing a nickel alloy on the surface, and a method for producing a black glittering material. 12. The method of manufacturing a black glittering material according to claim 11, further comprising an outermost layer forming step of further forming an outermost layer on the nickel alloy plating layer. Manufacturing method.