JPH07186322A - Weldable black metal sheet of excellent weather fastness - Google Patents

Abstract

PURPOSE:To provide a black metal sheet wherein excellent black external appearance is obtained with a weldable film thickness, and excellent weather fastness equivalent to that of a black coated steel sheet is provided. CONSTITUTION:A chromate cating of a specific deposited weight is provided as required on a surface of a metal sheet or a plated metal sheet. A black film of 0.3-5.0mum thickness composed of a composition wherein 10-200 pts.wt. of total of black dye and carbon black to 100 pts.wt. of thermosetting resin are blended on its upper layer in 100/1-1/1 of blending ratio (ratio by wt.) of the black dye to the carbon black, and as required, a specific lubricant or/and a specific rust proof additive are blended at a specific proportion, is provided. Since as a black-imparting agent, the black dye and the carbon black are mixedly added in a specific ratio, excellent black external appearance and weather fastness can be obtained in a thin film thickness in a weldable metal sheet.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a weldable black metal plate having excellent weather resistance, which is suitable for home electric appliances, office equipment, audio equipment, automobile parts, building material products and the like.

[0002]

2. Description of the Related Art In recent years, audio equipment, office equipment, and the like have tended to become high-grade, and for example, black metal plates such as black steel plates are widely used for parts such as audio products, copying machines, and word processors. Conventionally, as a black steel plate applied to these, the user applies black coating to the molded parts,
Use a steel sheet (black pre-coated steel sheet) that has been previously painted black by a steel manufacturer, or perform black chromate treatment with a treatment liquid containing silver ions on the surface of zinc plating (for example, JP-A-58-193376). , A blackened steel plate is used. However, the method (1) has a drawback that the cost of the coating process for the user is high, and the black precoated steel sheet (1) has a drawback that spot welding cannot be performed because the coating film thickness is as thick as about 20 μm. Since the steel sheet is expensive, it has a problem that the use part is limited. Further, the method (1) is not suitable for mass production in steel plate coil units because the black chromate treatment liquid contains silver ions and thus the cost of the treatment liquid is high, and the blackening treatment time is as long as 2 to 3 minutes. There is a problem.

Under such a background, the demand for a weldable black steel sheet that can be used without painting is very high.
In response to such a demand, a black-treated steel sheet in which the surface of a zinc-based plated steel sheet is subjected to a blackening treatment has been proposed. Heretofore, the following has been known as a black-treated steel sheet based on a zinc-based plated steel sheet. (A) A black steel plate in which a black resin film containing a black pigment such as carbon black is formed on the surface of a zinc-based plated steel plate to a thickness of several tens of μm. (B) A black steel sheet on which a black coating is formed on the surface of a zinc-based plated steel sheet by any one of dipping treatment, spraying treatment, anodic treatment and cathodic treatment, and a chromate coating and a resin coating are further formed as protective coatings (for example, , Japanese Sho 61-
38276, Japanese Patent Publication No. 62-30262, and Japanese Patent Laid-Open No. 62-62.
-30262, Japanese Patent Publication No. 5-36515). (C) A black steel plate formed by forming a chromate film on the surface of a zinc-based plated steel plate and further forming a black film made of a thermosetting resin and a specific black dye in a thickness of 3 μm or less (for example,
JP-A-4-301080).

[0004]

However, these conventional techniques have the following problems. First,
The black steel plate of (a) is a general coated steel plate, but spot welding is impossible because the usual coating film thickness is 10 μm or more. Further, when carbon black is used as the black-imparting agent, the blackness is insufficient at a weldable thin film thickness (film thickness of 5 μm or less).

Further, in the black steel sheet (b), the plating is eluted during the blackening treatment, so that when the steel sheet is continuously blackened, the metal ion concentration in the treatment liquid increases and In addition to problems such as deterioration of blackening ability and corrosion resistance of plating, temperature and concentration of blackening solution, spray pressure in spraying, flow rate and current in anodizing / cathodic processing. Due to non-uniformity such as density, there are many problems such as non-uniform appearance (unevenness), which lowers the commercial value, and the target base plating is limited to a specific alloy plating.

On the other hand, the black steel plate (c) solves the above problems of the steel plates (a) and (b) and is excellent in the weldable thin resin film (film thickness 5 μm or less) of black. This is the first time that it has been possible to impart sex. However, this black steel sheet is dyed and faded by a black dye under the environment where direct sunlight or light from a strong artificial light source is irradiated for a long time,
It has the drawback of being inferior in weather resistance to black painted steel sheets. Therefore, there is a problem that its use is limited to indoor products and the like which are not exposed to direct sunlight.

Further, a black aluminum alloy plate or a black stainless steel plate formed by forming a black film similar to the above (c) on an aluminum alloy plate or a stainless steel plate has been proposed, but it has the same problem as the black steel plate of (c). Have

In view of the above-mentioned problems of the prior art, the present invention provides a black coating in a black film by adding a black dye and carbon black in a specific mixing ratio, and thereby is as excellent as a black coated steel sheet. It was discovered that excellent weather resistance can be obtained. That is, the black metal plate of the present invention has the following configuration.

(1) A thermosetting resin is used as a base resin on the surface of a metal plate or a plated metal plate, and a total of 10 parts by weight of a black dye and carbon black as a black imparting agent is added to 100 parts by weight of the base resin. ~ 200 parts by weight, and the compounding ratio (weight ratio) of the black dye and carbon black is 100 /
A weldable black metal plate having a weather resistance of 0.3 to 5.0 μm and having a black film made of a composition blended as 1 to 1/1.

(2) A thermosetting resin is used as a base resin on the surface of a metal plate or a plated metal plate, and a total of 10 parts by weight of the base resin is a black dye and carbon black as a black imparting agent. ~ 200 parts by weight, and the compounding ratio (weight ratio) of the black dye and carbon black is 100 /
1 to 1/1, and at least one selected from polyethylene wax, fluororesin compound, molybdenum disulfide, graphite, fluorinated graphite, fatty acid amide compound, metal soap, boron nitride and polyalkylene glycol. A weldable black metal plate excellent in weather resistance, which has a black coating of 0.3 to 5.0 µm in thickness, which is composed of a composition containing 1 to 100 parts by weight in total.

(3) A thermosetting resin is used as a base resin on the surface of a metal plate or a plated metal plate, and 100 parts by weight of the base resin is combined with a black dye and carbon black as a black-imparting agent. 10 to 200 parts by weight, and the compounding ratio (weight ratio) of the black dye and carbon black is 100.
0.3 to 5.0 μm of a black film made of a composition in which 1 to 100 parts by weight of at least one selected from a sparingly soluble chromium compound and silica is further mixed. Weldable black metal plate with excellent film thickness and weather resistance.

(4) A thermosetting resin is used as a base resin on the surface of a metal plate or a plated metal plate, and 100 parts by weight of the base resin is combined with a black dye and carbon black as a black imparting agent in a total amount. 10 to 200 parts by weight, and the compounding ratio (weight ratio) of the black dye and carbon black is 100.
At least one selected from polyethylene wax, fluororesin compound, molybdenum disulfide, graphite, fluorinated graphite, fatty acid amide compound, metal soap, boron nitride and polyalkylene glycol. 1 to 100 parts by weight in total,
Welding with excellent weather resistance, which has a black coating of 0.3 to 5.0 μm and consists of a composition in which 1 to 100 parts by weight of at least one selected from a sparingly soluble chromium compound and silica is added in total. Black metal plate.

(5) Chromium adhesion amount (calculated as metal chromium) 1 to 200 on the surface of the metal plate or the plated metal plate.
A chromate film of mg / m ² is provided, and a thermosetting resin is used as a base resin on the top of the chromate film.
A total of 10 to 200 parts by weight of a black dye and carbon black as a black imparting agent, and a compounding ratio (weight ratio) of the black dye and carbon black of 100 parts by weight to 100 parts by weight.
A black film composed of the composition blended as 0.1 to 0.1 is used.
A weldable black metal plate having a film thickness of 3 to 5.0 μm and excellent in weather resistance.

(6) Chromium adhesion amount (calculated as metal chromium) 1 to 200 on the surface of the metal plate or the plated metal plate.
A chromate film of mg / m ² is provided, and a thermosetting resin is used as a base resin on the top of the chromate film.
A total of 10 to 200 parts by weight of a black dye and carbon black as a black imparting agent, and a compounding ratio (weight ratio) of the black dye and carbon black of 100 parts by weight to 100 parts by weight.
Blended as 1/1, and a total of at least one selected from polyethylene wax, fluororesin compound, molybdenum disulfide, graphite, fluorinated graphite, fatty acid amide compound, metal soap, boron nitride and polyalkylene glycol. 1. A weldable black metal plate having a weather resistance of 0.3 to 5.0 μm and a black film made of a composition blended in an amount of 1 to 100 parts by weight.

(7) Chromium adhesion amount (calculated as metallic chromium) 1 to 200 on the surface of the metal plate or the plated metal plate.
A chromate film of mg / m ² is provided, and a thermosetting resin is used as a base resin on the top of the chromate film.
10 parts by weight to 100 parts by weight of a black dye and carbon black as a black imparting agent, and a compounding ratio (weight ratio) of the black dye and carbon black of 100 /
1 to 1/1, and a black coating film of 0.3 to 5.0 μm having a composition of 1 to 100 parts by weight in total of at least one selected from a sparingly soluble chromium compound and silica. A weldable black metal plate with excellent film thickness and weather resistance.

(8) Chromium adhesion amount (calculated as metallic chromium) 1 to 200 on the surface of the metal plate or the plated metal plate.
A chromate film of mg / m ² is provided, and a thermosetting resin is used as a base resin on the top of the chromate film.
10 parts by weight to 100 parts by weight of a black dye and carbon black as a black imparting agent, and a compounding ratio (weight ratio) of the black dye and carbon black of 100 /
1 to 1/1, and at least one selected from polyethylene wax, fluororesin compound, molybdenum disulfide, graphite, fluorinated graphite, fatty acid amide compound, metal soap, boron nitride and polyalkylene glycol. A black film having a composition of 1 to 100 parts by weight in total, and a composition of 1 to 100 parts by weight in total of at least one selected from a sparingly soluble chromium compound and silica, having a thickness of 0.3 to 5.0 μm. A thick black weldable metal plate with excellent weather resistance.

(9) In the black metal plate of the above (1) to (8), the black dye is at least one selected from azo metal complex salt dyes, azo dyes and azine dyes, and has excellent weather resistance. Possible black metal plate.

(10) In the black metal plate of the above (1) to (8), the black dye is at least one selected from azo metal complex salt dyes, azo dyes and azine dyes,
A weldable black metal plate having at least one selected from phthalocyanine dyes, anthraquinone dyes, quinophthalone dyes, azomethine dyes and triphenylmethane dyes and having excellent weather resistance.

(11) The black metal plate according to any one of (1) to (8) above, wherein the black dye is at least one selected from the group consisting of azo metal complex salt dyes and has excellent weather resistance and is weldable.

(12) In the black metal plate of the above (1) to (8), the black dye is at least one selected from azo metal complex salt dyes, a phthalocyanine dye, an anthraquinone dye, a quinophthalone dye, an azomethine dye, and A weldable black metal plate having excellent weather resistance, which is composed of at least one selected from triphenylmethane dyes.

[0021]

The details of the present invention and the reasons for limitation thereof will be described below. The black metal plate of the present invention has a chromate film on the surface of the base metal plate or the plated metal plate, if necessary, and on the surface of the metal plate or the plated metal plate or on the chromate film, heat It has a black film made of a composition in which a black dye and carbon black are mixed in a specific ratio with a curable resin. Here, the black dye in the present invention includes, in terms of the chemical structure of the molecule, those exhibiting black only by the same kind of molecule and those exhibiting black by mixing several kinds of dyes having different molecular chemical structures. It is a waste.

There is no particular restriction on the metal plate or the plated metal plate which is the original plate of the black metal plate of the present invention, but when the ordinary steel plate for home electric appliances, automobile parts, building materials and the like is used as a base, corrosion resistance From the viewpoint of, a galvanized steel sheet or a zinc alloy plated steel sheet is particularly preferable.

The zinc plating and zinc alloy plating film applied to the steel sheet are, for example, Zn plating and Zn-Ni.
Alloy plating, Zn-Fe alloy plating, Zn-Cr alloy plating, Zn-Mn alloy plating, Zn-Co alloy plating,
It is possible to use Zn-Al alloy plating, and further, those in which one or more elements such as Ni, Fe, Mn, Co, Cr, Al and Mo are added to these plating components. Further, it is also possible to carry out dispersion plating in which silica, chromium compound, particulate polymer and the like are co-deposited during the above arbitrary plating. Further, it may be a multi-layer plating in which two or more kinds of the same kind or different kinds of plating as described above are applied. For example, a plating film in which two or more layers of Zn—Fe alloy plating having different Fe contents are applied may be used. As a method for forming the zinc plating or the zinc alloy plating, any of the electroplating method, the hot dipping method, the vapor phase plating method and the like that can be performed can be adopted. Further, in addition to the zinc-based plated steel sheet, a tin-plated steel sheet, a chrome-plated steel sheet (tin-free steel), or the like can be used.

As the metal plate other than the steel plate, for example, an aluminum alloy plate or a stainless steel plate can be used. The aluminum alloy plate is an aluminum alloy plate containing one or more of copper, manganese, silicon, magnesium, zinc, chromium, nickel and the like as an alloy element, and for example, 2002, 2117, 2036, 2037, 20.
38,3004,5052,5182,6009,60
There are aluminum alloy plates such as 10, 6015, 6016 and 6111.

The stainless steel plate is a steel plate containing chromium or chromium and nickel, and the stainless steel plate is austenitic (SUS304, 304L, 31).
6,316L, etc.), ferrite type (SUS430, etc.),
There are martensite type (SUS410 etc.). For the purpose of enhancing the adhesion to the black coating, these stainless steel sheets may be provided with surface roughness during rolling, or may be provided with surface roughness by pretreatment or the like, if necessary.

The above metal plate or plated metal plate (hereinafter,
These are collectively referred to as "metal plates"),
A chromate film is formed by a chromic acid treatment, if necessary, for the purpose of improving adhesion and corrosion resistance. Particularly when a plated steel sheet is used as a base, it is necessary to form a chromate film from the viewpoint of corrosion resistance. In the black metal plate of the present invention, the combination of this chromate film and a black film containing a specific black-imparting agent as described later provides extremely excellent corrosion resistance.

This chromate film has a chromium adhesion amount (d
ry) is 1 to 200 mg / m ² , preferably 10
80 mg / m ² (above, converted to metallic chromium). If the amount of deposited chromium exceeds 200 mg / m ² , workability and weldability tend to deteriorate. Also, the amount of deposited chromium is 1 mg /
If it is less than m ² , the coating may be non-uniform and the corrosion resistance may deteriorate. Further, it is preferable that hexavalent Cr be present in the chromate film. Hexavalent Cr ions have a repairing action, and when a metal plate is scratched, it has a function of suppressing corrosion from the scratch.

The chromate treatment for the undercoating film may be performed by any known method such as reaction type, coating type and electrolytic type. The coating type chromate treatment liquid contains a partially reduced chromic acid solution as a main component, and if necessary, an organic resin such as a water-dispersible or water-soluble acrylic resin and / or a particle size of several mμ to several hundred mμ. The above-mentioned silica (colloidal silica, fumed silica) is contained.
In this case, the ratio of trivalent Cr ions / hexavalent Cr ions is 1
/ 1-1 / 3, and the pH is preferably 1.5-4.0 (more preferably 2-3). The ratio of trivalent Cr ions / hexavalent Cr ions is adjusted to a predetermined ratio by using a general organic reducing agent (for example, sugar, alcohol, etc.) or an inorganic reducing agent.

As the coating type chromate treatment, any method such as a roll coater method, a dipping method and a spray method may be used. In the coating type chromate treatment, a film is obtained after the chromate treatment by drying without washing with water. The reason for drying without washing with water in this way is that hexavalent Cr ions are removed by the usual washing with water, and trivalent Cr is removed.
The ratio of ions / hexavalent Cr ions is kept stable as it is, and the resin film formed on the top suppresses the excessive outflow of hexavalent Cr ions in a corrosive environment, and effectively maintains a passive state for a long period of time. The chemical action can be maintained and high corrosion resistance performance can be obtained.

On the other hand, in the electrolytic chromate treatment, cathodic electrolysis is carried out in a bath containing chromic anhydride and one or more anions such as sulfuric acid, phosphoric acid fluoride or halogen oxygen acid, and then washed and dried with water. To form a film.

Comparing the chromate coatings obtained by the above two treatment methods, the coating type chromate is superior in corrosion resistance to the electrolytic type chromate because it contains a large amount of hexavalent chromium in the coating. When the heat treatment is performed as described above, the coating becomes dense and strong, so that the corrosion resistance becomes better than that of the electrolytic chromate. On the other hand, the electrolytic chromate has an advantage that the degree of completion of the film is high regardless of the presence or absence of heat treatment, and has an advantage that it is easy to control the amount of film adhesion. From the viewpoint of corrosion resistance, coating type chromate is most preferable.

Next, the components of the black film will be described. The black film in the present invention is characterized in that a thermosetting resin is used as a base resin, and a black dye and carbon black as a black-imparting agent are mixed in a specific ratio. Further, in the present invention, in addition to the above components, a solid lubricant may be contained for the purpose of improving the workability of the black film, and a rust preventive pigment may be contained for the purpose of improving the corrosion resistance.

In the following description, the blackness of the black film is evaluated by the lightness L value. The smaller the L value, the better the blackness, and the target of the black coating in the present invention is L ≦ 25, more preferably L ≦ 18. Note that L
The value was measured by a multi-source spectrophotometer (model MSC) manufactured by Suga Test Instruments Co., Ltd. The weather resistance was evaluated with a Sunshine Super Long Life Weather Meter (Model WEL-SUN-TC-B) manufactured by Suga Test Instruments Co., Ltd., and the degree of discoloration after 480 hours was determined by the following formula. It was evaluated by ΔE. The target of weather resistance in the present invention is ΔE ≦ 3, preferably ΔE ≦ 2.

[Equation 1]

The black coating must have the following functions. Excellent blackness in thin films (thickness of 5 μm or less) Excellent weather resistance in environments where light irradiation is relatively severe, such as in the semi-outdoors

Colorants generally used can be broadly classified into inorganic pigments, organic pigments and dyes. Of these, when using an inorganic pigment or an organic pigment in a thin coating film of several μm or less,
The hiding power of the pigment is important for blackness. Carbon black is a typical example of the black pigment for inorganic pigments, and since it is inexpensive, it is most often used among the black pigments, and many grades are available according to the purpose. However, when this carbon black is used alone as a black-color imparting agent, a weldable thin film (film thickness 5 μm 5 μm In the following), the blackness is not sufficient, and since it is a conductive pigment, the black coating has electrical conductivity, and the corrosion resistance of the metal plate is inferior. Also, other black inorganic pigments,
For example, iron oxide, titanium black and the like also have insufficient blackness.

Aniline black is typically used as a black organic pigment. However, it is also inferior in hiding power, so that sufficient blackness cannot be obtained. As another black organic pigment, there is perylene black, but this cannot similarly obtain sufficient blackness. Even when two or more kinds of the above-mentioned inorganic pigments and organic pigments are combined, the blackness is still insufficient.

On the other hand, it is said that there are several thousand kinds of dyes on the market at present, but these are roughly classified into two kinds, that is, a chemical structural classification method (1). , According to the practical classification method (2) based on dye characteristics (for example, published in "Organic Chemistry Handbook" by Gihodo, edited by The Society of Synthetic Organic Chemistry).

In the classification method (1) based on the chemical structure, the dyes are classified according to the main structure that causes color development in the dye molecule, and are classified into nitroso dyes, nitro dyes and azo dyes (monoazo dyes, disazo dyes, trisazo dyes, tetrakisazo dyes). ,
Examples include anthraquinone dye, indigo dye, azine dye, cyanine dye, phthalocyanine dye, stilbene dye, sulfur dye, triazole dye, triphenylmethane dye, acridine dye, diphenylmethane dye and oxazine dye. On the other hand, a practical classification method based on dye characteristics (2)
Then, direct dyes, acid dyes, basic dyes, acid mordant dyes, metal complex dyes, sulfur dyes, vat dyes, Izoc dyes, disperse dyes, reactive dyes, oxidation dyes, fluorescent brightening dyes,
There are oil-soluble (organic solvent-soluble) dyes and the like.

According to the above classification, for example, dyes classified into acid dyes according to the classification method of (2) are azo dyes (monoazo, disazo, trisazo, tetrakisazo) according to the classification method of (1). , Anthraquinone dye, triphenylmethane dye, azine dye, etc. On the other hand, color is an important characteristic of the dye, -CH = CH in its chemical structure -, - N = N-like groups having an unsaturated bond and (chromophore), -NH _2, -OH, etc. It is because light having a specific wavelength is absorbed by the group having a free electron pair of (auxiliary chromophore), and light having a wavelength that is not absorbed is caught by the naked eye as the color of the object. There will be dyes of different colors. See COLOR I below
"NDEX" classifies these colors as yellow, orange, red, violet, blue, green, brown, and black.

["The SOCIETY OF DYERS AND COLOURIST
S "and" AMERICAN ASSOCIATION OF TEXTILE CHEMISTS AN
`` COLOR INDEX (THIRD EDITION
Vol. 1-8) ”describes the classification, structure, properties, applications, etc. to which commercially available dyes belong. Each dye is classified and defined in this“ COLOUR INDEX ”,“ CI Gener ”.
ic Name ”. That is, this "COL
The classification method of "OUR INDEX" is that commercially available dyes are first divided into practical categories similar to the category of (2) above, and then the color categories are displayed. The dyes are classified (displayed by numbers starting from 1).
The ones that are clear up to the concrete structural formula represent the structure "CI
"Constitution Number" is described, but most of them are not, like the classification of (1) above.
For example, chemical structure classifications of azo (monoazo, disazo, etc.), anthraquinone, azine, etc. are described.

For example, a black dye in the classification of acid dyes is displayed as "CI Acid Black", and among them, "CI Acid Black 1" has a specific chemical structure of a disazo dye, "CI Acid Black 2" has a specific chemical structure of azine dye, "CI Acid Black"
3 ”is classified as having a specific chemical structure of the disazo dye, and the color, characteristics, use, etc. are described for each. And this "CI Generic Name" can be compared with the brand name of commercially available dye.

When such a black dye is added to the resin film as a black-imparting agent, as shown in JP-A-4-218678, a weldable thin film (film thickness of 5 μm or less) is obtained.
Also in, it is possible to obtain excellent blackness. However, this black film is not particularly problematic in the case of indoor applications where it is not exposed to direct sunlight, but applications where it is placed in a semi-outdoor environment where it is occasionally exposed to direct sunlight, for example,
In applications such as home electric appliances and building materials installed near windows, the weather resistance is insufficient, so that there is a drawback that the color gradually fades.

In contrast to the above problems of the pigment (carbon black or the like) and the dye as the black-imparting agent, respectively, in the present invention, by mixing the black dye and the carbon black in a specific ratio, It has been found that the same excellent blackness can be obtained as compared with the case where the black dye is used alone as the black-imparting agent, and the weather resistance is dramatically improved. The reason why such excellent characteristics are obtained is that, when a black dye is added alone, when the black film is irradiated with strong energy such as ultraviolet rays, the bond in the molecular structure of the dye is destroyed, and While the selective absorption of light is impaired, by combining black dye and carbon black in a specific ratio, carbon black particles linked in a chain in the black film scatter part of light.
It is considered that the absorption suppresses the breaking of the bond in the molecular structure of the dye. FIG. 1 schematically shows a cross section of the coating of the black metal plate of the present invention.

On the other hand, if a black pigment other than carbon black is blended with the black dye in the coating, an effect of improving weather resistance can be expected, but the blackness of the black coating is more significantly reduced than that of carbon black, which is not preferable.

In order to obtain the above-mentioned effects, the blending amount of the black dye and carbon black and the blending ratio thereof are extremely important. First, the total amount of black dye and carbon black is 10 to 2 with respect to 100 parts by weight of the base resin.
The amount is 00 parts by weight, preferably 40 to 100 parts by weight. If the blending amount is less than 10 parts by weight, the blackness is insufficient. On the other hand, if the blending amount is more than 200 parts by weight, not only is there no effect for improving the blackness, but also the binder effect of the base resin is reduced, and the workability is reduced. , Adhesion, and corrosion resistance are reduced.

The blending ratio of the black dye and carbon black is 10 by weight ratio of [black dye / carbon black].
0/1 to 1/1, preferably 50/1 to 2/1, and more preferably 20/1 to 5/1. If the [black dye / carbon black] exceeds 100/1, the effect of improving the weather resistance cannot be obtained, while if it is less than 1/1, the appearance of the black film is deteriorated, and the workability, adhesion and corrosion resistance are also deteriorated. . 2 and 3 show the relationship between the blending ratio of the black dye and carbon black, the blackness, and the weather resistance.

Since the dye is easily dissolved in a solvent, it is possible to form a black film composition by mixing it with a thermosetting resin. Further, carbon black can be uniformly dispersed in the solvent by a method such as sand grinder, attritor or roll mill. When these black dye and carbon black are blended as a black-imparting agent in the black coating at the above blending amounts and blending ratios, even a thin coating (film thickness of 5 μm or less) in a weldable range has a uniform and excellent black color. It has an external appearance and excellent weather resistance. Also, unlike the conventional black treatment that involves reactions such as etching type, electrolytic treatment, and displacement plating, there is no deterioration of the bath due to the treatment, and the type of base plating is not limited, the greatest advantage of the coating treatment. Can also be used.

The black coating has a thickness of 0.3 to 5.0 μm, preferably 0.7 to 3.0 μm. Film thickness is 0.3 μm
If less than, the coloring effect by the black-imparting agent is poor, while
If it exceeds 3.0 μm, the spot weldability deteriorates, and if it exceeds 5.0 μm, the weldability remarkably decreases.

The base resin, the black dye and the carbon black constituting the black film will be described below. The base resin forming the black coating of the black metal plate of the present invention is a thermosetting resin. The reason why the base resin is limited to such a resin is that when a thermoplastic resin is used, a problem occurs in the scratch resistance of the formed black film. Examples of the thermosetting resin include acrylic copolymer resin, alkyd resin, epoxy resin, polybutadiene resin, phenol resin, polyurethane resin, fluororesin, and a mixture of two or more kinds of these resins, and addition with other monomers. Examples thereof include condensates or modified derivatives with other resins. Of these, acrylic copolymer resins, alkyd resins, epoxy resins, fluororesins, acrylic silicone resins, and the like are preferable.

The acrylic copolymers are resins synthesized by a solution polymerization method, an emulsion polymerization method or a suspension polymerization method using a usual unsaturated ethylenic monomer. A hard monomer such as nitrile, styrene, acrylic acid, acrylamide, or vinyltoluene is used as an essential component, and an unsaturated vinyl monomer is appropriately blended for the purpose of imparting hardness, flexibility, and crosslinkability to the resin. Obtained by Further, this resin may be a resin modified with other alkyd resin, epoxy resin, phenol resin, or the like.

As the alkyd resin, known ones obtained by a usual synthetic method can be used, and examples thereof include oil-modified alkyd resin, rosin-modified alkyd resin, phenol-modified alkyd resin, styrenated alkyd resin,
Silicon modified alkyd resin, acrylic modified alkyd resin, oil-free alkyd resin (polyester resin) and the like can be mentioned.

Examples of the epoxy resin include epichlorohydrin type and glycidyl ether type straight epoxy resins, fatty acid-modified epoxy resins (epoxy ester resins), polybasic acid-modified epoxy resins, acrylic resin-modified epoxy resins, and alkyd (or polyester) modified epoxy resins. Epoxy resin, polybutadiene-modified epoxy resin, phenol-modified epoxy resin, amine- or polyamine-modified epoxy resin, urethane-modified epoxy resin and the like are used.

As the fluororesin, there is a fluoroolefin copolymer, and examples thereof include alkyl vinyl ether, synchroalkyl vinyl ether, carboxylic acid modified vinyl ester, hydroxyalkyl allyl ether, tetrafluoropropyl vinyl ether and the like as monomers. , And a copolymer with a fluorine monomer (fluoroolefin). When these fluororesins are used, excellent weather resistance can be expected.

As the acrylic silicone resin, there is a resin containing a hydrolyzable alkoxysilyl group at the side chain or terminal of an acrylic copolymer as a main component, and a curing agent added thereto. When these acrylic silicone resins are used, excellent weather resistance can be expected. A known predetermined curing agent is used for these resins. Examples of this curing agent include melamine, blocked isocyanate, and urea resin.

The black dye used in the present invention is not particularly limited, and either an organic solvent-soluble black dye or a water-soluble black dye can be used. These dyes include dyes classified according to the above classification (1), that is, azo dyes (monoazo dyes, disazo dyes, trisazo dyes,
Tetrakisazo dye), azo-methine dye, quinoline dye, ketonimine dye, fluorone dye, nitro dye,
There are xanthene dyes, acenaphthene dyes, quinophthalone dyes, anthraquinone dyes, aminoketone dyes, methine dyes, perylene dyes, coumarin dyes, perinone dyes, triphenyl dyes, triallylmethane dyes, phthalocyanine dyes, incrophenol dyes, azine dyes, etc.,
These 1 type (s) or 2 or more types of dyes can be used. Among these, azo dyes and azine dyes are particularly preferable in that excellent blackness can be obtained, and among them, azo metal complex salt dyes classified as azo dyes are most preferable.

The black dye easily dissolves in water or an organic solvent (for example, alcohol, cellosolve, ester, ketone), so that it is used together with water and a water-soluble or water-dispersible thermosetting resin, or an organic solvent and an organic solvent. A black film composition can be obtained by mixing with a soluble thermosetting resin. When this black dye is blended in the resin coating within the blending ratio with the above carbon black, even a thin coating (film thickness of 5 μm or less) in a weldable range exhibits excellent blackness. Further, since the dye itself has excellent fastness to light, there is no problem even when it is used for a black metal plate for home appliances, office equipment, etc. illuminated by various light sources.

In the black metal plate of the present invention having a black film containing such a black dye, the barrier effect due to the formation of the passive film of the underlying chromate (the action of trivalent Cr ions) and the barrier of the resin film itself. In addition to the anticorrosion effect due to the effect, the barrier effect due to the above-mentioned black dye itself makes the corrosion resistance higher, and further, the self-repairing effect of repairing defects of the passive film by hexavalent Cr ion → trivalent Cr ion of the underlying chromate. A high degree of corrosion resistance can be obtained due to factors such as good adhesion of the underlying Zn-based plating-chromate film-black film.

Among the black dyes, the black azo metal complex salt dye has the best light fastness and corrosion resistance. This black azo metal complex salt dye is a complex compound of an azo dye and a trivalent metal such as chromium, copper or cobalt.
Typical examples of "CI Generic Name" of "NDEX" are CI Solvent Black 6, 22, 23, 25, 2
8, 29, 30, 34, 35, 36, 37, 38, 3
9, 40, 41, 42, 43, 45, 47, 48, 49
Etc. (above, organic solvent-soluble black azo metal complex salt dye), CI Acid Black 8, 43, 49, 51, 52,
52: 1, 53, 55, 57, 60, 63, 65, 7
1, 82, 84, 92, 98, 99, 107, 108,
114, 115, 118, 119, 120, 121, 1
22, 124, 129, 132, 133, 134, 13
5, 136, 137, 138, 139, 140, 14
7, 148, 149, 150, 151, 153, 15
4, 155, 157, 158, 159, 164, 16
5, 168, 170, 171, 172, 174, 17
6, 178, 180, 181, 183, 184, 18
5, 187, 188, 192, 194, 195, 19
8, 199, 207, 211, 213, 215, 21
6, 217, 218, 220, 222, 223, 22
5, 226, 227, CI Direct Black 57, 10
9, 116, 130, 142, 143, 144, CI M
ordant Black 90 and the like (above, water-soluble black azo metal complex salt dye).

As described above, a black azo metal complex salt dye which is not registered in “COLOUR INDEX”, for example, a newly developed and unregistered dye, or a mixture of plural kinds of dyes, It goes without saying that a mixture containing at least one black azo metal complex salt dye in the mixture can be used.

The feature of this dye is that a complex compound of 1 atom of metal for 2 molecules of azo dye (2: 1 type metal complex salt) or a complex compound of 1 atom of metal for 1 molecule of azo dye (1: For structural reasons considered to be type 1 metal complex salt), the stability to light (fastness to light) is superior to other dyes, and the blackness is superior to other dyes. The metal capable of forming a complex salt with the dye is C
There are r, Co, Cu, Fe, Al, etc., but mainly Cr
Many of these are complex salts with.

Examples of commercially available black azo metal complex salt dyes soluble in organic solvents include OR manufactured by Ciba Geigy.
ASOL Black RL, ORASOL Black RLP (above, CI Solven
t Black 29), ORASOL Black CN (CI Solvent Blac
k 28), ORASOL Black BA (CI Solvent Black
6), BASF ZAPON Black X51 (CI Solvent
Black 27), Aizen Spilon made by Hodogaya Chemical Co., Ltd.
There are Black RLH Special (CI Solvent Black 42) etc. In addition to this, `` COLOUR INDEX (THIRD EDITIO
N) ”, such as Aizen Spilon Black MH Special manufactured by Hodogaya Chemical Co., Ltd. and Kayaset Black KR manufactured by Nippon Kayaku Co., Ltd., all of which exhibit excellent blackness. A black film is obtained.

By using a black azo chromium complex salt dye as the black azo metal complex salt dye, it is possible to obtain extremely excellent corrosion resistance, which is presumed to be a synergistic effect of the trivalent Cr ions and the underlying chromate. This is trivalent C
It is considered that the black azo metal complex salt dye containing r is stably present as a passive film and further improves the barrier effect. For this reason, it is most preferable that the metal forming the complex salt is trivalent Cr ions as the black azo metal complex salt dye.

As another black dye, a black azo dye which is not a metal complex salt can be welded into a thin film (film thickness 5 μm).
m or less), it exhibits an excellent blackness (L ≦ 25, preferably L ≦ 18) which is equal to or higher than that of the black azo metal complex salt dye. In addition, since the production unit price of this black azo dye is about 80% of that of the black azo metal complex salt dye, compared with a black metal plate using the black azo metal complex salt dye as a black-imparting agent,
There is an advantage that the raw material cost of the black film can be reduced.

The black azo dye can exhibit a deeper black color by lengthening the conjugated double bond of the chromophore in terms of chemical structure. On the other hand, although this black azo dye is inferior in light fastness to the black azo metal complex salt dye, an effect of improving light fastness is recognized when used in combination with carbon black.

As the organic solvent-soluble black azo dyes, the "COLOR INDEX" described above can be used as "CI Solvent Bla".
Among the organic solvent-soluble black dyes classified in “ck”, CISolvent Black 1, 2, 6, 15, 24, 35
(Above, monoazo dye), CI Solvent Black 3, 4,
39 (above, disazo dye), CI Solvent Black 2
6, 46, 51 (the number of azo groups in the molecule is unknown) and the like. In addition to this, an existing one or a new one not registered in “COLOUR INDEX” may be used.

Further, as commercially available products, for example, Neptun Black X60 (CI Solvent Black 3) manufactured by BASF, Nep
tun A Black X17 (CI Solvent Black 46), Mitsui Oil Black YG-6 (CI Sol manufactured by Mitsui Toatsu Dye Co., Ltd.)
Vent Black 39) and the like, and in each case, a black film exhibiting excellent blackness can be obtained. The black azo dye may be used as a mixture of two or more kinds, and further, a mixture of a black azo dye as a main component and a dye belonging to another type in terms of chemical structure classification It may be used as a blackening agent.

In addition, the black azine dye also has an excellent blackness (L) almost equal to that of the organic solvent-soluble black azo metal complex salt dye in a weldable thin film (film thickness of 5 μm or less).
≦ 25, preferably L ≦ 18). Since the production unit price of this black azine type dye is about half that of the black azo type metal complex salt dye, compared with the black metal plate using the black azo type metal complex salt dye as the black-imparting agent, the raw material cost of the black film is significantly increased. There is an advantage that it can be reduced. This black azine type dye is also inferior to the black azo type metal complex salt dye in terms of light fastness, but an effect of improving light fastness is recognized by using together with carbon black.

As the organic solvent-soluble black azine type dye, "CI Solvent Bla" in "COLOUR INDEX" described above can be used.
Among the organic solvent-soluble black dyes classified as “ck”, CI Solvent Black 5, 5: 1, 7, 31, 3
There are 2, 50, etc. In addition to this, "COLOR INDE
An existing one or a new one not registered in "X" may be used.

Examples of commercially available black azine dyes soluble in organic solvents include Basonyl Black X2 manufactured by BASF.
2 (CI Solvent Black 5), Orient Spirit Black SB manufactured by Orient Chemical Industry Co., Ltd. (CI Solvent Bl
ack 5), Orient Spirit Black SSBB (CI Solvent Bl
ack 5), Orient Nigrosine Base EX (CI Solvent Bl
ack 7), Orient Oil Black BS (CI Solvent Black
7), Orient Special BlackEB (CI Solvent Black
7), Sumitomo Chemical Co., Ltd. Sumisol Black AR (CI
Solvent Black 50) and the like, which all produce a black film exhibiting excellent blackness.

The black azine type dyes may be used as a mixture of two or more kinds, and further, the black azine type dyes are mainly used, and the dyes belonging to other types in terms of chemical structure classification are mixed. What was done may be used as a black provision agent.

When the above black azo dye and black azine dye are blended in a black film as a black-imparting agent, they exhibit excellent blackness even in a thin film (film thickness of 5 μm or less) in a weldable range. . Further, as described above, the light resistance of the dye itself is inferior to that of the black azo metal complex salt dye,
When used in combination with carbon black, the effect of improving light fastness is recognized.

The black azo type metal complex salt dye, the black azo type dye and the black azine type dye may be used in a suitable mixture of two or more kinds thereof. In addition to the above dyes, examples of black dyes include phthalocyanine dyes, azo / methine dyes, anthraquinone dyes, and quinophthalone dyes, and these dyes can be used.

As described above, as the black dye to be applied to the present invention, not only the black dye having only the same kind of molecule due to its chemical structure but also a mixture of several kinds of dyes having different chemical structures Some of them exhibit a black color by doing. Therefore, by utilizing the principle of subtractive color mixture, it belongs to one or more classifications among azo metal complex salt dyes, azo dyes, azine dyes, phthalocyanine dyes, azo / methine dyes, anthraquinone dyes, quinophthalone dyes, etc. A black dye obtained by mixing several color dyes can be applied.

Further, a black azo type metal complex salt dye, a black azo type dye, a black azine type dye as a main component, and a coloring dye other than black (for example, azo type metal complex salt dye, azo dye, phthalocyanine dye, azo methine dye) Dye, anthraquinone dye, quinophthalone dye, etc.) can be blended to finely adjust the color tone of the black film.

The carbon black used in the present invention can be classified into those produced by the thermal decomposition method and those produced by the incomplete combustion method in terms of the production method. The former method includes the thermal method and the acetylene method, and the latter method includes the contact method, the lamp / pine smoke method, the gas furnace method, and the oil furnace method, but use the method obtained by either method. You can Carbon black having a smaller average primary particle size, a larger specific surface area, and a greater dispersion stability in a coating is preferable from the viewpoint of blackness in a thin film. Specifically, the average primary particle size is 50 μm or less, especially 20 μm.
The specific surface area is preferably 50 m ² / g or more, more preferably 100 m ² / g or more, as measured by the BET method. As such carbon black, # 1000, # 950, # 90 manufactured by Mitsubishi Kasei Co., Ltd.
0, # 2300, MA7, # 7 manufactured by Tokai Carbon Co., Ltd.
700, # 7450, # 8200, # 8500 and the like.

The black film of the black metal plate of the present invention described above has sufficient necessary properties as it is, but more excellent properties can be obtained by adding the additives described below.

First, it is desirable to add a solid lubricant to the coating composition in order to impart good self-lubricating properties to the black coating. Examples of solid lubricants that can be used in the present invention include polyethylene wax, fluororesin compounds (for example, polyfluoroethylene resin, polyvinyl fluoride resin, polytetrafluoroethylene resin, polyvinylidene fluoride resin, etc.), fatty acid amide compounds (for example, Stearic acid amide, palmitic acid amide, methylene bis stearoamide, ethylene bis stearoamide, oleic acid amide, esyl acid amide, alkylene bis fatty acid amide, etc.), metal soap (for example, calcium stearate, lead stearate, calcium laurate, Calcium palmitate, etc.), molybdenum disulfide, graphite, fluorinated graphite, boron nitride and polyalkylene glycol, and these may be used alone or in combination of two or more.

The above solid lubricant is 1 to 100 parts by weight, preferably 10 to 6 parts by weight, based on 100 parts by weight of the thermosetting resin.
It is mixed in the range of 0 parts by weight. Less than 10 parts by weight,
Particularly, if it is less than 1 part by weight, the effect of improving the lubricity of the black film by adding the solid lubricant is poor, while if it is more than 60 parts by weight, particularly more than 100 parts by weight, the strength of the black film after curing is lowered, Not suitable because part of the coating adheres to the press mold.

The black coating obtained by applying the black coating composition consisting of the base resin and the black dye and carbon black has sufficient corrosion resistance due to the synergistic effect of the base plating and the chromate coating. In order to further improve the corrosion resistance in the part, a rust preventive pigment can be added to the black film composition, which provides more excellent corrosion resistance and expands the use of the black metal plate, which is preferable. As the rust preventive pigment, one or more selected from sparingly soluble chromate and silica are used.

As the sparingly soluble chromate, barium chromate (BaCrO ₄ ) and strontium chromate (Sr) are used.
CrO _4), lead chromate (PbCrO _4), zinc chromate _{(ZnCrO 4 · 4Zn (OH)} 2), calcium chromate (CaCrO _4), zinc chromate potassium (K ₂ O · 4
_{ZnO · 4CrO 3 · 3H 2 O} ), silver chromate (AgCr
There is O ₄ ).

As silica, dry silica (for example, AEROSIL 130 and AEROSI manufactured by Nippon Aerosil Co., Ltd.) is used.
L 200, AEROSIL 300, AEROSIL 380, AEROSIL
R972, AEROSIL R811, AEROSIL R805, AERO
SIL R974, etc., colloidal silica (for solvent type organic resins, for example, MA-S manufactured by Nissan Chemical Industries, Ltd.)
T, IPA-ST, NBA-ST, IBA-ST, EG
-ST, XBA-ST, ETC-ST, DMAC-ST
etc. Examples of water-dispersible and water-soluble organic resins include Snowtex 20, Snowtex C, Snowtex N, Snowtex O, and Snowtex S manufactured by Nissan Chemical Industries, Ltd.), wet silica-precipitation method ( For example, T-32 (S), K-41, F-80 etc. manufactured by Tokuyama Soda Co., Ltd.,
A wet silica gel method (for example, Syloid 244, Syloid 150, Syloid 72, Syloid 65, SHIELDEX, etc., manufactured by Fuji Devison Chemical Co., Ltd.) can be used. It is also possible to use a mixture of two or more of the above silicas.

One or more of the above rust-preventive pigments are added to the above-mentioned black film composition as its constituent components. The mixing ratio of the rust preventive pigment is 100 parts by weight of the thermosetting resin,
The range is 1 to 100 parts by weight, preferably 3 to 60 parts by weight. If the distribution ratio of the rust preventive pigment is less than 1 part by weight, the rust preventive effect due to the addition of the rust preventive pigment does not appear, while 100
If the amount is more than the amount by weight, the rust-preventive pigment itself has a coloring effect other than black, so that in the case of, for example, a yellow sparingly soluble chromate, there is a problem that the blackness is deteriorated.

When the solid lubricant and the particulate rust preventive pigment are added in combination, it is possible to form a black film excellent in workability and corrosion resistance of the processed part. At that time, the solid lubricant and the particulate rust preventive pigment are each 1 to 100 parts by weight, preferably 10 to 100 parts by weight of the base resin.
It is added in the range of 60 parts by weight.

Other pigments (inorganic pigments and organic pigments) may be added in order to adjust the delicate color tone of black color according to preference. For example, by adding black inorganic pigments such as graphite, aniline black, perylene black, and black titanium oxide, the glossiness can be adjusted and the jetness can be increased. Further, as a matting agent, organic resin particles (urethane resin particles, amine resin particles, epoxy resin particles, acrylic resin particles, acrylonitrile resin particles, polyamide resin particles, nylon resin particles, etc.),
Inorganic particles (TiO ₂ , Al ₂ O ₃ , SiO _2, etc.), fluorine compound resin particles and the like can be added.

The above black coating is prepared by diluting the composition with a solvent as necessary and applying it to a predetermined film thickness by a method such as roll squeezing, a roll coater, or an air knife, and then at a plate temperature of 80 to 300 ° C. (preferably Is obtained by heat curing at 120 to 250 ° C.). The coating method and the baking method are not particularly limited as they are performed by a general method, but in the production of the black metal plate of the present invention, the coating equipment for producing the highly corrosion-resistant surface-treated steel sheet possessed by the steel manufacturer can be used as it is. There is a big merit.

[0086]

EXAMPLES Black metal plates of the present invention and comparative examples were manufactured as black metal plates for semi-outdoor use. In this example,
Each original plate was degreased with alkali, washed with water and dried, and then, if necessary, a chromate film was formed by any of the following chromate treatments, and then a black film was formed on the original plate surface or on the chromate film.

Coating type chromate treatment conditions: trivalent Cr ion: hexavalent Cr ion = 1: 1, content of colloidal silica based on total solid content in the treatment liquid: 55 wt% chromate treatment liquid (solid content 25% , PH: 2.4) was diluted with water as needed, and this was applied to the surface of the original plate and then dried in a hot air oven to obtain a chromate film.

Electrolytic chromate treatment conditions: CrO ₃ : 5
0 g / l, H ₂ SO ₄ : 0.5 g / l, bath temperature of 50 ° C., cathodic electrolysis treatment with current density of 4.9 A / dm ² , electrolysis time of about 20 seconds, washing with water and drying, chromate film Got

Reactive chromate treatment conditions: Zincchrome 357S manufactured by Nihon Parkerizing Co., Ltd. was used for spray treatment under standard conditions, followed by washing with water and drying to form a chromate film.

Tables 1 to 8 show the types of the original plate, the base resin for forming the black film, the black dye, the pigment, the solid lubricant and the rust preventive pigment used in the examples of the present invention and the comparative examples. Tables 9 to 20 show the test results of the original plate, the chromate film, the composition for forming the black film, and the obtained black metal plate used in the examples of the present invention and the comparative examples. The black film-forming composition was prepared by mixing the components shown in Tables 2 to 8 in the amounts shown in Tables 9 to 20, and was diluted by adding a solvent as necessary. The test of the black metal plate prepared as described above was performed as follows.

(1) Blackness: The L value of the black film was measured using a multi-source spectrophotometer (model MSC) manufactured by Suga Test Instruments Co., Ltd. The evaluation criteria are as follows. ⊚: L ≦ 18 ○: 18 <L ≦ 25 x: L> 25

(2) Gloss: Gloss at an incident angle and a reflection angle of 60 ° was measured using a gloss meter manufactured by Suga Test Instruments Co., Ltd. The larger the value of glossiness, the higher the gloss.

(3) Weldability test: Spot welding was carried out under the following conditions, and evaluation was made by the number of continuous spots. Electrode: Cr-Cu, DR type Electrode diameter: 6 mmφ Welding current: 10 kA Energizing pressure: 300 kg Energizing time: 12 cycles / 60 Hz The evaluation criteria are as follows. ◎: 500 RBI or more ○: 200 RBI or more ×: Less than 200 RBI

(4) Corrosion resistance test of flat plate portion and processed portion;
A salt spray test (JIS-Z-2371) of the flat plate portion and the Erichsen 7 mm extruded portion was conducted for 720 hours. The corrosion resistance was evaluated by the time until the amount of white rust generated reached 5% in area ratio. The evaluation criteria are as follows. ◎: No white rust occurred ○: Over 72 hours, within 120 hours △: Over 24 hours, within 72 hours ×: Within 24 hours

(5) Adhesion of black film: 1 on black film surface
Adhesion was evaluated by making 100 pieces of burrs at intervals of mm and adhering / peeling an adhesive tape to the burrs. The evaluation criteria are as follows. ◎: Peeling area 0% ○: Peeling area less than 10% △: Peeling area 10% or more, less than 20% ×: Peeling area 20% or more

(6) Workability test; blank diameter φ100 m
m, die diameter φ53 mm, punch diameter φ50 mm, a cylindrical drawing test was performed, and the moldability was evaluated. The molding was performed without oil coating. The evaluation criteria are as follows. ○: Deep drawing possible ×: Fracture

(7) Weather resistance: Suga Test Instruments Co., Ltd. sunshine super long life weather meter JIS
A weather resistance test of K 5400 was conducted, and the degree of discoloration after 600 hours was evaluated by a color difference ΔE defined by the following formula.

[Equation 2] The evaluation criteria are as follows. ⊚: ΔE ≦ 2 ○: 2 <ΔE ≦ 3 ×: ΔE> 3

[0098]

[Table 1]

[0099]

[Table 2]

[0100]

[Table 3]

[0101]

[Table 4]

[0102]

[Table 5]

[0103]

[Table 6]

[0104]

[Table 7]

[0105]

[Table 8]

[0106]

[Table 9]

[0107]

[Table 10]

[0108]

[Table 11]

[0109]

[Table 12]

[0110]

[Table 13]

[0111]

[Table 14]

[0112]

[Table 15]

[0113]

[Table 16]

[0114]

[Table 17]

[0115]

[Table 18]

[0116]

[Table 19]

[0117]

[Table 20]

* 1: No. 1 of the original plate shown in Table 1. * 2: No. of the base resin shown in Table 2. * 3: Nos. Of black dyes shown in Tables 3 to 5. * 4: Represents parts by weight of the black dye based on 100 parts by weight of the base resin. * 5: Pigment No. shown in Table 6 * 6: Represents parts by weight of pigment with respect to 100 parts by weight of base resin. * 7: Compounding ratio (weight ratio) of black dye / pigment * 8: No. of solid lubricant described in Table 7. * 9: Represents parts by weight of solid lubricant with respect to 100 parts by weight of base resin. * 10: No. 1 of the rust preventive additive described in Table 8. * 11: Represents parts by weight of the rust preventive additive with respect to 100 parts by weight of the base resin.

[0119]

As described above, in the black metal plate of the present invention, the black coating is thinner than the conventional coated metal plate (thickness 5 μm).
Since it is less than m), welding is possible, and it has much better weather resistance than a black metal plate in which a black dye alone is added to a black film. In addition, this black metal plate,
In addition to the above characteristics, adhesion of black film, workability, corrosion resistance,
It is also excellent in light fastness, and because it can be manufactured by coating and baking with existing roll coater equipment etc., there is no problem of bath deterioration due to elution of plating, as compared with reaction etching type black metal plate, Therefore, the productivity can be greatly improved, and a black metal plate that is extremely excellent in terms of various performances and productivity can be provided.

A black metal plate whose black film contains a black azo metal complex salt dye soluble in an organic solvent as a black dye,
Particularly excellent lightfastness. Further, among the black azo-based metal complex salt dyes, the black-coated metal plate containing the black azo-based chromium complex salt dye exhibits excellent light fastness and particularly excellent corrosion resistance. In addition, a black metal plate containing a black azo dye or a black azine dye soluble in an organic solvent in the black film,
Lightfastness is slightly inferior to that of organic solvent-soluble black azo metal complex salt dyes, but there is no problem in indoor or semi-outdoor applications such as home appliances, and the price of these black dyes is About 5 of black azo metal complex dye
Since it is about 80%, there is an advantage that the raw material cost of the black film composition is low.

[Brief description of drawings]

FIG. 1 is an explanatory view schematically showing a film cross section of a black metal plate of the present invention.

FIG. 2 is a graph showing the effect of the black dye / carbon black blending ratio on the blackness.

FIG. 3 is a graph showing the effect of the blending ratio of black dye / carbon black on weather resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B05D 7/24 303 B 7717-4D C23C 22/30

Claims (12)

[Claims] 1. A thermosetting resin is used as a base resin on the surface of a metal plate or a plated metal plate.
10 parts by weight to 100 parts by weight of a black dye and carbon black as a black imparting agent, and a mixing ratio (weight ratio) of the black dye and carbon black is 100/1 to 1 part by weight.
A black film consisting of the composition blended as
A weldable black metal plate having a thickness of 5.0 μm and excellent in weather resistance. 2. A thermosetting resin is used as a base resin on the surface of a metal plate or a plated metal plate.
10 parts by weight to 100 parts by weight of a black dye and carbon black as a black imparting agent, and a mixing ratio (weight ratio) of the black dye and carbon black is 100/1 to 1 part by weight.
/ 1, and at least one selected from polyethylene wax, fluororesin compound, molybdenum disulfide, graphite, fluorinated graphite, fatty acid amide compound, metal soap, boron nitride and polyalkylene glycol in total of 1 A weldable black metal plate having a weather resistance of 0.3 to 5.0 μm and a black film made of a composition of 100 to 100 parts by weight. 3. A thermosetting resin is used as a base resin on the surface of a metal plate or a plated metal plate.
10 parts by weight to 100 parts by weight of a black dye and carbon black as a black imparting agent, and a mixing ratio (weight ratio) of the black dye and carbon black is 100/1 to 1 part by weight.
It is blended as 1/1, and at least one selected from a sparingly soluble chromium compound and silica is added in a total of 1 to 1.
0.3 parts of black coating composed of 100 parts by weight of the composition
A weldable black metal plate having a thickness of ˜5.0 μm and excellent in weather resistance. 4. A thermosetting resin is used as a base resin on the surface of a metal plate or a plated metal plate.
10 parts by weight to 100 parts by weight of a black dye and carbon black as a black imparting agent, and a mixing ratio (weight ratio) of the black dye and carbon black is 100/1 to 1 part by weight.
Blended as 1/1, polyethylene wax,
Fluororesin compounds, molybdenum disulfide, graphite,
Fluorinated graphite, fatty acid amide compound, metal soap, boron nitride and polyalkylene glycol are blended in a total amount of 1 to 100 parts by weight, and at least one selected from a sparingly soluble chromium compound and silica. Is a weldable black metal plate having a weather resistance of 0.3 to 5.0 μm, and a black film made of a composition containing 1 to 100 parts by weight of the above composition. 5. The amount of chromium deposited (calculated as metallic chromium) on the surface of the metal plate or the plated metal plate is 1 to 200 mg /
m ² chromate film, a thermosetting resin as a base resin on the top of the chromate film, and a total of 10 to 200 parts by weight of a black dye and carbon black as a black imparting agent to 100 parts by weight of the base resin. Parts, and the mixing ratio (weight ratio) of the black dye and carbon black is 100/1 to 1 /
A black film consisting of the composition blended as 1 to 0.3
A weldable black metal plate having a thickness of 5.0 μm and excellent in weather resistance. 6. The amount of chromium deposited (calculated as metallic chromium) on the surface of the metal plate or the plated metal plate is 1 to 200 mg /
m ² chromate film, a thermosetting resin as a base resin on the top of the chromate film, and a total of 10 to 200 parts by weight of a black dye and carbon black as a black imparting agent to 100 parts by weight of the base resin. Parts, and the mixing ratio (weight ratio) of the black dye and carbon black is 100/1 to 1 /
1, and at least one selected from polyethylene wax, fluororesin compound, molybdenum disulfide, graphite, fluorinated graphite, fatty acid amide compound, metal soap, boron nitride and polyalkylene glycol in total of 1 to 1 A weldable black metal plate having a weather resistance of 0.3 to 5.0 μm, which is a black film composed of 100 parts by weight of a composition. 7. Amount of chromium deposited (calculated as metallic chromium) on the surface of a metal plate or a plated metal plate of 1 to 200 mg /
m ² chromate film, a thermosetting resin is used as a base resin on the top of the chromate film, and a total amount of a black dye and carbon black as a black-imparting agent is 100 to 100 parts by weight of the base resin. By weight, the blending ratio (weight ratio) of the black dye and carbon black is 100/1 to 1
/ 1, and at least one selected from a sparingly soluble chromium compound and silica in total of 1 to 1
0.3 to 0.3% by weight of a black film composed of a composition blended with 100 parts by weight.
A weldable black metal plate having a thickness of 5.0 μm and excellent in weather resistance. 8. A chromium deposition amount (calculated as metal chromium) of 1 to 200 mg / on the surface of the metal plate or the plated metal plate.
m ² chromate film, a thermosetting resin is used as a base resin on the top of the chromate film, and a total amount of a black dye and carbon black as a black-imparting agent is 100 to 100 parts by weight of the base resin. By weight, the blending ratio (weight ratio) of the black dye and carbon black is 100/1 to 1
/ 1, and at least one selected from polyethylene wax, fluororesin compound, molybdenum disulfide, graphite, fluorinated graphite, fatty acid amide compound, metal soap, boron nitride and polyalkylene glycol in total of 1 To 100 parts by weight, and at least 1 selected from a sparingly soluble chromium compound and silica.
A weldable black metal plate having excellent weather resistance, which has a black coating film having a film thickness of 0.3 to 5.0 μm, the black film having a composition in which 1 to 100 parts by weight of the seeds are mixed in total. 9. The weather resistance according to claim 1, wherein the black dye comprises at least one selected from azo metal complex salt dyes, azo dyes and azine dyes. A weldable black metal plate with excellent properties. 10. The black dye is selected from at least one selected from azo metal complex salt dyes, azo dyes and azine dyes, and phthalocyanine dyes, anthraquinone dyes, quinophthalone dyes, azomethine dyes and triphenylmethane dyes. The weldable black metal plate having excellent weather resistance according to claim 1, 2, 3, 4, 5, 6, 7 or 8, comprising at least one kind. 11. The black dye comprises at least one selected from azo metal complex dyes.
A weldable black metal plate having excellent weather resistance as described in 4, 5, 6, 7 or 8. 12. The black dye comprises at least one selected from azo metal complex salt dyes and at least one selected from phthalocyanine dyes, anthraquinone dyes, quinophthalone dyes, azomethine dyes and triphenylmethane dyes. Item 1. A black metal plate which can be welded and has excellent weather resistance according to items 1, 2, 3, 4, 5, 6, 7 or 8.