JP2836469B2 - Weldable black metal plate with excellent weather resistance - Google Patents

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 excellent in weather resistance and suitable for home electric appliances, office equipment, audio equipment, automobile parts, building materials and the like.

[0002]

2. Description of the Related Art In recent years, audio equipment, office equipment, and the like have been increasingly sophisticated. For example, black metal plates, such as black steel plates, have been widely used for components such as audio products, copiers, and word processors. Conventionally, as a black steel sheet applied to these, users apply black paint to molded parts,
Use a steel plate (black pre-coated steel plate) that has been painted black in advance by a steel manufacturer, or perform a black chromate treatment (for example, JP-A-58-193376) with a treatment solution containing silver ions on the surface of galvanized steel. , Etc., are used. However, this method has the disadvantage that the cost of the coating process is high for the user, and the black pre-coated steel sheet has the disadvantage that spot welding cannot be performed because the thickness of the coating film is as large as about 20 μm. There is a problem that the use site is limited because the steel plate is expensive. Furthermore, the method of (1) is expensive in processing liquid because the black chromate processing liquid contains silver ions, and is unsuitable for mass production in steel sheet coil units because the blackening processing time is as long as 2-3 minutes. There is a problem.

Under such a background, a demand for a weldable black steel sheet which can be used without painting is increasing very much.
In response to such a demand, a black-treated steel sheet in which the surface of a galvanized steel sheet is subjected to a blackening treatment has been proposed. 2. Description of the Related Art Conventionally, the following are known as black-treated steel sheets based on galvanized steel sheets. (A) A black steel sheet in which a black resin film containing a black pigment such as carbon black is formed to a thickness of several tens of μm on the surface of a galvanized steel sheet. (B) A black steel sheet formed on the surface of a galvanized steel sheet by a method of dipping, spraying, anodic treatment, or cathodic treatment, and further having a chromate film and a resin film as a protective film (for example, , Tokiko Sho 61-
38276, JP-B-62-30262, JP-A-62
No.-30262, Japanese Patent Publication No. 5-36515). (C) A black steel sheet in which a chromate film is formed on the surface of a galvanized steel sheet, and a black film made of a thermosetting resin and a specific black dye is formed in a thickness of 3 μm or less (for example,
JP-A-4-301080).

[0004]

However, these prior arts have the following problems. First,
The black steel sheet in (a) is a general coated steel sheet, but spot welding is impossible because the normal coating film thickness is 10 μm or more. Further, when carbon black is used as the black imparting agent, the blackness is insufficient when the weldable thin film thickness (film thickness is 5 μm or less).

[0005] 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 processing solution increases, and In addition to causing problems such as lowering of blackening ability, lowering of corrosion resistance of plating, etc., temperature and concentration of blackening treatment solution, spray pressure in spray treatment, flow rate and current in anodic treatment / cathodic treatment There are a number of problems, such as the inhomogeneity of the density and the like, which tends to cause an inhomogeneous appearance (unevenness) and lower the commercial value, and that the target base plating is limited to a specific alloy plating.

On the other hand, the black steel sheet (c) solves the above-mentioned problems of the steel sheets (a) and (b), and is excellent in a resin film of a thin film thickness (5 μm or less in film thickness) which can be welded. This is the first time that it is possible to impart the property. However, this black steel sheet is dyed and faded by the black dye under the environment where direct sunlight or light from a strong artificial light source is irradiated for a long time,
There is a disadvantage that the weather resistance is inferior to that of a black painted steel sheet. Therefore, there is a problem that its use is limited to indoor products and the like that are not irradiated with direct sunlight.

A black aluminum alloy sheet or a black stainless steel sheet in which a black coating similar to the above (c) is formed on an aluminum alloy sheet or a stainless steel sheet has also been proposed. Have.

In view of the above-mentioned problems of the prior art, the present invention provides an excellent black equivalent to a black coated steel sheet by blending a black dye and carbon black at a specific blending ratio as a black imparting agent in a black film. It has been found 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 used for 100 parts by weight of the base resin. -200 parts by weight, and the mixing ratio (weight ratio) of the black dye and carbon black is 100 /
A weldable black metal plate having excellent weather resistance and having a black film having a thickness of 0.3 to 5.0 [mu] m, which is composed 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 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 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, graphite fluoride, fatty acid amide compound, metal soap, boron nitride and polyalkylene glycol. A weldable black metal plate having excellent weather resistance and having a black film having a thickness of 0.3 to 5.0 [mu] m comprising a composition in which a total of 1 to 100 parts by weight is blended.

(3) A thermosetting resin is used as a base resin on the surface of a metal plate or a plated metal plate, and a total amount of a black dye and carbon black as a black imparting agent is based on 100 parts by weight of the base resin. 10 to 200 parts by weight, and the mixing ratio (weight ratio) of the black dye and carbon black is 100
/ 1 to 1/1, and 0.3 to 5.0 μm of a black film made of a composition containing a total of 1 to 100 parts by weight of at least one selected from a hardly soluble chromium compound and silica. Weldable black metal plate with excellent weather resistance having a thickness of.

(4) A thermosetting resin is used as a base resin on the surface of a metal plate or a plated metal plate, and a total amount of a black dye and carbon black as a black imparting agent is used with respect to 100 parts by weight of the base resin. 10 to 200 parts by weight, and the mixing ratio (weight ratio) of the black dye and carbon black is 100
At least one selected from the group consisting of 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,
Weldable with excellent weather resistance having a black coating of 0.3 to 5.0 μm thick composed of a composition containing a total of 1 to 100 parts by weight of at least one selected from hardly soluble chromium compounds and silica. Black metal plate.

(5) Amount of chromium (converted to chromium metal) 1 to 200 on the surface of the metal plate or the plated metal plate
mg / m ² , and a thermosetting resin as a base resin on the chromate film.
A total of 10 to 200 parts by weight of a black dye and carbon black as a blackening agent and a mixing ratio (weight ratio) of the black dye and carbon black of 100/1 to 100 parts by weight.
A black film consisting of a composition formulated as 0.1 to 1/1 was added to 0.1%.
A weldable black metal plate having a thickness of 3 to 5.0 μm and having excellent weather resistance.

(6) Amount of chromium (converted to chromium metal) 1 to 200 on the surface of the metal plate or the plated metal plate
mg / m ² , and a thermosetting resin as a base resin on the chromate film.
A total of 10 to 200 parts by weight of a black dye and carbon black as a blackening agent and a mixing ratio (weight ratio) of the black dye and carbon black of 100/1 to 100 parts by weight.
And at least one selected from the group consisting of polyethylene wax, fluororesin compound, molybdenum disulfide, graphite, graphite fluoride, fatty acid amide compound, metal soap, boron nitride and polyalkylene glycol. A black film having a thickness of 0.3 to 5.0 μm and a weldable black metal plate excellent in weather resistance having a black film composed of a composition blended in an amount of 1 to 100 parts by weight.

(7) Amount of chromium (converted to chromium metal) on the surface of the metal plate or the plated metal plate is 1 to 200.
mg / m ² , and a thermosetting resin as a base resin on the chromate film.
The total amount of the black dye and carbon black is 10 to 200 parts by weight, and the mixing ratio (weight ratio) of the black dye and carbon black is 100/100 parts by weight.
0.1 to 1/1, and a black film of 0.3 to 5.0 μm in thickness, which is a composition containing 1 to 100 parts by weight of at least one selected from the hardly soluble chromium compound and silica. A weldable black metal plate with excellent weather resistance having a film thickness.

(8) Amount of chromium attached (in terms of chromium metal) to the surface of a metal plate or a plated metal plate is 1 to 200.
mg / m ² , and a thermosetting resin as a base resin on the chromate film.
The total amount of the black dye and carbon black is 10 to 200 parts by weight, and the mixing ratio (weight ratio) of the black dye and carbon black is 100/100 parts by weight.
1 to 1/1, and at least one selected from polyethylene wax, fluororesin compound, molybdenum disulfide, graphite, graphite fluoride, fatty acid amide compound, metal soap, boron nitride and polyalkylene glycol. A black film of 0.3 to 5.0 μm in which a total of 1 to 100 parts by weight is blended, and a black film made of a composition in which at least one selected from a poorly soluble chromium compound and silica is blended in a total of 1 to 100 parts by weight Weldable black metal plate with excellent weather resistance that is thick.

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

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

(11) A weldable black metal plate having excellent weather resistance, wherein the black dye is at least one selected from azo metal complex salt dyes in the black metal plate of (1) to (8).

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

[0021]

The details of the present invention and the reasons for limiting the same 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 as necessary, and heats the surface of the metal plate or the plated metal plate or the above-mentioned chromate film. It has a black film made of a composition in which a black dye and carbon black are blended in a specific ratio with a curable resin. Here, the black dye in the present invention includes a dye that exhibits black by only the same kind of molecule due to the chemical structure of the molecule and a dye that exhibits black by mixing several kinds of dyes having different chemical structures of the molecule. It is a thing.

There are no particular restrictions on the metal plate or plated metal plate used as the base plate of the black metal plate of the present invention. However, if the base material is a standard steel plate for home appliances, automobile parts, building materials, etc., the corrosion resistance is low. From the viewpoint of, a galvanized steel sheet or a zinc-based alloy-plated steel sheet is particularly preferable.

The zinc plating and the zinc alloy plating film applied to the steel sheet include, for example, Zn plating, Zn—Ni
Alloy plating, Zn-Fe alloy plating, Zn-Cr alloy plating, Zn-Mn alloy plating, Zn-Co alloy plating,
Zn-Al alloy plating, or a plating composition in which one or more elements such as Ni, Fe, Mn, Co, Cr, Al, and Mo are added to these plating components can be used. In addition, a dispersion plating in which silica, a chromium compound, a particulate polymer, or the like is co-deposited during any of the above-described platings can be used. Further, it may be a multi-layer plating in which two or more of the above-mentioned platings of the same type or different types are applied. For example, a plating film in which two or more Zn—Fe alloy platings having different Fe contents are applied can be used. As a method for forming the zinc plating or the zinc alloy plating, any of the feasible methods such as an electroplating method, a hot-dip plating method, and a vapor phase plating method can be adopted. Further, other than the zinc-based steel sheet, a tin-plated steel sheet or a chrome-plated steel sheet (tin-free steel) can be used.

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

The stainless steel sheet is a steel sheet containing chromium or chromium and nickel, and the stainless steel sheet is an austenitic (SUS304, 304L, 31
6,316L), ferrite (SUS430 etc.),
Martensite (SUS410 etc.) and the like. These stainless steel sheets may be provided with a surface roughness at the time of rolling, or may be provided with a surface roughness by a pretreatment or the like, if necessary, for the purpose of increasing the adhesion to the black film.

The above metal plate or plated metal plate (hereinafter referred to as
These are collectively referred to simply as "metal plates").
For the purpose of improving adhesion and corrosion resistance, a chromate film is formed by chromic acid treatment as necessary. In particular, 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, extremely excellent corrosion resistance can be obtained by combining this chromate film with a black film containing a specific black imparting agent as described later.

This chromate film has a chromium adhesion amount (d
ry) as 1 to 200 mg / m ² , preferably 10 to
80 mg / m ² (the above is converted to metal chromium). If the chromium adhesion amount exceeds 200 mg / m ² , workability and weldability tend to deteriorate. In addition, the amount of chromium attached was 1 mg /
If it is less than m ² , the coating may be uneven and the corrosion resistance may be degraded. It is preferable that hexavalent Cr be present in the chromate film. Hexavalent Cr ions have a repairing effect, and when a metal plate is damaged, it acts to suppress corrosion therefrom.

Such a chromate treatment for the undercoat may be performed by any known method such as a reaction type, a coating type, and an electrolytic type. The coating type chromate treatment solution is mainly composed of a partially reduced chromic acid solution, and if necessary, a water-dispersible or water-soluble organic resin such as an acrylic resin and / or a particle size of several μm to several hundred μm. (Colloidal silica, fumed silica).
In this case, the ratio of trivalent Cr ions / hexavalent Cr ions is 1
/ 1 to 1/3, and the pH is preferably 1.5 to 4.0 (more preferably, 2 to 3). The ratio of trivalent Cr ions / hexavalent Cr ions is adjusted to a predetermined ratio using a general organic reducing agent (for example, sugars, alcohols, 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 by drying without washing after the chromate treatment. The reason for drying without water washing is that hexavalent Cr ions are removed in the usual water washing.
The ion / hexavalent Cr ion ratio is stably maintained as it is, and the resin film formed on the upper portion suppresses the excessive outflow of hexavalent Cr ions in a corrosive environment, so that the passivation is effectively performed for a long period of time. A high corrosion resistance performance can be obtained by maintaining the chemical action.

On the other hand, in the electrolytic type chromate treatment, a cathodic electrolytic treatment is performed in a bath containing chromic anhydride and one or more anions such as sulfuric acid, phosphoric acid fluoride and halogen oxyacid, followed by washing and drying. To form a film.

When comparing the chromate films obtained by the above two treatment methods, the coating type chromate is superior in corrosion resistance because it contains more hexavalent chromium in the film than the electrolytic type chromate. When the heat treatment is performed such that the film becomes dense and strong, the corrosion resistance becomes better than that of the electrolytic type chromate. On the other hand, the electrolytic type chromate has the advantages that the degree of completion of the film is high irrespective of the presence or absence of the heat treatment, and has the advantage that the control of the amount of the film adhered is easy. In consideration of corrosion resistance, coating type chromate is most desirable.

Next, the components of the black film will be described. The black film according to the present invention is characterized in that a thermosetting resin is used as a base resin, and a black dye and carbon black are blended in a specific ratio as a black imparting agent. Further, in the present invention, in addition to the above components, a solid lubricant can be contained for the purpose of improving the processability of the black film, and a rust preventive pigment can 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. As for the L value, the smaller the value is, the better the blackness is, and the target of the black film in the present invention is L ≦ 25, more preferably L ≦ 18. Note that L
The measurement of the value was performed by a multi-light source spectrophotometer (model MSC) manufactured by Suga Test Instruments Co., Ltd. The weather resistance was evaluated by a sunshine super long life weather meter (model WEL-SUN-TC-B) manufactured by Suga Test Instruments Co., Ltd. The degree of discoloration after 480 hours was determined by the following equation. ΔE was evaluated. The target of weather resistance in the present invention is ΔE ≦ 3, preferably ΔE ≦ 2.

(Equation 1)

It is necessary that the black film has the following functions. Excellent blackness in thin films (thickness of 5 μm or less) Excellent weatherability in environments such as semi-outdoors where light irradiation is relatively severe

Colorants generally used can be broadly classified into inorganic pigments, organic pigments, and dyes. Of these, when inorganic pigments and organic pigments are used in a thin coating film of several μm or less,
The hiding power of the pigment is important for blackness. As a black imparting agent for an inorganic pigment, carbon black is typical and is inexpensive. For this reason, it is most frequently used among black imparting agents, and a variety of grades according to the purpose are available. However, when this carbon black is used alone as a black color-imparting agent, a weldable thin film (thickness: 5 μm In the following, the blackness is unsatisfactory because the blackness is insufficient and the conductive film is a conductive pigment, so the black film has electrical conductivity and the metal plate has poor corrosion resistance. Also, other black inorganic pigments,
For example, iron oxide, titanium black, and the like also have insufficient blackness.

A typical example of a black organic pigment is aniline black. However, since the concealing power is also poor, sufficient blackness cannot be obtained. As other black organic pigments, there is perylene black, which cannot similarly provide a sufficient degree of blackness. Even when two or more 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 thousands of dyes currently on the market as trade names, and these are roughly classified into two types of classification methods, namely, a chemical structural classification method (1) and a chemical structural classification method (1). It is classified according to a practical classification method (2) based on dye properties (for example, "Organic Chemistry Handbook" published by Gihodo, edited by the Society of Synthetic Organic Chemistry).

In the classification method (1) based on the chemical structure, the dye is classified according to the main structure that causes color development in the dye molecule, and is a nitroso dye, a nitro dye, an azo dye (monoazo dye, disazo dye, trisazo dye, tetrakisazo dye). ,
Examples include anthraquinone dyes, indigo dyes, azine dyes, cyanine dyes, phthalocyanine dyes, stilbene dyes, sulfur dyes, triazole dyes, triphenylmethane dyes, acridine dyes, diphenylmethane dyes, and oxazine dyes. On the other hand, a practical classification method based on dye properties (2)
In, 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 acidic dyes by the classification method of (2) are further classified into azo dyes (monoazo, disazo, trisazo, tetrakisazo) by the classification method of (1). , Anthraquinone dye, triphenylmethane dye, azine dye and the like. 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. Groups having a free electron pair (auxochromophore) absorb light of a specific wavelength, and light of a wavelength that is not absorbed is captured by the naked eye as the color of the substance. Dyes of various colors will be present. See “COLOUR I” below.
NDEX classifies these colors into 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, uses, etc., to which the commercially available dyes belong, respectively. Each dye is described in" CI Gener ", which is classified and defined in this" COLOUR INDEX ".
ic Name ". In other words, this "COL
The classification method of "OUR INDEX" divides commercially available dyes into practical categories similar to the category (2) above, then displays the color categories, and furthermore, identifies the same chemical structure. The dyes are classified by number (indicated by numbers in order from 1).
Those that are clear up to the specific structural formula represent the structure `` CI
Constitution Number ”is described, but even if it is not, most of them are classified as described in (1) above.
For example, chemical structural classifications of azo (monoazo, disazo, etc.), anthraquinone, azine and the like are described.

For example, black dyes in the class of acid dyes are represented by the classification “CI Acid Black”. Among them, “CI Acid Black 1” has a specific chemical structure of disazo dye, "CI Acid Black 2" has a specific chemical structure of azine dye.
"3" has a specific chemical structure of the disazo dye, and is classified into colors, characteristics, uses, and the like. This "CI Generic Name" can be mutually compared with the trade name of a commercially available dye.

When such a black dye is added as a blackening agent to a resin film, as described in JP-A-4-218678, a weldable thin film (film thickness of 5 μm or less) is provided.
, Excellent blackness can be obtained. However, this black coating is not particularly problematic for indoor applications that are not exposed to direct sunlight, but for applications that are placed in a quasi-outdoor environment that is sometimes exposed to direct sunlight, for example,
In applications such as home appliances and building materials installed near windows, there is a disadvantage that the weather resistance is insufficient and the color gradually discolors.

In order to solve the problems of the pigment (carbon black and the like) and the dye as the black imparting agent as described above, the present invention provides a black dye and a carbon black in a specific ratio. It has been found that, as compared with the case where a black dye is used alone as a black imparting agent, the same excellent blackness can be obtained and the weather resistance is dramatically improved. The reason why such excellent properties are obtained is that when a black dye is added alone, when strong energy such as ultraviolet rays is irradiated on the black film, the bonds in the molecular structure of the dye are broken, and the dye inherent in the dye is destroyed. While the selective absorption characteristics of light are impaired, carbon black particles linked in a chain in the black film scatter some of the light by blending black dye and carbon black in a specific ratio.
It is considered that the absorption suppresses the breakage 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, even if a black pigment other than carbon black is incorporated into the film together with the black dye, the effect of improving the weather resistance can be expected, but it is not preferable because the blackness of the black film is significantly reduced compared to carbon black.

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

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

Since the dye is easily dissolved in a solvent, it can be made into a black film composition by mixing with a thermosetting resin. Further, carbon black can be uniformly dispersed in a solvent by a method such as a sand grinder, an attritor, a roll mill or the like. When these black dyes and carbon black are blended in a black film in the above-described amounts and ratios as a black-imparting agent, even black films having a weldable range (thickness of 5 μm or less) are uniform and excellent in black. Shows the appearance and shows excellent weather resistance. In addition, unlike the conventional etching type, black treatment involving reactions such as electrolytic treatment and displacement plating, the biggest advantage of the coating treatment is that there is no deterioration of the bath due to the treatment and the type of base plating is not limited. Can also be used.

The thickness of the black film is 0.3 to 5.0 μm, preferably 0.7 to 3.0 μm. 0.3 μm thick
If less, the coloring effect by the black imparting agent is poor, while
If it exceeds 3.0 μm, the spot weldability decreases, and if it exceeds 5.0 μm, the weldability remarkably decreases.

Hereinafter, the base resin, black dye and carbon black constituting the black film will be described. The base resin constituting 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 an acrylic copolymer resin, an alkyd resin, an epoxy resin, a polybutadiene resin, a phenol resin, a polyurethane resin, a fluororesin, a mixture of two or more of these resins, and addition with other monomers. Examples include condensates and modified derivatives with other resins. Among them, acrylic copolymer resin, alkyd resin, epoxy resin, fluororesin, acrylic silicone resin and the like are preferable.

The acrylic copolymer is a resin synthesized by a solution polymerization method, an emulsion polymerization method or a suspension polymerization method using a normal unsaturated ethylenic monomer. Hard monomers such as nitrile, styrene, acrylic acid, acrylamide, and vinyltoluene are used as essential components, and unsaturated vinyl monomers are appropriately added thereto for the purpose of imparting resin hardness, flexibility, and crosslinkability. Obtained by: Further, this resin may be modified by another alkyd resin, epoxy resin, phenol resin or the like.

As the alkyd resin, known alkyd resins obtained by ordinary synthesis methods can be used. For example, oil-modified alkyd resins, rosin-modified alkyd resins, phenol-modified alkyd resins, styrenated alkyd resins,
Silicon-modified alkyd resins, acryl-modified alkyd resins, oil-free alkyd resins (polyester resins) and the like can be mentioned.

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

As the fluororesin, there are fluoroolefin-based copolymers such as alkyl vinyl ether, synchro alkyl vinyl ether, carboxylic acid-modified vinyl ester, hydroxyalkyl allyl ether, tetrafluoropropyl vinyl ether and the like. 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 which contains a hydrolyzable alkoxysilyl group in a side chain or a terminal of an acrylic copolymer as a main component, and is blended with a curing agent. When these acrylic silicone resins are used, excellent weather resistance can be expected. Known predetermined curing agents are used for these resins. Examples of the curing agent include melamine, blocked isocyanate, and urea resin.

There are no particular restrictions on the black dye used in the present invention, and any of an organic solvent-soluble black dye and 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 dyes), azo-methine dyes, quinoline dyes, ketone imine dyes, fluorone dyes, nitro dyes,
There are xanthene dye, acenaphthene dye, quinophthalone dye, anthraquinone dye, aminoketone dye, methine dye, perylene dye, coumarin dye, perinone dye, triphenyl dye, triallylmethane dye, phthalocyanine dye, incrophenol dye, azine dye, etc.
One or more of these dyes can be used. Among them, 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, or ketone), and therefore is used together with water and a water-soluble or water-dispersible thermosetting resin, or as an organic solvent and an organic solvent. By mixing with a soluble thermosetting resin, a black film composition can be obtained. When this black dye is blended in the resin film within the range of the mixing ratio with the carbon black, excellent blackness is exhibited even in a thin film (thickness of 5 μm or less) in a weldable range. Furthermore, since the light fastness of the dye itself is excellent, there is no problem even when it is used for a black metal plate for household 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 underlayer chromate (the action of trivalent Cr ions) and the barrier effect of the resin film itself In addition to the anti-corrosion effect, the above-mentioned barrier effect of the black dye itself makes the corrosion resistance higher, and the self-healing effect of repairing defects of the passive film by hexavalent Cr ion → trivalent Cr ion of the base chromate and A high degree of corrosion resistance can be obtained due to factors such as good adhesion between the Zn-based plating, the chromate film, and the black film.

Among the black dyes, black azo metal complex dyes have the best light fastness and corrosion resistance. This black azo metal complex dye is a complex compound of an azo dye and a trivalent metal such as chromium, copper, and cobalt.
Representative examples of “CI Generic Name” of “NDEX” include 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
(Above, organic solvent-soluble black azo metal complex 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, CIM
ordant Black 90 etc. (the above are water-soluble black azo metal complex dyes).

As described above, a black azo metal complex dye which is not registered in “COLOUR INDEX”, for example, a newly developed dye which has not been registered yet, or a mixture of a plurality of types of dyes, Needless to say, a mixture containing at least one kind of black azo metal complex dye in the mixture can be used.

This dye is characterized by a complex compound of one atom of metal to two molecules of azo dye (2: 1 type metal complex salt) or a complex compound of one atom of metal to one molecule of azo dye (1: 1). For structural reasons considered to be (type 1 metal complex salt), stability to light (light fastness) is superior to other dyes, and blackness is superior to other dyes. Metals that can form complex salts with dyes are C
r, Co, Cu, Fe, Al, etc.
There are many complex salts.

Commercially available organic solvent-soluble black azo metal complex dyes include, for example, ORC manufactured by Ciba-Geigy.
ASOL Black RL, ORASOL Black RLP (above, CI Solven
t Black 29), ORASOL Black CN (CI Solvent Blac
k28), ORASOL Black BA (CI Solvent Black
6), BASF ZAPON Black X51 (CI Solvent
Black 27), Aizen Spilon manufactured by Hodogaya Chemical Industry Co., Ltd.
Black RLH Special (CI Solvent Black 42) and the like. In addition, "COLOUR INDEX (THIRD EDITIO
N)), for example, Aizen Spilon Black MH Special manufactured by Hodogaya Chemical Industry Co., Ltd., Kayaset Black KR manufactured by Nippon Kayaku Co., Ltd., and all exhibit excellent blackness. A black film is obtained.

Also, by using a black azo-based chromium complex dye as the black azo-based metal complex dye, extremely excellent corrosion resistance, which is presumed to be a synergistic effect between the trivalent Cr ion and the base chromate, can be obtained. This is trivalent C
This is presumably because the black azo-based metal complex dye containing r is stably present as a passive film and the barrier effect is further improved. For these reasons, the most preferred black azo metal complex salt dye is one in which the metal forming the complex salt is trivalent Cr ion.

Further, as another black dye, a black azo dye which is not a metal complex salt is used as a thin film which can be welded (film thickness 5 μm).
m or less), it exhibits excellent blackness (L ≦ 25, preferably L ≦ 18) equal to or more than that of the black azo-based metal complex dye. In addition, since the production unit price of this black azo dye is about 80% of that of the black azo metal complex dye, the black azo dye is compared with a black metal plate using the above black azo metal complex 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 increasing the conjugated double bond of the chromophore chemically. On the other hand, this black azo dye is inferior in light fastness to the black azo metal complex salt dye, but when used in combination with carbon black, an effect of improving light fastness is recognized.

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

Examples of commercially available products include Neptun Black X60 (CI Solvent Black 3) manufactured by BASF and Nepun Black X60.
tun A Black X17 (CI Solvent Black 46), Mitsui Oil Black YG-6 (manufactured by Mitsui Toatsu Dye Co., Ltd.)
vent Black 39) and the like, and a black film exhibiting excellent blackness can be obtained. As the black azo dye, two or more dyes may be used in combination, or further, a mixture of a dye mainly belonging to a black azo dye and a dye belonging to another type in a chemical structural classification. It may be used as a black imparting agent.

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

As the organic solvent-soluble black azine-based dye, “CI Solvent Bla” in “COLOUR INDEX” described above is used.
Among the organic solvent-soluble black dyes classified in “ck”, CI Solvent Black 5, 5: 1, 7, 31, 3
2, 50, and the like. Also, besides this, "COLOUR INDE
Existing or new ones not registered in "X" may be used.

Commercially available organic solvent-soluble black azine-based dyes include, for example, 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 Industries, Ltd. Sumisol Black AR (CI
Solvent Black 50) and the like, and a black film exhibiting excellent blackness can be obtained.

The black azine dye may be used as a mixture of two or more dyes. Further, a black azine dye is mainly used, and a dye belonging to another type in the chemical structural classification is mixed with the black azine dye. This may be used as a blackening agent.

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

The above-mentioned black azo metal complex dyes, black azo dyes and black azine dyes can be used by appropriately mixing two or more of them. In addition to the above dyes, black dyes include, for example, phthalocyanine dyes, azomethine dyes, anthraquinone dyes, and quinophthalone dyes, and these dyes can be used.

As described above, as the black dye applied to the present invention, not only the same type of molecule that exhibits black due to the chemical structure of the molecule, but also several types of dyes having different molecular chemical structures are mixed. Some of them have a black color. Therefore, using the principle of subtractive color mixture, it belongs to one or more of azo metal complex dyes, azo dyes, azine dyes, phthalocyanine dyes, azomethine dyes, anthraquinone dyes, quinophthalone dyes and the like. A mixture of several coloring dyes to obtain a black dye can be used.

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

The carbon black used in the present invention can be classified into those obtained by the pyrolysis method and those obtained by the incomplete combustion method from the viewpoint 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 the method obtained by any of these methods must be used. Can be. Carbon black having a small average primary particle diameter, a large specific surface area, and a large dispersion stability in a coating composition is preferable from the viewpoint of blackness in a thin film. Specifically, the average primary particle diameter is 50 μm or less, particularly 20 μm.
m or less, and the specific surface area is preferably 50 m ² / g or more, particularly 100 m ² / g or more as measured by the BET method. Examples of such carbon black include # 1000, # 950, and # 90 manufactured by Mitsubishi Kasei Corporation.
0, # 2300, MA7, # 7 manufactured by Tokai Carbon Co., Ltd.
700, # 7450, # 8200, # 8500, and the like.

The above-described black coating of the black metal plate of the present invention has sufficient characteristics as it is, but more excellent characteristics 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. Solid lubricants that can be used in the present invention include polyethylene wax, fluororesin compounds (eg, polyfluoroethylene resin, polyvinyl fluoride resin, polytetrafluoroethylene resin, polyvinylidene fluoride resin, etc.), fatty acid amide compounds (eg, Stearic acid amide, palmitic acid amide, methylene bis stearamide, ethylene bis stearamide, oleic amide, esyl amide, alkylene bis fatty acid amide, etc., metal soap (for example, calcium stearate, lead stearate, calcium laurate, Calcium palmitate), molybdenum disulfide, graphite, fluorinated graphite, boron nitride and polyalkylene glycol, and one or more of these can be used in combination.

The solid lubricant is used in an amount of 1 to 100 parts by weight, preferably 10 to 6 parts by weight, per 100 parts by weight of the thermosetting resin.
It is blended in the range of 0 parts by weight. Less than 10 parts by weight,
In particular, when the amount is less than 1 part by weight, the effect of improving the lubrication of the black film by adding the solid lubricant is poor. On the other hand, when the amount is more than 60 parts by weight, especially when it is more than 100 parts by weight, the strength of the black film after curing decreases, It is not suitable because part of the coating adheres to the pressing mold.

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

As the hardly soluble chromate, barium chromate (BaCrO ₄ ), strontium chromate (Sr
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
O ₄ ).

As the silica, fumed silica (for example, AEROSIL 130, AEROSI manufactured by Nippon Aerosil Co., Ltd.)
L 200, AEROSIL 300, AEROSIL 380, AEROSIL
R972, AEROSIL R811, AEROSIL R805, AERO
SIL R974, etc.), colloidal silica (solvent-type organic resins include, 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 the water-dispersible and water-soluble organic resin include, for example, Snowtex 20, Snowtex C, Snowtex N, Snowtex O, and Snowtex S manufactured by Nissan Chemical Industries, Ltd., wet silica / sedimentation 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.) or the like 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 blended in the black coating composition as a component thereof. The mixing ratio of the rust preventive pigment is based on 100 parts by weight of the thermosetting resin.
The range is 1 to 100 parts by weight, preferably 3 to 60 parts by weight. When 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
If the amount is more than 10 parts by weight, the rust-preventive pigment itself has a coloring effect other than black. For example, in the case of a hardly soluble yellow chromate, there is a problem that the blackness is reduced.

When the solid lubricant and the particulate rust-preventive pigment are added in combination, a black film excellent in both processability and corrosion resistance of the processed portion can be formed. 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, based on 100 parts by weight of the base resin.
It is added in the range of 60 parts by weight.

Further, other pigments (inorganic pigments, organic pigments) may be added in order to adjust the subtle black color tone as desired. For example, by adding a black inorganic pigment such as graphite, aniline black, perylene black, or black titanium oxide, the glossiness can be adjusted or the jetness can be increased. 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-mentioned black film is prepared by diluting the composition in a solvent as required and applying the film to a predetermined thickness by a method such as a roll squeezing, a roll coater, or an air knife. Is obtained by heating and curing at 120 to 250 ° C.). The coating method and the baking method are performed by a general method and are not particularly limited. However, in the production of the black metal plate of the present invention, a coating facility for producing a highly corrosion-resistant surface-treated steel sheet possessed by a steel maker can be used as it is. There is a great merit.

[0086]

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

Coating type chromate treatment conditions: Chromate treatment solution (trivalent Cr ion: hexavalent Cr ion = 1: 1, colloidal silica content to total solid content in the treatment solution: 55 wt% (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
_{0g / l, H 2 SO 4} : 0.5g / l, the bath of the bath temperature 50 ° C., a current density of 4.9A / dm ^2, and cathodic electrolysis treatment in about 20 seconds electrolysis time, washed with water and dried, chromate film I got

Reaction type chromate treatment conditions: Spray treatment was performed under standard conditions using Zinchrome 357S manufactured by Nippon Parkerizing Co., Ltd., followed by washing 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 present invention and comparative examples. Tables 9 to 20 show the test results for the original plate, the chromate film, the composition for forming a black film, and the obtained black metal plate used in the present invention examples and comparative examples. The composition for forming a black film 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 ×: 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 higher the value of gloss, the higher the gloss.

(3) Weldability test: spot welding was performed under the following conditions, and evaluation was made based on 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 dots or more ○: 200 dots or more ×: Less than 200 dots

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

(5) Adhesion of black film;
Adhesiveness was evaluated by cutting 100 pieces of squares at mm intervals and attaching and peeling an adhesive tape to the pieces. The evaluation criteria are as follows. ◎: Peeled area 0% ○: Peeled area less than 10% △: Peeled area 10% or more, less than 20% ×: Peeled area 20% or more

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

(7) Weather resistance: JIS with Sunshine Super Long Life Weather Meter manufactured by Suga Test Instruments Co., Ltd.
K5400 was subjected to a weather resistance test, and the degree of discoloration after 600 hours was evaluated by a color difference ΔE defined by the following equation.

(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. of the original plate described in Table 1. * 2: No. of the base resin described in Table 2. * 3: No. of black dyes described in Tables 3 to 5. * 4: Represents parts by weight of black dye based on 100 parts by weight of base resin. * 5: No. of the pigments listed in Table 6 * 6: Indicates the parts by weight of the pigment with respect to 100 parts by weight of the base resin. * 7: Compounding ratio (weight ratio) of black dye / pigment * 8: No. of solid lubricant described in Table 7 * 9: The parts by weight of the solid lubricant are based on 100 parts by weight of the base resin. * 10: No. 8 of the rust preventive additives shown in Table 8. * 11: Indicates the 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 film is thinner (5 μm thick) than the conventional painted metal plate.
m or less) so that welding is possible, and it has much better weather resistance than a black metal plate in which a black dye is solely added to a black film. Also, this black metal plate
In addition to the above properties, black film adhesion, workability, corrosion resistance,
In addition to being excellent in light fastness, it can be manufactured by coating and baking with existing roll coater equipment etc., so there is no problem of bath deterioration due to plating elution as compared with reactive etching type black metal plate, For this reason, productivity can be greatly improved, and a black metal plate which is extremely excellent in both performance and productivity can be provided.

A black metal plate in which a black film contains a black azo metal complex dye which is soluble in an organic solvent as a black dye,
In particular, it shows excellent light fastness. Further, among black azo-based metal complex dyes, a metal plate having a black film containing a black azo-based chromium complex 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 a black film,
Lightfastness is slightly inferior to organic solvent-soluble black azo metal complex dyes, but there is no problem at all for indoor or semi-outdoor applications such as home appliances, and the price of these black dyes is About 5 to 5 black azo metal complex dyes
Since it is about 80%, there is an advantage that the raw material cost of the black film composition is low.

[Brief description of the 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 mixing ratio of black dye / carbon black on blackness.

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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ identification symbol FI B05D 7/24 303 B05D 7/24 303B C23C 22/30 C23C 22/30 (58) Investigated field (Int.Cl. ⁶ , DB B32B 15/08 B05D 5/00 B05D 5/06 B05D 7/14 B05D 7/24 301 B05D 7/24 303 C23C 22/30

Claims (12)

(57) [Claims] 1. A thermosetting resin is used as a base resin on the surface of a metal plate or a plated metal plate.
A total of 10 to 200 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 of 100/1 to 1 part by weight.
/ 0.3 to 0.3%
A weldable black metal plate having a thickness of 5.0 μm and having excellent weather resistance. 2. A thermosetting resin is used as a base resin on the surface of a metal plate or a plated metal plate.
A total of 10 to 200 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 of 100/1 to 1 part by weight.
/ 1, and at least one selected from polyethylene wax, fluororesin compound, molybdenum disulfide, graphite, graphite fluoride, fatty acid amide compound, metal soap, boron nitride and polyalkylene glycol in total of 1 A weldable black metal plate having excellent weather resistance and having a black film having a thickness of 0.3 to 5.0 [mu] m comprising a composition in which the composition is blended in an amount 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 to 200 parts by weight of a black dye and carbon black as a black imparting agent, and the blending ratio (weight ratio) of the black dye and carbon black is 100/1 to 100 parts by weight.
1/1, and at least one selected from the hardly soluble chromium compound and silica in total of 1 to 1
100 parts by weight of a black film made of a composition
A weldable black metal plate having a thickness of up to 5.0 μm and having excellent 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 to 200 parts by weight of a black dye and carbon black as a black imparting agent, and the blending ratio (weight ratio) of the black dye and carbon black is 100/1 to 100 parts by weight.
Compounded as 1/1, and further, polyethylene wax,
Fluororesin compound, molybdenum disulfide, graphite,
At least one selected from among fluorinated graphite, fatty acid amide compounds, metal soaps, boron nitride and polyalkylene glycol in a total amount of 1 to 100 parts by weight, and at least one selected from poorly soluble chromium compounds and silica A black coating having a thickness of 0.3 to 5.0 μm and a weldable black metal plate excellent in weather resistance and having a black coating composed of a composition containing 1 to 100 parts by weight in total. 5. A chromium deposition amount (calculated as chromium metal) on a surface of a metal plate or a plated metal plate of 1 to 200 mg /
has a chromate film of m ^2, 10 to 200 weight thermosetting resin as a base resin on top of the chromate film, with respect to the base resin 100 parts by weight, as a black imparting agent black dye and carbon black in a total Parts, and the mixing ratio (weight ratio) of the black dye and carbon black is 100/1 to 1 /
0.3 to 0.3%
A weldable black metal plate having a thickness of 5.0 μm and having excellent weather resistance. 6. The amount of chromium deposited (in terms of chromium metal) on the surface of a metal plate or a plated metal plate is 1 to 200 mg /
has a chromate film of m ^2, 10 to 200 weight thermosetting resin as a base resin on top of the chromate film, with respect to the base resin 100 parts by weight, as a black imparting agent black dye and carbon black in a total Parts, and the mixing ratio (weight ratio) of the black dye and carbon black is 100/1 to 1 /
And at least one selected from the group consisting of 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 and having a black film of a composition of 100 parts by weight and having a thickness of 0.3 to 5.0 μm. 7. The amount of chromium deposited (in terms of chromium metal) on the surface of a metal plate or a plated metal plate is 1 to 200 mg /
has a chromate film of m ^2, the thermosetting resin on top of the chromate film as a base resin for the base resin 100 parts by weight, a black dye and carbon black in a total amount as a black imparting agent 10 to 200 Parts by weight, and the mixing ratio (weight ratio) of the black dye and the carbon black is 100/1 to 1
/ L, and at least one selected from the hardly soluble chromium compound and silica in a total of 1 to 1
A black film composed of a composition of 00 parts by weight
A weldable black metal plate having a thickness of 5.0 μm and having excellent weather resistance. 8. The amount of chromium deposited on the surface of a metal plate or a plated metal plate (calculated as chromium metal) is 1 to 200 mg /
has a chromate film of m ^2, the thermosetting resin on top of the chromate film as a base resin for the base resin 100 parts by weight, a black dye and carbon black in a total amount as a black imparting agent 10 to 200 Parts by weight, and the mixing ratio (weight ratio) of the black dye and the carbon black is 100/1 to 1
/ 1, and at least one selected from polyethylene wax, fluororesin compound, molybdenum disulfide, graphite, graphite fluoride, fatty acid amide compound, metal soap, boron nitride and polyalkylene glycol in total of 1 -100 parts by weight, and at least one selected from poorly soluble chromium compounds and silica.
A weldable black metal plate excellent in weather resistance and having a black coating having a thickness of 0.3 to 5.0 μm, comprising a composition containing a total of 1 to 100 parts by weight of seeds. 9. The weather resistance according to claim 1, wherein the black dye comprises at least one selected from an azo metal complex dye, an azo dye and an azine dye. Black metal plate with excellent weldability. 10. The black dye is selected from at least one selected from azo metal complex dyes, azo dyes and azine dyes, and from phthalocyanine dyes, anthraquinone dyes, quinophthalone dyes, azomethine dyes and triphenylmethane dyes. The weldable black metal plate having excellent weather resistance according to claim 1, comprising at least one kind. 11. The method according to claim 1, wherein the black dye comprises at least one selected from azo metal complex dyes.
4. A weldable black metal plate excellent in weather resistance according to 4, 5, 6, 7, or 8. 12. A black dye comprising at least one selected from azo metal complex dyes and at least one selected from phthalocyanine dyes, anthraquinone dyes, quinophthalone dyes, azomethine dyes and triphenylmethane dyes. Item 6. A weldable black metal plate excellent in weather resistance according to Item 1, 2, 3, 4, 5, 6, 7 or 8.