JPH0732540A - Weldable black aluminum plate or black aluminum alloy plate with excellent decorativeness - Google Patents

Abstract

PURPOSE:To provide a weldable black aluminum plate or black aluminum alloy plate with an excellent decorativeness by a method wherein a substrate resin is provided on the surface of an aluminum plate or aluminum alloy plate, and a plurality of complex compounds represented by specified formulas are blended as a black color-imparting agent. CONSTITUTION:A thermosetting resin is provided on the surface of an aluminum plate or aluminum alloy plate as a substrate resin. 1 kind or 2 kinds or more of complex compounds represented by a formula I or formula II are blended by a total weight of 1-200 pts.wt. as a black color-imparting agent to obtain a black film, and a weldable black aluminum plate or black aluminum alloy plate with the black film of which the thickness is 0.3-3.0mum, which is superior in decorativeness, is obtained. Also, in the formula I, (A) represents -O- or -COO-, and R1, R2 independently represent H, Cl, NO2, SO2NH2, CH3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a weldable black aluminum plate or a black aluminum alloy plate which is used for office / OA equipment for home electric appliances, building materials, automobile parts, ornaments and the like and has an excellent appearance.

2. Description of the Related Art Aluminum alloy sheets are lighter in weight (smaller in specific gravity) than steel sheets and easy to process. The oxide film is stable in the atmosphere and has excellent corrosion resistance. Utilizing these features, it is widely used in home appliances, building materials, ornaments and the like. Most of them are used as a colored aluminum alloy plate by forming a colored film on the surface by anodizing or the like.

A conventional method for coloring an aluminum alloy plate is
Two methods, the anodizing method and the chemical coloring method, are the mainstream. Of these, the former is a coloring method that utilizes the performance of the porous oxide film itself formed on the aluminum surface, and the latter is the reactivity of aluminum as an amphoteric metal. If these coloring methods are further classified,
The following are the main coloring techniques for conventional aluminum. (Metallic Materials Vol. 7, No. 11, "Aluminum Coloring", Kinki Aluminum Surface Treatment Research Group, 19
May 1988 "Introduction to anodic oxidation of aluminum" etc.)

(1) Anodizing method (a) Spontaneous coloring method Anodizing in a sulfuric acid bath, an oxalic acid bath, a chromic acid bath, a sulfonic acid bath, or a mixed bath thereof or an alkaline bath for several minutes to several hours. Then, a method of forming various black films by a combination of the type of aluminum alloy and electrolysis conditions (electrolyte composition, type of current, bath temperature, electrolysis time, current density, electrolysis voltage, etc.) (b) Anodic oxide film dyeing method After forming the anodic oxide film, a method of immersing the porous film by immersing it in a dye solution at about 60 ° C. for several minutes to several tens minutes. (C) Immersing the anodic oxide film in a metal salt solution or AC electrolysis Method of treatment After forming an anodic oxide film, a method of immersing or alternating-current electrolytically treating in a metal salt solution to deposit metal salt or metal oxide in the pores to blacken it (2) Chemical coloring method Blackening treatment Examples of charcoal Immersion treatment in an aqueous solution containing soda and sodium chromate under conditions of 90 to 100 ° C. for 3 to 5 minutes, and then in an aqueous solution containing potassium permanganate as a main component at 80 ° C. for about 10 minutes There is a way to do it.

However, these conventional techniques have the following problems. That is, both the anodizing method and the chemical coloring method require a long processing time of several minutes to several hours, so continuous production using strips is not possible. Removal of aluminum ions dissolved in the bath during blackening treatment It requires high technology for bath management to match the color of the black film. High energy cost due to high temperature of tens of degrees of blackening treatment. Eliminating heat generated during electrolysis. There are problems such as the need for cooling equipment.

Further, in the anodizing method, it is necessary to carry out a sealing treatment for containing the dye or the metal salt in the pores of the oxide film after the blackening treatment. As described above, the conventional anodizing method and the chemical coloring method have many problems, and are not technically and costly suitable for mass production of a black aluminum alloy sheet by continuous strip processing.

[0006]

On the other hand, there is a method of painting a black color on the surface of an aluminum alloy sheet. However, in the conventional black painting, a sufficient blackness is given to the aluminum alloy sheet. Usually requires a film thickness of 10 μm or more, and spot welding is impossible with such a film thickness. That is, most of the black-coloring agents used for black coating are black pigments called carbon black, but the black coatings using such black pigments are concealed at a spot-weldable film thickness (3 μm or less). Insufficient force, resulting in a scaly or uneven appearance. Therefore, the conventional black film using the black pigment as the black-imparting agent cannot obtain sufficient blackness in a film thickness within a weldable range.

The present invention has been made in view of such a conventional problem, and its object is a black aluminum plate or a black aluminum plate having a black film having excellent blackness even at a spot weldable thin film thickness (3 μm or less). It is to provide an aluminum alloy plate. Another object of the present invention is to provide a black aluminum plate or a black aluminum alloy plate which is excellent not only in excellent blackness but also in corrosion resistance, adhesion and workability.

According to the present invention, a black film made of a composition in which a specific base resin and a specific complex compound are mixed in a predetermined mixing ratio is formed in a film thickness within a predetermined range. It was made by finding that excellent blackness can be obtained even with a weldable film thickness. That is, the black aluminum plate or the black aluminum alloy plate of the present invention has the following configuration.

[1] A thermosetting resin is used as a base resin on the surface of an aluminum plate or an aluminum alloy plate, and 100 parts by weight of this base resin is represented by the following general structural formula (1) as a black-color imparting agent. Two or more complex compounds represented by the following general structural formula (1), or one or more complex compounds represented by the following general structural formula (1) and one or more complex compounds represented by the following general structural formula (2) A weldable black aluminum plate or black aluminum alloy plate having a black coating having a film thickness of 0.3 to 3.0 μm, which is formed by mixing 1 to 200 parts by weight in total.

[Chemical 65] …… (1)

[Chemical formula 66] (2) [In the general formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are independently H, Cl, NO ₂ , and S.
Represents O ₂ NH ₂ and CH ₃ , and X is

[Chemical formula 67] ...... (3) {(3) wherein R ₅ is H,

[Chemical 68] (R ₆ is. Representing a _{H, CH 3, NO 2,} OCH 3, Cl) represents a. The azo group is bonded to the 1-position of the naphthalene ring. }
Or

[Chemical 69] (4) (In the formula (4), R ₇ represents H, CH ₃ , and C ₂ H ₅ , and R ₈ represents H, Cl, NO ₂ , SO ₂ NH ₂ , and CH _{3. The} azo group is pyrazole. It is attached to the 4-position of the ring.) Or

[Chemical 70] ... (5) (in the formula (5), R ₉ represents H, Cl, NO ₂ , CH ₃ , and C ₂ H _{5. The} azo group is bonded to the side of the carbonyl group.), And M is Represents Cr, Co, Fe atoms,

[Chemical 71] Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. In the general formula (2), CuPc represents a copper phthalocyanine residue, R ₃ and R ₄ each independently represent H, a C _{1 to} C ₁₂ alkyl group, or a substituted alkyl group,

[Chemical 72] Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. m is an integer of 0 to 3, n is 1 to 4
And the sum of m and n is 2, 3 or 4. ]

[2] A thermosetting resin is used as a base resin on the surface of an aluminum plate or an aluminum alloy plate, and 100 parts by weight of this base resin is represented by the following general structural formula (1) as a black-imparting agent. Two or more complex compounds represented by the following general structural formula (1), or one or more complex compounds represented by the following general structural formula (1) and one or more complex compounds represented by the following general structural formula (2) 1 to 200 parts by weight in total, and 1 to 100 parts by weight of a solid lubricant, and a black film having a film thickness of 0.3 to 3.0 μm and excellent in designability and weldable black aluminum plate Or black aluminum alloy plate.

[Chemical formula 73] …… (1)

[Chemical 74] (2) [In the general formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are independently H, Cl, NO ₂ , and S.
Represents O ₂ NH ₂ and CH ₃ , and X is

[Chemical 75] ...... (3) {(3) wherein R ₅ is H,

[Chemical 76] (R ₆ is. Representing a _{H, CH 3, NO 2,} OCH 3, Cl) represents a. The azo group is bonded to the 1-position of the naphthalene ring. }
Or

[Chemical 77] (4) (In the formula (4), R ₇ represents H, CH ₃ , and C ₂ H ₅ , and R ₈ represents H, Cl, NO ₂ , SO ₂ NH ₂ , and CH _{3. The} azo group is pyrazole. It is attached to the 4-position of the ring.) Or

[Chemical 78] ... (5) (in the formula (5), R ₉ represents H, Cl, NO ₂ , CH ₃ , and C ₂ H _{5. The} azo group is bonded to the side of the carbonyl group.), And M is Represents Cr, Co, Fe atoms,

[Chemical 79] Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. In the general formula (2), CuPc represents a copper phthalocyanine residue, R ₃ and R ₄ each independently represent H, a C _{1 to} C ₁₂ alkyl group, or a substituted alkyl group,

[Chemical 80] Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. m is an integer of 0 to 3, n is 1 to 4
And the sum of m and n is 2, 3 or 4. ]

[3] A thermosetting resin is used as a base resin on the surface of an aluminum plate or an aluminum alloy plate, and 100 parts by weight of this base resin is represented by the following general structural formula (1) as a black imparting agent. Two or more complex compounds represented by the following general structural formula (1), or one or more complex compounds represented by the following general structural formula (1) and one or more complex compounds represented by the following general structural formula (2) 1 to 200 parts by weight in total, and 1 to 100 parts by weight of a particulate rust-preventive pigment, and a black film having a film thickness of 0.3 to 3.0 μm and excellent in designability and weldable black. Aluminum plate or black aluminum alloy plate.

[Chemical 81] …… (1)

[Chemical formula 82] (2) [In the general formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are independently H, Cl, NO ₂ , and S.
Represents O ₂ NH ₂ and CH ₃ , and X is

[Chemical 83] ...... (3) {(3) wherein R ₅ is H,

[Chemical 84] (R ₆ is. Representing a _{H, CH 3, NO 2,} OCH 3, Cl) represents a. The azo group is bonded to the 1-position of the naphthalene ring. }
Or

[Chemical 85] (4) (In the formula (4), R ₇ represents H, CH ₃ , and C ₂ H ₅ , and R ₈ represents H, Cl, NO ₂ , SO ₂ NH ₂ , and CH _{3. The} azo group is pyrazole. It is attached to the 4-position of the ring.) Or

[Chemical 86] ... (5) (in the formula (5), R ₉ represents H, Cl, NO ₂ , CH ₃ , and C ₂ H _{5. The} azo group is bonded to the side of the carbonyl group.), And M is Represents Cr, Co, Fe atoms,

[Chemical 87] Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. In the general formula (2), CuPc represents a copper phthalocyanine residue, R ₃ and R ₄ each independently represent H, a C _{1 to} C ₁₂ alkyl group, or a substituted alkyl group,

[Chemical 88] Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. m is an integer of 0 to 3, n is 1 to 4
And the sum of m and n is 2, 3 or 4. ]

[4] A thermosetting resin is used as a base resin on the surface of an aluminum plate or an aluminum alloy plate, and 100 parts by weight of this base resin is represented by the following general structural formula (1) as a black-imparting agent. Two or more complex compounds represented by the following general structural formula (1), or one or more complex compounds represented by the following general structural formula (1) and one or more complex compounds represented by the following general structural formula (2) In a total amount of 1 to 200 parts by weight, a solid lubricant in an amount of 1 to 100 parts by weight, and a particulate rust preventive pigment in an amount of 1 to 100 parts by weight.
A weldable black aluminum plate or black aluminum alloy plate having a 3.0 μm black film and excellent in design.

[Chemical 89] …… (1)

[Chemical 90] (2) [In the general formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are independently H, Cl, NO ₂ , and S.
Represents O ₂ NH ₂ and CH ₃ , and X is

[Chemical Formula 91] ...... (3) {(3) wherein R ₅ is H,

[Chemical Formula 92] (R ₆ is. Representing a _{H, CH 3, NO 2,} OCH 3, Cl) represents a. The azo group is bonded to the 1-position of the naphthalene ring. }
Or

[Chemical formula 93] (4) (In the formula (4), R ₇ represents H, CH ₃ , and C ₂ H ₅ , and R ₈ represents H, Cl, NO ₂ , SO ₂ NH ₂ , and CH _{3. The} azo group is pyrazole. It is attached to the 4-position of the ring.) Or

[Chemical 94] ... (5) (in the formula (5), R ₉ represents H, Cl, NO ₂ , CH ₃ , and C ₂ H _{5. The} azo group is bonded to the side of the carbonyl group.), And M is Represents Cr, Co, Fe atoms,

[Chemical 95] Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. In the general formula (2), CuPc represents a copper phthalocyanine residue, R ₃ and R ₄ each independently represent H, a C _{1 to} C ₁₂ alkyl group, or a substituted alkyl group,

[Chemical 96] Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. m is an integer of 0 to 3, n is 1 to 4
And the sum of m and n is 2, 3 or 4. ]

[5] Chromium adhesion amount (calculated as metallic chromium) 1 to the surface of the aluminum plate or aluminum alloy plate
It has a chromate film of 200 mg / m ² , and a thermosetting resin is used as a base resin on the top of the chromate film, and 100 parts by weight of this base resin is used as a black imparting agent by the following general structural formula (1). Two or more of the complex compounds represented, or one or more of the complex compounds represented by the following general structural formula (1) and one or two of the complex compounds represented by the following general structural formula (2). A weldable black aluminum plate or a black aluminum alloy plate having a black film having a film thickness of 0.3 to 3.0 μm, which is formed by mixing 1 to 200 parts by weight in total of at least one kind.

[Chemical 97] …… (1)

[Chemical 98] (2) [In the general formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are independently H, Cl, NO ₂ , and S.
Represents O ₂ NH ₂ and CH ₃ , and X is

[Chemical 99] ...... (3) {(3) wherein R ₅ is H,

[Chemical 100] (R ₆ is. Representing a _{H, CH 3, NO 2,} OCH 3, Cl) represents a. The azo group is bonded to the 1-position of the naphthalene ring. }
Or

[Chemical 101] (4) (In the formula (4), R ₇ represents H, CH ₃ , and C ₂ H ₅ , and R ₈ represents H, Cl, NO ₂ , SO ₂ NH ₂ , and CH _{3. The} azo group is pyrazole. It is attached to the 4-position of the ring.) Or

[Chemical 102] ... (5) (in the formula (5), R ₉ represents H, Cl, NO ₂ , CH ₃ , and C ₂ H _{5. The} azo group is bonded to the side of the carbonyl group.), And M is Represents Cr, Co, Fe atoms,

[Chemical 103] Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. In the general formula (2), CuPc represents a copper phthalocyanine residue, R ₃ and R ₄ each independently represent H, a C _{1 to} C ₁₂ alkyl group, or a substituted alkyl group,

[Chemical 104] Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. m is an integer of 0 to 3, n is 1 to 4
And the sum of m and n is 2, 3 or 4. ]

[6] Chromium adhesion amount (calculated as metallic chromium) 1 to the surface of the aluminum plate or aluminum alloy plate
It has a chromate film of 200 mg / m ² , and a thermosetting resin is used as a base resin on the top of the chromate film, and 100 parts by weight of this base resin is used as a black imparting agent by the following general structural formula (1). Two or more of the complex compounds represented, or one or more of the complex compounds represented by the following general structural formula (1) and one or two of the complex compounds represented by the following general structural formula (2). 1 to 200 parts by weight in total of 1 or more parts by weight, and 1 to 100 parts by weight of a solid lubricant, and a black film having a film thickness of 0.3 to 3.0 μm and excellent in designability and weldable black aluminum. Plate or black aluminum alloy plate.

[Chemical 105] …… (1)

[Chemical formula 106] (2) [In the general formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are independently H, Cl, NO ₂ , and S.
Represents O ₂ NH ₂ and CH ₃ , and X is

[Chemical formula 107] ...... (3) {(3) wherein R ₅ is H,

[Chemical 108] (R ₆ is. Representing a _{H, CH 3, NO 2,} OCH 3, Cl) represents a. The azo group is bonded to the 1-position of the naphthalene ring. }
Or

[Chemical 109] (4) (In the formula (4), R ₇ represents H, CH ₃ , and C ₂ H ₅ , and R ₈ represents H, Cl, NO ₂ , SO ₂ NH ₂ , and CH _{3. The} azo group is pyrazole. It is attached to the 4-position of the ring.) Or

[Chemical 110] ... (5) (in the formula (5), R ₉ represents H, Cl, NO ₂ , CH ₃ , and C ₂ H _{5. The} azo group is bonded to the side of the carbonyl group.), And M is Represents Cr, Co, Fe atoms,

[Chemical 111] Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. In the general formula (2), CuPc represents a copper phthalocyanine residue, R ₃ and R ₄ each independently represent H, a C _{1 to} C ₁₂ alkyl group, or a substituted alkyl group,

[Chemical 112] Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. m is an integer of 0 to 3, n is 1 to 4
And the sum of m and n is 2, 3 or 4. ]

[7] Chromium adhesion amount (calculated as metallic chromium) 1 to the surface of the aluminum plate or aluminum alloy plate
It has a chromate film of 200 mg / m ² , and a thermosetting resin is used as a base resin on the top of the chromate film, and 100 parts by weight of this base resin is used as a black imparting agent by the following general structural formula (1). Two or more of the complex compounds represented, or one or more of the complex compounds represented by the following general structural formula (1) and one or two of the complex compounds represented by the following general structural formula (2). 1 to 200 parts by weight in total of 1 or more parts by weight, and 1 to 100 parts by weight of a particulate rust preventive pigment, and a black film having a film thickness of 0.3 to 3.0 μm and excellent in designability can be welded Black aluminum plate or black aluminum alloy plate.

[Chemical 113] …… (1)

[Chemical 114] (2) [In the general formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are independently H, Cl, NO ₂ , and S.
Represents O ₂ NH ₂ and CH ₃ , and X is

[Chemical 115] ...... (3) {(3) wherein R ₅ is H,

[Chemical formula 116] (R ₆ is. Representing a _{H, CH 3, NO 2,} OCH 3, Cl) represents a. The azo group is bonded to the 1-position of the naphthalene ring. }
Or

[Chemical 117] (4) (In the formula (4), R ₇ represents H, CH ₃ , and C ₂ H ₅ , and R ₈ represents H, Cl, NO ₂ , SO ₂ NH ₂ , and CH _{3. The} azo group is pyrazole. It is attached to the 4-position of the ring.) Or

[Chemical 118] ... (5) (in the formula (5), R ₉ represents H, Cl, NO ₂ , CH ₃ , and C ₂ H _{5. The} azo group is bonded to the side of the carbonyl group.), And M is Represents Cr, Co, Fe atoms,

[Chemical formula 119] Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. In the general formula (2), CuPc represents a copper phthalocyanine residue, R ₃ and R ₄ each independently represent H, a C _{1 to} C ₁₂ alkyl group, or a substituted alkyl group,

[Chemical 120] Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. m is an integer of 0 to 3, n is 1 to 4
And the sum of m and n is 2, 3 or 4. ]

[8] Chromium adhesion amount (calculated as metallic chromium) 1 to the surface of the aluminum plate or aluminum alloy plate
It has a chromate film of 200 mg / m ² , and a thermosetting resin is used as a base resin on the top of the chromate film, and 100 parts by weight of this base resin is used as a black imparting agent by the following general structural formula (1). Two or more of the complex compounds represented, or one or more of the complex compounds represented by the following general structural formula (1) and one or two of the complex compounds represented by the following general structural formula (2). 1 to 200 parts by weight in total, 1 to 100 parts by weight of a solid lubricant, and 1 to 100 parts by weight of a particulate rust preventive pigment, and a film thickness of 0.3 to 3.
A weldable black aluminum plate or black aluminum alloy plate having a 0 μm black film and excellent in design.

[Chemical 121] …… (1)

[Chemical formula 122] (2) [In the general formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are independently H, Cl, NO ₂ , and S.
Represents O ₂ NH ₂ and CH ₃ , and X is

[Chemical 123] ...... (3) {(3) wherein R ₅ is H,

[Chemical formula 124] (R ₆ is. Representing a _{H, CH 3, NO 2,} OCH 3, Cl) represents a. The azo group is bonded to the 1-position of the naphthalene ring. }
Or

[Chemical 125] (4) (In the formula (4), R ₇ represents H, CH ₃ , and C ₂ H ₅ , and R ₈ represents H, Cl, NO ₂ , SO ₂ NH ₂ , and CH _{3. The} azo group is pyrazole. It is attached to the 4-position of the ring.) Or

[Chemical formula 126] ... (5) (in the formula (5), R ₉ represents H, Cl, NO ₂ , CH ₃ , and C ₂ H _{5. The} azo group is bonded to the side of the carbonyl group.), And M is Represents Cr, Co, Fe atoms,

[Chemical 127] Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. In the general formula (2), CuPc represents a copper phthalocyanine residue, R ₃ and R ₄ each independently represent H, a C _{1 to} C ₁₂ alkyl group, or a substituted alkyl group,

[Chemical 128] Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. m is an integer of 0 to 3, n is 1 to 4
And the sum of m and n is 2, 3 or 4. ]

[0016]

[9] In the black aluminum plate or black aluminum alloy plate of the above [2], [4], [6] or [8], as a solid lubricant, a hydrocarbon compound such as a polyolefin wax, a fluororesin compound, a fatty acid Selected from the group of amide compounds, metallic soaps, metallic sulfides such as molybdenum disulfide, graphite, fluorinated graphite, boron nitride, polyalkylene glycol 1
A weldable black aluminum plate or a black aluminum alloy plate which contains one or more kinds and is excellent in design.

[10] The above [3], [4], [7],
[8] or

In the black aluminum plate or the black aluminum alloy plate of [9], as a particulate rust-preventive pigment, one or more selected from the group consisting of a sparingly soluble chromium compound and silica is welded and has excellent designability. Black aluminum plate or black aluminum alloy plate.

[11] In the black aluminum plate or the black aluminum alloy plate of any one of the above [1] to [10], the lightness and hue of the black coating surface are L ≦ 25 in the Hunter L, a, b color system. , A = -2 to 2, b =-
A weldable black aluminum plate or black aluminum alloy plate having a design property of 2.5 to 2.5.

[0019]

The details of the present invention and the reasons for limitation thereof will be described below. The black aluminum plate or the black aluminum alloy plate of the present invention uses an aluminum plate or an aluminum alloy plate as a starting material, and forms a chromate film on the surface thereof if necessary, and heat cures on the metal plate surface or the above chromate film. It has a black film formed of a composition in which a specific black dye is mixed with a base 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.

As an aluminum plate as a starting material,
For example, there are industrial pure aluminum plates such as 1100, 1200, 1050, and the aluminum alloy plate contains at least one of copper, manganese, silicon, magnesium, zinc, chromium, nickel, etc. as an alloying element.
For example, 2002, 2117, 2036, 2037, 2
038, 3004, 5052, 5182, 6009, 6
There are aluminum alloy plates such as 010, 6015, 6016 and 6111. In addition, in general, the above-mentioned industrial pure aluminum plate and aluminum alloy plate in a narrow sense are also referred to as "aluminum alloy plate", and therefore, in the following description, for the sake of convenience, aluminum alloy plate has the same meaning. Shall have.

On the surface of the aluminum alloy plate, adhesion,
For the purpose of improving the corrosion resistance, a chromate film is formed by chromic acid treatment if necessary. In the black aluminum alloy sheet of the present invention, a 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 (dry) of 1 to 200 mg /
m ² , preferably 10 to 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. It is preferable that hexavalent Cr be present in the chromate film. Hexavalent Cr ions have a repairing action, and when a base metal is scratched, it has an action 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.
The ratio of r ions / hexavalent Cr ions is kept stable as it is, and the resin film formed on the upper portion suppresses the excessive outflow of hexavalent Cr ions in a corrosive environment, and effectively prevents the long-term failure. Higher corrosion resistance can be obtained by maintaining the passive action.

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, followed by washing with water and drying. 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 heat-treated, the film becomes dense and strong, and therefore has better corrosion resistance than 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 coating in the present invention is a thermosetting resin as a base resin, which is mixed with a specific complex compound as a black-imparting agent, whereby a weldable thin coating (~ 3 μm) and jet black It is possible to obtain a black film having a characteristic black appearance, capable of arbitrarily adjusting the color tone, that is, redness, blueness, and the like, and having the characteristic that fingerprints are less noticeable.

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 particulate 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, preferably L ≦ 20, and more preferably L ≦ 15. A multi-source spectrophotometer (model MSC) manufactured by Suga Test Instruments Co., Ltd. was used for color measurement of the black film, and a standard light source C (JIS Z 8720-1983) was used as a light source. a and b (JIS Z 8730-1980) were measured (using a C light source 2 degree visual field).

The function required as a black-color imparting agent is that a film having a weldable thickness (3 μm or less) can exhibit sufficient blackness. Moreover, when the black-color-imparting agent is mixed with the base resin in a mixing ratio such that sufficient blackness is obtained, other properties required for the black film,
For example, it should not have any adverse effect on workability, corrosion resistance, etc.

Conventionally, pigments (inorganic pigments and organic pigments) are commonly used as colorants. 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, this carbon black has an insufficient blackness because the hiding power is not sufficient in a thin film having a thickness of 3 μm or less, which is the target of the present invention, unlike the case where the film thickness is several tens of μm as in ordinary paints. Moreover, since it is a conductive pigment, the black coating has electrical conductivity, and the corrosion resistance of the steel sheet is inferior, which is not suitable. Further, other black inorganic pigments such as iron oxide and titanium black have insufficient blackness.

Further, aniline black is a typical black organic pigment, but it is also inferior in hiding power and cannot provide sufficient blackness. There is perylene black as another black organic pigment, 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.

Therefore, the present inventors have conducted studies to find a black-coloring agent having the following functions. (1) Base resin (thermosetting resin) and solvent (water-based,
It can be dissolved or dispersed in any organic solvent system. (2) The formed black film has sufficient blackness even in a weldable thin thickness (up to 3 μm). (3) The color shall not deteriorate even when used as a material for home appliances, office equipment, etc. illuminated by various light sources. That is, it has good light fastness. And it must be a black-color-imparting agent that fulfills at least these three functions. Furthermore, office equipment for home appliances, OA
In order to respond to the demand for high designability of equipment, etc., it is also considered from the viewpoint of obtaining a versatile black aluminum alloy plate that can control the appearance color tone of the black film arbitrarily and can be applied to the outer plates of the above-mentioned devices I went.

As a result, two or more kinds of complex compounds represented by the following general structural formula (1), or one or more kinds of complex compounds represented by the following general structural formula (1) and the following general structural formula It was found that a black aluminum alloy plate satisfying all the above functions can be obtained by using one or more of the complex compounds represented by (2) in combination.

[Chemical formula 129] …… (1)

[Chemical 130] (2) [In the general formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are independently H, Cl, NO ₂ , and S.
Represents O ₂ NH ₂ and CH ₃ , and X is

[Chemical 131] ...... (3) {(3) wherein R ₅ is H,

[Chemical 132] (R ₆ is. Representing a _{H, CH 3, NO 2,} OCH 3, Cl) represents a. The azo group is bonded to the 1-position of the naphthalene ring. }
Or

[Chemical 133] (4) (In the formula (4), R ₇ represents H, CH ₃ , and C ₂ H ₅ , and R ₈ represents H, Cl, NO ₂ , SO ₂ NH ₂ , and CH _{3. The} azo group is pyrazole. It is attached to the 4-position of the ring.) Or

[Chemical 134] ... (5) (in the formula (5), R ₉ represents H, Cl, NO ₂ , CH ₃ , and C ₂ H _{5. The} azo group is bonded to the side of the carbonyl group.), And M is Represents Cr, Co, Fe atoms,

[Chemical 135] Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. In the general formula (2), CuPc represents a copper phthalocyanine residue, R ₃ and R ₄ each independently represent H, a C _{1 to} C ₁₂ alkyl group, or a substituted alkyl group,

[Chemical 136] Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. m is an integer of 0 to 3, n is 1 to 4
And the sum of m and n is 2, 3 or 4. ]

The diazo component used in the complex compound of the general structural formula (1) is, for example, 3-chloro-2-aminophenol, 4-chloro-2-aminophenol, 3,
5-dichloro-2-aminophenol, 4,6-dichloro-2-aminophenol, 3,4,6-trichloro-
2-aminophenol, 4-nitro-2-aminophenol, 5-nitro-2-aminophenol, 6-chloro-4-nitro-2-aminophenol, 4-chloro-5
-Nitro-2-aminophenol, 4-chloro-6-nitro-2-aminophenol, 4-methyl-2-aminophenol, 4,5-dimethyl-2-aminophenol, 4-methyl-5-nitro-2 -Aminophenol,
4,6-Dinitro-2-aminophenol, 4-aminosulfonyl-2-aminophenol, 2-aminobenzoic acid, 3-chloro-2-aminobenzoic acid, 4-chloro-2
-Aminobenzoic acid, 5-chloro-2-aminobenzoic acid,
Examples include 4-nitro-2-aminobenzoic acid and 4-chloro-5-nitro-2-aminobenzoic acid.

The coupling component used in the complex compound of the general structural formula (1) is, for example, 2-hydroxynaphthalene, 2-hydroxy-3-phenylcarbamoylnaphthalene, 2-hydroxy-3- (2-methyl). Phenyl) carbamoylnaphthalene, 2-hydroxy-
3- (4-chlorophenyl) carbamoylnaphthalene,
2-hydroxy-3- (4-methoxyphenyl) carbamoylnaphthalene, 2-hydroxy-3- (3-nitrophenyl) carbamoylnaphthalene, 1-phenyl-3-methylpyrazolone, 1-phenyl-3-ethylpyrazolone, 1- (4-chlorophenyl) -3-methylpyrazolone, 1- (4-methylphenyl) -3-methylpyrazolone, 1- (4-nitrophenyl) -3-methylpyrazolone, 1- (4-aminosulfonylphenyl)
-3-Methylpyrazolone or acetoacetic acid anilide, acetoacetic acid-4-chloroanilide, acetoacetic acid-4
-Methylanilide, acetoacetic acid-2-nitroanilide,
Acetoacetic acid-4-ethylanilide and the like can be mentioned.

In the general structural formulas (1) and (2),

[Chemical 137] Examples of the aliphatic ammonium ion represented by and the substituted aliphatic ammonium include the followings.

[0035]

[Chemical 138]

[0036]

[Chemical 139]

[0037]

[Chemical 140]

[0038]

[Chemical 141]

[0039]

[Chemical 142]

[0040]

[Chemical 143]

[0041]

[Chemical 144]

[0042]

[Chemical 145]

[0043]

[Chemical 146]

[0044]

[Chemical 147]

The features of the case where such a specific complex compound is blended as a black-color imparting agent will be described below. First of all, even if the thickness of the black film is 3 μm or less, it has excellent blackness.
It is possible to give a uniform and even glossy appearance. This is because in the case of a black pigment, in a thin film, sufficient hiding properties cannot be obtained due to contact / aggregation of pigments with each other, resulting in unevenness or a film with poor gloss and poor appearance. In the case of this complex compound,
400 nm-700 nm due to its unique chemical structure
Since it has excellent absorption properties for electromagnetic waves in the visible light region, it has excellent blackness, and it can be uniformly dissolved (or dispersed) in a thin resin film in a very fine state at the molecular level, so there is no unevenness. This is due to the characteristic property of this particular complex compound that a uniform film can be formed.

Next, the formed black film does not deteriorate in color even when it is illuminated by various light sources such as indoor lighting as an aluminum alloy plate for office equipment for home electric appliances, OA equipment and the like. This is due to the extremely stable chemical structure in which the specific complex compound does not change even when excited by the energy of light received from the light source.

Further, the formed black film has better corrosion resistance than the above-described black pigment blended as a black-imparting agent, and further better than the clear film without addition. This is because when a black pigment is added to a thin film at a certain concentration or more, the pigment particles come into contact with each other and agglomerate to accelerate the permeation of water or ions through the gaps, thereby deteriorating the corrosion resistance. On the other hand, this specific non-conductive complex compound is uniformly dispersed (dissolved) in the film in a very fine state at the molecular level, does not promote the permeation of water and ions, and rather improves the anticorrosion effect. This is because it has the function of

By forming such a black film on the surface of the chromate film described above, it has excellent corrosion resistance due to the synergistic effect of both the anticorrosive action of the chromate film and the black film. Further, since the black film can be formed by a coating process such as a roll coater, unlike the conventional blackening due to the reaction with the processing solution such as the etching process or the anodizing process, the plating does not dissolve, so that the treatment is performed. It is possible to overcome the drawbacks of the prior art of deterioration of liquid. As described above, in the present invention, the discovery of a specific complex compound as a black-color-imparting agent has made it possible to form an unprecedented black film having an excellent function.

The black coating of the black aluminum alloy sheet of the present invention comprises a thermosetting resin and a specific complex compound, and further contains a solid lubricant and a particulate rust preventive pigment, if necessary. The appearance of this black aluminum alloy plate is determined by the type and composition of each of these constituent components and the film thickness of the black film. In order for this black aluminum alloy plate to have a highly designed appearance that can also be used for the chassis and outer plates of the above-mentioned equipment, the blackness of the black film is sufficient, and the color tone with little redness and bluishness. In the process of assembling home electric appliances, it is preferable that fingerprints are not noticeable even when touched by human hands. To satisfy this condition, the brightness and hue of the black film surface should be the Hunter color system L, a and b, L ≦ 25 (preferably L ≦ 20, more preferably L
≦ 15) −2 ≦ a ≦ 2 (preferably −1.5 ≦ a ≦ 1.5,
More preferably 1 ≦ a ≦ 1) −2.5 ≦ b ≦ 2.5 (preferably −2.0 ≦ b ≦ 1,
It is more preferable that -1.5≤b≤0.5).

As the complex compound represented by the above general structural formula (1), not only black, but also yellow, red, and orange colors can be synthesized, and the complex compound is represented by the general structural formula (2). The complex compound mainly has a blue color. The present invention is
Two or more of the complex compounds represented by the general structural formula (1) are mixed, or one or more of the complex compounds represented by the general structural formula (1) and a complex represented by the general structural formula (2). One kind or two or more kinds of compounds are mixed and used as a black-color imparting agent. Therefore, the complex compounds contained in the black film as the black-imparting agent have the following combinations.

Mixture of the black complex compound represented by the general structural formula (1) and one or more complex compounds other than the black compound represented by the general structural formula (1). The black compound represented by the general structural formula (1). Mixing a plurality of complex compounds other than the above Mixing a black complex compound represented by the general structural formula (1) with one or more complex compounds represented by the general structural formula (2) In the general structural formula (1) A black complex compound represented by one or more complex compounds other than black represented by the general structural formula (1), and one or more complex compounds represented by the general structural formula (2) Mixed Mixture of a plurality of complex compounds other than black represented by the general structural formula (1) and one or more complex compounds represented by the general structural formula (2) By selecting the amount appropriately, It is possible to obtain a black coating color.

Next, in the black film of the present invention, the compounding ratio of the black-imparting agent to 100 parts by weight of the base resin is 1 to 2
The amount is 00 parts by weight, preferably 4 to 120 parts by weight. If it is less than 1 part by weight, the coloring effect of the black complex compound is poor, and
If it exceeds 200 parts by weight, not only is it uneconomical, but undissolved complex compounds remain. The thickness of the black coating is 0.3 to 3.0 μm, preferably 0.7 to 2.5 μm. If the film thickness is less than 0.3 μm, the coloring effect of the black complex compound is poor. On the other hand, if it exceeds 2.5 μm, the spot weldability deteriorates, and if it exceeds 3.0 μm, the weldability remarkably decreases. FIG. 1 shows the relationship between the thickness of the black coating and spot weldability.

The base resin for the black coating of the black aluminum alloy sheet of the present invention is a thermosetting resin. The base resin is defined as such a resin because 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 copolymer is a resin synthesized by a solution polymerization method, an emulsion polymerization method, a suspension polymerization method or the like 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. Further, as the alkyd resin, a known one obtained by a usual synthesis method can be used, and for example, an oil-modified alkyd resin,
Examples thereof include rosin-modified alkyd resin, phenol-modified alkyd resin, styrenated alkyd resin, silicon-modified alkyd resin, acrylic-modified alkyd resin, and oil-free alkyd resin (polyester resin).

As the epoxy resin, epichlorohydrin type, glycidyl ether type straight epoxy resin, fatty acid modified epoxy resin (epoxy ester resin), polybasic acid modified epoxy resin, acrylic resin modified epoxy resin, alkyd (or polyester) modified 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 are fluoroolefin-based copolymers, for example, alkyl vinyl ether, synchroalkyl vinyl ether, carboxylic acid modified vinyl ester, hydroxyalkyl allyl ether, tetrafluoropropyl vinyl ether, etc. as the monomer,
There is 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 one having a hydrolyzable alkoxysilyl group at the side chain or terminal of an acrylic copolymer as a main component, and further containing a curing agent. 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 coating of the aluminum alloy sheet 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 the solid lubricant applicable to the present invention include the following. Hydrocarbon lubricants: for example, natural paraffin, synthetic paraffin, microwax, polyethylene wax, chlorinated hydrocarbon, etc. -Fluorine resin: For example, polyfluoroethylene resin, polyvinyl fluoride resin, polytetrafluoroethylene resin, polyvinylidene fluoride resin and the like. -Fatty acid amide lubricants: for example, stearic acid amide,
Palmitic acid amide, methylene bis stearamide, ethylene bis stearamide, oleic acid amide, esyl acid amide, alkylene bis fatty acid amide and the like. Metallic soaps: for example, calcium stearate, lead stearate, calcium laurate, calcium palmitate, etc. -Metal sulfides: molybdenum disulfide, tungsten disulfide. -Others: graphite, fluorinated graphite, boron nitride, grease, alkali metal sulfate, etc.

The above solid lubricant is 1 to 100 parts by weight, preferably 3 to 60 parts by weight, based on 100 parts by weight of the thermosetting resin.
Blend in the range of parts by weight. If the blending amount is less than 10 parts by weight, particularly less than 1 part by weight, the effect of improving the lubricity of the black film by the addition of the solid lubricant is poor, while if it is more than 60 parts by weight, especially more than 100 parts by weight, it is This is not suitable because the strength of the black coating decreases and part of the coating adheres to the press mold.

The black coating film obtained by applying the black coating composition comprising the base resin and the specific complex compound has the anti-corrosion effect of the base aluminum alloy plate and the synergistic effect with the chromate coating formed as necessary. Although it has sufficient corrosion resistance, in order to further improve the corrosion resistance in the processed part, a rust preventive pigment can be added to the black film composition, whereby further excellent corrosion resistance can be obtained, and black It is preferable because the use of the aluminum alloy plate is widened.
As the rust preventive pigment, one or more selected from sparingly soluble chromate and silica are used. The sparingly soluble chromate includes barium chromate (BaCrO ₄ ),
Strontium chromate (SrCrO ₄ ), lead chromate (PbCrO ₄ ), zinc chromate (ZnCrO ₄ .4Zn)
(OH) ₂ ), calcium chromate (CaCrO ₄ ), zinc potassium chromate (K ₂ O.4ZnO.4CrO ₃ .3)
H ₂ O), there is a silver chromate (AgCrO _4).

The silica used in the present invention is dry silica (for example, AEROSIL 13 manufactured by Nippon Aerosil Co., Ltd.).
0, AEROSIL 200, AEROSIL 300, AEROSIL 38
0, AEROSIL R972, AEROSIL R811, AEROSIL R
805, AEROSIL R974, etc.), colloidal silica (for solvent type organic resins, for example, Nissan Chemical Industries, Ltd.
MA-ST, IPA-ST, NBA-ST, IBA-ST, EG-ST, XBA-ST,
ETC-ST, DMAC-ST, etc. Examples of water-dispersible water-soluble organic resins include Snowtex 20 manufactured by Nissan Chemical Industries, Ltd.,
Snowtex C, Snowtex N, Snowtex O, Snowtex S, etc.), wet silica / precipitation method (for example, T-32 (S), K-41, F- manufactured by Tokuyama Soda Co., Ltd.)
80), a wet silica gel method (for example, Syroid 244, Syloid 150, Syloid 72, Syloid 65, SHIELDEX manufactured by Fuji Davison Chemical Co., Ltd.) and the like can be used. It is also possible to use a mixture of one or more of the above silicas.

One or more of the above rust-preventive pigments are added to the black coating composition as a constituent component thereof. 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
When it exceeds the weight part, the rust preventive pigment itself has a black 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. Further, when the solid lubricant and the particulate rust preventive pigment are added in combination, it becomes possible to form a black film having excellent processability and corrosion resistance of the processed part. At that time, the solid lubricant and the particulate rust preventive pigment are added in an amount of 1 to 100 parts by weight, preferably 3 to 60 parts by weight, relative to 100 parts by weight of the base resin.

Other pigments (inorganic pigments, organic pigments) may be added in order to adjust the delicate color tone of black color according to preference. For example, black inorganic pigment carbon black,
Graphite, aniline black, perylene black,
By adding black titanium oxide or the like, the glossiness can be adjusted or the jetness can be increased. The above black film, the composition is diluted with a solvent as necessary,
After applying a predetermined film thickness by a method such as roll squeezing, roll coater, or air knife, plate temperature 80 to 300 ° C
It is obtained by heating and curing at (preferably 120 to 250 ° C.). The coating method and the baking method are carried out by a general method, and there is no particular limitation, but in the production of the aluminum alloy sheet of the present invention, the coating equipment for producing a highly corrosion-resistant surface-treated steel sheet owned by a steel manufacturer can be used as it is. There is a big merit.

[0063]

[Embodiment] [Embodiment 1] to [Embodiment 4] are shown below as black aluminum alloy plates for home appliances and office equipment. In these examples, the aluminum alloy plate was degreased with alkali, washed with water and dried, and if necessary, a coating type chromate treatment liquid was applied by a roll coater or electrolytic chromate treatment, and then a black imparting agent was added. After coating the resin composition with a roll coater, the resin composition was heated and baked at a predetermined temperature and air-cooled.

The conditions of the above-mentioned coating type chromate treatment and electrolytic chromate treatment are as follows. -Coating Chromate Treatment Conditions Trivalent Cr ion: Hexavalent Cr ion = 2: 3, pH = 2.
5 (pH adjusted with KOH), a chromate treatment liquid having a solid content of 20 g / l was applied with a room temperature roll coater and dried. Electrolytic chromate treatment conditions CrO ₃ : 50 g / l, H ₂ SO ₄ : 0.5 g / l, a bath temperature of 50 ° C., and a cathodic electrolysis treatment with a current density of 4.9 A / dm ² and an electrolysis time of 20 seconds, Washed and dried.

Tables 1 to 4 show the aluminum alloy plate, the base resin which is a black film component, the solid lubricant and the particulate rust preventive pigment used in each example. The black film-forming composition was blended in the blending amount shown in each example, and an organic solvent was added as necessary to dilute it, and coating was performed with a roll coater. As a representative example of the method for synthesizing the complex compound used in the examples, the present invention examples (1) and (2) of Example 1
The method of synthesizing the complex compound used in the above in the laboratory is shown below.

[Synthesis Example of Complex Compound Used in Inventive Example (1) of Example 1] Synthesis Example of Complex Compound (1-1)

[Chemical 148] -Synthesis of intermediate compound 15.4 g of 5-nitro-2-aminophenol was added to 150 ml of water, and 23.6 g of 35% hydrochloric acid was stirred.
Add. While keeping this solution at 10 ° C. or lower, an aqueous solution containing 20 ml of water and 7.2 g of sodium nitrite is poured into the solution. After stirring for 2 hours at the same temperature, excess nitrous acid was decomposed with sulfamic acid to prepare a diazonium solution. Into 150 ml of water, 14.9 g of B-naphthol is charged, and while stirring, 4 g of caustic soda and 5.3 g of sodium carbonate are added to prepare a coupler solution. While crushed ice was put into this coupler liquid and kept at 10 ° C or lower,
The diazonium solution prepared above is added and coupling is performed. After the coupling was completed, it was filtered off to obtain 92 g of an intermediate compound. Complexation reaction 92 g of the above intermediate compound was dispersed in 150 ml of water, and 29.5 g of 40% chromium sulfate, 20 g of salicylic acid and a chromium salicylate solution adjusted with caustic soda were added to adjust the pH to 10 to 10.
11 was added and the mixture was reacted at 90 to 100 ° C. for about 10 hours, cooled, filtered and dried to obtain 35 g of the desired product.

Synthesis example of complex compound (1-2)

[Chemical 149] -Synthesis of intermediate compound 150 ml of water was charged with 15.4 g of 4-nitro-2-aminophenol, and 23.6 g of 35% hydrochloric acid while stirring.
Add. This solution is cooled to 10 ° C. or lower, and an aqueous solution containing 20 ml of water and 7.2 g of sodium nitrite is poured into the solution. After stirring at the same temperature for 2 hours, excess nitrous acid is decomposed by adding sulfamic acid to prepare a diazonium solution. Acetoacetanilide (17.8 g) is added to water (150 ml), and 48% caustic soda (9.2 g) and sodium acetate (10 g) are added and dissolved with stirring. While adding crushed ice to the mixture and maintaining the temperature at 10 ° C. or lower, a diazonium solution is added to perform a coupling reaction. After coupling is completed, it is filtered off,
130 g of intermediate compound was obtained.・ Complexation reaction 400 ml of water was charged with the above intermediate compound, 17.1 g of cobalt chloride (hexahydrate) was charged, and the pH was adjusted with 48% caustic soda.
It was adjusted to 9 to 10 and reacted at 90 to 100 ° C. for 3 hours, then cooled, filtered and dried to obtain 36 g of the desired product.

[Synthesis Example of Complex Compound Used in Inventive Example (2) of Example 1] Synthesis Example of Complex Compound (2-1)

[Chemical 150] After dispersing 37.5 g of the complex compound (1-2) in 300 ml of water, an aqueous solution of 100 ml of water, 5.7 g of 35% hydrochloric acid and 12.6 g of dodecylethanolamine was added to adjust the pH.
Heat to 60-70 ° C at 6-7 and stir for 2 hours. After cooling, it was separated by filtration and dried to obtain 48 g of the target product with counterions exchanged.

Synthesis example of complex compound (2-2)

[Chemical 151] -Synthesis of intermediate compound Into 150 ml of water, 16.6 g of anthranilic acid is charged, and 24.8 g of 35% hydrochloric acid is added while stirring. This solution is cooled to 10 ° C. or lower, and an aqueous solution containing 20 ml of water and 7.2 g of sodium nitrite is poured into the solution. After stirring for 2 hours at the same temperature, excess nitrous acid is decomposed with sulfamic acid to prepare a diazonium solution. 150 ml of water
18.1 g of 1-phenyl-3-methylpyrazolone is charged to the above, and 9.2 g of 48% caustic soda and 13.6 g of sodium acetate are added and dissolved with stirring. Add crushed ice to this 1
While keeping the temperature below 0 ° C., a diazonium solution is added to carry out a coupling reaction. After the coupling was completed, it was filtered off to obtain 90 g of an intermediate compound.・ Complexation reaction 150g of water was charged with 90g of wet mordant, and the same amount of chromium salicylate solution as shown in the synthesis example of complex compound (1-1) was added thereto, and the mixture was reacted at 90 to 100 ° C for 20 hours and cooled. After that, it was filtered and dried to obtain 39 g of the desired product.

Synthesis Example of Complex Compound (2-3)

[Chemical 152] -Synthesis of intermediate compound 15.4 g of 5-nitro-2-aminophenol was added to 150 ml of water, and 23.6 g of 35% hydrochloric acid was stirred.
Add. 20 ml of water and an aqueous solution of 7.2 g of sodium nitrite are added while cooling to 10 ° C or lower. After stirring for another 2 hours at the same temperature, excess nitrous acid is decomposed by adding sulfamic acid to prepare a diazonium solution. Water 1
50 ml of 1-phenyl-3-methylpyrazolone 18.
Charge 1 g and stir with stirring 48% sodium hydroxide 9.2
g and 13.6 g of sodium acetate are added and dissolved. Crushed ice is added to this, and a diazonium solution is added while maintaining the temperature at 10 ° C or lower to perform a coupling reaction. After the reaction was completed, it was separated by filtration to obtain 90 g of intermediate compound (I). -Complexation reaction 90g of intermediate compound (I) was charged into 150 ml of water, and the same amount of chromium salicylate solution as shown in the synthesis method of complex compound (1-1) was added thereto, and reacted at 90 to 100 ° C for 20 hours. After cooling, the mixture was filtered, filtered, and dried to obtain 39 g of the intermediate compound (II). Amination 39 g of the intermediate compound (II) was dispersed in 300 ml of water,
20.2 g of N, N-dimethyl-N-benzyl-2-hydroxytetradecyl ammonium chloride was added to pH 6
It was adjusted to ~ 7 and reacted at 60-70 ° C for 2 hours. After cooling, it was filtered and dried to obtain 56 g of the desired product.

Synthesis example of complex compound (2-4)

[Chemical 153] After dispersing 37.5 g of the complex compound (1-1) in 300 ml of water, an aqueous solution consisting of 100 ml of water, 5.7 g of 35% hydrochloric acid and 12.6 g of 3-methoxypropylamine was added to adjust the pH.
Heat to 60-70 ° C at 6-7 and stir for 2 hours. After cooling, it was separated by filtration and dried to obtain 48 g of the target product with counterions exchanged.

Synthesis example of complex compound (2-5)

[Chemical 154] To 182 g of chlorosulfonic acid, 24 g of copper phthalocyanine was added at 20 to 25 ° C. and reacted at 110 to 140 ° C. for 4 hours,
After cooling to 80 ° C., 48.5 g of thionyl chloride is gradually added and the reaction is carried out at 70 to 80 ° C. for 2 hours. After cooling, the mixture is poured into ice water containing salt, and the precipitated crystals are separated by filtration. Disperse the wet cake in ice water, adjust the pH to 4-5 with sodium carbonate, add 16.4 g of 3- (2-ethylhexyloxy) propylamine, adjust to pH 9 with sodium carbonate, and stir for a while to complete sulfonamidation. To do. Next, the pH is raised to 12 with caustic soda, and the mixture is stirred at 70 to 80 ° C for 2 hours.
After hydrolysis, if the mineral acid was made acetic acid with hydrochloric acid, 16.4 g of 3- (2-ethylhexyloxy) propylamine was added,
React at 0 ° C. for 2 hours. After cooling, it is separated by filtration and dried, 60 g
I got the object.

The test of the black aluminum alloy plate prepared as described above was conducted as follows. (1) Blackness In Example 1, a multi-source spectrophotometer (model MSC) manufactured by Suga Test Instruments Co., Ltd. was used, and a Hunter color system of a black film,
It evaluated by L, a, and b value. The appearance of the black film was also visually evaluated. Further, in Examples 2 to 4, the L value was similarly evaluated. The evaluation criteria are as follows. ⊚: L ≦ 15 + ◯: 15 <L ≦ 20 ◯: 20 <L ≦ 25 x: L> 25

(2) Weldability test Spot welding was carried out under the following conditions, and evaluation was performed by the number of continuous welding points. Electrode: Cr-Cu, D type Electrode diameter: 6 mmφ Welding current: 10 kA Energizing pressure: 200 kg Energizing time: 12 cycles / 60 Hz The evaluation criteria are as follows. ◎: 400 points or more ○: 200 points or more ×: Less than 200 points

(3) Adhesion of the black film 100 pieces of burrs are engraved on the surface of the black film at 1 mm intervals,
Adhesive tape was adhered to and peeled from the edges. The evaluation criteria are as follows. ◎: Peeling area 0% ○: Peeling area less than 10% △: Peeling area 10% or more and less than 20% ×: Peeling area 20% or more

(4) Machinability test 10 m with blank diameter φ120 mm and die diameter φ50 mm
A hat drawing process by m extrusion was performed, the side surface processed portion of the steel sheet was peeled off with an adhesive tape, and the degree of peeling of the coating film on the tape and the change in the appearance of the black coating film were evaluated.
The evaluation criteria are as follows. ⊚: No powdery peeling. + ○: Some powdery peeling occurs locally, but the appearance of the black film is almost unchanged. ◯: The tape becomes extremely thin and black due to the powdery peeling, but the appearance of the black film is almost unchanged. -○: The tape becomes light black due to the powdery peeling, and the appearance of the black film becomes slightly white. Δ: The tape becomes black due to the powdery peeling, and the whitening of the black film is noticeable. X: The tape becomes remarkably black due to the powdery peeling, and the black film is completely peeled off.

(5) Corrosion resistance test of flat plate part Salt spray test (JIS-Z-2371) of flat plate part is 48
I went for 0 hours. The evaluation criteria are as follows. ◎: No rust generation ○: Rust generation area ratio 10% or less ×: Rust generation area ratio over 10%

(6) Lightfastness The black coating was irradiated with a fade meter according to JIS L-0842 second exposure method, and graded on a blue scale. ◎: Blue scale 7-8 grade ○: Blue scale 5-6 grade △: Blue scale 3-4 grade ×: Blue scale 1-2 grade

(7) Anti-fingerprint property Vaseline intended for fingerprints was applied to the surface of the black film,
A visual comparison was made between the coated part and the uncoated part. The evaluation criteria are as follows. ⊚: The applied part is hardly noticeable. ○: The applied part is slightly conspicuous. X: The applied part is noticeable.

Example 1 The following invention examples (1) to
Table 5 shows the test results for the black steel sheets of (8) and Comparative Examples (1) and (2). In this example, the baking temperature of the black coating was 210 ° C. Inventive Example (1) A coating type chromate film of 50 mg / m ² was formed on the surface of an aluminum alloy plate (No. 1 in Table 1), and a complex compound (1-1) having the following chemical structure was formed on the chromate film. 1) and (1-2) are mixed in the following proportions with respect to 100 parts by weight of the base resin to form a film having a thickness of 1.
A 5 μm black film was formed. Base resin: No. 2 in Table 2. 1 Complex compound (1-1): 69 parts by weight Complex compound (1-2): 11 parts by weight Complex compound (1-1)

[Chemical 155] Complex compound (1-2)

[Chemical 156]

Inventive Example (2) A coating type chromate film of 10 mg / m ² was formed on the surface of an aluminum alloy plate (No. 2 in Table 1), and a complex compound of the following chemical structure ( 2-1) ~
(2-5) is mixed with the black-color-imparting agent in the following proportion with respect to 100 parts by weight of the base resin, and a film thickness of 0.
A 4 μm black film was formed. Base resin: No. 2 in Table 2. 2 Complex compound (2-1): 12.4 parts by weight Complex compound (2-2): 2.5 parts by weight Complex compound (2-3): 7.8 parts by weight Complex compound (2-4): 62. 3 parts by weight complex compound (2-5): 15.0 parts by weight complex compound (2-1)

[Chemical 157] Complex compound (2-2)

[Chemical 158] Complex compound (2-3)

[Chemical 159] Complex compound (2-4)

[Chemical 160] Complex compound (2-5)

[Chemical 161]

Inventive Example (3) A coating type chromate film of 70 mg / m ² was formed on the surface of an aluminum alloy plate (No. 3 in Table 1), and a complex compound of the following chemical structure ( 3-1) ~
A black coating having a film thickness of 2.0 μm was formed of a composition in which the black-color imparting agent mixed with (3-3) and the solid lubricant were mixed in the following proportions with respect to 100 parts by weight of the base resin. Base resin: No. 2 in Table 2. 1 Complex compound (3-1): 43.8 parts by weight Complex compound (3-2): 22.8 parts by weight Complex compound (3-3): 3.4 parts by weight Solid lubricant: No. 20 parts by weight of 1 Complex compound (3-1)

[Chemical 162] Complex compound (3-2)

[Chemical formula 163] Complex compound (3-3)

[Chemical 164]

Inventive Example (4) A coating type chromate film 30 mg / m ² was formed on the surface of an aluminum alloy plate (No. 4 in Table 1), and a complex compound of the following chemical structure ( 4-1) and (4-2) mixed black imparting agent and solid lubricant,
With respect to 100 parts by weight of the base resin, a black film having a film thickness of 3.0 μm and having a composition mixed in the following proportions was formed respectively. Base resin: No. 2 in Table 2. 1 Complex compound (4-1): 68 parts by weight Complex compound (4-2): 12 parts by weight Solid lubricant: No. 20 parts by weight of 2 Complex compound (4-1)

[Chemical 165] Complex compound (4-2)

[Chemical 166]

Inventive Example (5) A coating type chromate film of 5 mg / m ² was formed on the surface of an aluminum alloy plate (No. 5 in Table 1), and a complex compound of the following chemical structure ( 5-1) and (5-2) are mixed with a black-color imparting agent and a particulate rust-preventive pigment in the following proportions with respect to 100 parts by weight of the base resin. A film was formed. Base resin: No. 2 in Table 2. 1 Complex compound (5-1): 45 parts by weight Complex compound (5-2): 15 parts by weight Particulate rust preventive pigment: No. 20 parts by weight of 1 Complex compound (5-1)

[Chemical 167] Complex compound (5-2)

[Chemical 168]

Inventive Example (6) A coating type chromate film 50 mg / m ² was formed on the surface of an aluminum alloy plate (No. 1 in Table 1), and a complex compound of the following chemical structure ( 6-1) ~
A black colorant having a film thickness of 1.5 μm, which has a composition in which a black-color imparting agent mixed with (6-3), a solid lubricant and a particulate rust preventive pigment are mixed in the following proportions relative to 100 parts by weight of the base resin. A film was formed. Base resin: No. 2 in Table 2. 1 Complex compound (6-1): 42 parts by weight Complex compound (6-2): 12 parts by weight Complex compound (6-3): 12 parts by weight Solid lubricant: No. 15 parts by weight of particulate rust preventive pigment: No. 1 in Table 4 15 parts by weight of 2 Complex compound (6-1)

[Chemical 169] Complex compound (6-2)

[Chemical 170] Complex compound (6-3)

[Chemical 171]

Inventive Example (7) A coating type chromate film 50 mg / m ² was formed on the surface of an aluminum alloy plate (No. 1 in Table 1), and a complex compound of the following chemical structure ( 7-1) and (7-2) mixed black-imparting agent, a solid lubricant and a particulate rust preventive pigment in the following proportions with respect to 100 parts by weight of the base resin. 1.5 μm
The black film of was formed. Base resin: No. 2 in Table 2. 1 Complex compound (7-1): 56 parts by weight Complex compound (7-2): 16 parts by weight Solid lubricant: No. 20 parts by weight of particulate rust preventive pigment: No. 1 in Table 4 20 parts by weight of 3 Complex compound (7-1)

[Chemical 172] Complex compound (7-2)

[Chemical 173]

Inventive Example (8) A coating type chromate film of 50 mg / m ² was formed on the surface of an aluminum alloy plate (No. 1 in Table 1), and a complex compound of the following chemical structure ( 8-1) and (8-2) mixed black-imparting agent, a solid lubricant and a particulate rust-preventive pigment in the following proportions with respect to 100 parts by weight of the base resin. 1.5 μm
The black film of was formed. Base resin: No. 2 in Table 2. 3 Complex compound (8-1): 68 parts by weight Complex compound (8-2): 12 parts by weight Solid lubricant: No. 3 in Table 3 10 parts by weight of particulate rust preventive pigment: No. 2 in Table 4 10 parts by weight of 2 Complex compound (8-1)

[Chemical 174] Complex compound (8-2)

[Chemical 175]

Comparative Example (1) A coating type chromate film of 50 mg / m ² was formed on the surface of an aluminum alloy plate (No. 1 in Table 1), and on the chromate film, the above-mentioned invention example (1) was used. A black coating film having a thickness of 0.1 μm was formed with a composition in which the complexing compounds (1-1) and (1-2) used were mixed in the following proportions with 100 parts by weight of the base resin. It was Base resin: No. 2 in Table 2. 1 Complex compound (1-1): 69 parts by weight Complex compound (1-2): 11 parts by weight

Comparative Example (2) A coating type chromate film of 50 mg / m ² was formed on the surface of an aluminum alloy plate (No. 1 in Table 1), and on the chromate film, the above-mentioned invention example (1) was used. A black coating having a film thickness of 10 μm was formed with a composition in which the black imparting agent containing the complex compounds (1-1) and (1-2) used was mixed with 100 parts by weight of the base resin in the following proportions. Base resin: No. 2 in Table 2. 1 Complex compound (1-1): 69 parts by weight Complex compound (1-2): 11 parts by weight

Example 2 Using the black imparting agent used in Example (1) of the present invention of Example 1, as shown in Table 6, test materials having different black film composition (black imparting agent concentration) and film thickness about,
The blackness, weldability, workability, adhesion, corrosion resistance and light fastness were examined. The results are shown in Table 7.

[Example 3] Using the black-imparting agent used in Example (1) of the present invention of Example 1, a sample material having a black coating film and a chromate coating film having different compositions as shown in Table 8 was attached. , Blackness, weldability, workability, adhesion, corrosion resistance and light fastness were examined. The results are shown in Table 9.

[Example 4] Using the black-imparting agent used in Example (1) of the present invention of Example 1, a sample material having a black film having a different composition as shown in Table 10 was tested for blackness and weldability. , Workability, adhesion, corrosion resistance and light fastness were investigated. The results are shown in Table 11.

[0093]

[Table 1]

[0094]

[Table 2]

[0095]

[Table 3]

[0096]

[Table 4]

[0097]

[Table 5]

[0098]

[Table 6]

[0099]

[Table 7]

[0100]

[Table 8]

[0101]

[Table 9]

[0102]

[Table 10]

[0103]

[Table 11]

In Table 6, Table 8 and Table 10, * 1
The numbers or numerical values of each item with * 7 indicate the following contents. * 1: No. 1 of the aluminum alloy plate shown in Table 1. * 2: Nos. Of the resins listed in Table 2 * 3: Parts by weight of the black imparting agent based on 100 parts by weight of the base resin * 4: No. of the solid lubricant described in Table 3. * 5: Part by weight of solid lubricant relative to 100 parts by weight of base resin * 6: No. * 7: Part by weight of particulate rust preventive pigment based on 100 parts by weight of base resin

[0105]

According to the present invention described above, since the black film is thinner (3 μm or less) than the conventional painted aluminum plate or aluminum alloy plate, welding is possible and the blackness is excellent. A black aluminum plate or a black aluminum alloy plate is obtained. Further, this black aluminum plate or black aluminum alloy plate is excellent not only in blackness and weldability but also in adhesion of the black film, workability, corrosion resistance, light fastness, and coating with existing roll coater equipment etc. Since it can be produced by baking and baking, continuous blackening treatment can be performed in a much shorter time than the conventional anodizing treatment method, and there is no problem of deterioration of the treatment bath. Since no post-treatment such as sealing treatment is required, the process can be simplified, and from the above points, it is possible to provide a black aluminum plate or a black aluminum alloy plate that is extremely excellent in terms of both quality characteristics and productivity.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the thickness of a black coating and spot weldability.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masaaki Yamashita 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Nihon Steel Pipe Co., Ltd.

Claims (11)

[Claims] 1. A thermosetting resin is used as a base resin on the surface of an aluminum plate or an aluminum alloy plate, and 100 parts by weight of this base resin is represented by the following general structural formula (1) as a black-imparting agent. Two or more complex compounds, or one or more complex compounds represented by the following general structural formula (1) and one or more complex compounds represented by the following general structural formula (2) A weldable black aluminum plate or a black aluminum alloy plate having a black film having a film thickness of 0.3 to 3.0 μm, which is compounded in a total amount of 1 to 200 parts by weight and excellent in design. [Chemical 1] …… (1) [Chemical 2] (2) [In the general formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are independently H, Cl, NO ₂ , and S.
Represents O ₂ NH ₂ and CH ₃ , and X is ...... (3) {(3) wherein R ₅ is H, ## STR4 ## (R ₆ is. Representing a _{H, CH 3, NO 2,} OCH 3, Cl) represents a. The azo group is bonded to the 1-position of the naphthalene ring. }
Or, (4) (In the formula (4), R ₇ represents H, CH ₃ , and C ₂ H ₅ , and R ₈ represents H, Cl, NO ₂ , SO ₂ NH ₂ , and CH _{3. The} azo group is pyrazole. Attached to the 4-position of the ring) or ... (5) (in the formula (5), R ₉ represents H, Cl, NO ₂ , CH ₃ , and C ₂ H _{5. The} azo group is bonded to the side of the carbonyl group.), And M is Representing Cr, Co and Fe atoms, Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. In the general formula (2), CuPc represents a copper phthalocyanine residue, R ₃ and R ₄ each independently represent H, a C _{1 to} C ₁₂ alkyl group or a substituted alkyl group, and Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. m is an integer of 0 to 3, n is 1 to 4
And the sum of m and n is 2, 3 or 4. ] 2. A thermosetting resin is used as a base resin on the surface of an aluminum plate or an aluminum alloy plate, and 100 parts by weight of this base resin is represented by the following general structural formula (1) as a black-imparting agent. Two or more complex compounds, or one or more complex compounds represented by the following general structural formula (1) and one or more complex compounds represented by the following general structural formula (2) , 1 to 200 parts by weight in total,
Further, a weldable black aluminum plate or a black aluminum alloy plate having a black film having a film thickness of 0.3 to 3.0 μm, which is formed by mixing 1 to 100 parts by weight of a solid lubricant, and having excellent designability. [Chemical 9] …… (1) [Chemical 10] (2) [In the general formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are independently H, Cl, NO ₂ , and S.
Represents O ₂ NH ₂ and CH ₃ , and X is ...... (3) {(3) wherein R ₅ is H, embedded image (R ₆ is. Representing a _{H, CH 3, NO 2,} OCH 3, Cl) represents a. The azo group is bonded to the 1-position of the naphthalene ring. }
Or, (4) (In the formula (4), R ₇ represents H, CH ₃ , and C ₂ H ₅ , and R ₈ represents H, Cl, NO ₂ , SO ₂ NH ₂ , and CH _{3. The} azo group is pyrazole. Bonded to the 4-position of the ring) or ... (5) (in the formula (5), R ₉ represents H, Cl, NO ₂ , CH ₃ , and C ₂ H _{5. The} azo group is bonded to the side of the carbonyl group.), And M is Representing Cr, Co and Fe atoms, Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. In the general formula (2), CuPc represents a copper phthalocyanine residue, R ₃ and R ₄ each independently represent H, a C _{1 to} C ₁₂ alkyl group or a substituted alkyl group, and Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. m is an integer of 0 to 3, n is 1 to 4
And the sum of m and n is 2, 3 or 4. ] 3. A thermosetting resin is used as a base resin on the surface of an aluminum plate or an aluminum alloy plate, and 100 parts by weight of this base resin is represented by the following general structural formula (1) as a black-imparting agent. Two or more complex compounds, or one or more complex compounds represented by the following general structural formula (1) and one or more complex compounds represented by the following general structural formula (2) , 1 to 200 parts by weight in total,
Further, a weldable black aluminum plate or black aluminum alloy plate having a black film having a film thickness of 0.3 to 3.0 μm, which is prepared by mixing 1 to 100 parts by weight of a particulate rust preventive pigment, and having excellent designability. [Chemical 17] …… (1) [Chemical 18] (2) [In the general formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are independently H, Cl, NO ₂ , and S.
Represents O ₂ NH ₂ and CH ₃ , and X is ...... (3) {(3) wherein R ₅ is H, embedded image (R ₆ is. Representing a _{H, CH 3, NO 2,} OCH 3, Cl) represents a. The azo group is bonded to the 1-position of the naphthalene ring. }
Or, (4) (In the formula (4), R ₇ represents H, CH ₃ , and C ₂ H ₅ , and R ₈ represents H, Cl, NO ₂ , SO ₂ NH ₂ , and CH _{3. The} azo group is pyrazole. Attached to the 4-position of the ring) or ... (5) (in the formula (5), R ₉ represents H, Cl, NO ₂ , CH ₃ , and C ₂ H _{5. The} azo group is bonded to the side of the carbonyl group.), And M is Representing Cr, Co, Fe atoms, Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. In the general formula (2), CuPc represents a copper phthalocyanine residue, R ₃ and R ₄ each independently represent H, a C _{1 to} C ₁₂ alkyl group or a substituted alkyl group, and Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. m is an integer of 0 to 3, n is 1 to 4
And the sum of m and n is 2, 3 or 4. ] 4. A thermosetting resin is used as a base resin on the surface of an aluminum plate or an aluminum alloy plate, and 100 parts by weight of this base resin is represented by the following general structural formula (1) as a black-imparting agent. Two or more complex compounds, or one or more complex compounds represented by the following general structural formula (1) and one or more complex compounds represented by the following general structural formula (2) , 1 to 200 parts by weight in total,
Furthermore, a film thickness of 0.3 to 3.0 μ is obtained by blending 1 to 100 parts by weight of a solid lubricant and 1 to 100 parts by weight of a particulate rust preventive pigment.
A weldable black aluminum plate or black aluminum alloy plate having a black coating of m and excellent in design. [Chemical 25] …… (1) [Chemical 26] (2) [In the general formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are independently H, Cl, NO ₂ , and S.
Represents O ₂ NH ₂ , CH ₃ , and X is ...... (3) {(3) wherein R ₅ is H, embedded image (R ₆ is. Representing a _{H, CH 3, NO 2,} OCH 3, Cl) represents a. The azo group is bonded to the 1-position of the naphthalene ring. }
Or, (4) (In the formula (4), R ₇ represents H, CH ₃ , and C ₂ H ₅ , and R ₈ represents H, Cl, NO ₂ , SO ₂ NH ₂ , and CH _{3. The} azo group is pyrazole. Attached to the 4-position of the ring) or ... (5) (in the formula (5), R ₉ represents H, Cl, NO ₂ , CH ₃ , and C ₂ H _{5. The} azo group is bonded to the side of the carbonyl group.), And M is Representing Cr, Co, Fe atoms, Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. In the general formula (2), CuPc represents a copper phthalocyanine residue, R ₃ and R ₄ each independently represent H, a C _{1 to} C ₁₂ alkyl group or a substituted alkyl group, and Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. m is an integer of 0 to 3, n is 1 to 4
And the sum of m and n is 2, 3 or 4. ] 5. Amount of chromium adhered to the surface of the aluminum plate or aluminum alloy plate (calculated as metallic chromium) of 1 to 200.
It has a chromate film of mg / m ^2, on top of the chromate film, a thermosetting resin as a base resin for the base resin 100 parts by weight, the following general structural formula as a black imparting agent (1) Two or more of the complex compounds represented, or one or two of the complex compounds represented by the following general structural formula (1)
1 or more of the complex compounds represented by the following general structural formula (2)
A weldable black aluminum plate or black aluminum alloy plate having a black film having a film thickness of 0.3 to 3.0 μm, which is formed by mixing 1 to 200 parts by weight in total of 1 or 200 parts by weight or more. [Chemical 33] …… (1) [Chemical 34] (2) [In the general formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are independently H, Cl, NO ₂ , and S.
Represents O ₂ NH ₂ and CH ₃ , and X is ...... (3) {(3) wherein R ₅ is H, embedded image (R ₆ is. Representing a _{H, CH 3, NO 2,} OCH 3, Cl) represents a. The azo group is bonded to the 1-position of the naphthalene ring. }
Or, (4) (In the formula (4), R ₇ represents H, CH ₃ , and C ₂ H ₅ , and R ₈ represents H, Cl, NO ₂ , SO ₂ NH ₂ , and CH _{3. The} azo group is pyrazole. Bonded to the 4-position of the ring) or ... (5) (in the formula (5), R ₉ represents H, Cl, NO ₂ , CH ₃ , and C ₂ H _{5. The} azo group is bonded to the side of the carbonyl group.), And M is Representing Cr, Co and Fe atoms, Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. In the general formula (2), CuPc represents a copper phthalocyanine residue, R ₃ and R ₄ each independently represent H, a C _{1 to} C ₁₂ alkyl group or a substituted alkyl group, and Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. m is an integer of 0 to 3, n is 1 to 4
And the sum of m and n is 2, 3 or 4. ] 6. Amount of chromium deposited on the surface of an aluminum plate or an aluminum alloy plate (calculated as metallic chromium) of 1 to 200.
It has a chromate film of mg / m ^2, on top of the chromate film, a thermosetting resin as a base resin for the base resin 100 parts by weight, the following general structural formula as a black imparting agent (1) Two or more of the complex compounds represented, or one or two of the complex compounds represented by the following general structural formula (1)
1 or more of the complex compounds represented by the following general structural formula (2)
1 or 200 parts by weight in total, and 1 to 100 parts by weight of a solid lubricant in a total amount of 0.1 to 200 parts by weight.
A weldable black aluminum plate or black aluminum alloy plate having a black coating of 3 to 3.0 μm and excellent in design. [Chemical 41] …… (1) [Chemical 42] (2) [In the general formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are independently H, Cl, NO ₂ , and S.
Represents O ₂ NH ₂ and CH ₃ , and X is ...... (3) {(3) wherein R ₅ is H, embedded image (R ₆ is. Representing a _{H, CH 3, NO 2,} OCH 3, Cl) represents a. The azo group is bonded to the 1-position of the naphthalene ring. }
Or, (4) (In the formula (4), R ₇ represents H, CH ₃ , and C ₂ H ₅ , and R ₈ represents H, Cl, NO ₂ , SO ₂ NH ₂ , and CH _{3. The} azo group is pyrazole. Attached to the 4-position of the ring) or ... (5) (in the formula (5), R ₉ represents H, Cl, NO ₂ , CH ₃ , and C ₂ H _{5. The} azo group is bonded to the side of the carbonyl group.), And M is Representing Cr, Co, Fe atoms, Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. In the general formula (2), CuPc represents a copper phthalocyanine residue, R ₃ and R ₄ each independently represent H, a C _{1 to} C ₁₂ alkyl group or a substituted alkyl group, and Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. m is an integer of 0 to 3, n is 1 to 4
And the sum of m and n is 2, 3 or 4. ] 7. Amount of chromium adhered to the surface of an aluminum plate or aluminum alloy plate (calculated as metallic chromium) of 1 to 200.
It has a chromate film of mg / m ^2, on top of the chromate film, a thermosetting resin as a base resin for the base resin 100 parts by weight, the following general structural formula as a black imparting agent (1) Two or more of the complex compounds represented, or one or two of the complex compounds represented by the following general structural formula (1)
1 or more of the complex compounds represented by the following general structural formula (2)
1 to 200 parts by weight in total of 1 or 200 parts by weight, and 1 to 100 parts by weight of a particulate rust preventive pigment, and a black film having a film thickness of 0.3 to 3.0 μm and excellent in design Weldable black aluminum plate or black aluminum alloy plate. [Chemical 49] …… (1) [Chemical 50] (2) [In the general formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are independently H, Cl, NO ₂ , and S.
Represents O ₂ NH ₂ and CH ₃ , and X is ...... (3) {R _{5 in the} formula (3) is H, and (R ₆ is. Representing a _{H, CH 3, NO 2,} OCH 3, Cl) represents a. The azo group is bonded to the 1-position of the naphthalene ring. }
Or, (4) (In the formula (4), R ₇ represents H, CH ₃ , and C ₂ H ₅ , and R ₈ represents H, Cl, NO ₂ , SO ₂ NH ₂ , and CH _{3. The} azo group is pyrazole. Attached to the 4-position of the ring) or ... (5) (in the formula (5), R ₉ represents H, Cl, NO ₂ , CH ₃ , and C ₂ H _{5. The} azo group is bonded to the side of the carbonyl group.), And M is Representing Cr, Co, Fe atoms, Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. In the general formula (2), CuPc represents a copper phthalocyanine residue, R ₃ and R ₄ each independently represent H, a C _{1 to} C ₁₂ alkyl group or a substituted alkyl group, and Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. m is an integer of 0 to 3, n is 1 to 4
And the sum of m and n is 2, 3 or 4. ] 8. Amount of chromium adhered to the surface of an aluminum plate or aluminum alloy plate (calculated as metallic chromium) of 1 to 200.
It has a chromate film of mg / m ^2, on top of the chromate film, a thermosetting resin as a base resin for the base resin 100 parts by weight, the following general structural formula as a black imparting agent (1) Two or more of the complex compounds represented, or one or two of the complex compounds represented by the following general structural formula (1)
1 or more of the complex compounds represented by the following general structural formula (2)
1 to 200 parts by weight, a total amount of 1 to 100 parts by weight, a solid lubricant of 1 to 100 parts by weight, and a particulate rust preventive pigment of 1 to 100 parts by weight, and a film thickness of 0.3 to 3. 0 μm
A weldable black aluminum plate or black aluminum alloy plate having a black coating and excellent in design. [Chemical 57] …… (1) [Chemical 58] (2) [In the general formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are independently H, Cl, NO ₂ , and S.
Represents O ₂ NH ₂ and CH ₃ , and X is ...... (3) {(3) wherein R ₅ is H, embedded image (R ₆ is. Representing a _{H, CH 3, NO 2,} OCH 3, Cl) represents a. The azo group is bonded to the 1-position of the naphthalene ring. }
Or, (4) (In the formula (4), R ₇ represents H, CH ₃ , and C ₂ H ₅ , and R ₈ represents H, Cl, NO ₂ , SO ₂ NH ₂ , and CH _{3. The} azo group is pyrazole. Attached to the 4-position of the ring) or ... (5) (in the formula (5), R ₉ represents H, Cl, NO ₂ , CH ₃ , and C ₂ H _{5. The} azo group is bonded to the side of the carbonyl group.), And M is Representing Cr, Co, Fe atoms, Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. In the general formula (2), CuPc represents a copper phthalocyanine residue, R ₃ and R ₄ each independently represent H, a C _{1 to} C ₁₂ alkyl group or a substituted alkyl group, and Represents a hydrogen ion, an alkali metal ion, an ammonium ion, an aliphatic ammonium ion, or a substituted aliphatic ammonium ion. m is an integer of 0 to 3, n is 1 to 4
And the sum of m and n is 2, 3 or 4. ] 9. As solid lubricants, hydrocarbon compounds such as polyolefin wax, fluororesin compounds, fatty acid amide compounds, metallic soaps, metal sulfides such as molybdenum disulfide, graphite, fluorinated graphite and boron nitride. , Selected from the group of polyalkylene glycols 1
A weldable black aluminum plate or a black aluminum alloy plate having excellent design properties according to claim 2, 4, 6 or 8, containing one or more kinds. 10. The design property according to claim 3, 4, 7, 8 or 9, wherein the particulate rust preventive pigment contains one or more selected from the group consisting of a sparingly soluble chromium compound and silica. Excellent weldable black aluminum plate or black aluminum alloy plate. 11. The lightness and hue of the surface of the black coating are L ≦ 25, a = −2 to 2, b in the Hunter L, a, b color system.
= -2.5-2.5, Claim 1 characterized by the above-mentioned.
A weldable black aluminum plate or a black aluminum alloy plate having excellent design properties according to 2, 3, 4, 5, 6, 7, 8, 9 or 10.