JPH0732535A - Weldable colored stainless steel plate - Google Patents

Abstract

PURPOSE:To provide a colored stainless steel plate with a beautiful appearance by a spot-weldable thin film thickness by a method wherein on the surface of a stainless steel plate, a colored film with a specified thickness, of which the substrate is a thermosetting resin, and for which a plurality of complex compounds being represented by specific formulas are blended, is applied to make a stainless steel plate with a colored film. CONSTITUTION:For a weldable colored stainless steel plate, a colored film (excluding a black film) with a film thickness of 0.3-3.0mum, for which a thermosetting resin is made as the base resin, and one kind or more complex compounds being selected from a group consisting of complex compounds represented by a formula I and formula II are blended by a total weight of 1-200 pts.wt. to 100 pts.wt. of the base resin, is applied on the surface of a stainless steel plate. 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 colored stainless steel sheet which is excellent in appearance and is used for office / office equipment for home appliances, building materials, automobile parts, ornaments and the like.

2. Description of the Related Art Recently, the needs for colored stainless steel sheets have been increasing with the diversification and upsizing of home electric appliances and office equipment. Conventionally, the Inco method is known as a coloring method of stainless steel. This is a method of obtaining a colored oxide film having an interference color by immersion treatment. However, since this technique requires a long treatment time of about several minutes, continuous treatment with a strip is impossible. Further, in recent years, a method of forming a colored oxide film similarly by alternating electrolysis in a chromic acid-sulfuric acid mixed aqueous solution (Japanese Patent Laid-Open No. 61-1278).
No. 99) has been proposed, but there have been problems such as fluctuations in components due to dissolution of stainless steel in the treatment bath and differences in the components of the stainless steel, resulting in subtle differences in color tone.

[0002]

On the other hand, there is a method of applying a colored coating to the surface of a stainless steel plate, but in the conventional colored coating, it is usually 10 μm or more in order to give a uniform colored appearance. A film thickness is necessary, and there is a problem that spot welding cannot be performed with such a film thickness. That is, although inorganic pigments and organic pigments are used as colorants in conventional coating, the hiding power is insufficient at a film thickness (3 μm or less) capable of spot welding, resulting in an appearance with scaliness and unevenness. I will end up. As described above, the conventional colored film using the color pigment as the colorant cannot obtain a uniform appearance with a film thickness within a weldable range.

The present invention has been made in view of such conventional problems, and its object is a colored film (a colored film other than black) having a thin film thickness (3 μm or less) capable of spot welding and having a uniform and beautiful appearance. It is to provide a colored stainless steel plate having Another object of the present invention is to provide a colored stainless steel sheet excellent in corrosion resistance, adhesion and workability.

[0004]

According to the present invention, a colored 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 with a film thickness within a predetermined range. It was found that a colored film having a uniform and beautiful appearance can be obtained even with a weldable film thickness. That is, the colored stainless steel sheet of the present invention has the following constitution.

[1] A thermosetting resin is used as a base resin on the surface of a stainless steel plate, and a complex compound represented by the following general structural formula (1) A film thickness of 0.3-3. 3 which comprises 1 to 200 parts by weight in total of one or more complex compounds selected from the group consisting of complex compounds represented by the general structural formula (2).
A weldable colored stainless steel plate having a 0 μm colored film (excluding black film).

[Chemical 65] …… (1)

[Chemical formula 66] (2) [In the general structural formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are each independently H, Cl, NO ₂ ,
Represents SO ₂ NH ₂ , 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. CuPc in the general structural formula (2)
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 a stainless steel plate, and 100 parts by weight of the base resin is used as a colorant for a complex compound represented by the following general structural formula (1) and The total amount of one or more complex compounds selected from the group consisting of the complex compounds represented by the general structural formula (2) is 1 to 200 parts by weight, and the solid lubricant is 1 to 10 parts by weight.
A weldable colored stainless steel sheet having a colored film (excluding a black film) having a film thickness of 0.3 to 3.0 μm formed by blending 0 part by weight.

[Chemical formula 73] …… (1)

[Chemical 74] (2) [In the general structural formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are each independently H, Cl, NO ₂ ,
Represents SO ₂ NH ₂ , 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. CuPc in the general structural formula (2)
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 a stainless steel plate, and a complex compound represented by the following general structural formula (1) and a coloring agent are added to 100 parts by weight of the base resin. The total amount of one or more complex compounds selected from the group consisting of the complex compounds represented by the general structural formula (2) is 1 to 200 parts by weight, and the particulate rust preventive pigment is 1 to
A weldable colored stainless steel sheet having a colored film (excluding a black film) having a film thickness of 0.3 to 3.0 μm formed by mixing 100 parts by weight.

[Chemical 81] …… (1)

[Chemical formula 82] (2) [In the general structural formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are each independently H, Cl, NO ₂ ,
Represents SO ₂ NH ₂ , 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. CuPc in the general structural formula (2)
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 a stainless steel plate, and 100 parts by weight of the base resin is used as a colorant to form a complex compound represented by the following general structural formula (1) and The total amount of one or more complex compounds selected from the group consisting of the complex compounds represented by the general structural formula (2) is 1 to 200 parts by weight, and the solid lubricant is 1 to 10 parts by weight.
A weldable colored stainless steel sheet having a colored film (excluding a black film) having a film thickness of 0.3 to 3.0 μm, which is obtained by mixing 0 part by weight and 1 to 100 parts by weight of a particulate rust preventive pigment.

[Chemical 89] …… (1)

[Chemical 90] (2) [In the general structural formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are each independently H, Cl, NO ₂ ,
Represents SO ₂ NH ₂ , 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. CuPc in the general structural formula (2)
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] A stainless steel plate has a chromate film with a chromium adhesion amount (calculated as metal chromium) of 1 to 200 mg / m ^{2 on} the surface of the stainless steel plate, and a thermosetting resin as a base resin on the top of the chromate film. One or more selected from the group consisting of a complex compound represented by the following general structural formula (1) and a complex compound represented by the following general structural formula (2) as a colorant with respect to 100 parts by weight of the resin. Of a complex compound of 1 to 200 parts by weight in total, and a film thickness of 0.3 to 3.0
Weldable colored stainless steel plate with a colored coating of μm (excluding black coating).

[Chemical 97] …… (1)

[Chemical 98] (2) [In the general structural formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are each independently H, Cl, NO ₂ ,
Represents SO ₂ NH ₂ , 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. CuPc in the general structural formula (2)
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] A stainless steel plate has a chromate film with a chromium adhesion amount (calculated as metal chromium) of 1 to 200 mg / m ^{2 on} the surface thereof, and a thermosetting resin as a base resin on the top of the chromate film. One or more selected from the group consisting of a complex compound represented by the following general structural formula (1) and a complex compound represented by the following general structural formula (2) as a colorant with respect to 100 parts by weight of the resin. 1 to 200 parts by weight in total, and 1 to 100 parts by weight of solid lubricant.
A weldable colored stainless steel sheet having a colored film (excluding a black film) having a film thickness of 0.3 to 3.0 μm formed by mixing in parts by weight.

[Chemical 105] …… (1)

[Chemical formula 106] (2) [In the general structural formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are each independently H, Cl, NO ₂ ,
Represents SO ₂ NH ₂ , 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. CuPc in the general structural formula (2)
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] A chromate film having a chromium adhesion amount (calculated as metal chromium) of 1 to 200 mg / m ² is provided on the surface of a stainless steel plate, and a thermosetting resin is used as a base resin on the top of the chromate film. One or more selected from the group consisting of a complex compound represented by the following general structural formula (1) and a complex compound represented by the following general structural formula (2) as a colorant with respect to 100 parts by weight of the resin. 1 to 200 parts by weight of the complex compound of, and 1 to 1 of the particulate rust preventive pigment.
A weldable colored stainless steel sheet having a colored film (excluding a black film) having a film thickness of 0.3 to 3.0 μm, which is compounded with 00 parts by weight.

[Chemical 113] …… (1)

[Chemical 114] (2) [In the general structural formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are each independently H, Cl, NO ₂ ,
Represents SO ₂ NH ₂ , 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. CuPc in the general structural formula (2)
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] A stainless steel plate has a chromate film with a chromium adhesion amount (calculated as metal chromium) of 1 to 200 mg / m ^{2 on} the surface of the stainless steel plate, and a thermosetting resin as a base resin on the chromate film. One or more selected from the group consisting of a complex compound represented by the following general structural formula (1) and a complex compound represented by the following general structural formula (2) as a colorant with respect to 100 parts by weight of the resin. 1 to 200 parts by weight in total, and 1 to 100 parts by weight of solid lubricant.
A weldable colored stainless steel plate having a colored film (excluding a black film) having a film thickness of 0.3 to 3.0 μm, which is obtained by mixing 1 part by weight to 1 part by weight of a particulate rust preventive pigment.

[Chemical 121] …… (1)

[Chemical formula 122] (2) [In the general structural formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are each independently H, Cl, NO ₂ ,
Represents SO ₂ NH ₂ , 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. CuPc in the general structural formula (2)
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. ]

[0013]

[9] In the colored stainless steel sheet according to the above [2], [4], [6] or [8], a hydrocarbon compound such as a polyolefin wax as a solid lubricant,
One or more selected from the group consisting of fluororesin compounds, fatty acid amide compounds, metal soaps, metal sulfides such as molybdenum disulfide, graphite, graphite fluoride, boron nitride, and polyalkylene glycol. Weldable colored stainless steel plate including.

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

In the colored stainless steel plate of [9], a weldable colored stainless steel plate containing, as the particulate rust preventive pigment, one or more selected from the group consisting of a sparingly soluble chromium compound and silica.

[0015]

The details of the present invention and the reasons for limitation thereof will be described below. The colored stainless steel sheet of the present invention is made of a stainless steel sheet as a starting material, and a chromate film is formed on the surface thereof as required, and a thermosetting resin is used as a base on the surface of the stainless steel sheet or on the chromate film. It has a colored film made of a composition containing the organic dye.

The present invention is directed to a colored steel plate other than a so-called black steel plate having a black film (a black film substantially containing only a black-coloring agent such as a black dye or a black pigment as a colorant). The colored steel plate and the colored film to be described do not include a black steel plate and a black film. here,
In the present invention, in order to distinguish the colored steel sheet from the black steel sheet, the colored steel sheet has a lightness L.
Value: Defined as having a chromatic or achromatic colored coating film having a value of more than 25. However, as will be described later, it does not prevent the black dye from being added to the film by mixing it with a dye of another color. In general, most of the colored steel plates are chromatic, but as described above, the present invention does not exclude achromatic colored steel plates other than black from the target.

The stainless steel plate as a starting material is a steel plate containing chromium or chromium and nickel, and the stainless steel plate is austenitic (SUS304, 304).
L, 316, 316L, etc., ferrite type (SUS43
0), martensite type (SUS410, etc.), and the like. These stainless steel plates may be provided with a surface roughness during rolling, or may be provided with a surface by pretreatment or the like, if necessary, for the purpose of enhancing the adhesion with the colored film.

On the surface of the stainless steel plate, if necessary, a chromate film by chromic acid treatment is formed for the purpose of improving adhesion and corrosion resistance. In the colored stainless steel sheet of the present invention, by combining this chromate film with a colored film containing a specific colorant as described later, extremely excellent corrosion resistance can be obtained. 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, and then washed and dried with water. To form a film.
Comparing the chromate coatings obtained by the above two treatment methods, the coating type chromate is superior in corrosion resistance to the electrolytic type chromate because it contains a large amount of hexavalent chromium in the coating. When 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 colored film will be described. The colored film in the present invention is characterized by using a thermosetting resin as a base resin and containing a specific complex compound as a coloring agent. Further, in the present invention, in addition to the above components, a solid lubricant may be contained for the purpose of improving the processability of the colored film, and a rust preventive pigment may be contained for the purpose of improving the corrosion resistance. The function required as a colorant is that a film having a weldable thickness (3 μm or less) can exhibit a uniform and beautiful color. Moreover, when the colorant is mixed with the base resin in a mixing ratio that provides a sufficient appearance, there are some that adversely affect other performances required for the colored film, such as processability and corrosion resistance. Don't

Conventionally, pigments (inorganic pigments and organic pigments) have been generally used as colorants, and paints in which particulate pigments are dispersed are widely used for coating automobiles and home electric appliances. Examples of pigments used as such colorants include inorganic pigments such as dark blue and yellow lead, and organic pigments such as xacridone pigments and phthalocyanine pigments. However, a conventional coating film using such a pigment as a colorant requires a film thickness of 10 μm or more in order to obtain a sufficient hiding power of the colorant, and therefore cannot be welded. That is, when a pigment is used as a colorant in a weldable thin film (3 μm or less), which is the object of the present invention, the pigment comes into contact with and agglomerates in the thin film, and thus a sufficient hiding power cannot be obtained. There is a problem that the film is not glossy. In addition, particularly when a large amount of pigment is added to the resin film, the processability and adhesion of the film deteriorate, and further, water easily penetrates into the base through the gaps of the pigment particles, which lowers the corrosion resistance. There are also problems.

When a pigment is used as a coloring agent in such a thin film, a good appearance cannot be obtained, and particularly when added in a large amount, the performance of the film is impaired. Therefore, conventionally, it has been impossible to obtain a colored film which is a weldable thin film and has various properties such as good appearance, corrosion resistance and workability. Even when two or more kinds of the above-mentioned inorganic pigments and organic pigments are combined, sufficient performance cannot be obtained.

Therefore, the present inventors have conducted investigations to find a colorant having the following functions. (1) Base resin (thermosetting resin) and solvent (water-based,
Capable of being dissolved or dispersed in any organic solvent system (2) The formed colored film has a uniform and clear color even in a thin weldable thickness (up to 3 μm) (3) Color does not deteriorate even when used as a material for home appliances, office equipment, etc. illuminated by various light sources, that is, it has good lightfastness.

As a result of the investigation, a specific complex compound, namely,
It was found that the complex compound represented by the following general structural formula (1) and the complex compound represented by the general structural formula (2) satisfy the above functions.

[Chemical formula 129] …… (1)

[Chemical 130] (2) [In the general structural formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are each independently H, Cl, NO ₂ ,
Represents SO ₂ NH ₂ , 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. CuPc in the general structural formula (2)
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. ]

Examples of the diazo component used in the general structural formula (1) include 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, 4-nitro-2- Aminobenzoic acid, 4-chloro-5-nitro-2-
Examples include aminobenzoic acid.

The coupling component used in the general structural formula (1) is, for example, 2-hydroxynaphthalene, 2-hydroxy-3-phenylcarbamoylnaphthalene, 2-hydroxy-3- (2-methylphenyl).
Carbamoylnaphthalene, 2-hydroxy-3- (4-
Chlorophenyl) carbamoylnaphthalene, 2-hydroxy-3- (4-methoxyphenyl) carbamoylnaphthalene, 2-hydroxy-3- (3-nitrophenyl)
Carbamoylnaphthalene or 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.

[0030]

[Chemical 138]

[0031]

[Chemical 139]

[0032]

[Chemical 140]

[0033]

[Chemical 141]

[0034]

[Chemical 142]

[0035]

[Chemical 143]

[0036]

[Chemical 144]

[0037]

[Chemical 145]

[0038]

[Chemical 146]

[0039]

[Chemical 147]

The characteristics of the case where such a specific complex compound is blended as a colorant will be described below. First, the complex compound can impart a uniform, clear, and glossy appearance even with a thin film having a thickness of 3 μm or less. This is because in the case of colored pigments, sufficient hiding properties cannot be obtained due to contact and aggregation of pigments in a thin film,
This complex compound has unevenness and is a film with poor appearance, but in the case of this complex compound, it has various excellent properties against electromagnetic waves in the visible light region of 400 nm to 700 nm due to its peculiar chemical structure. It has a clear color due to its excellent absorption characteristics, and it can be uniformly dissolved (or dispersed) in a thin resin film in a very fine state at the molecular level, forming a uniform and glossy film. This is due to the unique properties of this complex compound.

The formed colored film does not deteriorate in color even when illuminated by various light sources such as indoor lighting as a material for office equipment for home appliances, office automation 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. Also,
In the conventional coloring technique by reaction, for example, only the color peculiar to the Cr compound of the chromate film was obtained, whereas in the present invention, the complex compound of any color represented by the general structural formulas (1) and (2) is obtained. And by blending two or more of them in an arbitrary ratio, a colored film having an arbitrary color tone can be formed.

Further, the formed colored film is more preferable than the one in which the coloring pigment described above is blended as a coloring agent.
It has better corrosion resistance than the clear coating without additives. This is because in the case of a coloring pigment, if it is added at a certain concentration or more in a thin film, the pigment particles come into contact with each other and agglomerate to accelerate the permeation of water or ions through the gaps, thereby decreasing the corrosion resistance. On the other hand, this specific non-conductive complex compound disperses (dissolves) uniformly in the film in a very fine state at the molecular level, does not promote the permeation of water and ions, and is rather anticorrosive. It is presumed that this is because it has a function of improving the effect (insulation effect). By forming such a colored film on the surface of the chromate film described above, excellent corrosion resistance can be obtained due to the synergistic effect of the anticorrosive action of both the chromate film and the colored film.

Further, since the colored film of the present invention can be formed by coating treatment with a roll coater or the like, unlike the conventional coloring such as coloring chromate treatment or anodizing by reaction with a treatment liquid, plating or the like is performed. Since the dissolution of the metal does not occur, it is possible to overcome the drawback of the prior art of deterioration of the processing liquid. As described above, by using the specific complex compound as described above as the coloring agent, it becomes possible to form an unprecedented colored film having an excellent function.

Next, in the colored film of the colored stainless steel sheet of the present invention, the compounding ratio of the specific complex compound to the thermosetting resin, the range of the film thickness, and the reason for the limitation will be described. The specific complex compound is added in an amount of 1 to 200 parts by weight, preferably 5 to 120 parts by weight, based on 100 parts by weight of the thermosetting resin. The thickness of the colored film is 0.3 to 3.0 μm,
It is preferably 0.7 to 2.5 μm.

First, the upper limit of the compounding amount of the specific complex compound is set to 200 parts by weight, preferably 120 parts by weight, relative to 100 parts by weight of the thermosetting resin. Not only is it uneconomical to exceed,
This is because undissolved complex compound remains, which is not preferable. Further, the lower limit of the compounding amount is set to 1 part by weight, preferably 5 parts by weight, based on 100 parts by weight of the thermosetting resin, because the coloring effect is small at the compounding amount lower than this lower limit, particularly 1 part by weight. is there.

Next, the reason why the upper limit of the film thickness is set to 3.0 μm, preferably 2.5 μm is that the film thickness is the upper limit, particularly 3.
This is because if it exceeds 0 μm, the spot weldability is significantly reduced. The reason why the lower limit of the film thickness is 0.3 μm, preferably 0.5 μm is that the lower limit of the film thickness is 0.3 μm, especially 0.3 μm.
This is because when the thickness is less than μm, the hiding power becomes insufficient, so that the base can be seen through or the color tone becomes uneven. FIG. 1 is a summary of the specified ranges of the present invention as described above.

The base resin of the colored film of the colored stainless steel sheet of the present invention is a thermosetting resin. The reason why the base resin is defined as such a resin is that when a thermoplastic resin is used, a problem occurs in the scratch resistance of the formed colored 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 above-mentioned 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).

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

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

As the acrylic silicone resin, there is one in which a main component is a hydrolyzable alkoxysilyl group in the side chain or terminal of an acrylic copolymer, and a curing agent is added to this. 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 colored film of the colored stainless steel 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 colored coating. Examples of the solid lubricant applicable to the present invention include the following.・ Hydrocarbon lubricants such as natural paraffin, synthetic paraffin, microwax, polyethylene wax,
Chlorinated hydrocarbons, etc. Fluorine resin; for example, polyfluoroethylene resin, polyvinyl fluoride resin, polytetrafluoroethylene resin, polyvinylidene fluoride resin, etc. Fatty acid amide lubricant; 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, etc.-Metal 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 sulfates, etc.

However, it is preferable that the solid lubricant does not affect the color of the colored film by the addition thereof. For example, achromatic hydrocarbon lubricants, fluororesins, etc. can be applied to colored films of any color, but black molybdenum disulfide should be applied only to dark colored films. Is. The solid lubricant is added in an amount of 1 to 100 parts by weight, preferably 3 to 60 parts by weight, based on 100 parts by weight of the thermosetting resin. If the blending amount is less than 3 parts by weight, particularly less than 1 part by weight, the effect of improving the lubricity of the colored film by the addition of the solid lubricant is poor, while if it is more than 60 parts by weight, particularly more than 100 parts by weight, the curing It is not suitable because the strength of the colored film decreases and a part of the film adheres to the press mold.

The colored film obtained by applying the colored film composition consisting of the base resin and the specific complex compound is sufficient due to the anticorrosive effect of the base stainless steel plate and the synergistic effect with the chromate film formed if necessary. Although it has corrosion resistance, in order to further improve the corrosion resistance in the processed part, it is possible to add a particulate rust-preventive pigment in the colored film composition, whereby further excellent corrosion resistance can be obtained, and coloring It is preferable because it can be used for a wide range of applications. As the particulate rust preventive pigment, one or more selected from sparingly soluble chromate and silica are used. As the sparingly soluble chromate, barium chromate (BaCr
O ₄ ), strontium chromate (SrCrO ₄ ), lead chromate (PbCrO ₄ ), zinc chromate (ZnCrO ₄ ·
4Zn (OH) ₂ ), calcium chromate (CaCr
O ₄ ), zinc potassium chromate (K ₂ O ・ 4ZnO ・ 4C
rO ₃ .3H ₂ O) and 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 example, MA-ST, IPA-ST, NBA-S manufactured by Nissan Chemical Industries, Ltd.)
T, IBA-ST, EG-ST, XBA-ST, ETC-ST, DMAC-ST), wet silica / precipitation method (for example, T-32 manufactured by Tokuyama Soda Co., Ltd.)
(S), K-41, F-80), wet silica gel method (for example, Syloid 24 manufactured by Fuji Devison Chemical Co., Ltd.)
4, Syloid 150, Syloid 72, Syloid 6
5, SHIELDEX, etc.) can be used. Also,
It is also possible to use a mixture of two or more of the above silicas. However, it is preferable that the addition of the rust preventive pigment has a small effect on the color of the colored film.

One or more of the above rust-preventive pigments are added to the above colored film composition as its constituent components. The amount of rust preventive pigment compounded is 1 with respect to 100 parts by weight of thermosetting resin.
To 100 parts by weight, preferably 3 to 60 parts by weight. If the amount of the rust preventive pigment distributed is below the lower limit, particularly 1 part by weight, the rust preventive effect due to the addition of the rust preventive pigment does not appear, while if the amount exceeds the upper limit, particularly 100 part by weight, Since the amount of the rust pigment is excessive, not only the lubricity of the colored film is lowered, but also the gloss of the surface is lowered and the color is significantly changed.

When the solid lubricant and the particulate rust preventive pigment are added in combination, it is possible to form a colored film having excellent processability and corrosion resistance in the processed part. At that time, the solid lubricant and the particulate rust preventive pigment are each 1 to 100 parts by weight, preferably 3 to 60 parts by weight, based on 100 parts by weight of the base resin.
It is added in the range of parts by weight. In addition, other pigments (inorganic pigments, organic pigments) may be added in order to adjust the color tone and gloss of the colored film as desired. For example, by adding inorganic pigments (dark blue, yellow lead, white titanium oxide, etc.) and organic pigments (quinacridone, quinophthalone, isoindolinone, metal complex pigments, azo pigments, etc.), the hiding power is improved and the depth is increased. It is possible to set a certain color, adjust the color tone, or adjust the glossiness. Further, an organic compound having a coloring effect other than the above general structural formulas (1) and (2) may be added to adjust the color tone.

The above-mentioned colored film is prepared by diluting the composition with a solvent as needed and applying it to a predetermined film thickness by a method such as roll squeezing, a roll coater, or an air knife, and then a plate temperature of 80 to 300 ° C. (preferably). Is obtained by heat curing at 120 to 250 ° C.). The coating method and the baking method are carried out by general methods, and there is no particular limitation, but in the production of the colored stainless steel sheet of the present invention, the coating equipment for producing a highly corrosion-resistant surface-treated steel sheet possessed by a steel manufacturer can be used as it is. There is a big merit.

[0059]

EXAMPLES Examples 1 to 4 will be described below. In these examples, each stainless steel plate is degreased with alkali and then washed with water.
After drying, if necessary, a coating type chromate treatment liquid is applied by a roll coater or electrolytic chromate treatment is performed, and then a resin composition containing a colorant is applied by a roll coater and then baked at a predetermined temperature. Then 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 at room temperature by a roll coater and then 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 5 show the stainless steel plate, the base resin for forming the colored film, the colorant, the solid lubricant and the particulate rust preventive pigment used in each example, and
Tables 6 to 13 show the configurations and characteristics of the stainless steel plates of each example. The composition for forming a colored film was prepared by blending the components shown in Tables 2 to 5 in the blending amounts shown in Table 6 and below, and was diluted by adding a solvent as needed. In addition, the colorant No. 1-No. The structural formula of 10 (all are complex compounds) is as follows.

Colorant No. 1:

[Chemical 148]

Colorant No. 2:

[Chemical 149]

Colorant No. 3:

[Chemical 150]

Colorant No. 4:

[Chemical 151]

Colorant No. 5:

[Chemical 152]

Colorant No. 6:

[Chemical 153]

Colorant No. 7:

[Chemical 154]

Colorant No. 8:

[Chemical 155]

Colorant No. 9:

[Chemical 156]

Colorant No. 10:

[Chemical 157]

As a representative example of the method for synthesizing the above colorant, colorant No. 1, No. 2, No. 4, No. 7,
No. The following is an example of synthesis performed in 10 laboratories. [Colorant No. Synthesis Method 1] (Synthesis of Intermediate Compound) 15.4 g of 4-
Nitro-2-aminophenol is charged, and while stirring, 23.6 g of 35% hydrochloric acid is added. After cooling to 10 ° C. or below, 20 ml of water and an aqueous solution of 7.2 g of sodium nitrite are added. After stirring for another 2 hours at the same temperature, excess nitrous acid is decomposed by adding sulfamic acid to prepare a diazonium solution. Acetoacetanilide 1 in 150 ml of water
Charge 7.8 g, add 9.2 g of 48% caustic soda and 10 g of sodium acetate, and dissolve with stirring. While adding crushed ice to the mixture and maintaining the temperature at 10 ° C. or lower, a diazonium solution is added to carry out a coupling reaction. After completion of the reaction, filtration was performed to obtain 130 g of an intermediate compound. (Complexation reaction) 400 ml of water was charged with the above intermediate compound, and 17.1 g of cobalt chloride (hexahydrate) was charged.
Adjust to pH 9-10 with 90% caustic soda, 90-100 ° C
After reacting for 3 hours, the mixture was cooled, filtered and dried to obtain 36 g of the desired product.

[Colorant No. Synthesis method of 2] (Synthesis of intermediate compound) Anthranilic acid 1 was added to 150 ml of water.
Charge 6.6 g and stir 35% hydrochloric acid 24.8 g with stirring.
Charge. While cooling to 10 ° C. or lower, 20 ml of water and an aqueous solution of 7.2 g of sodium nitrite are added. After stirring for 2 hours at the same temperature, excess nitrous acid is decomposed with sulfamic acid to prepare a diazonium solution. 1 in 170 ml of water
First, 18.1 g of -phenyl-3-methylpyrazolone was charged, and while stirring, 9.2 g of 48% caustic soda and 14 g of sodium acetate were added and dissolved. Crushed ice is added to the mixture, 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 92 g of an intermediate compound. (Complexation reaction) To 150 ml of water was charged 92 g of the intermediate compound, and 29.5 g of 40% chromium sulfate and 2% of salicylic acid were added to this.
Add 0 g and chromium salicylate solution adjusted with caustic soda.
H9-10 was added, and the mixture was reacted at 90-100 ° C for about 10 hours. After cooling, it was filtered, washed and dried to obtain 34 g of the desired product.

[Colorant No. Synthesis method of 4] (Synthesis of intermediate compound) 15.4 g of 5-
Nitro-2-aminophenol is charged, and while stirring, 23.6 g of 35% hydrochloric acid is added. 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. Into 150 ml of water was charged 18.1 g of 1-phenyl-3-methylpyrazolone and stirred while stirring.
% 9.2 g of sodium hydroxide 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) 90 g of intermediate compound (I) in 150 ml of water
Was charged, and the coloring agent No. The same amount of the chromium salicylate solution as shown in the synthesis method of 2 was added, the reaction was carried out at 90 to 100 ° C. for 20 hours, and after cooling, filtration and drying were performed to give 39 g.
To obtain the intermediate compound (II). (Amination) 39 g of intermediate compound (II) in 300 m of water
After dispersion in 1 l, 20.2 g of N, N-dimethyl-N-benzyl-2-hydroxytetradecyl ammonium chloride
Was added to adjust the pH to 6 to 7, and the mixture was reacted at 60 to 70 ° C for 2 hours. After cooling, it was filtered and dried to obtain 56 g of the desired product.

[Colorant No. Synthesis method of 7] (Synthesis of intermediate compound) 14.5 g of 4-
Charge chloro-2-aminophenol and add 24 g of 35% hydrochloric acid with stirring. While keeping this solution at 5 ° C. or lower, 7.2 g of sodium nitrite is added little by little. After stirring at the same temperature for 2 hours, excess nitrous acid was decomposed with urea to prepare a diazonium solution. 1 to 160 ml of water
4.9 g of B-naphthol is added, and while stirring, 4 g of caustic soda and 5.3 g of sodium carbonate are added to adjust the coupler solution. Crushed ice is added to the coupler solution, and the diazonium solution prepared above is added at 5 ° C or lower to perform coupling. After completion of the coupling, the intermediate compound is obtained by filtering. (Complexation reaction) The above intermediate compound was dispersed in 150 ml of water, and 29.5 g of 40% chromium nitrate and salicylic acid 2
0 g and a solution of chromium salicylate adjusted with caustic soda were added, reacted at 90 to 100 ° C. for 8 hours, cooled, filtered,
After drying, 32 g of the desired product was obtained.

[Colorant No. Synthesis method of 10] Copper phthalocyanine 2 was added to 182 g of chlorosulfonic acid at 20 to 25 ° C.
After adding 4 g and reacting at 110 to 140 ° C. for 4 hours and cooling to 80 ° C., 48.5 g of thionyl chloride was gradually added, and 7
React at 0-80 ° 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,
3- (2-ethylhexyloxy) propylamine 1
After adding 6.4 g and adjusting the pH to 9 with sodium carbonate, the mixture is stirred for a while to complete the sulfonamidation. The pH is then raised to 12 with caustic soda and stirred at 70-80 ° C for 2 hours. After hydrolysis, if mineral acetic acid was added with hydrochloric acid, 16.4 g of 3- (2-ethylhexyloxy) propylamine was added, and 6
React at 0 ° C. for 2 hours. After cooling, it was filtered and dried to obtain 60 g of the desired product.

The test of the colored stainless steel sheet was carried out as follows. (1) Appearance Evaluation The appearance of the obtained colored film, in particular, the unevenness of the color tone was visually evaluated. The evaluation criteria are as follows. ⊚: Uniform and beautiful appearance ○: Almost uniform and beautiful Δ to ×: Surface is rough and not glossy, or color tone is not uniform and is not beautiful. (2) Glossiness Glossiness at an incident angle and a reflection angle of 60 ° was measured using a gloss meter manufactured by Suga Test Instruments Co., Ltd. The larger the value of glossiness, the higher the gloss.

(3) Weldability test Spot welding was carried out under the following conditions, and evaluation was made by the number of continuous 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. ◎: 1000 points or more ○: 700 points or more ×: Less than 700 points

(4) Adhesion of the colored film 100 pieces of burrs are formed on the surface of the colored 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, less than 20% ×: Peeling area 20% or more

(5) Press Formability Test 10 m with blank diameter φ120 mm and die diameter φ50 mm
Hat-drawing was performed by extrusion, and the side surface processed part of the colored stainless steel plate was peeled off with an adhesive tape, and the degree of peeling of the film onto the tape and the change in the appearance of the colored film were evaluated. The evaluation criteria are as follows. ⊚: No powdery peeling. + ○: Some powdery peeling occurs locally, but the appearance of the colored film is almost unchanged. ○: The tape is colored very lightly due to the powdery peeling,
The appearance of the colored film is almost unchanged. -○: The tape is lightly colored due to powdery peeling, and the appearance of the colored film is slightly white. Δ: The tape is colored due to the powdery peeling, and the whitening of the colored film is noticeable. X: The tape is markedly colored due to the powdery peeling, and the colored film is completely peeled off.

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

Example 1 The appearance, glossiness, weldability, workability, adhesion and light fastness of the material of the present invention having a colored film containing different coloring agents were examined. Also,
Similar measurements and tests were performed on the comparative material. The results are shown in Tables 6 and 7. In this example, the composition of the colored film was constant at 70 parts by weight of the colorant with respect to 100 parts by weight of the base resin, and the film thickness was also constant at 1.5 μm. According to Table 7, the material of the present invention using the specific complex compound as the colorant has the target appearance and gloss in the range of the film thickness at which welding is possible. On the other hand, the comparative material using the color pigment has poor appearance and gloss in the range of weldable film thickness, and also has poor press moldability and adhesion.

Example 2 Using a specific complex compound as a colorant, the effects of the film thickness of the colored film and the blending amount of the colorant on each characteristic were investigated. The results are shown in Tables 8 and 9. FIG. 2 is a summary of the weldability measurement results of Example (2) and Comparative Example (2).
It can be seen that when the thickness exceeds μm, it begins to decrease, and particularly when the coating thickness exceeds 3.0 μm, proper welding becomes impossible.

Example 3 Using a specific complex compound as a colorant, the influence of the amount of the chromate film deposited and the type of the base resin forming the colored film on each characteristic was examined. The results are shown in Tables 10 and 11.

Example 4 The properties of a colored stainless steel sheet containing a specific complex compound as a colorant and a solid lubricant and a particulate rust preventive pigment as additives were examined.
At the same time, the effects of the blending amounts of the solid lubricant and the particulate rust preventive pigment on the respective properties were also investigated. The results are shown in Tables 12 and 13.

[0086]

[Table 1]

[0087]

[Table 2]

[0088]

[Table 3]

[0089]

[Table 4]

[0090]

[Table 5]

[0091]

[Table 6]

[0092]

[Table 7]

[0093]

[Table 8]

[0094]

[Table 9]

[0095]

[Table 10]

[0096]

[Table 11]

[0097]

[Table 12]

[0098]

[Table 13]

The numbers or numerical values of the items marked with * 1 to * 8 in Table 6, Table 8, Table 10 and Table 12 indicate the following contents. * 1: No. 1 of the stainless steel plate described in Table 1. * 2: No. of the base resin described in Table 2. * 3: No. of the colorant described in Table 3. * 4: Represents parts by weight of the colorant with respect to 100 parts by weight of the base resin. * 5: No. of the solid lubricant described in Table 4. * 6: Represents parts by weight of the solid lubricant with respect to 100 parts by weight of the base resin. * 7: No. 1 of the particulate rust preventive pigment shown in Table 5. * 8: Represents parts by weight of the particulate rust preventive pigment with respect to 100 parts by weight of the base resin.

[0100]

EFFECTS OF THE INVENTION According to the present invention described above, since the colored film is thinner (3 μm or less) than the conventional coated stainless steel plate, welding is possible, and a uniform color tone and glossy appearance are obtained. An excellent colored stainless steel plate can be obtained. Further, this colored stainless steel sheet is excellent not only in appearance and weldability but also in adhesion of the colored film, workability, corrosion resistance and light fastness. Furthermore, since it can be manufactured by coating and baking with existing roll coater equipment, etc., it can be manufactured in a shorter time compared to colored stainless steel plate by anodizing treatment, and productivity can be greatly improved. It is possible to provide a colored stainless steel sheet which is extremely excellent in terms of both productivity.

[Brief description of drawings]

FIG. 1 is a graph showing the blended amount of a complex compound as a coloring agent and the range of the thickness of a colored film in the present invention.

FIG. 2 is a graph showing the relationship between the thickness of the colored film and the weldability of the sample material in the examples.

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

Claims (10)

[Claims] 1. A thermosetting resin is used as a base resin on the surface of a stainless steel plate.
As the colorant, one or more complex compounds selected from the group consisting of the complex compound represented by the following general structural formula (1) and the complex compound represented by the general structural formula (2) are added in a total amount of 1 ~ 200 parts by weight compounded film thickness 0.3-3.0 μm
Weldable colored stainless steel plate with the colored film (excluding black film). [Chemical 1] …… (1) [Chemical 2] (2) [In the general structural formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are each independently H, Cl, NO ₂ ,
SO ₂ NH ₂ , CH ₃ is represented, 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. CuPc in the general structural formula (2)
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 a stainless steel plate, and 100 parts by weight of the base resin is
As the colorant, one or more complex compounds selected from the group consisting of the complex compound represented by the following general structural formula (1) and the complex compound represented by the general structural formula (2) are added in a total amount of 1 ~ 200 parts by weight, and a weldable colored stainless steel sheet having a colored film (excluding black film) having a film thickness of 0.3 to 3.0 µm, which is prepared by further mixing 1 to 100 parts by weight of a solid lubricant. [Chemical 9] …… (1) [Chemical 10] (2) [In the general structural formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are each independently H, Cl, NO ₂ ,
SO ₂ NH ₂ , CH ₃ is represented, 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. CuPc in the general structural formula (2)
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 a stainless steel plate, and 100 parts by weight of this base resin is
As the colorant, one or more complex compounds selected from the group consisting of the complex compound represented by the following general structural formula (1) and the complex compound represented by the general structural formula (2) are added in a total amount of 1 To 200 parts by weight, and 1 to 100 parts by weight of the particulate rust preventive pigment.
A weldable colored stainless steel sheet having a colored film (excluding a black film) having a film thickness of 0.3 to 3.0 μm formed by mixing in parts by weight. [Chemical 17] …… (1) [Chemical 18] (2) [In the general structural formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are each independently H, Cl, NO ₂ ,
SO ₂ NH ₂ , CH ₃ is represented, 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. CuPc in the general structural formula (2)
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 a stainless steel plate, and 100 parts by weight of this base resin is used.
As the colorant, one or more complex compounds selected from the group consisting of the complex compound represented by the following general structural formula (1) and the complex compound represented by the general structural formula (2) are added in a total amount of 1 To 200 parts by weight, 1 to 100 parts by weight of a solid lubricant, and 1 to 100 parts by weight of a particulate rust preventive pigment to form a colored film (excluding black film) having a film thickness of 0.3 to 3.0 μm. Weldable colored stainless steel plate. [Chemical 25] …… (1) [Chemical 26] (2) [In the general structural formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are each independently H, Cl, NO ₂ ,
SO ₂ NH ₂ , CH ₃ is represented, 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. CuPc in the general structural formula (2)
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; 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. A stainless steel sheet has a chromate film having a chromium adhesion amount (converted to metallic chromium) of 1 to 200 mg / m ^{2 on} the surface thereof, and a thermosetting resin as a base resin on the top of the chromate film. For 100 parts by weight,
As the colorant, one or more complex compounds selected from the group consisting of the complex compound represented by the following general structural formula (1) and the complex compound represented by the general structural formula (2) are added in a total amount of 1 ~ 200 parts by weight compounded film thickness 0.3-3.0 μm
Weldable colored stainless steel plate with the colored film (excluding black film). [Chemical 33] …… (1) [Chemical 34] (2) [In the general structural formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are each independently H, Cl, NO ₂ ,
SO ₂ NH ₂ , CH ₃ is represented, 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. CuPc in the general structural formula (2)
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. A stainless steel sheet has a chromate film having a chromium adhesion amount (calculated as metal chromium) of 1 to 200 mg / m ^{2 on} the surface thereof, and a thermosetting resin as a base resin on the top of the chromate film. For 100 parts by weight,
As the colorant, one or more complex compounds selected from the group consisting of the complex compound represented by the following general structural formula (1) and the complex compound represented by the general structural formula (2) are added in a total amount of 1 ~ 200 parts by weight, and a weldable colored stainless steel sheet having a colored film (excluding black film) having a film thickness of 0.3 to 3.0 µm, which is prepared by further mixing 1 to 100 parts by weight of a solid lubricant. [Chemical 41] …… (1) [Chemical 42] (2) [In the general structural formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are each independently H, Cl, NO ₂ ,
Represents SO ₂ NH ₂ , CH ₃ , and X represents ...... (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. CuPc in the general structural formula (2)
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; 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. A stainless steel sheet has a chromate film with a chromium adhesion amount (calculated as metal chromium) of 1 to 200 mg / m ² , and a thermosetting resin is used as a base resin on the top of the chromate film. For 100 parts by weight,
As the colorant, one or more complex compounds selected from the group consisting of the complex compound represented by the following general structural formula (1) and the complex compound represented by the general structural formula (2) are added in a total amount of 1 To 200 parts by weight, and 1 to 100 parts by weight of the particulate rust preventive pigment.
A weldable colored stainless steel sheet having a colored film (excluding a black film) having a film thickness of 0.3 to 3.0 μm formed by mixing in parts by weight. [Chemical 49] …… (1) [Chemical 50] (2) [In the general structural formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are each independently H, Cl, NO ₂ ,
Represents SO ₂ NH ₂ , CH ₃ , and X represents ...... (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. CuPc in the general structural formula (2)
Represents a copper phthalocyanine residue, R ₃ and R ₄ each independently represent H, a C ₁ -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. A stainless steel sheet has a chromate film having a chromium adhesion amount (calculated as metal chromium) of 1 to 200 mg / m ² , and a thermosetting resin is used as a base resin on the top of the chromate film. For 100 parts by weight,
As the colorant, one or more complex compounds selected from the group consisting of the complex compound represented by the following general structural formula (1) and the complex compound represented by the general structural formula (2) are added in a total amount of 1 To 200 parts by weight, 1 to 100 parts by weight of a solid lubricant, and 1 to 100 parts by weight of a particulate rust preventive pigment to form a colored film (excluding black film) having a film thickness of 0.3 to 3.0 μm. Weldable colored stainless steel plate. [Chemical 57] …… (1) [Chemical 58] (2) [In the general structural formula (1), A represents —O— or —COO—, and R ₁ and R ₂ are each independently H, Cl, NO ₂ ,
Represents SO ₂ NH ₂ , CH ₃ , and X represents ...... (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. CuPc in the general structural formula (2)
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 a solid lubricant, 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. The weldable colored stainless steel sheet according to claim 2, 4, 6 or 8, containing one or more selected from the group consisting of :, a polyalkylene glycol. 10. The weldable product 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. Colored stainless steel plate.