JP2855343B2 - Metal complex dyes for dyeing metal tanned leather - Google Patents

Description

The present invention relates to a novel metal complex dye mainly used for dyeing leather, a method for producing the same, and a method for dyeing metal leather using the metal complex dye. And metal complex dyes for dyeing metal tanned leather.

[PRIOR ART] Most of dyes used in leather dyeing are acidic dyes having a water-soluble group, direct dyes, metal complex dyes, anionic dyes such as mordant dyes, and have high cationic properties.
Conventionally, dyes having a sulfone group have been mostly used for chrome leather.

For example, JP-A-58-40357, JP-A-56-59871, JP-A-57-171776, JP-A-57-171778 and JP-A-60-171778
No. 259685 proposes metal complex salt dyes for the purpose of improving various properties such as friction fastness, water resistance, washing resistance, light resistance, dyeing properties, leveling properties, permeability, etc. Each of the dyes has a sulfone group or a carboxyl group as a water-soluble group.

[Problems to be Solved by the Invention] However, the dyes and dyeing methods conventionally used for dyeing leather, especially metal tanned leather, are sufficiently satisfactory in terms of the strength of dyeing, the fastness to friction, and the permeability. It wasn't possible.

The present invention has been made in view of the above points, and has a good permeability in the dyeing of metal tanned leather, the fastness to rubbing of the dyed material, and excellent light fastness, especially, a metal complex dye for dyeing metal tanned leather. The purpose is to provide.

[Means for Solving the Problems] The present inventors have conducted intensive studies in order to achieve the above object, and as a result, a novel metal complex salt dye of a specific disazo dye having a phosphone group has been obtained, particularly for dyeing metal leather. When used for, it is found that the permeability is good, and the rub fastness of the dyed material is excellent in light fastness, especially.
The present invention has been completed.

That is, the metal complex dye for dyeing a metal tanned leather of the present invention has a formula (I) [Wherein Ps represents a phosphon group in the form of a free acid or salt, and R ¹
Represents OH, OCH ₃ , OC ₂ H ₅ or CO ₂ H, and R ² represents H, CH ₃ , OC
A sulfone group is shown in the form of H ₃ , OC ₂ H ₅ or a free acid or salt, and A represents a coupling component residue having a metallizable hydroxyl group at a position adjacent to the azo group. And a metal complex salt dye of a disazo dye represented by the formula:

In this specification, the term "position adjacent to the azo group" means "the second position counted from the carbon atom to which the azo group is bonded".

As the metal complex dye for dyeing metal tanned leather, formula (II) [Wherein Me represents copper, nickel, cobalt, iron or chromium, X represents -O- or -COO-, Ps, R ² and A
Is as defined above. However, the metallizable hydroxyl group of A is represented by -O- by metallization. ] The metal complex dye represented by these is mentioned.

The metal complex dye for metal leather dyeing of the present invention is, for example, a compound represented by the formula (III) [Wherein, Ps, R ¹ and R ² are as defined above. Wherein a diazonium salt of a monoazo compound represented by the formula (I) is reacted with a coupler that forms a coupling component residue A (A is as defined above) to obtain a disazo dye, and the disazo dye is converted to an acidic or tertiary dye. It can be produced by reacting with a metal imparting agent in water and / or an organic solvent under a cutting atmosphere.

The disazo dye in this case, that is, the disazo dye represented by the formula [I], can be metallized with one azo group.

In the present invention, Ps is a phosphonic group represented by -P (= O) (OM) ₂ , and in the form of a free acid, M is hydrogen,
In the salt form, M can be an alkali metal such as sodium, potassium, lithium, an ammonium such as NH ₄ or an amine such as an alkanolamine.

Further, the dye of the present invention may have a sulfone group.
The sulfone group in this case takes the form of a free acid or salt, as in the case of the above-mentioned phosphone group. If the free acid or salt form of the sulfone group is expressed as —SO ₃ M, in the free acid form, M is hydrogen, and in the salt form, M is an alkali metal, ammonium or amine.

However, in the dye of the present invention, Ps and M in one or more of the above sulfone groups may be the same or different.

R ^{1 of} the phenylene group sandwiched between two azo groups in the formula [I] is a metallizable hydroxyl group or alkoxy group (C ₁ to
C ₂ ) or a carboxyl group, and is coordinated to a metal to become —O— or —CO ₂ —, for example, as shown in the formula [II].

R ² in the formulas [I], [II] and [III] is substituted para to R ¹ and represents a hydrogen atom, a methyl group, an alkoxy group (C ₁ -C ₂ ) or a sulfone group .

Examples of the coupler that forms the coupling component residue A (hereinafter, referred to as coupler A) include β-naphthols, α-naphthols, pyrazolones, phenols,
Examples include acetoacetic anilide derivatives.

The metallizable disazo dye represented by the formula (I) is
It can be obtained by reacting a diazonium salt of a monoazo compound represented by the formula [III] with a coupler A.

The monoazo compound represented by the formula [III] can be synthesized by a usual diazotization and coupling reaction. That is, it is obtained by a coupling reaction between a diazonium salt of o-, m- or p-aminobenzenephosphonic acid and an aniline or aminobenzene derivative having substituents R ¹ and R ² . Examples of the aniline or aminobenzene derivative having the substituents R ¹ and R ² include cresamine, p-cresidine, o-anisidine, o-phenetidine, 2,5-
Examples include dimethoxyaniline, 3-amino-4-hydroxybenzenesulfonic acid, and anthranilic acid.

Suitable examples of Coupler A include 8-amino-2-naphthol, shafaic acid, R acid, G acid, γ acid, H acid, J acid,
Naphthols such as S-acid, SS-acid, L-acid, M-acid, 2R-acid, NW-acid, K-acid and sulfonic acid derivatives thereof, pyrazolones such as 3-methyl-5-phenylpyrazolone and its derivatives, resorcinol, cresol; Examples include phenols such as p-phenylphenol, acetoacetic anilide and the like.

The metal complex dye for metal-tanning leather dyeing of the present invention can be obtained by reacting the above disazo dye with a metal-imparting agent in water and / or an organic solvent in an acidic or basic atmosphere. The metallization in this case can be performed by a method known per se, for example, a method described in JP-A-58-40357.

Specifically, a metal-providing agent (the amount of the metal is 1.1 mol) per 1 mol of the metallizable disazo dye represented by the formula [I].
0 g atoms or more, preferably 1.2 to 1.5 g atoms) and reacting in an acidic or basic atmosphere in water and / or an organic solvent at 70 ° C. to 150 ° C. until the dye is completely absent. can get.

In the above production method, the copper or nickel complex salt is 1: 1.
Formed as complex salts, cobalt, iron or chromium complex,
Formed as 1: 1 and / or 1: 2 complex salts.

The formed metal complex salt dye can be isolated by direct means such as spray drying and drum drying, or by acid precipitation, salt precipitation and the like. When the acid precipitate is treated with an amine, a desired amine salt can be obtained.

Solvents that can be used for metallization include water-soluble organic solvents such as formamide or dimethylformamide, glycols or their monoalkyl ethers.

As the metal imparting agent, a copper, nickel, cobalt, iron or chromium salt of an inorganic or organic acid can be used. Examples of the copper imparting agent include copper sulfate, copper chloride, copper acetate, copper formate and copper carbonate. Examples of the nickel imparting agent include nickel sulfate, nickel chloride, nickel acetate and nickel formate. As other metal-imparting agents, for example, cobalt acetate, cobalt chloride, ferric chloride, chromium acetate, chromium formate, chromium sulfate and chromium salicylate can be used.

Metallation is preferably carried out in the presence of alkali metal and alkaline earth metal carbonates or ammonia or lower amines.

In the above production method, the substituent R ¹ of the disazo dye
Is a C ₁ -C ₂ alkoxy, the metallization is preferably carried out in an organic solvent.

The novel metal complex dye having a phosphonic group obtained in this way is required for leather dyeing at a temperature of about 50 ° C.
Under the conditions of 3 to 6, it can be used for dyeing in the same treatment method as the conventional acid dye.

As the dyeing process for metal tanned leather, a general dyeing process can be used.

The types of metal tanning of leather to be dyed include chrome tanning, aluminum tanning, titanium tanning,
There is zirconium tanning and the like.

 The following is an example of the dyeing process.

On chrome leather shaved to a certain thickness,
After performing a water washing step and a neutralization step as a pretreatment step for the dyeing, the dyeing is performed, formic acid is added to fix the dye, and then the fat is greased and neutralized.

The water washing step in the pretreatment step is intended to remove the unbound tanning agent in the leather, remove the unbound acid in the leather, remove foreign substances attached to the leather, and loosen the leather structure, This can be done by running water using a drum.

The neutralization step in the pretreatment step is to neutralize the acid bound to the collagen or chromium complex of the leather, which is not removed only by washing with water, and to achieve a uniform permeation of the dye and the fatliquoring agent. The neutralization can be carried out at a pH of 5 to 6 for 30 minutes to 2 hours using a neutralizing agent such as a weak alkaline salt.

Examples of the neutralizing agent include sodium bicarbonate, sodium acetate, sodium formate and the like.

The dyeing is carried out by drum dyeing, paddle dyeing or the like using the metal complex dye of the present invention for dyeing metal tanned leather. Drum dyeing, 190-300 based on shaving weight
% Water (50-60 ° C.), adding the dye solution while rotating, and treating at pH 4,5-6 for a predetermined time.

The fatliquoring can be carried out after dyeing by adding a fatliquoring agent in a new bath. As the fatliquoring agent, nonionic, anionic, cationic fatliquoring agents and the like can be used in addition to raw oils and synthetic fats and oils.

The dyeing with the metal complex dye of the present invention for dyeing metal tanned leather is applicable to not only tanned leather such as wet blue but also tanned leather after tanning and tanned tanned leather after tanning. it can. And if it ’s chrome-tanned leather, cows, pigs,
Any kind of leather, such as horses, sheep, and goats. Further, the present invention can be applied to aluminum leather, titanium leather, and zirconium leather.

[Action] Although the mechanism of the action of the metal complex dye of the present invention in dyeing metal tanned leather is not clear, the phosphonic group of the dye of the present invention is coordinated or reacted with a metal in the metal tanned leather, for example, chromium ion. By combining with a dye having a sulfone group or a carboxyl group, it has excellent friction fastness and good permeability as compared with a dye having a sulfone group or a carboxyl group which has been conventionally used. It is presumed that a complex salt structure is formed and light resistance is improved.

[Effects of the Invention] The metal complex dye of the present invention has good permeability to metal tanning leather, and the dyed product of metal tanning by the metal complex dye of the present invention is compared with azo acid dyes having no phosphone group. It has excellent fastness to friction and light fastness compared to azo dyes having a phosphon group.

[Examples] Hereinafter, the present invention will be described in more detail with reference to examples. However, needless to say, the present invention is not at all limited by the following examples unless it exceeds the gist thereof.

Example 1 Synthesis of Metallizable Disazo Dye 104 g (0.6 mol) of m-aminobenzenephosphonic acid was
The resultant was dissolved in an aqueous solution in which 90 g of concentrated hydrochloric acid was dissolved in 400 ml of water, and ice was added thereto to adjust the temperature to 0 ° C., followed by diazotization using an aqueous solution in which 42 g of sodium nitrite was dissolved. Then, after the excess nitrous acid in the solution of the generated diazonium salt is decomposed using sulfamic acid, 30% is added to the solution of the diazonium salt.
g of urea was added and stirred at 0 ° C. for 30 minutes. Then 83g
A solution prepared by dissolving (0.6 mol) of p-cresidine in 2000 ml of water and 72 g of aqueous hydrochloric acid was slowly added to the diazonium salt solution, and the mixture was stirred at 5 ° C to 10 ° C overnight. The reaction solution was filtered and washed with water, and the obtained cake (monoazo compound represented by the general formula [III]) was dispersed in 4000 ml of water, and 120 g of hydrochloric acid was added and stirred. Next, after diazotization at 30 to 40 ° C. using an aqueous solution in which 42 g of sodium nitrite was dissolved,
g of urea was added and stirred for a while. Next, 96g (0.6mo
l) An aqueous solution in which 1-amino-7-naphthol and 60 g of sodium hydroxide were dissolved in 1200 ml of water was prepared, and the diazonium salt solution of the above monoazo compound was added thereto.
The mixture was stirred at 8.0 to 8.5 for 4 hours. Thereafter, the mixture was acidified (pH = 4) with dilute hydrochloric acid, heated to 70 ° C., filtered, washed with water, and dried to obtain 250 g of disazo dye (dye example (1). It will be described later in the form of acid).

[Metal Synthesis of complex dyes] copper complex dye 150g of ethylene glycol in 30g of copper sulfate (CuSO ₄ · 5H
₂ O) was completely dissolved, and 50 g (about 0.1 mol) of Dye Example (1) was added.
The mixture was stirred at 40 ° C to 150 ° C for 5 hours. After confirming that there is no unreacted dye, 100 g of ammonium chloride and 500 ml of warm water are added, and the mixture is filtered, washed with water and dried to give a copper complex salt dye represented by the following structural formula (Dye Example 1; The results are shown in Table 1 below, where the colors are the colors of the dyed leather as the object to be dyed.) 50 g was obtained.

30g of copper sulfate of ethylene glycol copper complex dye 150g (CuSO ₄ · 5H
After dissolving ₂ O), add 50 g of ammonia and then
Add 56 g (about 0.1 mol) of Dye Example (6) and add
Stir for 15 hours. After confirming that there is no unreacted dye,
100 g of ammonium chloride and 500 ml of warm water were added, and salting out, filtration, washing with water and drying were performed to obtain 65 g of a copper complex salt dye (Dye Example 6).

Copper complex salt dye 25 g of copper chloride (CuCl ₂ .2H ₂ O), 60 g of ammonia 1
After completely dissolving in an aqueous solution dissolved in 000 ml of water, 62 g (about 0.1 mol) of Dye Example (4) was added thereto, and the mixture was stirred at 70 ° C. to 80 ° C. until there was no unreacted dye. After adding ammonium and 500 ml of warm water, salting out with sodium chloride, filtration and drying, 70 g of a copper complex salt dye (Dye Example 4) was obtained.

Nickel complex dye 29.8g of nickel acetate _{(Ni (CH 3 COO) 2} · 4H 2 O) 100
It was completely dissolved in 0 ml of water, 56 g (about 0.1 mol) of Dye Example (13) was added, and the mixture was stirred at 70 to 80 ° C. and pH 5 to 6.5 for 10 hours. After confirming that there was no unreacted dye, salting out, filtration and drying gave 65 g of a nickel complex salt dye (Dye Example 13).

Chromium complex salt dye 25 g of chromium acetate (Cr (CH ₃ COO) ₃ .H ₂ O) is added to 800 ml of water, and the mixture is completely dissolved by heating. Dye example (7) 64 g (about 0.1 mol)
And stirred at 70 ° C. to 80 ° C. and pH 5 to 6.5 until there is no unreacted dye. After salting out with sodium chloride, filtration,
By drying, 65 g of chromium complex dye (Dye Example 7)
I got

Cobalt complex dye 30g of cobalt sulfate _{(CoSO 4 · 7H 2 O)} , the 60g ammonia completely dissolved in an aqueous solution dissolved in water of 1000 ml, dye example (2) 56 g (about 0.1 mol) was added, 70 ° C. ~ 80 ℃, pH7 ~ 8
After stirring until the unreacted dye disappeared, treated with 8 g of ethanolamine, filtered, washed with water, and dried,
Cobalt complex dye represented by the following structure (Dye example 2) 67
g was obtained as the ethanolamine salt.

Dye Examples 3, 5, 8 to 12 and 14 to 17 Metal complex salt dyes for the metals shown in the metal column of Table 1 were obtained using the dyes shown in the dye column of Table 1 in accordance with the above procedures.

Example 2 [Dyeing of chrome tanned leather using the metal complex dye of the present invention (Dye Examples 1 to 17)] As a pretreatment step, wet blue (chrome tanned cowhide, 1 mm thick clothing leather) was washed with running water The solution was maintained at 30 to 40 ° C. at pH 5 to 6 using an aqueous solution of sodium bicarbonate and neutralized for 30 minutes. Then, using 2% of the dye shown in Table 1 and 190% of water based on the weight of the wet blue, at 60 ° C.
For 30 minutes. When the water-soluble group of the dye was in the form of a free acid, it was dissolved in aqueous ammonia in advance and used as a dye solution. After dyeing, formic acid was added to fix. Furthermore, 250% of water is added to the weight of wet blue to reach 60 ° C., and 1.4% of neutral oil (manufactured by Yoshikawa Oil Co., Ltd., fat for leather fatliquoring) and 5.6% of synthetic fat and oil (manufactured by Orient Chemical Industries,
MMP) was added as a fatliquor and treated for 60 minutes. Finally, formic acid was added for neutralization to obtain a dyed leather.

The rub fastness and permeability of the obtained dyed leather are shown in Table 2 below. All leveling properties were good. The light fastness was measured with a fade meter (carbon arc type) for 40 hours, and a comparison with a normal state was examined using a blue scale (JIS L0841). The friction fastness indicates the result of a wet test performed using a Gakushin type friction tester according to a friction test (JIS L0849). The permeability was determined by observing the cross section of the dyed leather.

Comparative Example 1 Black dyed leather in the same manner as in Example 2 except that the metal complex salt dye of Dye Example 1 used in Example 2 was replaced with the corresponding disazo dye (Comparative Dye a) of Dye Example (1). I got The test results are shown in Table 3 below.

Comparative Example 2 Black dyed leather in the same manner as in Example 2 except that the metal complex salt dye of Dye Example 4 used in Example 2 was replaced with the corresponding disazo dye (Comparative Dye b) of Dye Example (4). I got The test results are shown in Table 3 below.

Comparative Example 3 Using a dye represented by the following structural formula c (comparative dye c), a red dyed leather was obtained in the same manner as in Example 2. The test results are shown in Table 3 below.

Comparative Example 4 Dyeing was carried out in the same manner as in Example 2 using a dye represented by the following structural formula d (Comparative Dye d). The test results are shown in Table 3 below.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Minako Terasaki, Inventor, 8-1, Sanarahigashicho, Neyagawa-shi, Osaka Orient Chemical Industry Co., Ltd. (56) References JP-A-51-133325 (JP, A) Kohei 5-80956 (JP, B2) JP-B Hei 7-30518 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09B 45/00-45/48 D06P 3/32 D06P 1/10 CA (STN)

Claims (3)

(57) [Claims] 1. A metal complex dye for dyeing metal tanned leather, wherein the metal complex dye has the formula [I] [Wherein Ps represents a phosphon group in the form of a free acid or salt, and R ¹
Represents OH, OCH ₃ , OC ₂ H ₅ or CO ₂ H, and R ² represents H, CH ₃ , OC
A sulfone group is shown in the form of H ₃ , OC ₂ H ₅ or a free acid or salt, and A represents a coupling component residue having a metallizable hydroxyl group at a position adjacent to the azo group. A metal complex dye for metal tanning, which is a metal complex salt dye of a disazo dye represented by the formula: 2. The metal complex dye according to claim 1, wherein said metal complex dye is a copper, nickel, cobalt, iron or chromium complex dye. 3. The formula [II] Wherein Me represents copper, nickel, cobalt, iron or chromium, X represents —O— or —COO—, Ps represents a phosphonic group in the form of a free acid or salt, R ² represents H, CH _{3, OCH 3, OC 2 H} 5
Or a sulfone group in the form of a free acid or salt, wherein A is
A coupling component residue having a metallizable hydroxyl group at a position adjacent to an azo group is shown. However, the metallizable hydroxyl group of A is represented by -O- by metallization. The metal complex salt dye for dyeing metal tanned leather according to claim 1, which is represented by the following formula: