JPH06184452A - Blue chrome complex dye and its preparation - Google Patents

Abstract

PURPOSE: To obtain a novel compound exhibiting uniformly dyeing property, exhibiting blue color, having fastness and useful in dyeing leather or the like.

CONSTITUTION: By metalizing a dysazo compound of formula III with a chrome producing agent, this compound of formula I [wherein R₁ represents H, NO₂, SO₃M (wherein M represents H or a cation); R₂ represents NO₂ or SO₃M; R₃ represents H, COOM, COOR₄, CONH₂ or CONR₄R₅; R₄ represents a 1-4C alkyl, a 2-3C hydroxyalkyl or the like; R₅ represents H, a 1-4C alkyl or a 2-3C hydroxyalkyl], for example a compound of formula II is obtained.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

In dyeing different leathers and different shades, there is a high levelness and fastness and a high color yield.
It is desirable to obtain good dyeing of d). Furthermore, it is often desirable to use dyes that are as pure as possible to avoid the undesired haze effect when mixing dyes of different hues. In blue dyes, to obtain a wide range of blue color depths or to have a high-purity blue component of mixed dyes, especially trichrome dyes, it imparts a high-purity blue hue to leather, and a leather with low affinity. Even in, it is desirable to have a dye that gives the possibility of giving a very deep blue hue.

It has been found that the 1: 2 chromium complex dyes specified below are suitable for the above conditions. The present invention is a novel dye,
It relates to its manufacturing method and its use.

The present invention has the following formula

[Chemical 5] (In the above formula, each R ₁ independently represents hydrogen, —NO ₂ or —SO ₃ M, each R ₂ independently represents —NO ₂ or —SO ₃ M, each R ₃ independently represents hydrogen, COOM, -COOR ₄ , -CONH ₂ or -CONR ₄ R ₅ , each R ₄ independently represents C _1-4 alkyl, C _2-3 hydroxyalkyl, unsubstituted phenyl or methyl, ethyl, methoxy,
Chlorine, -NO _2, phenyl substituted with one or more substituents selected from the group consisting of -SO ₃ M and -COOM, each R ₅ is independently hydrogen, C _1-4 alkyl or C _{2- 3} hydroxyalkyl, M represents hydrogen or a cation, wherein _one of R ₁ and R ₂ represents —SO ₃ M and the other represents other than —SO ₃ M); There is provided a blue dye which is a mixture of 1: 2-chromium complexes of formula (I).

When R ₁ represents --SO ₃ M, R ₂ (at the same time a benzene ring, especially in formula (VI) below) represents --NO ₂ .
When R ₂ represents —SO ₃ M, R ₁ (at the same time benzene ring, especially in formula (VI) below) represents hydrogen or —NO ₂ . formula
In (I), two R _{1 s} may have the same or different ones, and two R _{2 s} may have the same or different ones. Preferably R ₁ represents -NO ₂ .

Of the C _1-4 alkyl groups of R ₄ and R ₅ , low molecular weight ones are preferred, especially ethyl and methyl, especially methyl, especially C _2-3 hydroxyalkyl, especially β-hydroxyethyl and β-Hydroxypropyl is exemplified. The phenyl ring of R ₄ is mono-, di- or tri-substituted, preferably at most one substituent is the group -S.
O ₃ M or —COOM, preferably up to 2 substituents are chlorine. Preferably methoxy R ₃ is hydrogen, -COOM, -CONH ₂ or a group -CONR ₄ H (R ₄ is optionally chlorine or -COOM
Represents a phenyl group substituted with). Two R ₃ may have the same or different. Most preferably R ₃ represents hydrogen.

The cation M may be any cation customary in anionic metal complexes, conveniently non-color forming cations, preferably ammonium and alkali metal cations (especially unsubstituted ammonium, mono, di, tri- (C _{1 -2} alkyl) or (C _{2 -3} hydroxyalkyl) ammonium, lithium, sodium or potassium, sodium being particularly preferred.

The chromium complex compounds of the present invention are synthesized by known methods, preferably by chromation, diazotization and coupling of the corresponding starting materials. 1 of the present invention
The two chromium complexes are a)

[Chemical 6] At least one disazo compound of
omium-yielding agent), or b)

[Chemical 7] The bisdiazo compound of the 1: 2 chromium complex or a mixture of the bisdiazo compounds of

[Chemical 8] Prepared by coupling to a coupling component of or a mixture of coupling components of formula (IV).

The disazo compound of formula (II) has the following formula

[Chemical 9] It is prepared by coupling a diazo compound of an amine of formula (IV) with a coupling component of formula (IV).

The compound of formula (V) has the formula

[Chemical 10] The amine diazo compound of

[Chemical 11] It is produced by coupling to the coupling component of.

The metal complex of formula (III) is prepared by chromization of a compound of formula (V) with a chromium generator.

The diazotization and coupling reaction may be carried out by conventional methods. Diazotization may be carried out as usual,
For example, in an acidic medium (preferably hydrochloric acid), preferably 20 ° C
Hereinafter, for example, with sodium nitrite at a temperature of 0 to 15 ° C. Coupling to a compound of formula (VII) may be carried out under mildly acidic to alkaline conditions, preferably pH.
4-12, preferably 9-11, the coupling to the compound of formula (IV) is carried out in an alkaline medium which is evident from weak acidity, optionally in the presence of a coupling activator, preferably 7-12. , Preferably at a pH of 9-11 and at a temperature of -5 ° C to + 80 ° C, preferably 0-50 ° C, in an aqueous or aqueous / organic medium. formula
For chlorination of (II) or (V), conventional chromium compounds, especially chromium salts such as chromium trichloride, chromium trifluoride, chromium sulfate, chromium acetate, chromium sulfate potassium, chromium ammonium sulfate (eg chromium alum), Used, and optionally reducing agents such as glucose, sodium or potassium chromate or sodium or potassium chromite are added. Chromation is carried out directly up to the 1: 2-chromium complex stage, or by complexing up to the 1: 1 -chromium complex and then further up to the 1: 2-chromium complex stage (the latter especially 2 R ₃ and 2
In the case of the preparation of compounds of formula (I) in which each R ₁ does not have the same and / or two R ₂ do not have the same, or 2 R ₁ and 2 R ₂ In the case of the production of formula (III) in which each does not have the same). Chromation is carried out in an aqueous medium, preferably at a pH of 2 to 10 and at a temperature of 95 to 130 ° C., optionally under pressure. If desired, this reaction is carried out with or in addition to an organic solvent. Suitable organic solvents are preferably water-miscible, have a boiling point above 100 ° C. and are soluble in azo dyes and chromium salts, such as glycols, ether alcohols,
Or an amide (for example, ethylene glycol, polyethylene glycol, β-ethoxyethanol, β-methoxyethanol, formamide or dimethylformamide). To produce an asymmetric 1: 2-chromium complex compound, the chromation first involves the addition of one of the complexing materials, 1: 1.
By forming a chromium complex and then with this second complexing substance a 1: 2-Cr complex. 1:
The 1-chromium complex is prepared in conventional manner, for example under the same conditions as for the 1: 2-chromium complex, but preferably at a stronger acidic pH value, advantageously at a pH of 3 or less. Also, by simultaneously metallizing different complexing substances of formula (II) or (V), or by coupling a bisazo compound of formula (III) to a mixture of coupling components of formula (IV), or By coupling the compound of formula (IV) or the mixture of compounds of formula (IV) with the bisdiazo compound of the mixed complex of formula (III) 1: 2-
It is advantageous to synthesize chromium mixed complexes.

1: 2-Chromium complex of symmetrical structure, ie two R ₁ have the same, two R ₂ have the same and two R ₃ have the same 1 : It is preferable to provide a 2-chromium complex.

The 1: 2-Cr complex of the present invention is a blue dye and is essentially free of other metal complexes and other chromium complexes. By "essentially free" is meant free of interfering amounts of other metal complexes. By interfering amount is meant the amount of other complexes which obviously alters the properties of the dye, for example 10% by weight or more, or 5% by weight or more. However, the presence of other complexes as by-products from the synthesis of the dyestuffs according to the invention, for example in amounts of up to 10% by weight, in particular 2 to 8% by weight, with respect to the compound of formula (I) is acceptable as a compatible impurity. To be done.

The 1: 2-chromium complexes according to the invention are suitable as blue dyes for leather, especially tanned leather or fur. The dye may be used at any desired concentration up to substrate saturation. The dyeing is carried out by a method suitable for the substrate to be dyed, for example preferably by discharge from an aqueous solution or by impregnation (eg padding or printing).
The dyes of the present invention have preferred dyeing properties which make them suitable as blue shade dyes for all types of leather.

Suitable are all kinds of leather dyed from aqueous media, in particular grain leather (eg sheep, goat or cattle Napa, calf or cattle box leather), suede leather (eg sheep, Goat or calf velour, and hunting leather), split velor (spl
Suitable are it velours (eg from cow or calf skin), buckskin and nubuck leather, and wool-containing skin and fur (eg fur-containing suede leather). Leather is tanned by conventional tanning methods, especially for plants,
Mineral, synthetic or mixed tanned (eg chrome tanned, zirconyl tanned, aluminum tanned or semi-chrome tanned). If desired, the leather may be re-tanned and for this re-tanning conventional tanning agents such as mineral, vegetable, animal or synthetic tanning agents (e.g. chromium, zirconyl or aluminum derivatives, oak, quebracho or tadpole) may be used. (mimos
a) extract, polypeptide, aromatic syntans,
Polyurethanes, (meth) acrylic acid compounds or (co) polymers of melamine, dicyandiamide and / or urea / formaldehyde resins) may be used.

The leather may be of various thicknesses, such as very thin leathers such as book binder leather or glove leather (Napa), medium thickness leathers such as shoe uppers, bag leathers and handbag leathers. Thick leather such as leather or sole leather, leather for chairs, leather for suitcases, belts and sports equipment may also be used, and fur may also be used. After tanning (especially after retanning) and before dyeing, the pH of the leather is preferably set in the range of 4-8 (leather is "neutral").
Is). The optimum pH range is selected depending on the type of leather, eg pH 4-6 for grain leather, 4.5 for suede leather and split velor and very thin leather.
A pH of -8, a medium dry suede leather and a medium dry split velor a pH of 5-8 are selected. Conventional auxiliaries are used for adjusting the pH value of leather, and for acidic tanned leather the pH is adjusted to a suitable base, such as ammonia, ammonium hydrogen carbonate or alkali metal salts of weak acids, such as sodium formate, sodium acetate, hydrogen carbonate. It is adjusted by the addition of sodium, sodium carbonate, sodium bisulfite, of which sodium formate and ammonia are preferred. Sodium carbonate and sodium hydrogen carbonate can be used in particular as secondary bases for the exact adjustment of the surface pH of leather. Mineral tanned leather may optionally be masked with, for example, formic acid, oxalic acid or an alkali metal polyphosphate, or for example titanium / potassium oxalate.

The dyeing is carried out in a known manner suitable in an aqueous medium,
Conventional temperature and pH conditions, eg 20-80 ° C, preferably
It is carried out at a temperature of 20 to 70 ° C., more preferably 25 to 60 ° C., and a milder temperature condition for dyeing the leather portion of the skin and fur containing wool without dyeing the wool or hair portion, particularly 25 ~ 40 ° C is preferred. The pH values of the dye bath are usually in a wide range, mainly pG9 to pH 3, the dyeing advantageously starting at higher pH and ending at lower pH. Preferably, the dyeing is carried out at a pH value of 4 or more, especially at 9-4, in order to finish the dyeing, the pH value is preferably reduced to a value of 4-3 (eg leather dyeing such as acetic acid or formic acid. By the addition of common acids). The dye concentration ranges over a wide range, optionally up to saturation of the substrate and depends on the type of leather, for example up to 10% of the wet weight of the substrate or of the dry weight of the substrate.
Up to 20%. Staining may be carried out in one or more steps, for example two steps, optionally with charge conversion of the substrate by conventional cationic auxiliaries. If desired, the dyeing is carried out in the presence of dyeing auxiliaries, which are mainly conventional nonionic or anionic products (especially hydrophilic surfactants,
Preferred are hydrophilic polysaccharide derivatives, polyoxyethylated alkylphenols or fatty alcohols, lignosulfonates or sulfo group-containing aromatic compounds).
The dyestuffs according to the invention are distinguished by their surprising acid resistance, this dyeing is distinguished by its surprising acid fastness, the dyeing process and dyeing requiring addition of acid during or even after dyeing. Not (the resulting dyeing is also suitable as a substrate for post-treatment and finishing, eg in acidic conditions).

If desired, fatting may be carried out before and / or after dyeing. Since the fatting is carried out after dyeing, the pH of the liquid is advantageously 3
Add the fatting agent before dropping to a value of ~ 4.

In the fatting process, any conventional natural animal, vegetable or mineral fat, fatty oil, wax, resin or resin oil, or chemically modified animal or vegetable fat or oil (particularly beef tallow, fish oil, beef foot oil, olive oil) , Castor oil, rapeseed oil, linseed oil, wood oil, sesame oil, corn oil, and their chemical modification products (for example, hydrolysis, transesterification, oxidation, hydrogenation or sulfonation products), beeswax, Chinese wax, carnauba Wax, montan wax, wool fat, colophony, birch oil, shellac, 300
Mineral oils with boiling points of ~ 370 ° C (especially so-called "heavy alkylate"), soft paraffin, medium paraffin, hard paraffin, petrolatum, ceresin, and C
Methyl esters of _14-22 fatty acids, and synthetic leather fatting agents, including esters, especially partial esters of polybasic acids (eg, phosphoric acid), including optionally oxyethylated fatty alcohols, may be used. Among the above, methyl ester, sulfonation product and phosphoric acid partial ester are particularly preferable. "Sulfonation" means the introduction of sulfo groups, including the formation of sulfate groups and the introduction of sulfo groups by reaction with sulfite or SO ₂ .

If desired, conventional leather softeners, especially cationic leather softeners, may be used in the final step, especially when the fatting is carried out with a sulfonated fatting agent. According to a feature of the invention, the dye is post-treated with a polycation fixing agent.

The polycationic post-treatment agent (fixing agent) may be a conventional water-dispersible or preferably water-soluble, essentially colorless fixing agent used in dyeing leather with water-soluble dyes. The polycationic post-treatment agents considered are predominantly amino compounds, which may be quaternary and / or protonated ammonium compounds, or nonquaternary and nonquaternary which form ammonium ions in aqueous, especially acidic media. It may be a protonated amine.

The amino compound used as the fixing agent is
Having one or more C _9-24 aliphatic hydrocarbon groups and optionally benzylated and / or alkylated with C _1-4 alkyl groups, for example as described in DE-A 2508242, 2924471 and 3534102 Aliphatic polyamines (e.g. polymethylenediamines having 2-6 methylene groups in the polymethylene bridge or polyalkylenepolyamines in which the alkylene contains 2-4 carbon atoms and 3-6 amino groups, Or cyclic amine), or DE-A 3216913, 34
46284 and 3525104, PCT specification WO 81-2423 and EP 151
1 or 2 Cs as described in 370A2
_1-4 Polyamine or monoamine containing alkyl group and cyanamide, dicyanodiamide, guanidine, biguanidine, epichlorohydrin, formaldehyde, dicarboxylic acid and / or methylolated nitrogen compound, and optionally an alkylating agent or other reactant Basic nitrogen atom-containing reaction products, or amino group-containing guanyl compounds as described in British Patent No. 1238091, or aromatic amino compounds. The polycationic compounds may optionally be mixed with conventional additives, in particular nonionic, preferably hydrophilic dispersants, especially for the preparation of aqueous dispersions of dispersed amino compounds. Examples of such polycationic fixing agents include those shown in the above-mentioned patents or condensation products of methylolated melamine and di (C _1-2 alkyl) amine with epichlorohydrin (0.9: 1 to 5: 4). Is mentioned.

Preferably, the polycation fixing agent comprises a fatty group having 9 or more carbon atoms, preferably a hydrocarbon group having 7 or more carbon atoms, especially a hydrocarbon group having 4 or more carbon atoms. Absent.

Contrary to cationic softeners, polycationic fixing agents have a relatively high cationic charge density and are therefore preferably essentially long-chain nonionic groups, especially long-chain fatty groups (especially those mentioned above). And a nonionic hydrophilic chain, and particularly preferably a glycol group and a polyglycol ether group are not included.

The post-treatment with the polycation fixing agent is advantageously carried out in the same bath in which the dyeing is carried out, preferably 3-5, preferably 3-4, especially 3.3-in acidic conditions.
It is carried out at a pH of 4.

Preferably, the fixing agent has a pH of the dyed liquid above the above pH value, preferably below 4 and especially from 3.3 to 4.
It is added to the dyebath when acidified to a pH value of.

However, the work-up may also be carried out in a separate fresh bath, preferably after the pH of the dye bath is lowered by the addition of acid and then the bath is drained. The pH of the fresh liquid may be within a suitable range, for example pH 3 to 8, preferably pH 3 to 6.5, which depends on the pH of the polycationic fixing agent. Due to the above preferred pH range,
The leather is soaked in an acidic liquid, no tank acidification is required.

The post-treatment is advantageously carried out in the same temperature range as dyeing, fixing or fatting, preferably from 20 to 70
The pH value is lowered by the addition of an acid at a temperature of ° C, more preferably 25-60 ° C.

The concentration of the polycation fixing agent is preferably 0.1 to 4% of the wet weight of the leather, more preferably 0.2 to 2
%, Or preferably 0.2 to 8%, more preferably 0.4 to 4% of the dry weight of leather.

The final treatment with a leather softening agent, in particular a cationic leather softening agent, is preferably carried out after the aftertreatment with a polycation fixing agent.

The treated leather is then further treated by conventional methods, such as washing, drying and stake.

The 1: 2-chromium complexes according to the invention are in the form of the abovementioned salts, preferably the alkali metal salts, which are particularly readily soluble in water, exhibit surprisingly good fastness to acids and are good for leather. Good permeation dyeing of leather is also obtained, distinguished by good adhesion. Leather dyeings, especially those which have been post-fixed treated as described above, have excellent wet fastness (eg fastness to water, water drops and sweat), dry cleaning, fastness to rubbing and acids, fastness to light and resistance to PVC migration. Has robustness. A very uniform deep blue dyeing is obtained with a marked intensity and purity of hue, this very deep blue dyeing is also obtained on low-affinity leathers, the grainside and velorside being dyed very uniformly.

The blue dyes according to the invention are also suitable as combination elements with compatible dyes having different hues and similar dyeability and preferably also similar fastnesses. Other such compatible dyes are described, for example, in the following patent, DE-A 30080:
86 (corresponding to U.S. Pat. No. 4623720), DE-A 3015122 (corresponding to U.S. Pat. Nos. 4374064 and 4409142), DE-A 30346
86 (equivalent to US Pat. No. 5,008,379) and DE-A 3805746
(Equivalent to US Pat. No. 4,820,309). In mixtures with compatible dyes of other shades, very deep and even dyeings with high yields and optimum fastness are obtained.

In the examples below, parts and percentages are by weight unless otherwise indicated. Temperatures are given in degrees Celsius. In application example A, each dye is used in a mixed form containing 30% of each metal complex, the admixture is Glauber's salt (sodium sulphate), the other product used in the application example is an industrial leather treatment. The product used above. The dyeing method shown in the application examples is so-called drum dyeing, which is carried out in a rotating drum for dyeing leather.

Example 1 23.4 parts of 2-amino-6-nitro-1-phenol-4-sulfonic acid are diazotized with NaNO _{2 in} the presence of hydrochloric acid in the conventional manner at pH 9-9.5 and temperatures below 10 ° C. Coupling to 23.9 parts of 2-amino-5-hydroxynaphthalene-7-sulphonic acid. After the coupling reaction is complete,
Heat to 80 ° C. and add 12 parts sodium acetate and 27 parts chrome alum (Cr ³⁺ content = 10%). The pH was adjusted to 4.5-5 with 25% sodium hydroxide solution and the suspension was
Heat to 100 ° C. The end point of chromation is determined by thin layer chromatography. After the chromination is complete, the mixture obtained is cooled to 10 ° C. with ice and acidified by addition of 50 parts of 30% aqueous hydrochloric acid solution. The suspension of the 1: 2 chromium complex of the monoazo compound obtained is diazotized by addition of 22 parts by volume of 30% aqueous sodium nitrite solution. After the completion of the diazotization reaction, excess sodium nitrite is destroyed by adding 1 part of aminosulfonic acid. Then 14.4 parts of an aqueous solution of 2-naphthol in 50 parts of water and 15 parts of 25% aqueous sodium hydroxide solution are added and the pH is adjusted to 10 by addition of 50 parts of 25% aqueous sodium hydroxide solution. The pH is kept at 10 for 1 hour and then lowered to 5 by addition of 10 parts of 30% aqueous hydrochloric acid. The chromium complex dye formed is salted out with sodium chloride, suction filtered, dried and ground. This is the free acid form

[Chemical 12] And is obtained in the form of a sodium salt as a bluish black powder.

The following Table 1 is synthesized in the same manner as in Example 1 above, and R ₁ , R ₂ and R ₃ represent those shown in Table 1, and M
Includes other examples of blue 1: 2-chromium complex dyes of the present invention corresponding to the free acid form of formula (I) in which is hydrogen and M ⁺ is a hydroxonium ion.

[0037]

[Table 1]

Example 16 23.4 parts of 2-amino-6-nitro-1-phenol-4-sulfonic acid are diazotized with NaNO _{2 in} the presence of hydrochloric acid in the conventional manner at pH 9-9.5 and temperatures below 10 ° C. Coupling to 23.9 parts of 2-amino-5-hydroxynaphthalene-7-sulphonic acid. After the coupling reaction was completed, 22 parts by volume of 30% sodium nitrite aqueous solution was added, and the suspension was added to 50
Add to 30 parts of 30% aqueous hydrochloric acid and 50 parts of ice. The mixture is stirred for 2 hours and excess sodium nitrite is destroyed by addition of 1 part aminosulfonic acid. Then 14.4 parts of an aqueous solution of 2-naphthol in 50 parts of water and 15 parts of 25% aqueous sodium hydroxide solution are added and the pH is adjusted to 10 by addition of 50 parts of 25% aqueous sodium hydroxide solution. Keep pH at 10 for 1 hour. The suspension is then heated to 90 ° C., 12
Parts sodium acetate and 27 parts chromium alum (10% Cr
(Including ³⁺ ). The pH is adjusted to 4.5-5 with 25% sodium hydroxide solution and the suspension is heated to 100 ° C. The end point of chromation is determined by thin layer chromatography. After the chromination is complete, the pH is reduced to 5 by addition of 10 parts of 40% aqueous hydrochloric acid, the chromium complex dye formed is salted out with sodium chloride, suction filtered at 70 ° C., dried and ground. It is in the form of the free acid, represented by formula (VIII) above, and is obtained in the form of the sodium salt of a bluish black powder.

Similar to Example 16, the chromium complexes of Examples 2-15 are synthesized using the respective diazo and coupling components.

Application Example A 100 parts of moist cow box side leather in a dyeing drum
Neutralize for 45 minutes at 35 ° C with 250 parts water and 0.8 part sodium carbonate. Then this leather at 25 ℃
Wash with 1000 parts of water. After 5 minutes the leather is at 25 ° C for 25
Example 1 dissolved in 0 part of water and 80 parts of water at 50 ° C in advance
Or stain with 0.8 part of the chromium complex prepared in 16. After 20 minutes, add 4 parts of a suspension of 80% sulfite fish oil,
Continue fatting for 45 minutes. Next, add 0.5 parts of 85
Acidify with a% formic acid solution and continue drumming for 20 minutes. Finally, drain the liquid and let the leather stand at 25 ° C for 10
Wash with 00 parts of water. The leather is drained, dried and spatulated in the usual way. A navy blue dyed leather is obtained which has outstanding fastness properties, in particular wet fastness, fastness to dry cleaning, fastness to light and resistance to PVC migration.

Application Example B 100 parts of an intermediately dried chrome-tanned suede split leather are mixed with 800 parts of water at 50 ° C., 2 parts of a 25% ammonia solution and 1 mol of nonylphenol, the addition of 10 mol of ethylene oxide 0.5. Wet with parts for 90 minutes, then drain the bath and add 600 parts water at 50 ° C, 1 part 25% ammonia solution and 1 part fatting agent (emulsion of fatty acid ester). After 10 minutes, for preliminary dyeing, 4 parts of the chromium complex prepared according to Example 1 or 16 previously dissolved in 400 parts of water at 50 ° C. are added. After 60 minutes, add 2 parts of 85% formic acid solution and continue drumming for 20 minutes. 2 parts of a 20% solution of the product obtained by the quaternization of the benzylated product of diethylenetriamine with dimethylsulfate were added and after 20 minutes the same preliminary dyeing pre-dissolved in 200 parts of water at 50 ° C. Add 2 parts of dye. Drumming continued for 40 minutes, then the tank was washed twice at 10 minute intervals for 1.5 minutes.
Acidify by adding some 85% formic acid solution. After 10 minutes, drain the bath, wash the leather, dry and spatula. A navy blue dyed leather is obtained which has outstanding fastness properties, in particular wet fastness, fastness to dry cleaning, fastness to light and resistance to PVC migration.

Application Example C 100 parts of chrome-tanned cattle furniture leather are treated with 800 parts of water, 2 parts of 25% ammonia solution and 3 parts of an addition of 10 mol of ethylene oxide to 1 mol of nonylphenol at 50 ° C. Moisten for 90 minutes. Then drain the tank and
400 parts water, 1.5 parts 25% ammonia solution, 2 parts fatting agent (fatty acid ester emulsion) and 1
This leather is treated for 15 minutes with 1 part of phenol syntan (a condensation product of phenol and sulfuric acid). 60 at 50 ℃ in advance
6 parts of the chromium complex prepared according to Example 1 or 16 dissolved in 0 parts of water are added and drumming is continued at 40 ° C. for 60 minutes. The bath is then acidified by adding 1.5 parts of 85% formic acid solution twice at 10 minute intervals. After 10 minutes, drain the bath, wash the leather, dry and spatula. A navy blue dyed leather is obtained which has outstanding fastness properties, in particular wet fastness, fastness to dry cleaning, fastness to light and resistance to PVC migration.

APPLICATION EXAMPLE D 100 parts of chrome-tanned cow's furniture leather are treated with 800 parts of water, 2 parts of 25% ammonia solution and 3 parts of an addition of 10 mol of ethylene oxide to 1 mol of nonylphenol at 50 ° C. Moisten for 90 minutes. Then drain the tank and
400 parts water, 1.5 parts 25% ammonia solution, 2 parts fatting agent (fatty acid ester emulsion) and 1
This leather is treated for 15 minutes with 1 part of phenol syntan (a condensation product of phenol and sulfuric acid). Then this leather 40
Pre-stain at 4 ° C with 4 parts of the chromium complex prepared according to Example 1 or 16 dissolved in 400 parts of water at 50 ° C.
After 60 minutes the vessel is acidified with 1 part of 85% formic acid and after 10 minutes 2 parts of a 20% solution of the product obtained by quaternization of the benzylated product of diethylenetriamine with dimethylsulfate are added. After 20 minutes, the tank is drained and this leather is dyed at 50 ° C. for 40 minutes with 2 parts of the same dye used for the preliminary dyeing, which has been predissolved in 200 parts of water at 50 ° C. Then the tank
Acidify by addition of 1.5 parts of 85% formic acid solution, and after 20 minutes,
The leather is washed, dried and spatulated. A navy blue dyed leather is obtained which has outstanding fastness properties, in particular wet fastness, fastness to dry cleaning, fastness to light and resistance to PVC migration.

Application Example E 100 parts of low-affinity chromium / vegetable-tanned cow leather
Wet for 90 minutes at 50 ° C. with 1000 parts of water and 0.2 parts of an adduct of 10 mol of ethylene oxide with 1 mol of nonylphenol. The vessel is then drained and dyed with 1000 parts of water at 50 ° C. and 4 parts of the chromium complex obtained in Example 1 or 16 previously dissolved in 400 parts of water at 50 ° C. After 1 hour, the tank was acidified by adding 2 parts of 85% formic acid solution, 20
After the minutes, the leather is washed, dried and spatulated. A navy blue dyed leather is obtained which has outstanding fastness properties, in particular wet fastness, fastness to dry cleaning, fastness to light and resistance to PVC migration.

Application Example F 100 parts of semi-chrome sheep leather are moistened at 45 ° C. for 1 hour with 1000 parts of water and 0.5 part of an amphoteric masking agent (sulpho-containing fatty acid aminoamide). This leather is 80 at 50 ℃
Preliminary dyeing with 6 parts of the chromium complex dye obtained in Example 1 or 16 previously dissolved in 0 parts of water and 600 parts of water at 50 ° C. Continue drumming until the dye penetrates into the leather. The tank is then acidified with 1.5 parts of 85% formic acid solution,
After minutes, 2 parts of a 20% solution of the product obtained by quaternization of the benzylated product of diethylenetriamine with dimethylsulfate are added. 20 minutes later, 50 leather in advance
Dye with 600 parts of the same dye used for the pre-dye, dissolved in 600 parts of water at 60 ° C. The bath is then acidified with 2 parts of 85% formic acid solution, after 30 minutes the leather is washed, dried and spatulaed. Remarkable fastness (especially wet fastness, dry cleaning fastness, light fastness and PVC
A leather dyed in navy blue which has resistance to migration is obtained.

Application Example G 100 parts of chrome-tanned cattle furniture leather are wetted with 300 parts of water and 0.5 parts of an amphoteric masking agent (fatty acid aminoamide containing sulfo groups) at 35 ° C. for 20 minutes. The tank was drained and the leather was heated at 35 ° C with 150 parts of water, 1 part of phenol syntan (65% of the condensation product of phenol and sulfuric acid).
Solution) and 3 parts of a 40% solution of dimethyloldihydroxyethyleneurea. After 30 minutes, 1.5 parts of sodium formate are added, and after an additional 15 minutes, 5 parts of the polypeptide-based retanning agent. Drumming is continued for 30 minutes, then the pH of the bath is brought to 6 by the addition of 1.5 parts of sodium hydrogen carbonate. After 30 minutes, wash the leather at 40 ° C with 300 parts of water for 10 minutes. Then 150 parts of water at 45 ° C, 1 part of fatting agent (emulsion of fatty acid ester), 1 part of 25% ammonia solution and 0.5 part of phenolcintan (condensation product of phenol and sulfuric acid) are added. After 15 minutes, this leather is preheated at 45 ℃ at 50 ℃
Is dyed with 3 parts of the chromium complex prepared according to Example 1 or 16 in 300 parts of water for 90 minutes, ie until the dye has completely penetrated. 2 parts emulsion of fatty acid ester, 3 parts mixture of esterified synthetic fatty alcohol and partial phosphoric acid ester of ethoxylated fatty alcohol, and 6 parts emulsion of sulfite fish oil for fatting, 60 minutes later, 2 Parts of water soluble melamine / formaldehyde condensate are added for fixing. Drumming is continued for 20 minutes, then the bath is acidified twice with 0.75 parts of 85% formic acid diluted 1:20 v / v with water at 10 minute intervals. After 10 minutes, the leather is washed, dried and spatulated. A navy blue dyed leather is obtained which has outstanding fastness properties, in particular wet fastness, fastness to dry cleaning, fastness to light and resistance to PVC migration.

Application Example H 100 parts of sheep napa are washed with 200 parts of water and 0.5 part of an amphoteric masking agent (sulpho group-containing fatty acid aminoamide) at 40 ° C. for 20 minutes. Drain the tank to 200 at 35 ° C.
Add 1 part water and 1.2 parts sodium formate and continue drumming for 15 minutes. Add 4 parts of the polypeptide-based retanning agent, and after 30 minutes, add 0.6 parts of sodium carbonate to adjust the pH of the bath to 5.8-6.0. After 40 minutes, 4 parts of polyacrylic acid based tanning agent are added and drumming is continued for 30 minutes. Then 2 parts of water soluble urea / formaldehyde condensate are added and after 30 minutes the tank is drained. Then 150 parts water at 40 ° C. and 2 parts fatting agent (emulsion of fatty acid ester) are added. After 10 minutes, this leather is dyed at 40 ° C. for 90 minutes with 3 parts of the chromium complex prepared according to Example 1 or 16 previously dissolved in 300 parts of water at 50 ° C. Add 2 parts emulsion of fatty acid ester, 6 parts emulsion of sulfite fish oil and 3 parts aqueous emulsion of fatty alcohol phosphoric acid partial ester for fatting. Drumming is continued for 60 minutes and then the bath is acidified with 1.5 parts of 85% formic acid. After 30 minutes, the leather is washed, dried and spatulated. A blue dyed leather is obtained which has outstanding fastness properties, especially wet fastness, fastness to dry cleaning, fastness to light and resistance to PVC migration.

Application Example I After fettling and before addition of formic acid, drain the vessel and let
200 parts of water and 2 parts of a water-soluble polymer reaction product of epixulhydrin and dimethylamine were added, and drumming was performed at 30
For 2 minutes, then add 0.5 parts of a 2-fatty alkyl imidazoline and continue drumming for an additional 20 minutes.
Application Example H is repeated. The tank is then drained, the leather washed, dried and spatulaed. A blue dyed leather is obtained which has outstanding fastness properties, especially wet fastness, fastness to dry cleaning, fastness to light and resistance to PVC migration.

Table 2 below shows, in place of the blue dye of Example 1 or 16, the blue dye of Example 1 or 16 indicated as "Bulue Ex1" in the table below and the other dyes indicated by "Color Index". Other applications are shown in which Application C, D or G is repeated, except that the same amount of dye mixture is used. The two dyes of this mixture are used in a weight ratio of 1 part dye 2 to 2 parts dye 1.

[0050]

[Table 2]

Formula (VIII) in the sodium salt form of Example 1 or 16
The blue dyes of Examples 2 to 15 as well as the blue dyes of Examples 2 to 15 are used in the above Application Examples A to U to give dyeings of corresponding hue, depth and fastness.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hordi Berenger Barra El Prat de Llobregat, Barcelona, Spain, 1.3. , Say / Narcis Montreal 64

Claims (6)

[Claims] 1. The following formula: (In the above formula, each R ₁ independently represents hydrogen, —NO ₂ or —SO ₃ M, each R ₂ independently represents —NO ₂ or —SO ₃ M, each R ₃ independently represents hydrogen, COOM, -COOR ₄ , -CONH ₂ or -CON
R ₄ R ₅ represents each R ₄ independently from C _1-4 alkyl, C _2-3 hydroxyalkyl, unsubstituted phenyl or methyl, ethyl, methoxy, chlorine, —NO ₂ , —SO ₃ M and —COOM. 1 selected from the group
Represents phenyl substituted with one or more substituents, each R ₅ independently represents hydrogen, C _1-4 alkyl or C _2-3 hydroxyalkyl, M represents hydrogen or a cation, provided that R ₁ and R ₂ One represents -SO ₃ M, the other is -SO ₃ M
Other than 1): 2-chromium complex, or 1 in formula (I):
A blue dye that is a mixture of 2-chromium complexes. 2. A blue dye according to claim 1, wherein R ₁ represents —NO ₂ . 3. The blue dye according to claim 1, wherein R ₃ represents hydrogen. 4. The following formula: At least one disazo compound of
omium-yielding agent), or b) the following formula: A 1: 2 chromium complex bisdiazo compound or a mixture of these bisdiazo compounds of the following formula: The method for producing a dye according to claim 1, wherein the dye is coupled to at least one naphthol coupling component of 5. A method for dyeing leather or fur, which comprises dyeing leather or fur with the blue dye according to claim 1. 6. A process according to claim 5, wherein the dye according to claim 1 is mixed with one or more compatible dyes having different hues and similar dyeing properties.