ES2362751T3 - METHOD FOR REACTIVELY LEATHER DYEING, AS WELL AS DYES AND THEIR USE. - Google Patents

Abstract

Method for dyeing leather with at least one dye F, which has at least one group of the formula A: activatable under alkaline conditions, where ---- means the bond to the dye molecule, X represents a residue that attracts electrons, k represents 1, 2 or 3, n means 0 or 1, and B represents a group CH = CH2 or a group CH2-CH2-Q, where Q represents a dissociable group under alkaline conditions, which comprises treating the leather with a liquid aqueous immersion, which contains at least one dye F, at a pH value of 7; 5 to 11.

Description

The present invention relates to a method for dyeing leather and new dyes that are particularly suitable for reactively dyeing leather.

Tanning leather dyeing is currently carried out with acid dyes, direct dyes, sulfur dyes or basic dyes. The achievement of high color intensities and high color stabilities, in particular color fastness in the face of moisture and sweat is resolved with difficulty for these dyes and for medium to high color depths until today has not been satisfactorily resolved. .

To improve the color fastness against moisture and sweat, the leather is often treated with cationic agents for complex formation which complex the dye and thus decrease the solubility on contact with water. However, color retention with moisture and sweat and friction stability that can be achieved are not yet sufficient for intense shades of color. In addition, leather articles made from them tend to fade during use. The achievement of high color retention in the case of medium to high color depths requires a very careful selection of dye and the harmonization of the dye used with the auxiliaries used in leather, as well as proper selection of greasing agents and materials re-tanning In addition, regularly to achieve the desired color retention, it is required to apply colorant and grease impregnating agent, and in some cases also the re-tanning agent, in a separate immersion liquid; which results in a prolongation of the duration of the entire process and also an increased production of wastewater, due to the change of immersion liquid required.

As a consequence, the dyeing process in aqueous and acidic medium using conventional dyeing for leather is complex, neat and expensive due to the different process steps and the chemicals used together. In addition, the retention problems described above are not fundamentally resolved by these measures. The reason for this is that the conventional dyes used bind to leather through ionic interactions. The action of aqueous alkaline solutions, such as, for example, immersion liquids for washing or in sweat retention tests, destroys the ionic bond between the leather and the dye, such that the dye breaks off the leather and dyes surrounding materials, such as adjacent tissues.

In a different way it has been tried to improve the retention of the color of the dyed leather before dyes and the humidity by reactive dyeing. Reactive dyeing means the use of dyes that have functional groups that can form a covalent chemical bond with the functional groups of the leather.

So, T.C. Mullen in "The Leather Manufacturer", 1964, page 18 and following, and in J. Soc. Leather, Trades, Chem. 46, 1962, page 162 and following, as well as M.L. Fein et al. in J. Am. Leather Chem. Assoc. 65, 1970, pages 584591, describe the use of reactive dyes having a dichlorotriazine group as a reactive fraction. The fixing yields achieved, that is to say the chemically bonded dye portion, which although with approximately 70 to 75% are only moderate and do not solve the problems described above. In addition, the method is limited to chrome tanned leather.

To overcome these disadvantages, for leather dyeing DE-A 3529294 proposes to use dyes that have at least one 1,3,5-triazinyl group to which a substituent having a quaternary nitrogen atom is bound. However, the applicant's own studies on N-acetyl-lysine as a model system have shown that under the dyeing conditions described there is not a significant formation of covalent bonds between the dye and the N-acetyl amino group. lysine

K. Rosenbusch et al. in "Das Leder" (El Cuero) 19, 1968, page 284, they describe the use of Remazol® dyes that have a vinylsulfonic group or a group from which a vinyl-sulphonic group is released by the alkali action, to dye suede leather . To achieve sufficient fixation, however, long durations of dyeing at a pH value of 10 are required. Due to the applied dyeing conditions, that is, at a higher pH in connection with long dyeing times of 7 hours and more, this The process can only be used to dye suede leather which is resistant to alkalis in a known way. In the case of other types of leather, the dyeing conditions described lead to leather damage. The applicant's own studies also show that using Remazol® dyes that have a vinyl sulphonic group does not achieve a satisfactory fixation.

In summary, it can be said that the known processes for dyeing leather with reactive dyes do not provide good fixing yields of 85% and higher in the case of shades depths of medium to high. In order to achieve high solidity against moisture and sweat and a good migration stability, the fixing yields achieved in the state of the art of 70 to 75% are not sufficient to solve the problems described herein and that the portion of dye that is not bound must be removed by washing in an arduous manner. The disadvantages described here for dyeing leather with reactive dyes are also referred to in The Leather Manufacturer, 1964, pages 18-23. Therefore, it is not surprising that leather dyeing with reactive dyes has not been imposed. On the contrary, nowadays other ways of linking dyes covalently to leather are sought, for example by pre-treating leather with aldehydes.

10 polyfunctional having at least one reactive group which can react with a reactive group of the dye and a bond is formed. (See DE 100 44 642 A1).

Due to the disadvantages described herein, the methods are not particularly suitable for the production of leather goods for special segments such as shoes, clothing, automobiles, gloves and furniture, which have high color fastness, particularly solidity before washing, sweat, friction and migration in

15 medium and high color depths.

In this way, the task that serves as the basis for the present invention is to provide a method for dyeing leather in which high strength is achieved, in particular moisture fastness, sweat and friction, as well as high strength in depth migration. medium and high color intensities (color intensities). In addition, the method should be able to be carried out in conditions that do not lead, or only to a small extent, to leather damage. In

In particular, the method should be suitable for producing leather goods for special segments such as footwear, clothing, cars, gloves and furniture, which are particularly robust, particularly when washing, sweating, friction and migration. , in medium and high color depths.

It has surprisingly been found that using F dyes having at least one functional group of the formula A defined below, in immersion liquid at pH values of 7.5 to 11, this problem is solved. The

25 dyeing and fixing in this case go so fast that only a short dyeing duration of 4 hours and less is required to achieve a satisfactory color intensity and a high solidity of 85% and more.

Accordingly, the present invention relates to a method for dyeing leather with at least one dye F having at least one group of formula A activatable under alkaline conditions

image 1

30 where .... represents the bond with the residue of the dye molecule; X represents a residue that attracts electrons, k represents 1, 2 or 3, n means 0 or 1, and

B represents a group CH = CH2 or a group CH2CH2-Q, where Q represents a group that can be dissociated into

alkaline conditions; The method comprises treating the leather with an aqueous immersion liquid containing at least one dye F, according to the invention at a pH value of 7.5 to 11, regularly in the range of 8 to 11, preferably in the range of 8.5 to 10.5 and especially in the range of 8.5 to 10.

Here and hereafter the term "alkyl" regularly represents a linear or branched hydrocarbon residue with 1 to 6 and preferably with 1 to 4 C atoms (C1-C6 alkyl or C1-C4 alkyl) as methyl, ethyl, propyl, Isopropyl and the like. Haloalkyl represents alkyl in which hydrogen atoms have been partially or totally replaced by halogen atoms, especially fluorine atoms, such as trifluoromethyl, trichloromethyl, pentafluoroethyl, and the like. Alkoxy represents an alkyl residue linked by an oxygen atom, as previously defined. Optionally substituted phenyl means that the phenyl residue may have one or more, for example 1, 2, 3 or 4 substituents that are selected from halogen, alkyl, alkoxy, nitro, cyano, COOH, SO3H and the like. Halogen particularly represents fluorine, chlorine or bromine.

Wastes that attract electrons are those that exert an –M effect and / or –I effect on the aromatic residue to which they are bound. They include, for example, fluorine or chlorine, CN, NO2 as well as groups of the formulas -C (O) -R1 and S (O) 2R2, where R1 and R2 independently of each other represent OH, alkyl, haloalkyl, alkoxy or phenyl optionally substituted. As long as residue A has several groups (k> 1), then the groups can be equal or different. Preferably, at least one of the groups represents X represents a hydroxysulfonyl group (SO3H).

The variable k preferably represents 1 or 2, that is to say that the residue A has 1 or 2 residues that attract electrons. In formula A, preferably n represents 0, that is to say that residue A is derived from benzene. Whenever n represents 1, residue A is derived from naphthalene. In these cases the SO2-B group can be found in the same benzene nucleus as at least one X group or in another benzene nucleus.

A dissociable Q group under alkaline conditions is understood as residues that dissociate under alkaline conditions, that is to say pH values of 7.5 or higher, eliminating or forming a vinyl sulfonic group. Examples of groups of this type are halogens, for example chlorine, bromine or iodine, in addition -O-SO3H, -SSO3H, dialkylamino, quaternary ammonium residues such as tri- alkyl (C1-C4) ammonium, benzyldi-alkyl (de C1-C4) -ammonium or N-linked pyridinium, as well as residues of the formulas R3S (O) 2-, R4S (P) 2-O-, R5C (O) -O-. Here, R3, R4 and R5 independently represent each other optionally substituted alkyl, haloalkyl or phenyl, in which case R5 can also synthesize hydrogen. Q preferably represents a group -O- (CO) CH3 and in particular -O-SO3H.

According to the invention in formula A, B preferably represents CH = CH2, a CH2-CH2-O-C (O) CH3 group or a CH2-CH2-O-SO3H group. Mainly residue A is selected from the following residues A1 to A12:

image 1

image 1

Among these, colorants are particularly preferred in which at least one residue A has the formula A1, A2 or A9.

Conveniently, the dye used in the method of the invention has 1, 2 or 3, preferably 1 or 2 of the previously named residues A. This residue A can be, but should not be, a component of the chromophore of the dye and is preferably linked through a group -NH- or -N = N- with the dye molecule.

Usually, colorant F has one or more functional groups, for example 1 to 10, mainly 2 to 8 functional groups per dye molecule that confer water solubility to colorant F. They are usually anionic or acid functional groups that dissociate at a Weakly acidic or alkaline pH, usually at pH values above 4, forming anionic groups. Examples of such groups are hydroxysulfonium groups (-SO3H), carboxyl groups (COOH) and hdroxysulfonyloxy groups (-O-SO3H) as well as the anions of these groups. These anionic / acid groups may be linked to group A and / or other parts of the dye molecule. Provided that these groups are present in the dye F as anionic groups, it is understood by itself that the dye also comprises the counterions required for neutralization. Suitable counterions are primarily alkali metal ions, especially sodium, potassium and lithium ions as well as ammonium ions, for example ammonium ions that are derived from mono-, di- or triethanolamine.

Also suitable for the method of the invention are metal complexes, preferably transition metal complexes of the above-mentioned F dyes, mainly complexes of the transition metals of groups VI to X of the periodic system and among them mainly Cu, Cr , Fe, Ni, Co, Mn, Zn and Cd. The molar ratio between the transition metal and the dye molecule in these metal complexes is usually in the range of 2: 1 to 1: 2. Usually in these dyes the formation of metal ion complexes is not carried out by the above-mentioned anionic groups but by the deprototonized hydroxyl groups, by the amino groups, by the imino groups, nitrogen atoms that bind to an aromatic system of -electrons, or by azo groups.

Typical F dyes in the method of the invention are selected from the group of the following dye classes: dyes of the phthalocyanine series, anthraquinone dyes, azocolorants, formazan dyes, triphenylthioxazine dyes and triarylmethane dyes.

F colorants of this type are known from the prior art, for example from WO 94/18381, EP-A 356 931, EP-A 559 617, EP-A 201 888, DE-A 195 23 245, DE-A 197 31 166, EP 745 640, EP-A 889 098, EP-A 1 097 971, EP-A 880 098 or they can be prepared analogously to the known methods of preparation for dyes For the preparation of dyes F a reaction is reacted amino compound of formula B

image 1

5 with a pre-dye product having a nucleophilically movable group, in a manner known per se. Examples of nucleophilically movable groups are halogen, mainly chlorine or bromine, which is linked to an aromatic, as presented in halotriazine residues, or in the form of a halosulfonyl group or a halocarbonyl group. Methods for this purpose are known from the state of the art mentioned herein or they can be applied analogously to prepare the dyes F. Alternatively, the

The amino compound B initially can also be deazotized and then coupled to a corresponding pre-coloring product. The reaction product obtained during the reaction of the amino compound or its diazonium salt with the pre-dye product may already be the dye F or, in turn, a pre-product may represent the dye F which, analogously to known methods, it can be processed even to the dye F.

It is understood by itself that both pure dyes and mixtures of dyes can be used in the method of the invention. In the case of leather dyeing, in addition to the aforementioned high retention requirements, there are requirements for the quality of dyeing, for example penetration, hue, purity, homogeneity of dyeing, covering of damaged grains as well as equality in the color hue of the side of meat and grain. The experiences of the inventors of the present invention show that for the entire profile of

20 industrial application it may be advantageous to use dye mixtures.

The dye mixtures can be both mixtures that are produced by mixing different dyes F, as well as mixtures that are obtained during the production of the dyes F. The fraction of the dyes F in these mixtures is preferably at least 70% by weight, mainly of at least 90% by weight and particularly preferably of at least 99% by weight, based on the organic chemical fraction of color in the dye. In addition to

Dyes F, the dye mixtures used in the method of the invention may also contain conventional dyes for leather, which does not have a group A. The fraction of dyes of this type usually constitutes less than 30% by weight, mainly less than 10% by weight and especially not more than 5% by weight, with respect to the organic chemical fraction of color in the dye.

Provided that the dyes F are mixtures of dyes F with similar shades of color, the amount of the dye

30 individually is at least 10% molar, mainly at least 20% molar, with respect to the total amount of colorant F in the mixture. Among these, mixtures of two F dyes are preferred, in which case the individual components have a molar ratio of 9: 1 to 1: 9 and mainly in the range of 2: 8 to 8: 2.

In addition, mixtures of dyes in which F dyes have different shades of color are also of interest. One embodiment of this is the tinting of dyes, for example black dyes with 35 dyes of other colors, for example with red, green or blue dyes. Whenever a dye is mixed with one or more dyes to color, the amount of dyes they color will usually be 0.1 to 15 mol%, relative to the organic chemical fraction of color in the dye. Another embodiment is mixtures of dyes for the so-called trichromatic dyeing. Here the dye mixture contains 3 or more F dyes with different shades of color. In this case, the individual component usually regulates at least 1 molar%,

40 mainly at least 5 mol%, for example 5 to 90 mol%, with respect to the total amount of colorant F in the mixture.

At the same time it is to be taken into consideration that the dyes may contain inorganic salts and also flow conditioners, depending on the production conditions. The fraction of components of this type, hereinafter referred to as colorless components, is usually not more than 60% by weight and is found

45 many times in the range of 10 to 50% by weight, with respect to the total weight of color and colorless components of the dye. In a preferred embodiment of the invention, the colorant F is an azocolourant and preferably an azocolorant which is selected from the colorants of the general formulas I to XV and their metal complexes:

Dk1-N = N- [P-N = N-] pKk1 {-N = N-Dk2] m

(I)

Dk1-N = N-Napht1 [-N = N-Tk1] r-N = N-Kk1] k [-N = N-Dk2] n

(II)

Dk1-N = N-Napht1-N = N-Tk1-N = N-Kk1-N = N-Tk2-N = N-Napht2-N = N-Dk2

(III)

Dk1-N = N-Kk1-N = N-Tk1-N = N-Kk2-N = N-Dk2

(IV)

5

Dk1-N = N- [P-N = N-] pNapht1 [-N = N- R] r-NH-Tr1-NH-Dk2 (V)

Dk1-N = N-P-NH-Tr1-NH-R-N = N-Dk2

(SAW)

Dk1-N = N-Napht1-N = N-Tk1-N = N-P-NH-Tr1-NH-Dk2

(VII)

Dk1-N = N-Napht1-NH-Tr1-NH-P-NH-Tr2-NH-Napht2-N = N-Dk2

(VIII)

Dk1-N = N-Napht1-NH-Tr1-NH-Tk1-NH-Tr2-NH-Napht2-N = N-Dk2

(IX)

10

Dk1 [-N = N-L] k-NH-Tr1-NH-M-N = N-Napht1-N = N-P-NH-Tr2-NH- [R-N = N-] nDk2 (X)

Dk1-N = N-Kk1-N = N-Tk1-NH-Tr1-NH-Dk2

(XI)

Dk1-N = N- [P-N = N-] pR-N = N-Kk1 [-N = N-Dk2] n

(XII)

Dk1-N = N-Pyr-A

(XIII)

Kk3-N = N-Tk1-N = N-Kk1-N = N-A

(XIV)

fifteen

Dk1-N = N-P-N = N-Kk1-N = N-R-N = N-Dk2 (XV)

where:

k, n, p and r

independently of each other they represent 0 or 1, in which case k + n + r in formula II is = 1, 2 or 3;

m

means 0, 1 or 2;

twenty

Dk1, Dk2 independently of each other they represent a residue derived from an aromatic amine or means a group of the formula A, in which case in formulas I-XII and XV at least one of the residues Dk1 or Dk2 respectively represents a residue of the formula A

25 30 35 40

Kk1, Kk2, 7 independently of each other, represent a mono-, di, or trivalent aromatic residue that has been derived from benzene, naphthalene, pyrazol, quinoline, diphenylamine, diphenylmethane, pyrimidine, pyridine or diphenyl ether, which may optionally have one or several of the following residues as substituents: SO3H, COOH, CN, CONH2, OH, NH2, NO2, halogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, C1-C4 carboxy-alkyl, C1-C4 alkoxy, alkyl (from C1-C4) amino, dialkyl (from C1-C4) amino, alkyl (C1-C4) aminocarbonyl, dialkyl (C1-C4) aminocarbonyl, (C1-C4) alkyl carbonylamino, N- (C1-C4 alkyl ) carbonyl) -N- (C1-C4 alkyl) carbonyl) amino, (C1-C4) aminocarbonyloxy, dialkyl (C1C4) aminocarbonyloxy, (C1-C4) aminocarbonylamino, dialkyl (C1-C4) aminocarbonylamino, phenylaminocarbonyloxy, phenylaminocarbonylamino , (C1-C4) alkoxycarbonylamino, C1-C4-hydroxy-alkyl (C1C4) amino, carboxy-C1-C4 alkyl amino, phenylcarbonylamino, (C1-C4) alkyl sulfonyl, hydroxyalkyl (C1-C4) sulfonyl, al quil (C1-C4) aminosulfonyl, (C1-C4) alkyl sulfonylamino, phenylsulfonyl, phenylsulfonylamino, formamide, a residue of the formula SO2NR56R57, where R56 and R57, independently of one another, represent hydrogen, C1-C4 alkyl, formyl, (C1-C4) alkylcarbonyl, (C1-C4) oxycarbonyl, NH2CO or (C1-C4) aminocarbonyl, (C1-C4) alkyl aminosulfonylamino, di-(C1-C4) aminosulfonylamino, phenylsulfonylamino, which may have in the phenyl ring one or two substituents selected from C1-C4 alkyl, C1-C4 alkoxy or halogen, or 5- or 6-membered heterocyclyl, which is optionally substituted by 1, 2 or 3 of the following residues: OH, halogen, C1-C4 alkyl or phenyl, in which case the 5-membered aromatic heterocyclyl optionally has a phenyl group or a naphthyl group in the nitrogen, which may optionally have one or two of the following residues: OH, SO3H, alkyl C1-C4, and / or C1-C4 alkoxy;

Kk3 represents a monovalent residue derived from benzene, pyrimidine, pyridine or naphthalene, which optionally has 1 or 2 hydroxysulfonyl groups and optionally 1, 2 or 3 other substituents selected from SO3H, COOH, CN, CONH2, OH, NH2, NO2, halogen , C1-C4 alkyl, hydroxyalkyl-C1-C4, carboxyalkyl-C1-C4, alkoxy-C1-C4, alkyl-C1-C4-amino, dialkyl-C1-C4-amino, alkyl-C1-C4-aminocarbonyl, dialkyl -C1-C4-aminocarbonyl, alkyl-C1-C4-carbonylamino, N- (alkyl-C1-C4-carbonyl) -N- (alkyl-C1-C4carbonyl) amino, alkyl-C1-C4-aminocarbonyloxy, dialkyl-C1- C4-aminocarbonyloxy, alkyl-C1-C4-aminocarbonylamino, dialkyl-C1-C4-aminocarbonylamino, phenylaminocarbonyloxy, phenylaminocarbonylamino, C1-C4-alkoxycarbonylamino, hydroxy-C1-C4-C1-C4-alkyl-alkyl, carboxy-C1-C4-alkyl amino, phenylcarbonylamino, alkyl-C1-C4-sulfonyl, hydroxyalkyl-C1-C4-sulfonyl, alkyl-C1-C4sulfonylamino, phenylsulfonyl, phenylsulfonylamino, formamide, a residue of the formula SO2NR56R57, where R56 and R57, ind ependiently from each other, they represent hydrogen, C1-C4 alkyl, formyl, C1-C4 alkylcarbonyl, C1-C4 alkyl oxycarbonyl, NH2-CO or C1-C4 alkyl aminocarbonyl; it also represents C1-C4-aminosulfonylamino, di-C1-C4-aminosulfonylamino, phenylsulfonylamino, which may have on the phenyl ring one or two substituents selected from C1-C4 alkyl, C1-C4 alkoxy or halogen , or 5 or 6 membered heterocyclyl, which is optionally substituted by 1, 2 or 3 of the following residues: OH, halogen, C1-C4 alkyl or phenyl, in which case the 5-membered aromatic heterocyclyl has nitrogen optionally a phenyl group or a naphthyl group, which may optionally have one or two of the following residues: OH, SO3H, C1-C4 alkyl, and / or C1-C4-alkoxy;

Tk1, Tk2, independently of each other, represent a divalent aromatic residue that is derived from benzene, diphenylamine, diphenyl, diphenylmethane, 2-phenylbenzimidazole, phenylsulfonylbenzene, phenylamino sulfonylbenzene, stilbene or phenylaminocarbonylbenzene, which may optionally have one or more of the following residues as substituents: SO3H, COOH, OH, NH2, NO2, halogen, C1-C4 alkyl;

L, M, P and R, independently of one another, represent a bivalent aromatic residue which is derived from benzene or naphthalene, which may optionally have one or more, for example 1, 2, 3, 4 or 5 of the following residues as substituents: SO3H, COOH, CN, CONH2, OH, NH2, NO2, halogen, C1-C4 alkyl, hydroxy C1-C4 alkyl, carboxy-C1-C4 alkyl, C1-C4 alkoxy, C1-alkyl C4-amino, dialkyl-C1-C4-amino, alkyl-C1-C4-aminocarbonyl, dialkyl-C1-C4-aminocarbonyl, alkyl-C1-C4carbonylamino, N-alkyl-C1-C4-carbonyl) -N- (alkyl- C1-C4-carbonyl) amino, alkyl-C1-C4-aminocarbonyloxy, dialkyl-C1-C4-aminocarbonyloxy, alkyl-C1-C4-aminocarbonylamino, dialkyl-C1-C4-aminocarbonylamino, phenylaminocarbonyloxy, phenylaminocarbonylamino, C1-C4 alkoxy carbonylamino, hydroxy-C1-C4-alkyl-C1-C4amino, carboxy-alkyl-C1-C4-amino, phenylcarbonylamino, alkyl-C1-C4-sulfonyl), alkyl-C1-C4aminosulfonyl, hydroxyalkyl-C1-C4-sufonyl, alkyl -C1-C4-sulfonylamino, phenylsulfonyl, phenylsulfonyl amino, formamide, a residue of the formula SO2NR58R57, where R56 and R57, independently of one another, represent hydrogen, C1-C4 alkyl, formyl, C1-C4 alkylcarbonyl, C1-C4 alkyl oxycarbonyl, NH2CO or C1-C4-aminocarbonyl, C1-C4-aminosulfonylamino, di-C1-C4-aminosulfonylamino, phenylsulfonylamino, which may have one or two substituents on the phenyl ring, selected from C1-C4 alkyl, C1-C4 alkoxy or halogen, or 5- or 6-membered heterocyclyl, which is optionally substituted by 1, 2 or 3 of the following residues: OH, halogen, C1-C4 alkyl or phenyl, in which case the aromatic heterocyclyl 5-membered optionally has a phenyl group or a naphthyl group in the nitrogen which may optionally have one or two of the following residues: OH, SO3H, C1-C4 alkyl, and / or C1-C4 alkoxy;

Napht1, Napht2, independently of one another, represent a bivalent naphthalene-derived residue, which has 1 or 2 hydroxysulfonyl groups and may optionally have 1, 2 or 3 other substituents selected from OH, NH2, C1-C4-amino alkyl, dialkyl-C1-C4-amino, alkyl-C1-C4-sulfonylamino, phenylsulfonylamino, 4-methylphenylsulfonylamino, alkyl-C1-C4-aminosulfonyl, di-alkyl-C1-C4-aminosulfonyl, phenylaminosulfonyl, 4-methylphenylaminosulfonyl and NHC residues (O ) Rx, where Rx represents hydrogen, C1-C4 alkyl, maleinyl or phenyl;

Pyr represents pyrazol-1,4-diyl which is bonded with the nitrogen atom of group A and optionally has one or 2 substituents that are selected from halogen, C1-C4 alkyl, hydroxy

or C1-C4 alkoxy;

Tr1, Tr2, independently of one another, represent a 1,3,5-triazine-2,4-diyl residue, which optionally also has a halogen atom, a methyl group or a methoxy group as substituents.

Here and hereafter C1-C4 alkyl (as well as the alkyl parts in C1-C4 alkoxy, C1-C4 alkyl-amino, di-C1-C4-amino alkyl, C1-C4 alkyl-sulfonyl, hydroxyalkyl- C1-C4-sulfonyl, alkyl-C1-C4-aminosulfonyl, alkyl-C1-C4-aminocarbonyl, di-alkyl-C1-C4-aminosulfonyl, di-alkyl-C1-C4-aminocarbonyl and alkyl-C1-C4-carbonylamino and the like represents a linear or branched aliphatic hydrocarbon residue, such as methyl, ethyl, N-propyl, isopropyl, n-butyl and the like.

C1-C4 hydroxyalkyl represents C1-C4 alkyl having an OH group such as 2-hydroxyethyl. Correspondingly hydroxyalkyl-C1-C4-amino represents alkyl-C1-C4-amino, which has in the alkyl residue an OH group, such as 2-hydroxyethylamino.

C1-C4 carboxy alkyl represents C1-C4 alkyl having a carboxyl group (COOH group) such as carboxymethyl (CH2COOH) and 2-carboxy ethyl (CH2CH2COOH). Correspondingly, carboxy-C1-C4-amino represents alkyl-C1-C4-amino which in the alkyl part has a carboxyl group (COOH group) such as carboxymethylamino (NH-CH2COOH) and 2-carboxy-ethylamino (NH-CH2CH2COOH).

Heterocyclyl of 5 or 6 members usually has 1, 2 or 3 heteroatoms selected from nitrogen, oxygen and sulfur, mainly 1 or 2 nitrogen atoms and optionally an oxygen or sulfur atom as a ring member and can be saturated, unsaturated or aromatic. Examples of saturated heterocyclyl are morpholinyl, piperidinyl, piperazinyl and pyrrolidinyl. Examples of aromatic heterocyclyl are pyridinyl, pyrazolyl, oxazolyl, thiazolyl, etc.

The dyes of formulas 1 to XV can be used, both in free form, in the form of their salts and - provided that two residues linked by a diazo group -N = N- respectively have an OH, COOH or NH2 residue in ortho position towards the diazo group - like metal complexes.

In the dyes of formulas I to XIII and XV, residues DK1 and DK2 are derived from aromatic amines DK1-NH2 or DK2-NH2, which can also be referred to as diazonium components. DK1-NH2 or DK2-NH2 amines are usually optionally substituted aniline, optionally substituted α- or β-naphthylamine or optionally substituted aminoquinoline. Correspondingly, in general, residues DK1 and DK2, independently of one another, represent residues derived from benzene, naphthalene or quinoline, where naphthalene, quinoline and benzene optionally have one or more, for example 1, 2 or 3 substituents. Examples of substituents are the following residues: SO3H, COOH, OH, NH2, NO2, CN, CONH2, halogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, C1-C4 carboxyalkyl, C1-C4 alkoxy, alkyl- C1-C4-amino, dialkyl-C1-C4-amino, alkyl-C1-C4-aminocarbonyl, dialkyl-C1C4-aminocarbonyl, alkyl-C1-C4-aminocarbonyloxy, dialkyl-C1-C4-aminocarbonyloxy, alkyl-C1-C4- aminocarbonylamino, dialkyl-C1-C4-aminocarbonylamino, phenylaminocarbonyloxy, phenylaminocarbonylamino, alkoxy-C1-C4-carbonylamino, alkyl-C1-C4-carbonylamino, N- (alkyl-C1-C4-carbonyl) -N- (alkyl-C1-C4 -carbonyl) amino, hydroxy-C1-C4-alkyl-C1-C4amino, carboxy-alkyl-C1-C4-amino, phenylcarbonylamino, alkyl-C1-C4-sulfonyl, hydroxyalkyl-C1-C4-sulfonyl, alkyl-C1C4-aminosulfonyl , C1-C4-sulfonylamino, phenylsulfonyl, phenylsulfonylamino, formamide, SO2NR56R57, where R56 and R57, independently of one another, represent hydrogen, C1-C4 alkyl, formyl, C1-C4-carbonyl, C1-C4 alkyl- oxycarbonyl, NH2CO, C1-C4 alkyl aminocarbonyl, or 5 or 6 membered heterocyclyl which is optionally substituted by 1, 2 or 3 of the following residues: OH, halogen, C1-C4 alkyl or phenyl, in which case the 5-membered aromatic heterocyclyl optionally has nitrogen a phenyl group or a naphthyl group, which may optionally have one or two of the following residues: OH, SO3H, C1-C4 alkyl, and / or C1-C4 alkoxy;

In addition, as Dk1-NH2 or Dk2-NH2 amines, 4-amino-1-phenylpyrazoles are also taken into consideration where the pyrazole ring and also the phenyl ring have one or more, for example 1, 2 or 3 substituents of the named type previously or a group B-SO2, where B has the previously named meanings. In these cases Dk1 or Dk2 mainly represent pyrazole-4-yl, which in position 1 has a phenyl residue or a group of the formula A and optionally has 1 or 2 substituents that are selected from halogen, C1-C4 alkyl, hydroxy, COOH, hydroxysulfonyl or C1-C4 alkoxy,

Dk1 and Dk2 represent, independently of one another, preferably residues that are derived from optionally substituted aniline, from an optionally substituted α- or β-naphthylamine, or represent a group A.

Examples of suitable amines Dk1-NH2 or Dk2-NH2 are the compounds DK1 to DK39 indicated below:

image 1

image 1

image 1

Residues Q in the formulas DK21 to DK25 mean hydrogen C1-C4 alkyl, carboxy-C1-C4 alkyl, hydroxy-C1-C4 alkyl, C1-C4 alkoxy or phenylcarbonyl.

Suitable diazo components are the naphthylamines DK40 to DK59 indicated below: 4-amino-3-hydroxynaphthalene-1-sulfonic acid (DK40), 4-amino-3-hydroxy-6-nitronaphthalene-1-sulfonic acid (DK41), 6-amino acid -4-hydroxynaphthalene-2-sulfonic acid (gamma acid, DK42), 4-amino-5-hydroxynaphthalene-1-sulfonic acid (-S-Chicago, DK43), 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid ( H-acid DK44), 4-amino-5-hydroxynaphthalene-1,710 disulfonic acid (K-acid, DK45), 8-aminonaphthalene-2-sulfonic acid (Cleve acid 7, DK146), 6-aminonaphthalene-1 sulfonic acid (acid D, DK47), 4-aminonaphthalene-2,7-sulfonic acid (DK48), 5-aminonaphthalene-2-sulfonic acid (DK49), 7-amino-4,8-dihydroxynaphthalene-2-sulfonic acid (DK50), acid 2-amino-5-hydroxynaphthalene-1,7-disulfonic acid (DK51), 3-amino-5-hydroxynaphthalene-2,7-disulfonic acid (DK52), 3-amino-1,5-disulfonic acid (DK53), acid 7-aminonaphthalene-1sulfonic acid (DK54), 4-aminonaphthalene-1-sulfonic acid (DK55), 5-am acid inonaphthalene-1-sulfonic acid (DK56), acid 7

15 aminonaphthalene-1,3, btrisulfonic acid (DK57), 4-amino-3-hydroxy-7 - [(4-methylphenyl) sulfonylamino] naphthalene-1-sulfonic acid (DK58) and 7-amino-4-hydroxynaphthalene-2 acid -sulfonic acid (acid I, DK59),

Examples of suitable monoamines Dk1-NH2 or Dk2-NH2 are the compounds DK60 to DK83 indicated below:

image 1

image 1

5 As residues Kk1 and Kk2, essentially all mono-, bi- or trivalent aromatic residues are considered, as Kk3 residues all monovalent ones, which are derived from benzene, naphthalene, pyrazole, diphenylamine, diphenylmethane, pyridine, pyrimidine or diphenyl ether optionally substituted, which also have 1, 2 or 3 free positions, to which a diazonium compound can be successively coupled once, twice or three times. The compounds that serve as the basis of the residues Kk1, Kk2 and Kk3 are hereinafter referred to as components of

10 coupling

Suitable coupling components are, for example, benzene-derived compounds of the general formula Kk-A, naphthalene-derived compounds of the formula Kk-B, quinoline-derived compounds of the formula PCk-C, pyrazole-derived compounds of the formula Kk-D, diphenylmethane-derived compounds of the formula Kk-E, diphenylamine-derived compounds of the formula Kk-F, pyridine-derived compounds of the

Kk-G formula and pyridone-derived compounds of the formula Kk-H: In the formula Kk-A R11 represents NH2, OH, C1-C4 alkoxy, C1-C4 alkyl-amino, di-C1-C4 alkyl -amino, hydroxy-C1-C4-amino, carboxy-C1-C4-alkyl, amino-C1-C4-carbonylamino or phenylamino, R12 represents hydrogen, NH2, OH, C1-C4 alkoxy, hydroxy-C1-alkyl -C4-amino, carboxy-alkyl-C1-C4-amino, alkyl-C1-C4-amino, di-alkyl-C1-C4-amino and

image 1

R13

 represents hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4-aminocarbonyloxy, dialkyl-C1-C4-aminocarbonyloxy, C1-C4-alkylcarbonylamino, dialkyl-C1-C4-aminocarbonylamino, phenylaminocarbonyloxy, phenylaminocarbonylamino, alkoxy -C1-C4-carbonylamino, SO3H, alkyl-C1-C4-sulfonyl, hydroxyalkyl-C1-C4-sulfonyl, COOH, Cl, Br, F, SO2NR56R57, NO2, or NH2, in which case R56 and R57 independently of each other represents hydrogen, C1-C4 alkyl, formyl, C1-C4 alkylcarbonyl, C1-C4 alkyl oxycarbonyl, NH2-CO, C1-C4 alkylcarbonylalkyl.

In the formula Kk-B R14 and R15, independently of one another, represents hydrogen or have one of the meanings named as R11, in which case R15 may also represent SO3H. R16 represents hydrogen, OH, SO3H, alkyl-C1-C4-sulfonylamino, alkyl-C1-C4-aminosulfonyl, alkyl-C1-C4-aminosulfonylamino, Di-alkyl-C1-C4aminosulfonylamino, alkoxy-C1-C4-carbonylamino, phenylsulfonylamino which may have one or two substituents on the phenyl ring, selected from C1-C4 alkyl, C1-C4 alkoxy or halogen. R17 represents hydrogen, an OH group or an SO3H group.

In the formula Kk-C R18 to R20, independently of one another, represent hydrogen, OH or C1-C4 alkyl.

In the formula Kk-D, R21 represents hydrogen, phenyl or naphthyl, in which case the last two groups mentioned may have 1, 2 or 3 substituents that are selected from hydrogen, OH, halogen, C1-C4 alkyl, SO3H, NO2 and of the pre-defined group B-SO2-. In one embodiment of the invention R21 represents one of the previously defined groups A and mainly represents one of the groups A1 to A12. R22 means hydrogen, COOH or C1-C4 alkyl.

In the formula Kk-E, R23 and R25, independently of one another, represents hydrogen, COOH, hydroxy or C1-C4 alkyl. R24 and R26, independently of each other, represent hydrogen, hydroxy or C1-C4 alkyl,

In the formula Kk-F, R27 and R29, independently of one another, they mean hydrogen, SO3H, COOH, hydroxy or C1-C4 alkyl. R28 and R30 represent, independently of each other, hydrogen, hydroxy or C1-C4 alkyl,

In the formula Kk-G, R48, R49, R50 and R51, independently of one another, hydrogen, SO3H, COOH, NH2, CN, hydroxy

or C1-C4 alkyl.

Examples of coupling components of the formula Kk-A are the previously mentioned aniline compounds DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK118, DK21 to DK27, DK29, DK30, DK33, DK36, DK38, DK39, also salicylic acid (Kk1), 3-aminophenol (Kk2), resorcinol (Kk3), 3-phenylaminophenol (Kk4), 1,3diaminobenzene (Kk5), 3-acetylamino-aniline (Kk6), 2-nitro-aniline ( Kk7), 3- (diethylamino) phenol (Kk8), 3- (morpholin-1yl) phenol (Kk9), 3- (diethylamino) aniline (Kk10), N-acetyl-3- (diethylamino) aniline (Kk11), N - (3-hydroxyphenyl) glycine (Kk12), 3 (2-hydroxyethyl) aminophenol (Kk13), 2,4-diaminotoluene (Kk14), 2,4-diaminobenzenesulfonic acid (Kk15), 2,4-diamino1-nitrobenzene (Kk16 ), N- (3-amino-6-methylphenyl) -glycine (Kk17), 2,4-diamino-5-methylbenzenesulfonic acid (Kk18), 2,4 diamino-1-hydroxybenzene (Kk54), 2,4-diamino -1-methoxybenzene (Kk55), 2,4-diamino-1-chlorobenzene (Kk56), 1,2,4-triaminobenzene (Kk57), 3- (dimethylamino) -aniline (Kk58), 3- (dimethylamino) -1 -nitrobenzene (Kk59), 2- (N, N-diethylamino) -4-acetylamino-1-methoxybenzene (Kk60), 2- (N, N-diethylamino) -4-amino-1-methoxybenzene (Kk61), 2,4-diamino-1-benzenesulfonamide (Kk62), 2-amino- 4-acetylamino-1-methoxybenzene (Kk63), 2-amino-4-acetylamino-1-chlorobenzene (Kk64), 2,4-diamino-1-methylsulfonylbenzene, (Kk65), 2,4-diamino-1-ethylsulfonylbenzene, (Kk66 ) and 2,4-diamino-1-2-hydroxyethyl) sulfonylbenzene (Kk67).

Examples of coupling components of the formula Kk-B are 2-naphthol- (Kk19), 2-phenylaminonaphthalene (Kk20), 4-methyl-1-naphthol (Kk21), 8-methoxycarbonylamino-2-naphthol (Kk22), 8-acetylamino -2-naphthol (Kk23), 8-methylaminosulfonyl-2naphthol (Kk24), 8-dimethylaminosulfonylamino-2-naphthol (Kk25), 6 - [(4-methylphenyl) sulfonyl] amino-4-hydroxynaphthalene-2sulfonic acid (Kk26), 8-Phenylaminonaphthalene-1-sulfonic acid (Kk27), 6-amino-4-hydroxynaphthalene-2-sulfonic acid (DK42), 4-amino-5-hydroxynaphthalene-1-sulfonic acid (DK43), 7-amino-4 acid -hydroxynaphthalene-2-sulfonic acid (DK59), 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid (DK44), 4-amino-5-hydroxynaphthalene-1,7-disulfonic acid (DK45), 8-aminonaphthalene-2-sulfonic acid (DK46), 6-aminonaphthalene-1-sulfonic acid (DK147), 4-aminonaphthalene-2,7-sulfonic acid (DK48), 4-hydroxynaphthalene-2,7-disulfonic acid (Kk28), 3-hydroxynaphthalene-2 acid , 7-disulfonic acid (Kk29), 4 (phenylcarbonyl) amino-5-hydroxynaphthalene-2,7-disulfonic acid (Kk30), acid 4,6-dihydroxynaphthalene-2-sulfonic acid (Kk31), 4,5-dihydroxynaphthalene-2,7-disulfonic acid (Kk32), 4- (phenylcarbonyl) amino-5-hydroxynaphthalene-1-sulfonic acid (Kk33), 4-hydroxynaphthalene- 1-sulfonic acid (Kk34), 4,5-dihydroxynaphthalene-1-sulfonic acid (Kk35), 5-aminonaphthalene-2-sulfonic acid (DK49), 7-hydroxynaphthalene-1,3-disulfonic acid (Kk36), 7- amin-4,8-dihydroxynaphthalene-2-sulfonic acid (DK50), 8-hydroxynaphthalene-1-sulfonic acid (Kk37), 2-amino-5-hydroxynaphthalene-1,7-disulfonic acid (DK51), 3-amino-5-hydroxynaphthalene- 2,7-disulfonic acid (DK52), 3-amino-1,5-disulfonic acid (DK53), 4,8-dihydroxy-7hydroxycarbonylnaphthalene-2-sulfonic acid (Kk38), 7-aminonaphthalene-1-sulfonic acid (DK54) , 4-aminonaphthalene-1sulfonic acid (DK55), 5-aminonaphthalene-1-sulfonic acid (DK56), 7-aminonaphthalene-1,3,5-trisulfonic acid (DK57) and 4-acetylamino-5-hydroxynaphthalene-2,7- disulfonic (Kk39).

Examples of Kk-C coupling components are 2,4-dihydroxyquinoline (Kk40) and 8-hydroxyquinoline (Kk41).

Examples of Kk-D coupling components are 3-methyl-5-hydroxypyrazole (Kk42), 1-phenyl-3-methyl-5-hydroxypyrazole (Kk43), 1- [4- (2-hydroxysulfonyloxyethyl) -2-hydroxysulfonylphenyl] -3-methyl-5-hydroxypyrazole (Kk44), 1- [4- (2-hydroxysulfonyloxyethyl) -2-hydroxysulfonylphenyl] -hydroxypyrazol-3-carboxylic acid (Kk45), 1- [4-hydroxysulfonylphenyl] -5-hydroxypyrazole-3- carboxylic (Kk46) and 1- [6-hydroxysulfonylnaphthalene-2-yl] -5-hydroxy-3-methylpyrazole (Kk47), 1-14 hydroxysulfonylphenyl] -3-methyl-5-hydroxypyrazole (Kk48).

An example of Kk-E coupling components is 4,4’-dihydroxydiphenylmethane-3,3’-dicarboxylic acid (Kk49).

An example of a Kk-F coupling component is 4,4′-dihydroxydiphenylamine (Kk50).

An example of a coupling component Kk-G is 2,6-diamino-pyridine (Kk51).

Examples of Kk-H coupling components are 1-methyl-2-pyridone (Kk52) and 3-cyano-4-methyl-6-hydroxy-1-ethylpyridone (Kk53).

Suitable Kk3 wastes are mainly monovalent residues derived from optionally substituted benzene

or naphthalene, for example monovalent residues derived from coupling components Kk-A and Kk-B, such as residues derived from aniline DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK21 bis DK27, DK29, DK30, DK33, DK36, DK38, DK39, DK42 bis DK83, Kk1 to Kk48 and Kk51 to Kk67.

The residues Tk1 and Tk2 are bivalent aromatic residues that are derived from aromatic diamines of the formulas Tk1 (NH2) 2 or Tk2 (NH2) 2. These diamines are also referred to as tetraazo components.

Suitable tetraazo components are, for example, benzene-derived compounds of the general formula Tk-A, diphenyl-derived compounds of the formula Tk-B, phenylbenzimidazole-derived compounds of the formula Tk-C, diphenylmethane-derived compounds of the formula Tk- D, diphenylamine derived compounds of the formula Tk-E, phenylsulfonylbenzene derived compounds of the formula Tk-F, phenylaminosulfonylbenzene derived compounds of the formula Tk-G, stylobenze derived compounds of the formula Tk-H and phenylaminocarbonylbenzene derived compounds of the Tk-J formula:

image2

In the formula Tk-A R31 represents, for example, hydrogen, C1-C4 alkyl, C1-C4 alkoxy, COOH or SO3H. Both NH2 groups are preferably positioned in position for, one in relation to the other. Examples of compounds of the formula Tk-A are 1,4-diaminobenzene (Tk1), 1,4-diamino-2-methoxybenzene (Tk2), 2,5-diaminobenzoic acid (Tk3) and 2,5-diaminobenzenesulfonic acid (Tk4 ).

In the formula Tk-B, R32 and R33 represent, independently of one another, for example, hydrogen, OH, C1-C4 alkyl, C1-C4 alkoxy, COOH or SO3H. Both NH2 groups are preferably located at position 4 and position 4 ’. Examples of compounds of the formula Tk-B are 4,4'-diaminobiphenyl (Tk5), 4,4'-diamino-3,3'-dimethylbiphenyl (Tk6), 4,4'-diamino-3,3'-dimethoxybiphenyl (Tk7), 4,4'-diamino-3,3'-dihydroxybiphenyl (Tk8), 4,4'-diamino-3-hydroxysulfonylbiphenyl (Tk9), 4,4'-diamino-3,3'-bis (hydroxysulfonyl ) biphenyl (Tk10) and 4,4'-diamino-3,3'-dicarboxybiphenyl (Tk11).

In the formula Tk-C, R34 and R35, independently of each other they represent, for example, hydrogen, OH, C1-C4 alkyl or C1-C4 alkoxy. An example of a compound of the formula Tk-C is 6-amino-2- [4-aminophenyl] benzimidazole (Tk12).

In the formula Tk-D, R36 and R37, independently of each other they represent, for example, hydrogen, OH, C1-C4 alkyl, C1-C4 alkoxy, COOH or SO3H. Both NH2 groups are preferably located at position 4 and position 4 ’. Examples of Tk-D compounds are bis (4-aminophenyl) methane (Tk13), bis (4-amino-3-carboxyphenyl) methane (Tk14) and bis (4-amino-3-methylphenyl) methane (Tk15).

In the formula Tk-E R38 and R39, independently of one another, represent for example hydrogen, OH, C1-C4 alkyl, C1-C4 alkoxy, COOH or SO3H. Both NH2 groups are preferably located at position 4 and position 4 ’. An example of a Tk-E compound is (4-aminophenyl) (4’-amino-2’-hydroxysulfonylphenyl) amine or 4,4’-diaminodiphenylamin-2-sulfonic acid (Tk16).

In the formula Tk-F, R40 and R41, independently of one another for example represents hydrogen, OH, C1 alkyl

10 C4, C1-C4 alkoxy, COOH or SO3H. Both NH2 groups are preferably located at position 4 and position 4 ’. An example of a Tk-F compound is bis- (4-aminophenyl) sulfone (Tk17).

In the formula Tk-G R42 and R43, independently of one another, represent for example hydrogen, OH, C1-C4 alkyl, C1-C4 alkoxy, COOH or SO3H. Both NH2 groups are preferably located at position 4 and at 4 ’. An example of a Tk-G compound is N- (4’-aminophenyl) -4-aminobenzenesulfonamide (Tk18).

In the formula Tk-H R44 and R45, independently of one another, represent for example hydrogen, C1-C4 alkyl, COOH or SO3H. Both NH2 groups are preferably located at position 4 and at 4 ’. An example of a Tk-H compound is 1,2-bis- (4-amino-2-hydroxysulfonylphenyl) ethene (flavonic acid, Tk19).

In the formula Tk-J R46 and R47, independently of one another, represent for example hydrogen, OH, C1-C4 alkyl, C1-C4 alkoxy, COOH or SO3H. Both NH2 groups are preferably located at position 4 and at 4 ’. A

An example of a Tk-J compound is N- (4′-aminophenyl) 4-aminobenzoic acid (Tk20) amide.

Preferred residues Napht1 and Napht2 obey the general formula Napht-II:

image 1

where R1 and R2, independently of one another, mean hydrogen, OH, NH2 or NHC (O) R3, where R3 represents hydrogen, C1-C4 alkyl, maleinyl or phenyl, and at least one of the residues R1 and R2 is different of hydrogen,

25 ------ represents the links to the azo groups, s and t represent 0 or 1. The sum s + t preferably has the value 1 or 2.

Examples of suitable Napht1 or Napht2 residues encompass residues II-1 through II-14 listed below:

2-hydroxysulfonyl-4-hydroxynaphthalene-3,6-diyl (II-1), 6-amino-2-hydroxysulfonyl-4-hydroxynaphthalene-3,5-diyl (II-2),

1-Hydroxysulfonyl-5-hydroxynaphthalene-4,6-diyl (II-3), 4-amino-1-hydroxysulfonyl-5-hydroxynaphthalene-3,6-diyl (H-4), 2-hydroxysulfonyl-4-hydroxynaphthalene -3,7-diyl (II-5), 7-amino-2-hydroxysulfonyl-4-hydroxynaphthalene-3,8-diyl- (II-6), 5-hydroxy-2,7-bishydroxysulfonylnaphthalene-4,6- diyl (II-7),

4-Amino-5-hydroxy-2,7-bishydroxysulfonylnaphthalene-3,6-diyl (II-8) 5-hydroxy-1,7-bishydroxysulfonylnaphthalene-4,6-diyl (II-9),

4-amino-5-hydroxy-1,7-bishydroxysulfonylnaphthalene-3,6-diyl (II-10),

2-hydroxysulfonylnaphthalene-5,8-diyl (II-11),

2-amino-5-hydroxy-1,7-bishydroxysulfonylnaphthalene-3,6-diyl (II-12),

5 5-hydroxy-2,7-bishydroxysulfonylnaphthalene-3,6-diyl (II-13),

3-amino-5-hydroxy-2,7-bishydroxysulfonylnaphthalene-4,6-diyl (II-14),

2-hydroxysulfonylnaphthalene-5,8-diyl (II-15) and

1-hydroxysulfonylnaphthalene-5,8-diyl (II-16).

L, M, P and R residues are bivalent residues, benzene or naphthalene derivatives, for example derived residues

10 of the coupling components of the formulas Kk-A and Kk-B as well as the residues derived from the previously named diazo components, which have a free position to which a diazonium compound can be coupled. Examples of these are the aniline compounds DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK21 bis DK27, DK29, DK30, DK33, DK36, DK38, DK39, and DK60 to DK83 as well as naphthylamines DK42 to DK59.

Among the aforementioned compounds of formulas I to XV, dyes of general formulas IIa, IIIa and IVa are particularly preferred:

Dk1-N = N-Napht1-N = N-Tk1 [-N = N-Kk1] k [-N = N-Dk2] n (IIa)

Dk1-N = N-Napht1-N = N-Tk1-N = N-Kk1-N = N-Tk2-N = N-Napht2-N = N-Dk2 (IIIa)

20 Dk1-N = N-Napht1-N = N-Tk1-N = N-Napht2-N = N-Dk2 (IVa)

In formulas IIa, IIIa and Iva, Dk1, Dk2, Napht1, Napht2, Kk1, TK1, Tk2 and Kk1 have the meanings previously named, in which case one of the residues Dk1 and Dk2 represent a residue of the formula A, such as It was previously defined, and mainly means one of the residues A1 to A12. The numbers n and k represent 0 or 1, in which case n + k is = 1 or 2. Compounds of this type are new if Tk1 in formula IIa does not represent a residue

Diphenylamine derivative, if k is = 0. Therefore, compounds of this type and mixtures thereof are also the subject of the present invention.

A particularly preferred embodiment of the dyes II or IIa are the dyes of the general formula IIb

Dk1-N = N-Napht1-N = N-Tk1-N = N-Kk1 [-N = N-Dk2] n (IIb)

30 where A, Dk2, Napht1 and Kk1 have the meanings already mentioned, n represents 0 or 1, and where Tk1 represents a bivalent residue, derived from diphenyl, diphenylmethane, 2-phenylbenzimidazole, phenylsulfonylbenzene, phenylaminosulfonylbenzene, diphenylamine, stilbene or phenylaminocarbonyl, phenylaminocarbonyl which may optionally have one or more of the following residues as a substituent: SO3H, COOH, OH, NH2, NO2, halogen, C1-C4 alkyl, in which case Tk1 does not represent a residue derived from diphenylamine, if n is = 0, and in which case the residue Dk2

35 may also represent a residue of formula A, as previously defined. Dyes of the general formula IIb and mainly their mixtures are a particularly preferred object of the present invention.

Among the dyes of the invention of the general formulas IIa IIb IIIa and IVa, those dyes are particularly preferred, where at least one of the groups Tk1 and / or Tk2 represents a residue of the formula

image 1

where -------- represents the links to the azo groups.

Among the compounds of the general formulas IIa, IIb, IIIa and IVa, those dyes are particularly preferred where Napht1 and / or Napht2 represent a bivalent residue of the general formula Napht-II defined above and mainly possess the specific meanings listed therein.

Among the compounds of the general formulas IIa, IIb, IIIa and IVa, those dyes are particularly preferred where one or both residues Dk1 and Dk2 represent one of residues A1 to A12 already defined previously.

In the dyes of the general formula IIb, Kk1 represents, for example, a residue derived from the coupling components of the formulas Kk1 to Kk67, DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK21 a DK27, DK29, DK30, DK33, DK36, DK38, DK39 or DK42 to DK83. Among the dyes of the formula IIa, IIb and IIIa, those where Kk1 is derived from a Kk-A compound are mainly preferred.

Particularly preferred are mixtures of the dyes of the general formula IIb. Mixtures of dyes IIb are made up of at least two, for example 2, 3 or 4, individual dyes IIb. The amount of the individual dye IIb is at least 10% molar and mainly at least 20% molar, with respect to the total amount of dye F. Mixtures of two dyes F are preferred, where the individual components are in the molar ratio in the range of 9: 1 to 1: 9, mainly in the range of 2: 8 to 8: 2 and particularly preferable in the range of 3: 7 to 7: 3. A particularly preferred embodiment is mixtures of dyes IIb, where the individual dyes only differ in the Kk1 residue.

The preparation of the azocolorants of the general formulas ia XV and their metal complexes, used according to the invention, is carried out in a manner known per se by means of a sequence of several diazotization / coupling steps, in which case the dye is structure diazotizing / coupling successively, that is to say that the coupling of the individual building blocks of the diazogrupon or NH groups is carried out by successive synthesis or by convergent synthesis, that is to say groups of dye molecules that already have diazo groups or groups are generated NH and then connected by another diazotization / coupling with another part of the dye molecule that also already has one or more diazo groups, optionally by means of a coupling component or a tetraazocomponent.

When diazotizing / coupling successively, first, for example, the diazonium components Dk1 or Dk2 are diazotized and coupled to a Napht1 or Napht2, Kk1 or Kk2 group or to a P or R group, then the reaction product is diazotized again and couple to another coupling counterpart and optionally repeat this operation until the dye has been structured. Alternatively, during successive synthesis, the ration product can also react successively with one or more diazonium compounds.

During the first coupling, a tetrazocomponent Tk1 (NH2) 2 or Tk2 (NH2) 2 is also transferred to the corresponding tetrazonium salt and one after the other is reacted with the coupling counterpart Kk1, P, Napht1, Napht2, etc. and then diazotization / coupling reactions are performed.

Mixtures of two or more dyes F can be prepared, both by mixing the desired mixture components, and also by using mixtures of starting materials used for the preparation of dyes F. For example, mixtures of azocolorants I to XV can be prepared using in the preparation mixtures of at least two amines Dk1-NH2, Dk2-NH2 or A-NH2, mixtures of at least two coupling components H-Kk1 or H-Kk2, mixtures of at least two tetrazo components (H2N) 2-Tk1 or (H2N ) 2-Tk2 or mixtures of at least two different compounds Napth1H2 or Napth2H2. Of course, mixtures of 3 or more components can also be used.

Corresponding to the proportion of the mixture of the dyes F in the mixture, a mixture of the respective starting material is used in the preparation of the dye F, in which the individual starting material is present in an amount of at least 10 Molar%, mainly at least 20% molar, particularly preferably at least 30% molar, with respect to the mixture. In mixtures of two starting materials, for example in a mixture of two coupling components H-Kk (1) or H-Kk (2), or in mixtures of two diazo components or in a mixture of two tetrazo components, the molar ratio of The individual components of the mixture are in the range of 9: 1 to 1: 9, mainly in the range of 8: 2 to 2: 8 and particularly preferable in the range of 3: 7 to 7: 3.

The preparation of the azocolorants of the general formulas I to XV is illustrated by examples by means of the preparation of the dyes of the general formula IIb. The methods used for this purpose can be modified in a manner known per se to structure other azo-colorings of the general formulas I to XV. Colorants of the general formula II b can be produced, for example, in a first step by tetrazotization of the diamine compound Tk1 (NH2) 2 that serves as the basis for the tetrazocomponent Tk1 and then initially coupled to the naphthalene compound Napht1H2 which serves as a Basis for the Napht1 residue. Then, the diazonium compound, obtained in this way, is H-Napht1-N = N-Tk1-N2 + a diazonium compound Dk1N2 or A-N2 +, in which case the compound Dk1-N = N-Napht1- is obtained N = N-Tk1-N2 + or AN = N-Napht1-N = N-Tk1-N2 +. This compound is coupled to a coupling component Kk1H, in which case the compound of the formula is obtained

10 IIb with n = 0. Alternatively, the diazonium compound H-Napht1-N = N-Tk1-N2 + can be coupled to a coupling component Kk1H, in which case the compound H-Napht1-N = N- is obtained Tk1-N = N-Kk1. To this is coupled a diazonium compound Dk1-N2 + or AN2 +, in which case the dye of the formula IIb is obtained with n = 0.

Colorants of the formula IIb can also be prepared by coupling the compound Dk1-N2 + A-N2 + to a compound Napht1H2, in which case the compound of the formula Dk1-N = N-Napht1-H or A-N = N-Napht1-H is obtained. To this

The compound is then coupled to the tetrazotization product of the diamino compound Tk1 (NH2) 2 which serves as the basis for the tetrazo component Tk1, in which case the compound Dk1-N = N-Napht1-N = N-Tk1-N2 + or AN is obtained = NNapht1-N = N-Tk1-N2 +. This compound is coupled to a coupling component Kk1H, in which case the dye of the formula IIb is obtained with n = 0.

In addition, dyes of the general formula IIb can be prepared in a first step by tetrazotization of the

20 diamino compound Tk1 (NH2) 2, which is the basis for the azo component Tk1 and then initially coupled to the coupling component Kk1H. At the same time the compound + N2-Tk1-N = N-Kk1 is obtained, which is then coupled to the compound Napht1H2, in which case the compound of the formula H-Napht1-N = N-Tk1-N = NKk1 is obtained . To this is coupled a diazonium compound Dk1-N2 + or A-N2 +, in which case the compound of the formula IIb is obtained with n = 0. Alternatively, the compound + N2-Tk1-N = N-Kk1 is coupled to the compound Dk1-N = N-Napht1-H

25 or A-N = NNapht1-H, in which case the dye of formula IIb is obtained with n = 0.

In another step of the reaction to the compound of the formula IIb with n = 0 a Dk2-N2 + compound can then be coupled, in which case the dyes of the formula IIb with n = 1 are obtained.

Dyes of the general formula IIb can also be prepared with n = 1 initially by diasotization of a compound of the formula Dk2-NH2 and then coupled to the coupling component Kk1H, in which case

30 obtains the compound of the formula Kk1-N = N-Dk2. The compound Dk1-N = N-Napht1N = N-Tk1-N2 + or AN = N-Napht1-N = N-Tk1-N2 + is then coupled to this compound, in which case s dyes of formula IIb are obtained with n = one.

Dyes of the general formula IIb can also be prepared with n = 1 by tetrazotization of the diamino compound Tk1 (NH2) 2 which forms the basis for the tetrazo component Tk1 and is coupled to the compound Kk1-N = N-Dk2, in which case it is obtained the compound + N2-Tk1-N = N-Kk1-N = N-Dk2. This compound is then coupled to the compound

Dk1-N = N-Napht1H, in which case dyes of the formula IIb are obtained with n = 1.

To prepare the preferred mixtures of the dyes of the general formula IIb, in which the individual dyes IIb differ from their HKk1 residue, preferably a mixture of at least two different coupling components Kk1 is used, where the individual components are as They have been indicated.

Provided that the dyes have a triazine residue Tr1 and / or Tr2, the preparation of the dyes also encompasses the reaction of a triazine compound of the formula C

image 1

where Ra and Rc represent halogen, mainly chlorine and Rb represents halogen, methyl or methoxy, with two amino components. The amino components are, for example, the monoamine compounds Dk1-NH2 or Dk2-NH2 called as diazo components, the diamino compounds Tk1 (NH2) 2 or Tk2 (NH2) 2 called as

Tetrazocomponents, as well as dye molecule parts that have a primary amino group.

The diazotization and coupling of the diazonium or tetrazonium compound obtained therein is usually carried out in an aqueous reaction medium under pH control in a manner known per se.

As long as the component parts of the molecule that have been used already have a group A that has a residue B of the formula CH2CH2-Q, then the pH value of the reaction mixture will not exceed a value of 8 since otherwise a dissociation of group Q is performed and a vinyl group is formed.

In the couplings of a diazonium component or a tetrazonium component to a naphthalene compound of the formulas II or Kk-B, which already has an OH group as well as an amino group and has at least two possible coupling sites, it should be taken note that the first coupling is carried out regioselectively in ortho position towards the amino group at pH values of maximum 3, while at pH values of pH ≥6, preferably pH ≥8 a regioselective coupling is made in the ortho position of the group OH

The reaction of an amine with a triazine C compound is usually carried out at acidic pH values, preferably at pH 7 and mainly in the range of pH 1 to pH 4.

The reaction temperatures required for diazotization7 coupling or for the reaction with triazines are usually in the range of 0 ° C to 50 ° C and mainly in the range of 0 to 30 ° C. The required reaction times are usually in the range of 5 min to 2 h and mainly in the range of 20 minutes to 1 h.

The reactions are usually carried out stoichiometrically, that is, the reactants are reacted with each other in the desired stoichiometry. The individual reactants can, however, be used both in excess and also in defect with respect to the desired stoichiometry. The deviation from the desired stoichiometry is usually not more than 20% molar and mainly no more than 10% molar. In other words, for the reaction of a diazonium component with a coupling counterpart the molar ratio of both components is in the range of 1: 1.2 to 1.2: 1 and mainly in the range of 1.1: 1 a 1: 1,1. For the reaction of a tetrazonium compound with 2 molar equivalents of a coupling counterpart, it will be used correspondingly in an amount of 1.6 to 2.4 mol and mainly in an amount of 1.8 to 2.2 mol per mole of tetrazonium compound.

Following the diazotization / coupling sequence, for the preparation of the transition metal complexes the desired transition metal salt is added in the form of a suitable salt, preferably soluble in water in the desired stoichiometric amount and optionally heated to the temperature required for complexing, for example at temperatures in the range of 40 to 100 ° C.

Obtaining the dye from the aqueous reaction mixture in a usual manner, for example by evaporating and, especially, by spray drying the aqueous reaction mixture, by precipitation of the dye by saturation of the solution with neutral salts and drying of The pressed cake. The pressed cake, preferably still wet, preferably in water can be redissolved, preferably in water and a diafiltration and / or ultrafiltration can be performed, so that the inorganic salts produced in the synthesis can be depleted and / or the solution can be enriched with respect to the dye. The purified dye can then be obtained in this way by spray drying from the solution.

To prepare a liquid brand or a liquid formulation of the dye the pressed dye cake or the dye powder obtained by evaporating or spray drying can be dissolved, for example in water, in a water / solvent mixture, in an aqueous acid or in an aqueous base, in which case the aqueous acid and the aqueous base may also contain solvent. As solvents, mainly water-miscible solvents such as C1-C4 alkanols, organic carboxylic acids such as formic acid, acetic acid and propionic acid, alkanolamines, dialkanolamines and trialkanolamines, such as ethanolamine, diethanolamine, triethanolamine, also amides as formamide, are taken into consideration. acetamide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and the like. It is also possible to prepare a liquid formulation of the dye directly from the reaction solution or by ultrafiltration and spray drying. Optionally, for a sufficiently high concentration and for the stability of the liquid suspension it is then required to carry out a dia- and / or ultrafiltration process in order to deplete the resulting inorganic salts during preparation and to concentrate the solution.

The process of the invention encompasses a dyeing step at a pH value of 7.5 to 11. For this purpose the leather to be dyed is treated in an aqueous immersion liquid having a pH value of at least 7.5 and preferably of at least 8.0 and containing at least one dye F of the type designated above. According to the invention, the pH value of the immersion liquid will not exceed a value of pH 11 and preferably pH 10.5. Mainly, the pH value of the immersion liquid is in the range of 8.5 to 10. Through the alkaline pH value a fixation of the dye on the leather is achieved since in these conditions group A reacts with the amino groups of the leather forming a covalent bond.

To obtain the alkaline pH for fixation, any alkalis and buffer systems can be used. By way of example, alkali metal carbonates and hydrocarbonates, such as sodium carbonate, potassium carbonate and sodium hydrocarbonate, may also be referred to as alkali metal hydroxides such as sodium hydroxide, sodium metasilicate, pyrophosphates such as sodium or potassium pyrophosphate, phosphate tripotassium, trisodium phosphate, borax / sodium hydroxide buffer and phosphate buffer.

The temperatures required for fixing the dye are advantageously not greater than 60 ° C, mainly not more than 50 ° C, and particularly preferably not more than 40 ° C, so that a careful dyeing of the leather is possible. Usually, the dyeing is carried out at temperatures of at least 10 ° C, preferably at least 20 ° C, mainly at least 30 ° C in order to achieve a sufficient reaction rate and thereby accelerate the dyeing operation . However, basically low temperatures are also possible. For organically tanned leathers the preferred temperature range is 15 to 50 ° C and particularly 30 to 40 ° C. For tanned leathers with metal oxides a temperature range of 15 to 60 ° C and particularly 30 to 50 ° C is preferred.

For sufficient fixation, treatment durations of 0.5 h to 4 h are usually required, depending on the pH value and temperature. The duration of treatment can be ascertained by the person skilled in the art by means of simple routine experiments for each of the dyes used. Mainly, at strongly alkaline pH values in the range of 9.5 to 11, mainly 9.5 to 10.5, the duration of dyeing is preferably not longer than 2 h, for example 0.5 to 2 h.

In dyeing salts can also be added, for example Glauber salt.

Together with the dyes F used in accordance with the invention, the immersion liquid may also have acidic or direct dyes. Its fraction, however, will preferably not be more than 10% by weight, mainly not more than 5% by weight, with respect to the total amount of dyes in the immersion liquid (calculated respectively as a pure, chemical-organic colored component of the dye ).

Usually, the colorant F is used according to the desired color depth in an amount of at least 0.2% by weight, often at least 0.5% by weight and mainly at least 1% by weight, based on the weight recessed of the leather used or of the semi-finished product, in which case the amounts indicated herein refer to the dye including synthetic salts and flow conditioners optionally present. With respect to the chemical-organic components of color, the dye is usually used in an amount of at least 0.1% by weight, often at least 0.3% by weight and mainly at least 0.5% by weight , with respect to the reduced weight of the leather used or the semi-finished product. Usually the dye calculated is used as a mixture of chemical-organic components + synthesis salts and flow conditioners optionally present, in an amount of up to 20% by weight, or in an amount of up to 15% by weight, calculated as components chemical-organic color and with respect to the reduced weight, in which case larger amounts of dye can also be used. To achieve medium to high color depths, the colorant F is used depending on its molar extinction coefficient and its molecular weight regularly in an amount of 2 to 20% by weight, often 3 to 20% by weight and mainly in a amount of 4 to 20% by weight, with respect to the weight reduced from the weight or the semi-finished product and calculated as a mixture of chemical-organic components + synthesis salts and flow conditioners optionally present, or in an amount of 1 to 15% by weight, often 1.5 to 10% by weight and mainly 2 to 10% by weight, with respect to the reduced weight of the leather or the semi-finished product and calculated as chemical-organic components of color.

The aqueous immersion liquid may contain usual anionic dyeing auxiliaries, non-ionic surfactants and wet-end chemicals usually used for post tanning treatment, for example tanning agents, for example polymeric retanning agents, vegetable tanning agents as well as greasing agents (grease liquids ) and hydrophobicizing agents.

As re-tanning agents for the process of the invention all the usual commercial systems are considered, for example:

one.

 Vegetable tanning agents such as mimosa, chestnut, quebracho;

2.

 mineral tanning materials such as chrome, iron, aluminum and zirconium tanning materials;

3.

 Filler material, for example laminated silicates, saccharides, polysaccharides such as starch and flour;

Four.

 Synthetic tanning agents (syntanes), for example the substances described in EP 0459 168, EP 0 520 182, US 5, 342, 915 and US 5,186 846, such as:

to.

 Condensation products of naphthalene sulfonic acid-formaldehyde,

b.

 Condensation products of phenolsulfonic acid-formaldehyde,

C.

Co-condensation products of naphthalene sulfonic acid and / or phenolsulfonic acid with hydroxyarylsulfones such as bis (hydroxyphenyl) sulfone and formaldehyde,

d.

 Co-condensation products of naphthalene sulfonic acid and / or phenolsulfonic acid with oligosulfones (mixtures of poly-nuclear aromatics linked by sulfone bridges and which may be substituted with -OH or -SO3H) and formaldehyde,

and.

 Co-condensation products of naphthalene sulfonic acid, phenolsulfonic acid with formaldehyde and with N-containing compounds as well as optionally with hydroxyarylsulfones or with oligosulfones. Examples of N-containing compounds are urea, melamine, melamine derivatives such as hydroxy-C2-C20-melamines, bis-hydroxy-C2-C20-melamine or tris-hydroxy-C2-C20-melamine, hydroxyarylmelamine or melanins with one to three chains of polyalkylene oxide in the atoms of N, melem (2,5,8-triamino-1,3,4,6,7,9,9bheptaazafenalene) or derivatives of melem, such as hydroxy-alkyl -C2-C20-melemos or melemos with polyalkylene oxide side chains on the N atoms, guanamines (2,4-diamino-1,3,5-triazines substituted in position 6) such as benzoguanamine, acetoguanamine, caprinoguanamine or isobutyrogogyamine ; guanamine derivatives such as N-hydroxy-C2-C20 alkyl-guanamines, as well as guanamines with one or two polyalkylene oxide chains in the N atoms, and dicyandiamide,

F.

 Mixtures of substances named under paragraphs 4.a to 4.e with compounds of Cr (III);

5. Resin tanning agents, for example:

to.

 Condensation products containing naphthalene sulfonic acid sulfide and formaldehyde,

b.

 Condensation products containing phenolsulfonic acid and formaldehyde sulfite,

C.

 Mixtures of 5.a. and 5.b .;

6. Polymeric tanning agents that can be anionic, cationic or amphoteric in nature. Anionic polymeric tanners may have carboxyl groups, for example, cationic polymeric tanners may have amino groups and amphoteric polymeric tanners have both cationic and anionic groups. Depending on the pH value, amphoteric polymers can have either an anionic or cationic character. Examples of polymeric tanning agents are:

to.

 Homo- and copolymers of acrylic acid and methacrylic acid,

b.

 Homo- and copolymers of acrylic acid and / or methacrylic acid with alkyl-C1-C30-acrylates and / or alkyl-C1-C30 methacrylates,

C.

 Functionalized copolymers of alkyl-C1-C30-acrylate and / or alkyl-C1-C30-methacrylates with monomers having cationic or anionic or acidic groups,

d.

 Copolymers of ethylenically unsaturated carboxylic acid anhydrides, such as maleic anhydride with C3-C40 alphaolefins, such as propene, 1-butene, 1-hexene, 1-octene, diisobutene, 1-decene and the like,

and.

 Copolymers of dicarboxylic acid - styrene anhydride

F.

 Homo- and copolymers of ethylenically unsaturated nitriles such as acrylonitrile and methacrylonitrile, optionally with other monoethylenically unsaturated monomers such as acrylic acid, methacrylic acid, acrylamide, methacrylamide

or C1-C10-alkyl (meth) acrylates. Examples of polymeric tanning agents are set forth in EP-A 1335029 and WO 96/15276, to which reference is made in this regard.

7. Aldehydes, such as:

to.

 Formaldehydes,

b.

 Glutardialdehydes,

C.

 Oligoaldehydes as described in WO 03/095681,

d.

 Tanning aldehyde generators, as described in the Bibliothek des Leders (Leather Library), volume 3, Umschau Verlag editorial, 1984, pages 26-27, for example oxazolidines and phosphonium compounds;

8. Dispersing agents as described in US 5, 186 846, for example:

to.

 Condensation products of naphthalene sulfonic acid and formaldehyde and

b.

 Ligninosulfonates.

In addition, all the usual commercial tanning agents can be used as tanning agents, such as chrome tanning, mineral tanning, syntane, polymeric tanning and vegetable tanning, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, volume A 15, pages 259 to 282 and mainly page 268 and following, 5. Edition, (1990), Verlag Chemie Weinheim Editorial. Usual tanning agents in the market may also be mixtures of the tanning classes named under section 1.-8.

As fat impregnating agents, all the usual fat impregnating agents can be used in the production of leather, mainly all the fat impregnating agents that are customary in trade. Fat impregnating agents naturally contain at least one hydrophobic substance, which is based on a hydrocarbon, for example a natural or synthetic wax, a native or synthetic oil or a native or synthetic fat. The hydrocarbon base for fat impregnating agents also includes polyisobutene-based substances. The hydrocarbon bases illustrated in greater detail below can be chemically modified, for example:

one.

 sulfate

2.

 sulphonate

3.

 sulphite

Four.

 sulfoxidate

5.

 sulfochlorinate

6.

 ethoxylate or esterify in general

Fat impregnating agents may also contain mixtures of non-functionalized components, mixtures of functionalized components with non-functionalized components or mixtures of functionalized components as a hydrocarbon base.

Natural waxes suitable for grease impregnating agents include beeswax, montana wax and carnaúba wax.

Synthetic waxes suitable for fat impregnating agents include:

-

Polyethylene waxes and ethylene copolymer waxes, such as can be obtained by free radical polymerization of ethylene or free radical copolymerization of ethylene with, for example, (meth) acrylic acid or by Ziegler-Natta catalysis;

-

Polyisobutylene waxes

- Paraffin blends, that is mixtures of hydrocarbons having 12 or more carbon atoms and usually a melting point in the range of 25 to 45 ° C. Mixtures of paraffin of this type can be obtained in refineries or by cracking, for example, and are known to those skilled in the art as residual paraffinic wax and sasol wax; as well as

- montana ester waxes.

Natural oils suitable for fat impregnating agents mainly include liquid triglycerides at room temperature, such as fish oil, beef leg oil, olive oil, cottonseed oil, castor oil, sunflower oil and sunflower oil. peanut or peanut.

Synthetic oils suitable for fat impregnating agents include mainly white oil, paraffin oil, functionalized paraffins such as, for example, chlorinated or sulfochlorinated paraffins as well as polyalkylene glycols such as, for example, polyethylene glycol.

Natural fats suitable for fat impregnating agents mainly include native triglycerides, solid at room temperature, such as lanolin, shellac wax and mixtures thereof.

Examples of polyisobutene-based fat impregnating agents are described in WO 03/023070.

Other examples of fat impregnating agents are described in WO 03/023069.

In addition to hydrocarbon bases, grease impregnating agents may also contain surfactants. These include all emulsifiers contained in grease impregnating agents, tanning agents, water repellent agents and other auxiliary agents for leather preparation. The surfactants can be nonionic, anionic, cationic or also zwitterionic in nature. In the fat impregnating agents according to the invention, non-ionic or anionic substances can be conveniently employed as emulsifiers, preferably fatty alcohols (ie mixtures of alcohols with 10 to 25 C atoms) or oxalkylated fatty alcohols with 5 to 100 groups of alkylene oxide as non-ionic emulsifiers or their sulfates or phosphates as anionic emulsifiers, mainly sodium, potassium or ammonium salts of anionic emulsifiers.

As water-repellent agents in the process of the invention, all known water-repellent agents can be used for leather production, mainly commercially used systems, as described in M. Hollstein: Bibliothek des Leders (Leather Library), volume 4 - Degreasing , fat, hydrophobicization of leather, 1983.

Commercially available products mainly contain one or more of the components listed below:

one.

 Copolymers of alpha-olefins with dicarboxylic acid anhydrides, such as maleic anhydride

2.

 Paraffins

3.

 White oils

Four.

 Simple silicones

5.

 Functionalized Silicones

6.

 Emulsifiers

In addition, the hydrophobic agents may contain all the components that have been described for the fat impregnating agents.

In addition to other components of fat impregnating agents, silicon-based hydrophobic agents and hydrophobic agents based on copolymers of alpha-olefins with dicarboxylic acid anhydrides have been described extensively, for example in EP-A 213480, WO 95/22627, WO 98/04748, EP-A 1087021 and WO 01168584. Other examples of hydrophobic agents are found in WO 93/17130 and EP-A 372746.

Correspondingly, to prepare the leather, tanning agents are used in the following quantities:

Polymeric tanning agent (as a solution) in amounts of up to 20% by weight, often 3-8% by weight and / or

Syntanes (calculated as powder) in amounts up to 30% by weight, often 4-12% by weight, and / or

Resin tannery (calculated as powder) up to 15% by weight, often 3-6% by weight and / or up to 30% by weight of vegetable tan, often 4-12% by weight, in which case the total amount of Tannery is usually up to 40% by weight, for example 4 to 40% by weight and often 10 to 40% by weight, in which case all data refers to the wet weight of the leather.

Fat and water-repellent impregnating agents are usually used in the following amounts: up to 20% by weight of fat impregnating agent, often 6-12% by weight and up to 20% by weight of water-repellent agent, often 4-8% by weight, each case with respect to the wet weight of the leather.

Dyeing can be done both in a single stage and in 2 stages. In a two-stage dyeing, in a first stage the leather is first treated with the immersion liquid containing dye at values below 7.5, for example pH 3 to 7.4 and preferably at pH values in the range from 4 to 7.4. This step serves for uniform distribution of the dye in the cross section of the leather. Then in the second stage, at pH values of at least 8 to 11, mainly 8.5 to 10.5 and especially 8.5 to 10, the dye is fixed in the manner described above. It is also possible to perform the dyeing in a one-stage process without preceding a distribution stage to the fixing stage.

Optionally, after dyeing, a washing process is carried out to remove dye that has not been chemically bonded, as well as impurities contained in the dye, for example dyes that do not contain any group A. However, this washing process is not Required since in many cases a quantitative or almost quantitative fixation of the dye is already present. Whenever a washing process is carried out, after dyeing, the leather is washed with water 1 or several times, for example 1 to 6 times and mainly 1 to 4 times. The amount of water usually is not more than 300% by weight, with respect to the reduced weight of the semi-finished product, for example 100 to 300% by weight. The washing duration of the individual washing step will usually be 5 to 60 min and mainly 10 to 30 min.

In the washing process, non-ionic, anionic, cationic or zwitterionic auxiliary agents can also be used. Commercially common auxiliary agents are preferred, for example based on polyvinylformamides, polyvinyl pyrolidones, vinyl pyrollidone / vinylimidazole copolymers or may be based on dicarboxylic acid condensates or dicarboxylic acid anhydrides with amines or naphthalene sulfonic acid with formaldehyde. Auxiliaries of this type are described for example in EP 0459 168, EP 0 520 182, US 5,342,916 and US 5,186 846.

The use of auxiliaries is then particularly reasonable if colored by-products are contained in the dye or if colored by-products originate during fixation. The auxiliaries ensure that they are washed no more than three times, possibly only twice or, ideally only once, in order to remove all secondary components quantitatively or almost quantitatively.

Leather dyeing, including re-tanning, greasing and post-treatment, is otherwise carried out in a known manner, for example by dyeing on a drum or on a paddle wheel. Processes of this type are described in detail in the prior art, for example in: "Bibliothek des Leders" (Leather Library), volume 3 (Tanning, tanning and retanning) [1985], volume 4 (Degreasing, greasing and hydrophobicization in leather production) [1987] & volume 5 (Leather dyeing) [1987] Editorial Umschau Verlag; "Leather Technicians Handbook", 1983, by J. H. Sharfouse, published by Leather Producers Association; and "Fundamentals of Leather Manufacturing", 1993, by E. Heidenmann, published by Eduard Roether KG.

Dyeing is usually done after pre-tanning, that is before, during or after retanning. Dyeing can be done both in the same bath as the retanning as well as in a separate bath. The dyeing is preferably carried out before retanning. Preferably after dyeing and before post-cure and fat impregnation one or more of the steps described above are performed.

A dyeing and retanning operation usually follows a grease impregnation operation in order to establish the desired sensory properties of the leather. However, post-cure and fat impregnation can also be performed in a process step. The fat impregnation step can be performed at any stage of the wet terminal process and is preferably performed at the end of the wet terminal process.

5 As a rule, both fat impregnation and retanning are fixed at the end of the process by acidification, that is after dyeing and optionally after retanning and fat impregnation a final acidification is carried out. To acidify, the pH value of the aqueous treatment bath is usually adjusted by adding an acid, mainly formic acid, to a value below 3.7.

Through the process of the invention, all types of leather can be dyed, that is,

10 semi-finished non-tanned products, such as tanned leather with metal oxide (wet-blue in the case of chrome oxide tanning and wet-white in the case of tanning with aluminum oxide) and organically, for example tanned leather with aldehyde (wet-white) or leather tanned with vegetables, as well as re-dried semi-finished products such as bark or raw leather (bark).

The process of the invention makes possible mainly the production of dyed leather for articles

15 any leather, for example from the footwear, clothing, cars, gloves and furniture sector. The method of the invention also allows the production of leather for wallets and reptile leather for accessories. The establishment of the sensory, mechanical and physical properties, required for the respective leather article, is carried out in a known manner by a suitable selection for the respective article of the auxiliary agents, grease impregnating agents, water repellent agents and retanning agents. .

The dyed leather according to the method of the invention is distinguished, even at very large dye depths, by an excellent level of color fixation. Particularly outstanding are the fixations against friction and mainly fixations against washing, sweat and migration, which cannot be achieved, or can be achieved but on a very small scale, in conventionally dyed leathers. In migration fixation tests that even at high humidity and high temperatures, that is above 50 ° C, for example 60 to 100 ° C, the

25 dyed leathers according to the method of the invention do not show, or almost do not show, a fouling of the contact material.

The qualitative and quantitative determination by UV / VIS and HPLC spectroscopy shows that with the dyes of the invention, degrees of fixation are achieved between 85 and 100% and often above 90%.

The following examples should illustrate the invention without limiting it:

30 Example 1a:

image 1

1) 1 mol of MSP (3- (2-sulfatoethylsulfonyl) -6-aminobenzenesulfonic acid) was suspended in ice water and at pH <1 and at a temperature of 0-5 ° C it was diazotized with excess sodium nitrite and hydrochloric acid. 1 mole of gamma acid was dissolved in 25% sodium hydroxide and then by adding 21% hydrochloric acid by weight, the

PH value below 1. Gamma acid is obtained by precipitation. The diazotized MSP was poured into this suspension. The reaction mixture was stirred at pH <1 for one hour until no more diazotized MSP or free gamma acid could be detected. Then, the pH value was raised to 3 to 8 by the addition of 15% by weight sodium carbonate solution.

2) 1 mole of 4,6-dinitro-2-aminophenol was diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and a temperature of 0-5 ° C and then added to the reaction mixture obtained in the step 1). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, 0.20-0.30 mol of chromium (III) sulfate was added to the reaction mixture and stirring continued for 1 hour. He

The dye was precipitated by saturation of the solution with NaCl and filtered with suction.

In a manner similar to example 1a, the metal complexes of the dyes of the general formula Dk-N = NNapht-N = NA (= dyes of the general formula II where r = k = 0, n = 1), where Dk can be obtained represents a residue derived from diazo components DK1 to DK9, DK13, DK14, DK26, DK27, DK39 to DK41 or D58 or represents a residue derived from A1 to A12, Napht represents one of the bivalent residues II-2, II-4, II -6, II-8, II

10 10, II-12 and II-14 and A means one of residues A1 to A12. The coupling of the residue A-N = N- is carried out in an ortho position towards the amino group of residues II-2, II-4, II-6, II-8, II-10, II-12 and II-14. Examples of these are reported in the following table 1.

Example 2a:

The reaction was carried out according to the method described in example 1a with the difference that no reaction was carried out with the chromium salts.

In a manner similar to example 2a, the dyes of the general formula Dk-N = N-Napht-N = NA (= dyes of the general formula II where r = k = 0, n = 1) could be obtained, where Dk represents one of the diazo components DK1 to DK83 or represents a residue derived from A1 to A12, Napht represents one of the bivalent residues II-2, II-4, II6, II-8, II-10, II-12 and II-14 and A means one of the residues A1 to A12. The coupling of the residue A-N = N- is carried out

20 in ortho position towards the amino group of residues II-2, II-4, II-6, II-8, II-10, II-12 and II-14. Examples of these are indicated in the following table 1.

Table 1:

Example-No.

Dk Napht TO Metal

1st

DK5 DK42 A1 Cr

1 B

DK41 DK42 A1 Cr

1 C

DK41 DK44 A1 Cr

1d

DK5 DK44 A1 Cr

1e

DK3 DK44 A1 Cr

1f

DK5 DK43 A7 Cr

2nd

DK5 DK42 A1 -

2b

DK5 DK44 A1 -

2 C

DK12 DK44 A1 -

2d

A1 DK59 A1 -

2e

A1 DK44 A1 -

2f

A7 DK44 A7 -

2 g

A4 DK44 A4 -

2h

A6 DK44 A6 -

Example-No.

Dk Napht TO Metal

2i

A1 DK44 A6 -

2j

A1 DK45 A1 -

2k

A6 DK45 A6 -

Example 3:

image 1

1) 1 mole of 4,6-dinitro-2-aminophenol was diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and a temperature of 0-5 ° C. 1 mole of gamma acid was dissolved in 25% sodium hydroxide and then the value of

5 pH below 1 by adding 21% hydrochloric acid by weight. The gamma acid precipitated. To this suspension, diazotized 4,6-dinitro-2-aminophenol was poured. The reaction mixture continued to stir for one hour at pH <1 until no more azotized 4,6-dinitro-2-aminophenol or free gamma acid could be detected. The pH value was then raised by adding 15% by weight sodium carbonate solution to 3 to 8.

2) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at

10 pH <1 and at a temperature of 0-5 ° C and then added to a reaction mixture obtained in step 1). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction NaCl was added and the dye precipitated in this manner was filtered by suction.

Similar to example 3, the dyes of the general formula Dk-N = N-Napht-N = NA or their metal complexes (= dyes of the general formula II where r = k = 0, n = 1) can be obtained, where Dk represents a residue

15 derived from diazo components DK1 to DK83, Napht represents one of the bivalent residues II-2, II-4, II-6, II-8, II-10, II-12 and II-14 and A represents one of the residues A1 to A12. The coupling of the residue A-N = N- is carried out in an ortho position towards the hydroxy group of residues II-2, II-4, II-6, II-8, II-10, II-12 and II-14.

Example 4a:

image 1

20 Method A

1) 1 mol of trichloro-1,3,5-triazine was suspended in water at a temperature of 0-5 ° C. 1 mol of H-acid was dissolved in 25% sodium hydroxide and added dropwise to the trichlorotriazine suspension at a pH value of 1-4 and continued stirring for 30 min.

3) 1 mole of 5-nitro-2-aminophenol was diazotized at pH <1 and at a temperature of 0-5 ° C with excess sodium nitrite and hydrochloric acid and added to the reaction mixture obtained in step 2) . The pH value was maintained by

5 addition of 10% sodium hydroxide by weight between 3-8. After completion of the reaction, 0.20-0.30 mol of chromium (III) sulfate was added to the reaction mixture and stirring continued for 1 hour. The dye was precipitated by saturation of the solution by addition of NaCl and filtered with suction.

Method B

1) 1 mole of ticlorotriazine was suspended at a temperature of 0-5 ° C in water. 1 mole of acid - H dissolved in

10 25% by weight sodium hydroxide and trichlorotriazine suspension was added dropwise to a pH value of 1-4 and continued stirring for 30 min.

2) 1 mole of 5-nitro-2-aminophenol was diazotized at pH <1 and a temperature of 0-5 ° C with excess sodium nitrite and hydrochloric acid and added to the reaction mixture obtained in step 1) . The pH value was maintained between 3-8 by the addition of 10% by weight sodium hydroxide.

3 3) 1 mol of MSP was suspended in ice water and added to the reaction mixture obtained in step 2). Then, the pH value was adjusted between 5-8 by the addition of sodium carbonate and continued to stir for 1 hour. After completion of the reaction, 0.20-0.30 mol of chromium (III) sulfate was added to the reaction mixture and continued to stir for 1 hour. The dye was precipitated by saturation of the solution by addition of NaCl and filtered with suction.

In a manner similar to example 4a, the metal complexes of the dyes of the general formula Dk-N = NNapht-NH-Tr-NH-A (= dyes of the general formula V where r = p = 0), where Dk can be obtained represents a residue derived from the diazo components DK1 to DK9, DK13, DK14, DK26, DK27, Dk39-Dk41, Dk58, Napht represents one of the bivalent residues II-1, II-3, II-5, II-7, II- 9, II-11 and II-13, Tr is a 2-chloro-1,3,5-triazin-4,6-diyl residue and A means one of residues A1 to A12. The coupling of the residue Dk-N = N- is carried out in ortho position towards the

25 hydroxyl group of residues II-1, II-3, II-5, II-7, II-9, II-11 and II-13.

Example 5a:

The reaction was carried out according to the method described in example 4a with the difference that no reaction occurred with chromium salts.

Example 5b:

image 1

30

Method A:

1) 1 mol of 5-nitro-2-aminophenol was diazotized at pH <1 and a temperature of 0-5 ° C with excess sodium nitrite and hydrochloric acid and reacted with a solution of 1 mol of Cleve-7 acid in 25% sodium hydroxide. The pH value was kept below 3.

2) 1 mol of trichlorotriazine was suspended at a temperature of 0-5 ° C in water. To this suspension, the reaction mixture obtained in step 1) was added dropwise at a pH value of 1-4 and continued to stir for 30 min.

Method B:

5 1) 1 mol of trichlorotriazine was suspended at a temperature of 0-5 ° C in water. 1 mol of MSP was suspended in ice water and was added to the trichlorotriazine suspension at a pH value of 1-4 and continued to stir for 30 min.

2) 1 mol of 5-nitro-2-aminophenol was diazotized at pH <1 and a temperature of 0-5 ° C with excess sodium nitrite and hydrochloric acid and reacted with a solution of 1 mol of Cleve-7 acid in 25% sodium hydroxide. The pH value was kept below 3.

3) The product obtained in step 2) was added to the reaction mixture obtained in step 1). The pH value was then adjusted between 5-8 by the addition of sodium carbonate and continued to stir for 1 hour. After completion of the reaction the dye was precipitated by addition of NaCl and filtered with suction.

In a manner analogous to examples 5a and 5b, dyes of the general formula Dk1-N = NNapht-NH-Tr-NH-Dk2 or their metal complexes (= dyes of the general formula V where r = p = 0) can be obtained where Dk1 and

15 Dk2 respectively represent a residue derived from diazo components DK1 to DK83 or represent a residue derived from A1 to A12, in which case at least one of the residues Dk1 or Dk2 represents a residue of the formula A, Napht represents one of the bivalent residues II-1, II-3, II-5, II-7, II-9, II-11, II-13, II-15 and II-16, Tr is a 2-chloro-1,3,5- residue triazin-4,6-diyl and A means one of residues A1 to A12. The coupling of the residue Dk1N = N- is carried out in an ortho position towards the hydroxyl group of residues II-1, II-3, II-5, II-7, II-9, II-11 and II-13.

20 Example 6a:

image 1

Method A:

1) 1 mol of trichlorotriazine was suspended at a temperature of 0-5 ° C in water. 1 mole of gamma acid was dissolved in 25% sodium hydroxide and added dropwise to the trichlorotriazine suspension at a pH value of 1-4 and followed

25 stirring for 30 min.

2) 1 mol of anthranilic acid was suspended in ice water and added to the reaction mixture obtained in step 1). The pH value was then adjusted between 5 and 8 by the addition of sodium carbonate and continued to stir for 1 hour.

3) 1 mol of acid H was diazotized at pH <1 and a temperature of 0-5 ° C with excess sodium nitrite and acid

30 hydrochloric and was added to the reaction mixture obtained in step 2). The pH value was maintained between 3-8 by the addition of 10% by weight sodium hydroxide.

4) 1 mol of MSP was suspended in ice water, diazotized at pH <1 and a temperature of 0-5 ° C with excess sodium nitrite and hydrochloric acid and added to the reaction mixture obtained in step 3) . The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After the reaction is over the

Dye was precipitated by addition of NaCl and filtered with suction.

1) 1 mol of trichlorotriazine was suspended at a temperature of 0-5 ° C in water. 1 mol of gamma acid was dissolved in 25% sodium hydroxide and added dropwise to the trichloro-triazine suspension at a pH value of 1 to 4 and continued to stir for 30 min.

2) 1 mol of anthranilic acid was suspended in ice water and added to the reaction mixture obtained in step 5 1). Then, the pH value was adjusted between 5 and 8 by the addition of sodium carbonate and continued to stir for 1 hour.

3) 1 mol of acid H was dissolved in 25% sodium hydroxide and acetylated with 1.1-1.5 mol of acetic anhydride.

4) 1 mol of MSP was suspended in ice water and diazotized at pH <1 and a temperature of 0-5 ° C with excess sodium nitrite and hydrochloric acid and added to the reaction mixture obtained in step 3) . The pH value was adjusted

10 between 4 and 7 by addition of sodium carbonate and maintained. After completion of the coupling, the pH value was adjusted below 1 by the addition of 21% hydrochloric acid by weight and the reaction mixture was heated to 85-95 ° C. In this the acetyl group dissociated.

5) The product obtained in step 4) was diazotized at pH <1 and a temperature of 0-5 ° C with excess sodium nitrite and hydrochloric acid and added to the reaction mixture obtained in step 2). The pH value was adjusted between 4 and 7

15 by adding sodium carbonate and held. After the end of the reaction, the reaction mixture was ultrafiltered and dried.

In a manner analogous to example 6a, the dyes of the general formula AN = NPN = N-Napht1NHTr-NH-Dk or their metal complexes (= dyes of the general formula V where r = 0, p = 1 and P = Napht2 can be obtained ), where Dk represents a residue derived from diazo components DK1 to Dk83, P and Napht1 independently one of

The other represents one of the bivalent residues II-1, II-3, II-5, II-7, II-9, II-11, II-13, II-15 and II16 or represents a residue derived from the DK3 diazo components , DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK21 bis DK27, DK29, DK30, DK33, DK36, DK38, or DK39, Tr is a 2-chloro-1,3,5-triazin- residue 4,6-diyl and A means one of residues A1 to A12. The coupling of the residues A-N = N- and A-N = N-Napht2-N = N- is carried out in an ortho position towards the hydroxyl group in Napht2 or Napht1. Examples of this are indicated in the following table 2.

Table 2 1) 1 mol of trichlorotriazine was suspended in water at a temperature of 0-5 ° C and to this suspension 1 mol of paramine acid was added at einem pH value of 1-4 and continued to stir for 30 min.

Example No.

TO P Napht1 Dk Metal

6th

A1 DK44 DK42 DK4 -

6b

A1 DK39 DK43 DK5 Cr

6c

A1 DK4 DK42 DK17 Cr

6d

A1 DK27 DK59 DK4 Cr

6e

A7 DK44 DK42 DK4 -

6f

A2 DK44 DK42 DK4 -

6g

A4 DK44 DK42 DK4 -

6h

A6 DK27 DK59 DK4 -

image 1

2) 1 mol of anthranilic acid was suspended in ice water and added to the reaction mixture obtained in the step

5 1). Then, the pH value was adjusted between 5 and 8 by adding sodium carbonate between 5 and 8 and continued to stir for 1 hour. The reaction product was diazotized by adding excess sodium nitrite and hydrochloric acid at pH <1 and a temperature of 0-5 ° C.

3) 1 mol of acid K was dissolved in 25% sodium hydroxide and added to the reaction mixture obtained in step 2). The pH value was kept below 2.

10 4) 1 mol of MSP was suspended in ice water and by adding excess sodium nitrio and hydrochloric acid at pH <1 and a temperature of 0-5 ° C. Then, the diazotized MSP was added to the reaction mixture obtained in step 3). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction the dye was precipitated by addition of NaCl and filtered with suction.

In a manner analogous to Example 7, dyes of the general formula A-N = N-Napht1-N = N-R can be obtained

15 NH-Tr-NH-Dk or its metal complexes (= dyes of the general formula V where p = 0, r = 1), where Dk represents a residue derived from the diazo components DK1 to DK83, Napht1 represents one of the bivalent residues II-2, II-4, II-6, II-8, II-10, II-12 and II-14, R represents DK21, where Q = H, or represents a bivalent residue derived from Kk5 and Kk14 to Kk16, Tr is a 2-chloro-1,3,5-triazin-4,6-diyl residue and A means one of residues A1 to A12. The coupling of the residue A-N = N- is carried out in an ortho position towards the hydroxyl group in Napht1.

20 Example 8:

image 1

1) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and reacted with an aqueous solution of 1 mol of methanol. The pH value was kept below 3.

2) 1 mol of trichlorotriazine was suspended in water at a temperature of 0-5 ° C and the reaction mixture obtained in step 1) was added to this suspension at a pH value of 1 to 4 and added for 30 min.

3) 1 mol of paraminic acid was suspended in ice water and added to the reaction mixture obtained in step 2). Then, the pH value was adjusted between 5 and 8 by the addition of sodium carbonate and continued to stir for 1 hour. The reaction product was diazotized by the addition of excess sodium nitrite and hydrochloric acid at pH <1 and a temperature of 0-5 ° C.

In a manner analogous to Example 8, dyes of the general formula A-N = N-R-NH-Tr-NH-P can be obtained

5 N = NNapht-N = NP-NH-Tr-NH-RN = NA or its metal complexes (= dyes of the general formula X where Dk1 = Dk2 = A, k = n = 1), where Napht represents one of the bivalent residues II-2, II-4, II-6, II-8, II-10, II-12 and II-14, P represents DK21, where Q = H, or represents a bivalent residue derived from Kk5 and Kk14 a Kk16, R represents a bivalent residue derived from DK22 to DK25 or represents a bivalent residue II-1, II-3, II-5, II-7, II-9, II-11, II-13, II15 or II-16 , Tr is a 2-chloro-1,3,5-triazin-4,6-diyl residue and A means one of residues A1 to A12.

10 Example 9a:

image 1

1) 1 mol of p-nitroaniline was dissolved in 21% hydrochloric acid by weight, then diazotized with excess sodium nitrite at pH <1 and a temperature of 0-5 ° C and then added to a suspension of 1 mole of anthranilic acid and ice water. The reaction mixture was stirred at pH <2 and T <10 ° C for 1 hour.

15 2) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and a temperature of 0-5 ° C and reacted with a solution of 1 mol of cleve acid -7 in 25% sodium hydroxide. The pH value was kept below 3.

3) 1 mol of trichlorotriazine was suspended at a temperature of 0-5 ° C in water and to this suspension the reaction mixture obtained in step 1) was added at a pH value of 1 to 4 and continued to stir for 30 min.

4) The product obtained in step 2) was added to the reaction mixture obtained in step 3). The pH value was then adjusted between 5-8 by the addition of sodium carbonate and continued to stir for 1 hour. After completion of the reaction, the dye was precipitated by addition of NaCl and filtered with suction.

In a manner analogous to example 9a, the dyes of the general formula Dk1-N = NP-NH-Tr-NHRN = N-Dk2 or their metal complexes (= dyes of the general formula VI) can be obtained, where Dk1 and Dk2 respectively represent a residue derived from the diazo components DK1 to DK83 or represent a residue derived from A1 to A12, in which case at least one of the residues Dk1 or Dk2 represents a residue of the formula A, P and R represent a bivalent derivative derived from DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK21 to DK27, DK29, DK30, DK33, DK36, DK38, DK39 or DK60 to DK83 or represent one of the bivalent residues II-1, II-3, II-5, II-7, II9, II-11, II-13, II-15 or II-16, Tr is a 2-chloro-1,3,5-triazin-4,6-diyl residue and A means one one of the waste A1 to

30 A12. The coupling of the residue A-N = N is carried out in ortho position towards the hydroxyl group in II-1, II-3, II-5, II-7, II9, II-11 and II-13. Examples of dyes of this type are indicated in table 3.

Table 3:

Example No.

Dk1 P R Dk2 Metal

9a

A1 DK46 DK4 DK17 -

9b

A1 DK42 DK4 DK19 -

9c

DK5 DK42 DK4 A1 Cr

9d

DK4 DK43 DK4 A1 Co

Example No.

Dk1 P R Dk2 Metal

9e

DK40 DK59 DK22 A1 Cr

9f

DK5 DK44 DK22 A1 Cr

9g

A7 DK46 DK4 DK17 -

9h

DK5 DK42 DK4 A4 Cr

Example 10:

image 1

1) 1 mol of trichlorotriazine was suspended in water at a temperature of 0-5 ° C and to this suspension 1 mol 5 of H acid was added which had previously been dissolved in 25% sodium hydroxide at a pH value of 1 to 4 and kept stirring for 30 min.

2) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and added to the reaction mixture obtained in step 1) . The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide.

10 3) 0.5 mol of 4,4-diaminodiphenylsulfamide was suspended in water and added to the reaction mixture obtained in step 2). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, the dye was precipitated by addition of NaCl and filtered with suction.

In a manner analogous to Example 10, dyes of the general formula A-N = N-Napht-NH-Tr can be obtained

15 NH-Tk-NH-Tr-NH-Napht-N = NA or its metal complexes (= dyes of the general formula IX where DK1 = Dk2 = A), where Napht represents one of the bivalent residues II-1, II- 3, II-5, II-7, II-9, II-11 or II-13, Tr is a 2-chloro-1, 3,5-triazin-4,6-diyl residue, Tk represents a bivalent residue derived from a tetrazocomponent Tk1 to Tk20 and A means one of residues A1 to A12. The coupling of the residue A-N = N- is carried out in an ortho position towards the hydroxyl group in Napht.

20 Example 11a:

image 1

1) 1 mole of 4,4-diaminodiphenylsulfamide was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. 1 mol of acid I was dissolved in 25% sodium hydroxide and added to the solution of tetrazotized 4,4-diaminodiphenylsulfamide. The pH value was kept below 3 at the same time by the addition of hydrochloric acid.

5 2) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. Then, the reaction mixture was added to the reaction mixture obtained in step 1). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide.

3) 1 mol of methanol was added to the reaction mixture obtained in step 2) and the pH value was maintained between 10 3 and 8 by the addition of 10% by weight sodium hydroxide.

4) 1 mol of trichlorotriazine was suspended in water at a temperature of 0-5 ° C. To this suspension was added by dosing 1 mol of anthranilic acid and at a pH value of 1-4 it continued to stir for 30 min.

5) The product obtained in step 4) was added to the reaction mixture obtained in step 3). The pH value was then adjusted between 5 and 8 by the addition of sodium carbonate and continued to stir for 1 hour. After

At the end of the reaction, the dye was precipitated by the addition of NaCl and filtered with suction.

Example 11b:

image 1

1) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. 1 mol of acid I was dissolved in 25% sodium hydroxide and added to the

20 reaction mixture of diazotized MSP. The pH value was kept below 2.

2) 1 mole of 4,4-diaminodiphenylsulfamide was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and added to the reaction mixture obtained in step 1). The pH value was maintained between 3-8 by the addition of 10% by weight sodium hydroxide.

3) 1 mol of methanol was added to the reaction mixture obtained in step 2) and the pH value was maintained between 3-8 by adding 10% by weight sodium hydroxide between 3-8.

4) 1 mol of trichlorotriazine was suspended in water at a temperature of 0-5 ° C. To this suspension was added by dosing 1 mol of anthranilic acid and at a pH value of 1-4 it continued to stir for 30 min.

5) The product obtained in step 4) was added to the reaction mixture obtained in step 3). The pH value was then adjusted between 5 and 8 by the addition of sodium carbonate and continued to stir for 1 hour. After

After the reaction was over, the dye was precipitated by addition of NaCl and filtered with suction.

In a manner analogous to examples 11a and 11b, dyes of the general formula AN = N-Napht-N = N-Tk-N = NP-NH-Tr-NH-Dk or their metal complexes (= dyes of the general formula VII where DK1 = A), where Dk represents a residue derived from diazocomponents DK1 to DK83, Napht represents one of the bivalent residues II-1, II-3, II-5, II-7, II-9, II -11 or II-13, Tr is a 2-chloro-1,3,5-triazin-4,6-diyl residue, Tk represents

A bivalent residue derived from a tetrazo component Tk1 to Tk20 and A means one of residues A1 to A12. The coupling of the residue AN = N- is carried out in ortho position towards the hydroxyl group in Napht, when the reaction is carried out as indicated in example 11a, and in ortho position towards the amino group in Napht, when the reaction it is carried out as indicated in example 11b.

image 1

Method A

1) 1 mole of 4,4-diaminodiphenylsulfamide was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at

5 a temperature of 0-5 ° C. 1 mol of H-acid was dissolved in 25% sodium hydroxide and added dropwise to the solution of tetrazotized 4,4-diaminodiphenylsulfamide. The pH value was maintained at the same time below 3 by the addition of hydrochloric acid.

2) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. Then, the reaction mixture was added to the reaction mixture

10 obtained in step 1). The pH value was maintained between 3 and 8 by the addition of 15% by weight aqueous soda solution.

3) 1 mol of methane acid was added to the reaction mixture obtained in step 2) and the pH value was maintained between 3 and 8 by adding 15% by weight soda solution. After completion of the reaction, the dye was precipitated by addition of NaCl and filtered with suction.

15 Method B:

1) 1 mole of 4,4-diaminodiphenylsulfamide was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. 1 mol of acid H was dissolved in 25% sodium hydroxide and added dropwise to the reaction mixture of 4,4-diaminodiphenylsulfamide. The pH value was kept below 3.

2) 1 mol of methane acid was added to the reaction mixture obtained in step 1) and the pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide.

3) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and a temperature of 0-5 ° C. Then the reaction mixture was added to the reaction mixture obtained in step 2). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, the dye was precipitated by addition of NaCl and filtered with suction.

In a manner analogous to Example 12a, the dyes of the general formula A-N = N-Napht1-N = N-TkN = NKk can be obtained. (= dyes of the general formula II where r = k = 1, n = 0), where Kk represents a residue derived from the coupling components Kk1 to Kk67, DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15 , DK18, DK21 to DK27, DK29, DK30, DK33, DK36, DK38, DK39 or DK42 to DK83, Napht1 represents one of the bivalent residues II-2, II-4, II-6, II-8, II-10, II-12 and II-14, Tk represents a bivalent residue derived from one of the tetrazo components Tk1 a

30 Tk20 and A means one of the residues A1 to A12. The coupling of the residue A-N = N-takes place ortho towards the hydroxyl group in Napht1. Examples of these are compiled in Table 4.

Table 4

Example No.

TO Napht1 Tk Kk

12th

A1 DK44 Tk18 Kk15

Example No.

TO Napht1 Tk Kk

12b

A1 DK44 Tk18 Kk5

12c

A1 DK44 Tk18 Kk2

12d

A1 DK44 Tk18 Kk3

12e

A1 DK44 Tk18 Kk6

12f

A1 DK44 Tk18 Kk1

12g

A1 DK44 Tk18 Kk4

12h

A1 DK44 Tk18 Kk7

12i

A1 DK44 Tk18 Kk9

12j

A1 DK44 Tk18 Kk10

12k

A1 DK44 Tk18 Kk14

12l

 A1 DK44 Tk18 Kk16

12m

A1 DK44 Tk18 Kk26

12n

A1 DK44 Tk18 Kk27

12th

A1 DK44 Tk18 Kk40

12p

A1 DK44 Tk18 Kk46

12q

A1 DK44 Tk18 Kk48

12r

A1 DK44 Tk18 Dk4

12s

A1 DK44 Tk18 Dk11

12t

A1 DK44 Tk18 Dk18

12u

A1 DK44 Tk18 Dk29

12v

A1 DK44 Tk18 Dk30

12z

A1 DK44 K18 Dk39

12aa

A1 DK44 Tk16 Kk5

12ab

A1 DK44 Tk16 Kk3

12ac

A1 DK44 Tk16 Kk4

12ad

A1 DK44 K16 Dk4

Example No.

TO Napht1 Tk Kk

12ae

A1 DK44 Tk19 Kk5

12af

A1 DK45 Tk18 Kk5

12ag

A2 DK44 Tk18 Kk5

12ah

A7 DK44 Tk18 Kk15

12ai

A4 DK44 Tk18 Kk15

12aj

TO 5 DK45 Tk18 Kk10

12ak

A9 DK45 Tk18 Kk14

12al

A10 DK45 Tk18 Kk16

12 am

A11 DK45 Tk18 Kk26

12an

A1 DK44 Tk18 Kk11

12th

A1 DK44 Tk18 Kk51

12ap

A1 DK44 Tk18 Kk52

12aq

A1 DK44 Tk18 Kk53

12ar

A1 DK44 Tk18 Kk54

12th

A1 DK44 Tk18 Kk55

12at

A1 DK44 Tk18 Kk56

12au

A1 DK44 Tk18 Kk57

12av

A1 DK44 Tk18 Kk58

12aw

A1 DK44 Tk18 Kk59

12ax

A1 D44 Tk18 Kk60

12ay

A1 DK44 Tk18 Kk61

12az

A1 DK44 Tk18 Kk62

12ba

A1 DK44 Tk18 Kk63

12bb

A1 DK44 Tk18 Kk64

12bc

A1 DK44 Tk18 DK66

Example No.

TO Napht1 Tk Kk

12bd

A1 DK45 Tk18 Kk1

12be

A1 DK45 Tk18 Kk2

12bf

A1 DK45 Tk18 Kk3

12bg

A1 DK45 Tk18 Kk4

12bh

A1 DK45 Tk18 Kk6

12bi

A1 DK45 Tk18 Kk7

12bj

A1 DK45 Tk18 Kk10

12bk

A1 DK45 Tk18 Kk11

12bl

A1 DK45 Tk18 Kk14

12bm

A1 DK45 Tk18 Kk15

12bn

A1 DK45 Tk18 Kk16

12bo

A1 DK45 Tk18 Kk51

12bp

A1 DK45 Tk18 Kk53

12bq

A1 DK45 Tk18 Kk54

12br

A1 DK45 Tk18 Kk55

12bs

A1 DK45 Tk18 Kk56

12bt

A1 DK45 Tk18 Kk61

12bu

A1 DK45 Tk18 Kk62

12bv

A1 DK45 Tk18 Kk63

12bw

A1 DK45 Tk18 Kk64

12bx

A1 DK45 Tk18 DK66

12by

A1 DK44 Tk16 Kk10

12bz

A1 DK44 Tk16 Kk11

12ca

A1 DK44 Tk16 Kk14

12cb

A1 DK44 Tk16 Kk15

Example No.

TO Napht1 Tk Kk

12cc

A1 DK44 Tk16 Kk16

12cd

A1 DK44 Tk16 Kk51

12ce

A1 DK44 Tk16 Kk53

12cf

A1 DK44 Tk16 Kk54

12cg

A1 DK44 Tk16 Kk55

12ch

A1 DK44 Tk16 Kk56

12ci

A1 DK44 Tk16 Kk61

12cj

A1 DK44 Tk16 Kk62

12ck

A1 DK44 Tk16 Kk63

12cl

A1 DK44 Tk16 Kk64

12cm

A1 DK44 Tk16 DK66

12cn

A1 DK44 Tk19 Kk2

12co

A1 DK44 Tk19 Kk3

12cp

A1 DK44 Tk19 Kk10

12cq

A1 DK44 Tk19 Kk11

12cr

A1 DK44 Tk19 Kk14

12cs

A1 DK44 Tk19 Kk15

12ct

A1 DK44 Tk19 Kk18

12cu

A1 DK44 Tk19 Kk51

12cv

A1 DK44 Tk19 Kk53

12cw

A1 DK44 Tk19 Kk54

12cx

A1 DK44 Tk19 Kk55

12cy

A1 DK44 Tk19 Kk56

12cz

A1 DK44 Tk19 Bk61

12th

A1 DK44 Tk19 Kk62

Example No.

TO Napht1 Tk Kk

12db

A1 DK44 Tk19 Kk63

12dc

A1 DK44 Tk19 Kk64

12dd

A1 DK44 Tk19 DK66

12 of

A1 DK44 Tk20 Kk2

12df

A1 DK44 Tk20 Kk3

12dg

A1 DK44 Tk20 Kk5

12dh

A1 DK44 Tk20 Kk10

12di

A1 DK44 Tk20 Kk11

12dj

A1 DK44 Tk20 Kk14

12dk

A1 DK44 Tk20 Kk15

12dl

A1 DK44 Tk20 Kk16

12dm

A1 DK44 Tk20 Kk51

12dn

A1 DK44 Tk20 Kk53

12th

A1 DK44 Tk20 Kk54

12dp

A1 DK44 Tk20 Kk55

12dq

A1 DK44 Tk20 Kk56

12dr

A1 DK44 Tk20 Kk61

12ds

A1 DK44 Tk20 Kk62

12dt

A1 DK44 Tk20 Kk63

12du

A1 DK44 Tk20 Kk64

12dv

A1 DK44 Tk20 DK66

12dw

A1 DK45 Tk16 Kk2

12dx

A1 DK45 Tk16 Kk3

12dy

A1 DK45 Tk16 Kk5

12dz

A1 DK45 Tk16 Kk10

Example No.

TO Napht1 Tk Kk

12ea

A1 DK45 Tk16 Kk11

12eb

A1 DK45 Tk16 Kk14

12ec

A1 DK45 Tk16 Kk15

12ed

A1 DK45 Tk16 Kk16

12ee

A1 DK45 Tk16 Kk51

12ef

A1 DK45 Tk16 Kk53

12eg

A1 DK45 Tk16 Kk54

12eh

A1 DK45 Tk16 Kk55

12ei

A1 DK45 Tk16 Kk56

12ej

A1 DK45 Tk16 Kk61

12ek

A1 DK45 Tk16 Kk62

12el

A1 DK45 Tk16 Kk63

12em

A1 DK45 Tk16 Kk64

12in

A1 DK45 Tk16 DK66

12o

A1 DK45 Tk19 Kk2

12ep

A1 DK45 Tk19 Kk3

12eq

A1 DK45 Tk19 Kk5

12th

A1 DK45 Tk19 Kk10

12es

A1 DK45 Tk19 Kk11

12et

A1 DK45 Tk19 Kk14

12eu

A1 DK45 Tk19 Kk15

12ev

A1 DK45 Tk19 Kk16

12ew

A1 DK45 Tk19 Kk51

12ex

A1 DK45 Tk19 Kk53

12ey

A1 DK45 Tk19 Kk54

Example No.

TO Napht1 Tk Kk

12th

A1 DK45 Tk19 Kk55

12fa

A1 DK45 Tk19 Kk56

12fb

A1 DK45 Tk19 Kk61

12fc

A1 DK45 Tk19 Kk62

12fd

A1 DK45 Tk19 Kk63

12fe

A1 DK45 Tk19 Kk64

12ff

A1 DK45 Tk19 DK66

12fg

A1 DK45 Tk20 Kk2

12fh

A1 DK45 Tk20 Kk3

12fi

A1 DK45 Tk20 Kk5

12fj

A1 DK45 Tk20 Kk10

12fk

A1 DK45 Tk20 Kk11

12fl

A1 DK45 Tk20 Kk14

12fm

A1 DK45 Tk20 Kk15

12fn

A1 DK45 Tk20 Kk16

12fo

A1 DK45 Tk20 Kk51

12fp

A1 DK45 Tk20 Kk53

12fq

A1 DK45 Tk20 Kk54

12fr

A1 DK45 Tk20 Kk55

12fs

A1 DK45 Tk20 Kk56

12ft

A1 DK45 Tk20 Kk61

12fu

A1 DK45 Tk20 Kk62

12fv

A1 DK45 Tk20 Kk63

12fw

A1 DK45 Tk20 Kk64

12fx

A1 DK45 Tk20 DK66

Example No.

TO Napht1 Tk Kk

12fy

A1 DK44 Tk16 Kk65

12fz

A1 DK44 Tk16 Kk66

12ga

A1 DK44 Tk16 Kk67

12gb

A1 DK45 Tk16 Kk65

12gc

A1 DK45 Tk16 Kk66

12gd

A1 DK45 Tk16 Kk67

12ge

A1 DK44 Tk18 Kk65

12gf

A1 DK44 Tk18 Kk66

12gg

A1 DK44 K18 Kk67

12gh

A1 DK45 Tk18 Kk65

12g

A1 DK45 Tk18 Kk66

12gj

A1 DK45 Tk18 Kk67

12gk

A1 DK44 Tk19 Kk65

12gl

A1 DK44 Tk19 Kk66

12gm

A1 DK44 Tk19 Kk67

12gn

A1 DK45 Tk19 Kk65

12go

A1 DK45 Tk19 Kk66

12gp

A1 DK45 Tk19 Kk67

12gq

A1 DK44 Tk20 Kk65

12gr

A1 DK44 Tk20 Kk66

12gs

A1 DK44 Tk20 Kk67

12gt

A1 DK45 Tk20 Kk65

12gu

A1 DK45 Tk20 Kk66

12gv

A1 DK45 Tk20 Kk67

Method A

1) 1 mole of 4,4-diaminodiphenylsulfamide was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C tetrazotiert. 1 mol of acid H was dissolved in 25% sodium hydroxide and added dropwise to the solution of tetrazotized 4,4-diaminodiphenylsulfamide. At the same time, the pH value remained below

5 of 3 by adding hydrochloric acid.

2) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. Then the reaction mixture was added to the reaction mixture obtained in step 1). The pH value was maintained between 3 and 8 by adding 15% by weight soda solution.

3) 0.45 mol of methane acid and 0.55 mol of 2,4-diamino-1-methoxybenzene was added simultaneously to the

The reaction mixture obtained in step 2) and the pH value was maintained between 3 and 8 by adding 15% by weight soda solution. After completion of the reaction, the reaction mixture was ultrafiltered and spray dried.

Method B:

1) 1 mole of 4,4-diaminodiphenylsulfamide was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. 1 mol of acid H was dissolved in 25% sodium hydroxide and added dropwise to the

The reaction mixture of tetrazotized 4,4-diaminodiphenylsulfamide. The pH value was kept below 3.

2) 0.45 mol of methane acid and 0.55 mol of 2,4-diamino-1-methoxybenzene were added simultaneously to the reaction mixture obtained in step 1) and the pH value was maintained between 3 and 8 by addition of 10% by weight sodium hydroxide.

3) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid to

20 pH <1 and at a temperature of 0-5 ° C. The reaction mixture was then added to the reaction mixture obtained in step 2). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, the dye was pre-precipitated by the addition of NaCl and filtered with suction.

In a similar way to example 12gw, the dye mixtures indicated in Table 4a of the general formula AN = N-Napht1-N = N-Tk-N = N-Kk (formula IIb where n = 0) are prepared, in which case the coupling of the residue AN = N

25 is carried out in ortho position towards the hydroxyl group in Napht1.

Table 4a:

Example No.

TO Napht1 Tk Kk *)

12gw

A1 DK44 Tk18 Kk15: Kk55 (45:55)

12gz

A1 DK44 Tk18 Kk15: Kk56 (30:70)

12ha

A1 DK44 Tk18 Kk15: Kk66 (80:20)

12hb

A1 DK44 Tk18 Kk5: Kk10 (10:90)

12hc

A1 DK44 Tk18 Kk5: Kk14 (15:85)

12hd

A1 DK44 Tk18 Kk5: Kk15 (60:40)

12he

A1 DK44 Tk18 Kk5: Kk55 (75:25)

12hf

A1 DK44 Tk18 Kk5: Kk56 (40:60)

12hh

A1 DK44 Tk18 Kk5: Kk67 (20:80)

Example No.

TO Napht1 Tk Kk *)

12hi

A1 DK44 Tk18 Kk5: DK66 (50:50)

12hj

A1 DK45 Tk18 Kk15: Kk55 (45:55)

12hk

A1 DK45 Tk18 Kk15: Kk56 (30:70)

12hl

A1 DK45 Tk18 Kk15: Kk66 (80:20)

12hm

A1 DK45 Tk18 Kk5: Kk10 (10:90)

12hn

A1 DK45 Tk18 Kk5: Kk14 (15:85)

12ho

A1 DK45 Tk18 Kk5: Kk15 (60:40)

12hp

A1 DK45 Tk18 Kk5: Kk55 (75:25)

12hq

A1 DK45 Tk18 Kk5: Kk56. (40:60)

12hr

A1 DK45 Tk18 Kk5: Kk67 (20:80)

12hs

A1 DK45 Tk18 Kk5: DK66 (50:50)

12ht

A1 DK44 Tk16 Kk5: Kk15 (45:55)

12hu

A1 DK44 Tk16 Kk15: Kk55 (45:55)

12hv

A1 DK44 Tk19 Kk15: Kk55 (45:55)

12hw

A1 DK44 Tk20 Kk15: Kk55 (45:55)

* The value indicated in parentheses indicates the molar ratio of the respective coupling components.

Example 13a:

image 1

1) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. 1 mol of acid H was dissolved in 25% sodium hydroxide and added to the reaction mixture of the diazotized MSP. The pH value was kept below 2.

2) 1 mole of 4,4-diaminodiphenylsulfamide was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and added to the reaction mixture obtained in step 1). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide.

Analogously to example 13a, dyes of the general formula A-N = N-Napht1-N = N-Tk can be obtained

5 N = NKk (= dyes of the general formula II where r = k = 1, n = 0), where Kk represents a residue derived from coupling components Kk1 to KK64, DK3, DK4, DK6, DK7, DK11, DK13 , DK14, DK15, DK18, DK21 to DK27, DK29, DK30, DK33, DK36, DK38, DK39 or DK42 to DK83, Napht represents one of the bivalent residues II-2, II-4, II-6, II-8, II-10, II-12 and II-14, Tk a bivalent residue derived from one of the tetrazo components Tk1 to Tk20 and A means one of residues A1 to A12. The coupling of the residue A-N = N- is carried out in ortho position towards the

10 amino group in Napht1. Examples of these are indicated in the following table 5.

Table 5:

Example No.

TO Napht1 Tk Kk

13th

A1 DK44 Tk18 Kk15

13b

A1 DK44 Tk18 Kk5

13c

A1 DK44 Tk18 Kk2

13d

A1 DK44 Tk18 Kk3

13e

A1 DK44 Tk18 Kk6

13f

A1 DK44 Tk18 Kk1

13g

A1 DK44 Tk18 Kk4

13h

A1 DK44 Tk18 Kk7

13i

A1 DK44 Tk18 Kk9

13j

A1 DK44 Tk18 Kk10

13k

A1 DK44 Tk18 Kk14

13l

A1 DK44 Tk18 Kk16

13m

A1 DK44 Tk18 Kk26

13n

A1 DK44 Tk18 Kk27

13th

A1 DK44 Tk18 Kk40

13p

A1 DK44 Tk18 Kk46

13q

A1 DK44 Tk18 Kk48

13r

A1 DK44 Tk18 Dk4

13s

A1 DK44 Tk18 Dk11

13t

A1 DK44 Tk18 Dk18

Example No.

TO Napht1 Tk Kk

13u

A1 DK44 Tk18 Dk29

13v

A1 DK44 Tk18 Dk30

13z

A1 DK44 Tk18 Dk39

13aa

A1 DK44 Tk16 Kk5

13ab

A1 DK44 Tk16 Kk3

13ac

A1 DK44 Tk16 Kk4

13ad

A1 DK44 Tk16 Dk4

13ae

A1 DK44 Tk19 Kk5

13af

A1 DK45 Tk18 Kk5

13ag

A2 DK44 Tk18 Kk5

13ah

A7 DK44 Tk18 Kk15

13ai

A4 DK44 Tk18 Kk15

13aj

A1 DK44 Tk16 Kk15

13ak

A1 DK44 Tk16 Kk34

13al

A7 DK44 Tk18 Kk3

13am

A7 DK44 Tk18 Kk5

13an

A6 DK45 Tk18 Kk10

13th

A8 DK45 Tk18 Kk14

13ap

A11 DK45 Tk18 Kk16

13aq

A12 DK45 Tk18 Kk26

13ar

A1 DK44 Tk18 Kk11

13th

A1 DK44 Tk18 Kk51

13at

A1 DK44 Tk18 Kk52

13au

A1 DK44 Tk18 Kk53

13av

A1 DK44 Tk18 Kk54

Example No.

TO Napht1 Tk Kk

13aw

A1 DK44 Tk18 Kk55

13ax

A1 DK44 Tk18 Kk56

13ay

A1 DK44 Tk18 Kk57

13az

A1 DK44 Tk18 Kk58

13ba

A1 DK44 Tk18 Kk59

13bb

A1 DK44 Tk18 Kk60

13bc

A1 DK44 Tk18 Kk61

13bd

A1 DK44 Tk18 Kk62

13be

A1 DK44 Tk18 Kk63

13bf

A1 DK44 Tk18 Kk64

13bg

A1 DK44 Tk18 DK66

13bh

A1 DK45 Tk18 Kk1

13bi

A1 DK45 Tk18 Kk2

13bj

A1 DK45 Tk18 Kk3

13bk

A1 DK45 Tk18 Kk4

13bl

A1 DK45 Tk18 Kk6

13bm

A1 DK45 Tk18 Kk7

13bn

A1 DK45 Tk18 Kk10

13bo

A1 DK45 Tk18 Kk11

13bp

A1 DK45 Tk18 Kk14

13bq

A1 DK45 Tk18 Kk15

13br

A1 DK45 Tk18 Kk16

13bs

A1 DK45 Tk18 Kk51

13bt

A1 DK45 Tk18 Kk53

13bu

A1 DK45 Tk18 Kk54

Example No.

TO Napht1 Tk Kk

13bv

A1 DK45 Tk18 Kk55

13bw

A1 DK45 Tk18 Kk56

13bx

A1 DK45 Tk18 Kk61

13by

A1 DK45 Tk18 Kk62

13bz

A1 DK45 Tk18 Kk63

13ca

A1 DK45 Tk18 Kk64

13cb

A1 DK45 Tk18 DK66

13cc

A1 DK44 Tk16 Kk10

13cd

A1 DK44 Tk16 Kk11

13ce

A1 DK44 Tk16 Kk14

13cf

A1 DK44 Tk16 Kk16

13cg

A1 DK44 Tk16 Kk51

13ch

A1 DK44 Tk16 Kk53

13ci

A1 DK44 Tk16 Kk54

13cj

A1 DK44 Tk16 Kk55

13ck

A1 DK44 Tk16 Kk56

13cl

A1 DK44 Tk16 Kk61

13cm

A1 DK44 Tk16 Kk62

13cn

A1 DK44 Tk16 Kk63

13co

A1 DK44 Tk16 Kk64

13cp

A1 DK44 Tk16 DK66

13cq

A1 DK44 Tk19 Kk2

13cr

A1 DK44 Tk19 Kk3

13cs

A1 DK44 Tk19 Kk10

13ct

A1 DK44 Tk19 Kk11

Example No.

TO Napht1 Tk Kk

13cu

A1 DK44 Tk19 Kk14

13cv

A1 DK44 Tk19 Kk15

13cw

A1 DK44 Tk19 Kk16

13cx

A1 DK44 Tk19 Kk51

13cy

A1 DK44 Tk19 Kk53

13cz

A1 DK44 Tk19 Kk54

13th

A1 DK44 Tk19 Kk55

13db

A1 DK44 Tk19 Kk56

13dc

A1 DK44 Tk19 Kk61

13dd

A1 DK44 Tk19 Kk62

13 of

A1 DK44 Tk19 Kk63

13df

A1 DK44 Tk19 Kk64

13dg

A1 DK44 Tk19 DK66

13dh

A1 DK44 Tk20 Kk2

13di

A1 DK44 Tk20 Kk3

13dj

A1 DK44 Tk20 Kk5

13dk

A1 DK44 Tk20 Kk10

13dl

A1 DK44 Tk20 Kk11

13dm

A1 DK44 Tk20 Kk14

13dn

A1 DK44 Tk20 Kk15

13th

A1 DK44 Tk20 Kk16

13dp

A1 DK44 Tk20 Kk51

13dq

A1 DK44 Tk20 Kk53

13dr

A1 DK44 Tk20 Kk54

13ds

A1 DK44 Tk20 Kk55

Example No.

TO Napht1 Tk Kk

13dt

A1 DK44 Tk20 Kk56

13du

A1 DK44 Tk20 Kk61

13dv

A1 DK44 Tk20 Kk62

13dw

A1 DK44 Tk20 Kk63

13dx

A1 DK44 Tk20 Kk64

13dy

A1 DK44 Tk20 DK66

13dz

A1 DK45 Tk16 Kk2

13ea

A1 DK45 Tk16 Kk3

13eb

A1 DK45 Tk16 Kk5

13ec

A1 DK45 Tk16 Kk10

13ed

A1 DK45 Tk16 Kk11

13ee

A1 DK45 Tk16 Kk14

13ef

A1 DK45 Tk16 Kk15

13eg

A1 DK45 Tk16 Kk16

13eh

A1 DK45 Tk16 Kk51

13ei

A1 DK45 Tk16 Kk53

13ej

A1 DK45 Tk16 Kk54

13ek

A1 DK45 Tk16 Kk55

13el

A1 DK45 Tk16 Kk56

13em

A1 DK45 Tk16 Kk61

13in

A1 DK45 Tk16 Kk62

13o

A1 DK45 Tk16 Kk63

13ep

A1 DK45 Tk16 Kk64

13eq

A1 DK45 Tk16 DK66

13th

A1 DK45 Tk19 Kk2

Example No.

TO Napht1 Tk Kk

13es

A1 DK45 Tk19 Kk3

13et

A1 DK45 Tk19 Kk5

13eu

A1 DK45 Tk19 Kk10

13ev

A1 DK45 Tk19 Kk11

13ew

A1 DK45 Tk19 Kk14

13ex

A1 DK45 Tk19 Kk15

13ey

A1 DK45 Tk19 Kk16

13th

A1 DK45 Tk19 Kk51

13fa

A1 DK45 Tk19 Kk53

13fb

A1 DK45 Tk19 Kk54

13fc

A1 DK45 Tk19 Kk55

13fd

A1 DK45 Tk19 Kk56

13fe

A1 DK45 Tk19 Kk61

13ff

A1 DK45 Tk19 Kk62

13fg

A1 DK45 Tk19 Kk63

13fh

A1 DK45 Tk19 Kk64

13fi

A1 DK45 Tk19 DK66

13fj

A1 DK45 Tk20 Kk2

13fk

A1 DK45 Tk20 Kk3

13fl

A1 DK45 Tk20 Kk5

13fm

A1 DK45 Tk20 Kk10

13fn

A1 DK45 Tk20 Kk11

13fo

A1 DK45 Tk20 Kk14

13fp

A1 DK45 Tk20 Kk15

13fq

A1 DK45 Tk20 Kk16

Example No.

TO Napht1 Tk Kk

13fr

A1 DK45 Tk20 Kk51

13fs

A1 DK45 Tk20 Kk53

13ft

A1 DK45 Tk20 Kk54

13fu

A1 DK45 Tk20 Kk55

13fv

A1 DK45 Tk20 Kk56

13fw

A1 DK45 Tk20 Kk61

13fx

A1 DK45 Tk20 Kk62

13fy

A1 DK45 Tk20 Nk63

13fz

A1 DK45 Tk20 Kk64

13ga

A1 DK45 Tk20 DK66

13gb

A1 DK44 Tk16 Kk65

13gc

A1 DK44 Tk16 Kk66

13gd

A1 DK44 Tk16 Kk67

13ge

A1 DK45 Tk16 Kk65

13gf

A1 DK45 Tk16 Kk66

13gg

A1 DK45 Tk16 Kk67

13gh

A1 DK44 Tk18 Kk65

13gi

A1 DK44 Tk18 Kk66

13gj

A1 DK44 Tk18 Kk67

13gk

A1 DK45 Tk18 Kk65

13gl

A1 DK45 Tk18 Kk66

13gm

A1 DK45 Tk18 Kk67

13gn

A1 DK44 Tk19 Kk65

13go

A1 DK44 Tk19 Kk66

13gp

A1 DK44 Tk19 Kk67

Example No.

TO Napht1 Tk Kk

13gq

A1 DK45 Tk19 Kk65

13gr

A1 DK45 Tk19 Kk66

13gs

A1 DK45 Tk19 Kk67

13gt

A1 DK44 Tk20 Kk65

13gr

A1 DK44 Tk20 Kk66

13gs

A1 DK44 Tk20 Kk67

13gt

A1 DK45 Tk20 Kk65

13gu

A1 DK45 Tk20 Kk66

13gv

A1 DK45 Tk20 Kk67

Example 13gw

1) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. 1 mol of acid H was dissolved in 25% sodium hydroxide and added to the reaction mixture of the diazotized MSP. The pH value was kept below 2.

5 2) 1 mol of 4,4-diaminodiphenylsulfamide was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and added to the reaction mixture obtained in step 1). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide.

3) 0.45 mol of methane acid and 0.55 mol of 2,4-diamino-1-methoxybenzene were added to the reaction mixture obtained in step 2) and the pH value was maintained between 3 and 8 by addition of 10% sodium hydroxide in

10 weight After completion of the reaction, the dye was precipitated by addition of NaCl and filtered with suction.

Analogously to example 13gw, the dye mixtures, indicated in table 5a, of the general formula AN = N-Napht1-N = N-Tk-N = N-Kk (formula IIb where n = 0) can be prepared in in which case the coupling of the residue AN = N- is carried out in an ortho position towards the amino group.

Example 5a

Example

 TO Napht1 Tk Kk *)

13gw

A1 DK44 Tk18 Kk15: Kk55 (45:55)

13gz

A1 DK44 Tk18 Kk15: Kk56 (30:70)

13ha

A1 DK44 Tk18 Kk15: Kk66 (80:20)

13hb

A1 DK44 Tk18 Kk5: Kk10 (10:90)

Example

TO Napht1 Tk Kk *)

13hc

A1 DK44 Tk18 Kk5: Kk14 (15:85)

13hd

A1 DK44 Tk18 Kk5: Kk15 (60:40)

13he

A1 DK44 Tk18 Kk5: Kk55 (75:25)

13hf

A1 DK44 Tk18 Kk5: Kk56 (40:60)

13hh

A1 DK44 Tk18 Kk5: Kk67 (20:80)

13hi

A1 DK44 Tk18 Kk5: DK66 (50:50)

13hj

A1 DK45 Tk18 Kk15: Kk55 (45:55)

13hk

A1 DK45 Tk18 Kk15: Kk56 (30:70)

13hl

A1 DK45 Tk18 Kk15: Kk66 (80:20)

13hm

A1 DK45 Tk18 Kk5: Kk10 (10:90)

13hn

A1 DK45 Tk18 Kk5: Kk14 (15:85)

13ho

A1 DK45 Tk18 Kk5: Kk15 (60:40)

13hp

A1 DK45 Tk18 Kk5: Kk55 (75:25)

13hq

A1 DK45 Tk18 Kk5: Kk56 (40:60)

13hr

A1 DK45 Tk18 Kk5: Kk67 (20:80)

13hs

A1 DK45 Tk18 Kk5: DK66 (50:50)

13ht

A1 DK44 Tk16 Kk5: Kk15 (45:55)

13hu

A1 DK44 Tk16 Kk15: Kk55 (45:55)

13hv

A1 DK44 Tk19 Kk15: Kk55 (45:55)

13hw

A1 DK44 Tk20 Kk15: Kk55 (45:55)

* The value indicated in parentheses indicates the molar ratio of the respective coupling components.

image 1

1) 1 mole of 4,4-diaminodiphenylsulfamide was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. 1 mol of methane acid was dissolved in 25% sodium hydroxide and added dropwise to the reaction mixture of tetrazotized 4,4-diaminodiphenylsulfamide. The pH value of the reaction mixture is

5 maintained between 2-3 by adding 15% by weight sodium carbonate solution.

2) 1 mol of acid H was dissolved in 25% sodium hydroxide and added to the reaction mixture obtained in step 1). The pH value of the reaction mixture was maintained between 2-4 by the addition of 15% by weight sodium carbonate solution.

3) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid to

10 pH <1 and a temperature of 0-5 ° C and then added to the reaction mixture obtained in step 2). The pH value was maintained between 3-8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction the dye was precipitated by addition of NaCl and filtered with suction.

Example 15:

image 1

1) 1 mol of 4,4-diaminodiphenylsulfamide was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. 1 mol of methane acid was dissolved in 25% sodium hydroxide and added dropwise to the reaction mixture of tetrazotized 4,4-diaminodiphenylsulfamide. The pH value of the reaction mixture was maintained between 2-3 by adding 15% by weight sodium carbonate solution.

2) 1 mol of MSP was suspended in ice water and with excess sodium nitrite and hydrochloric acid at pH <1 and at

20 temperature from 0-5 ° C. 1 mol of acid H was dissolved in 25% sodium hydroxide and added to the reaction mixture of the diazotized MSP. The pH value was kept below 2.

3) The reaction mixture obtained in step 2) was added to the reaction mixture obtained in step 1). The pH value was maintained between 3-8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, the dye was precipitated by addition of NaCl and filtered with suction.

image 1

1) 1 mole of 4,4-diaminodiphenylsulfamide was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C tetrazotiert. 1 mol of H acid was dissolved in 25% sodium hydroxide and added dropwise to the reaction mixture of tetrazotized 4,4-diaminodiphenylsulfamide. The pH value was maintained between 2 and 3

5 of the reaction mixture by adding 15% by weight sodium carbonate solution.

2) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and then added to the reaction mixture obtained in step 1 ). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide.

3) 1 mol of resorcinol was added to the reaction mixture obtained in step 2) and the pH value was maintained between 10 3 and 8 by the addition of 10% by weight sodium hydroxide.

4) 1 mol of p-nitroaniline was dissolved in 21% hydrochloric acid by weight, then diazotized with excess sodium nitrite at pH <1 and at a temperature of 0-5 ° C and then added to the reaction mixture obtained in step 3). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, the dye was precipitated by the addition of NaCl and filtered by suction.

15 Example 17a:

image 1

1) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. 1 mol of acid H was dissolved in 25% sodium hydroxide and added to the reaction mixture of the diazotized MSP. The pH value was kept below 2.

2 2) 1 mol of 4,4-diaminodiphenylsulfamide was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and added to the reaction mixture obtained in step 1). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide.

3) 1 mol of resorcinol was added to the reaction mixture obtained in step 2) and the pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide.

4 4) 1 mol of p-nitroaniline was dissolved in 21% hydrochloric acid by weight, then diazotized with excess sodium nitrite at pH <1 and a temperature of 0-5 ° C and then added to the mixture of reaction obtained in step 3). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, the dye was precipitated by addition of NaCl and filtered with suction.

image 1

1) 1 mole of 4,4-diaminodiphenylsulfamide was diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C tetrazotiert. 1 mol of H acid was dissolved in 25% sodium hydroxide and added dropwise to the reaction mixture of tetrazotized 4,4-diaminodiphenylsulfamide. The pH value of the reaction mixture is

5 maintained between 2 and 3 by adding 15% by weight sodium carbonate solution.

2) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and then added to the reaction mixture obtained in step 1 ). The pH value was maintained between 3-8 by the addition of 10% by weight sodium hydroxide.

3) 1 mol of p-nitroaniline was dissolved in 21% hydrochloric acid by weight and then diazotized with excess of

10 sodium nitrite at pH <1 and at a temperature of 0-5 ° C. 1 mole of resorcinol was dissolved in 50% by weight sodium hydroxide at a pH value> 12 and diazotized p-nitroaniline was added dropwise to this solution for 30 min at a temperature below 10 ° C, in which case The pH value was maintained above 9 by the addition of 10% by weight sodium hydroxide.

4) The reaction mixture obtained in step 3) was added to the reaction mixture obtained in step 2).

The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, the dye was precipitated by addition of NaCl and filtered with suction.

Example 19:

image 1

1) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid to

20 pH <1 and at a temperature of 0-5 ° C. 1 mol of acid H was dissolved in 25% sodium hydroxide and added to diazotized MSP. The pH value was kept below 2.

2) 1 mole of 4,4-diaminodiphenylsulfamide was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and added to the reaction mixture obtained in step 1). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide.

3 3) 1 mol of p-nitroaniline was dissolved in 21% hydrochloric acid by weight and then diazotized with excess sodium nitrite at pH <1 and at a temperature of 0-5 ° C. 1 mol of resorcinol was dissolved in 50% by weight sodium hydroxide at a pH value> 12 and diazotized p-nitroaniline was added dropwise to this solution within 30 min at a temperature of 10 ° C, at which case by adding 10% by weight sodium hydroxide the pH value was maintained above 9.

4) The reaction mixture obtained in step 3) was added to the reaction mixture obtained in step 2). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, the dye was precipitated by addition of NaCl and filtered with suction.

image 1

1) 1 mol of p-nitroaniline was dissolved in 21% hydrochloric acid by weight and then diazotized with excess sodium nitrite at pH <1 and a temperature of 0-5 ° C. 1 mol of resorcinol was dissolved in 50% sodium hydroxide in

5 weight at a pH value> 12 and p-nitroaniline was added dropwise to this solution within 30 min at a temperature below 10 ° C, in which case the pH value was maintained above 9 by addition of 10% by weight sodium hydroxide.

2) 1 mole of 4,4-diaminodiphenylsulfamide was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C tetrazotiert and added to the reaction mixture obtained in step 1). The pH value is

10 maintained between 3 and 5 by adding 10% by weight sodium hydroxide.

3) 1 mol of MSP was suspended in ice water and with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. 1 mol of acid H was dissolved in 25% sodium hydroxide and added to diazotized MSP. The pH value was kept below 2.

4) The reaction mixture obtained in step 3) was added to the reaction mixture obtained in step 2). The value

The pH was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, the dye was precipitated by addition of NaCl and filtered with suction.

In a manner analogous to examples 16a and 18, the dyes of the general formula Dk1N = NNapht1-N = N-Tk-N = N-Kk-N = N-Dk2 or their metal complexes (= dyes of the general formula can be obtained II where r = k = n = 1), where Dk1 and Dk2 respectively represent one of the diazo components DK1 to DK83 or represent a residue derived from A1 to A12, in which case at least one of the residues Dk1 or Dk2 represents a residue of the formula A, Kk represents a bivalent residue derived from the coupling components Kk2, Kk3, Kk5, Kk6, Kk14, Kk15, Kk16, Kk49 or Kk50, Napht1 represents one of the bivalent residues II-2, II-4, II -6, II-8, II-10, II-12 and II14, Tk represents a bivalent residue derived from one of the tetrazo components Tk1 to Tk20 and A means one of residues A1 to A12. The coupling of the residue Dk1-N = N- is carried out in an ortho position towards the hydroxyl group in

25 Napht1. Examples of these are the dyes and metal complexes indicated in the following table 6.

Table 6:

Example No.

Dk1 Napht1 Tk Kk Dk2 Metal

16th

A1 DK44 Tk18 Kk3 DK17 -

16b

A1 DK44 Tk18 Kk3 DK5 Faith

16c

A1 DK44 Tk18 Kk3 DK5 Cr

16d

A1 DK44 Tk18 Kk3 DK40 -

16e

DK17 DK44 Tk18 Kk3 A1 -

16f

DK17 DK44 Tk18 Kk3 A7 -

16g

DK17 DK44 Tk18 Kk5 A7 -

4pm

DK5 DK44 Tk18 Kk3 A1 Faith

Example No.

Dk1 Napht1 Tk Kk Dk2 Metal

16i

DK5 DK44 Tk18 Kk3 A1 Cr

16j

DK5 DK44 Tk16 Kk5 A12 -

16k

DK17 DK45 Tk16 Kk3 A10 -

In a manner analogous to examples 17a, 19 and 20 the dyes of the general formula Dk1N = NNapht1-N = N-Tk-N = N-Kk-N = N-Dk2 or their metal complexes (= dyes of the general formula II where r = k = n = 1), where Dk1 and Dk2 respectively represent one of the diazo components DK1 to DK83 or a residue 5 derived from A1 to A12, in which case at least one of the residues Dk1 or Dk2 represents a residue of the formula A, Kk represents a bivalent residue derived from the coupling components Kk2, Kk3, Kk5, Kk6, Kk14, Kk15, Kk16, Kk49 or Kk50, Napht1 represents one of the bivalent residues II-2, II-4, II-6, II-8, II-10, II-12 and II-14, Tk represents a bivalent residue derived from one of the tetrazo components Tk1 to Tk20 and A means one of residues A1 to A12. The coupling of the residue Dk1-N = N- is carried out in ortho position towards the amino group in

10 Napht1. Examples of these are the dyes and metal complexes indicated in the following table 7.

Table 7

Example No.

Dk1 Napht1 Tk Kk Dk2 Metal

17th

A1 DK44 Tk18 Kk3 DK17 -

17b

A1 DK44 Tk18 Kk3 DK5 Faith

17c

A1 DK44 Tk18 Kk3 DK5 Cr

17d

A1 DK44 Tk18 Kk3 DK40 -

17e

DK17 DK44 Tk18 Kk3 A1 -

17f

DK17 DK44 Tk18 Kk3 A7 -

17g

DK17 DK44 Tk18 Kk5 A1 -

17h

DK5 DK44 Tk18 Kk3 A1 -

17i

DK5 DK44 Tk18 Kk3 TO 5 -

17j

A1 DK44 Tk18 Kk3 A1 -

17k

DK5 DK44 Tk16 Kk5 A9 -

17l

DK17 DK45 Tk16 Kk3 A11 -

image 1

1) 1 mole of 4,4-diaminodiphenylsulfamide was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. 1 mol of acid H was dissolved in 25% sodium hydroxide and added dropwise to the reaction mixture of tetrazotized 4,4-diaminodiphenylsulfamide. The pH value of the reaction mixture is

5 maintained between 2 and 3 by adding 15% by weight sodium carbonate solution.

2) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and then added to the reaction mixture obtained in step 1 ).

The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide.

3) 0.5 mol of resorcinol was added to the reaction mixture obtained in step 2) and the pH value was maintained

10 between 3 and 8 by adding 10% by weight sodium hydroxide. After completion of the reaction, the dye was precipitated by addition of NaCl and filtered with suction.

In a manner analogous to Example 21, the dyes of the general formula [AN = N-Napht1-N = N-Tk-N = N] 2-Kk (= dyes of the general formula III where Dk1 = Dk2 = A, can be obtained Napht1 = Napht2 and Tk1 = Tk2), where Kk represents a bivalent residue derived from one of the coupling components Kk2, Kk3, Kk5, Kk6, Kk14,

15 Kk15, Kk16, Kk49 or Kk50, Napht1 represents one of the bivalent residues II-2, II-4, II-6, II-8, II-10, II-12 and II-14, Tk represents a derived bivalent residue of one of the tetrazo components Tk1 to Tk20 and A means one of residues A1 to A12. The coupling of the residue A-N = N- is carried out in an ortho position towards the hydroxyl group in Napht1.

Example 22:

image3

1) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. 1 mol of acid H was dissolved in 25% sodium hydroxide and added to the diazotized MSP. The pH value was kept below 2.

3) 0.5 mol of resorcinol was added to the reaction mixture obtained in step 2) and the pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, the dye was precipitated by addition of NaCl and filtered with suction.

In a manner analogous to example 22, the dyes of the general formula [AN = N-Napht1-N = N-Tk-N = N] 2-Kk (= dyes of the general formula III where Dk1 = Dk2 = A, can be obtained Napht1 = Napht2 and Tk1 = Tk2), where Kk represents a bivalent residue derived from one of the coupling components Kk2, Kk3, Kk5, Kk6, Kk14,

10 Kk15, Kk16, Kk49 or Kk50, Napht1 represents one of the bivalent residues II-2, II-4, II-6, II-8, II-10, II-12 and II-14, Tk represents a derived bivalent residue of one of the tetrazo components Tk1 to Tk20 and A means one of residues A1 to A12. The coupling of the residue A-N = N- is carried out in an ortho position towards the amino group in Napht1.

Example 23:

image 1

1 1) 1 mol of gamma acid was dissolved in 25% sodium hydroxide, diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and added dropwise to a solution 1 mol aqueous anthranilic acid. The pH value of the reaction mixture was maintained between 5 and 10 by the addition of 10% by weight sodium hydroxide.

2) 1 mol of acid H was dissolved in 25% sodium hydroxide and diazotized with excess sodium nitrite and acid

20 hydrochloric at pH <1 and at a temperature of 0-5 ° C. The reaction mixture obtained in step 1) was added to this reaction mixture. The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide.

3) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and then added to the reaction mixture obtained in step 2 ). He

The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, the dye was precipitated by addition of NaCl and filtered with suction.

Similarly to example 23, the dyes of the general formula AN = N-Napht1-N = NNapht2N = N-Kk (= dyes of the general formula XII where p = 1, n = 0, P = Napht1, R = Napht2), where Kk represents a bivalent residue derived from one of the coupling components Kk1 to Kk48 or Kk51 to Kk67, Napht1 and Napht2

30 represents respectively one of the bivalent residues II-1, II-3, II-5, II-7, II-9, II-11, II-13 or II-15 and A means one of the residues A1 to A12. The coupling of the Napht1-N = N- residue is carried out in an ortho position towards the hydroxyl group in Napht2.

image 1

1) 1 mol of gamma acid was dissolved in 25% sodium hydroxide, diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and added dropwise to an aqueous suspension of 1 mol of 3-phenylaminophenol. The pH value of the reaction mixture was maintained between 5 and 10 by the addition of hydroxide.

5 10% sodium by weight.

2) 1 mol of Cleve-7 acid was dissolved in 25% sodium hydroxide. Simultaneously 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and then added to the Cleve-7 acid solution, in which case the pH value was kept below 2.

3) The reaction mixture obtained in step 2) was diazotized with excess sodium nitrite and hydrochloric acid a

10 pH <1 and at a temperature of 0 - 5 ° C. The reaction mixture obtained in step 1) is added to this reaction mixture. The pH value was maintained between 3-8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, the dye was precipitated by addition of NaCl and filtered with suction.

In a manner analogous to example 24, the dyes of the general formula AN = N-Napht1N = NNapht2-N = N-Kk (= dyes of the general formula XII where p = 1, n = 0, P = Napht1, R can be obtained = Napht2), where Kk

15 represents a bivalent residue derived from one of the coupling components Kk1 to Kk48 or Kk51 to Kk67, Napht1 and Napht2 respectively represent one of the bivalent residues II-1, II-3, II-5, II-7, II-9 , II-11, II-13 or II15 and A means one of residues A1 to A12. The coupling of the residue A-N = N-Napht1-N = N- is carried out in an ortho position towards the hydroxyl group in Napht2.

Example 25:

image3

1) 1 mol of Cleve-7 acid was dissolved in 25% sodium hydroxide. Simultaneously 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and a temperature of 0-5 ° C and then added to the Cleve-7 acid solution, in in which case the pH value remained below 2.

2 2) 1 mol of acid H was dissolved in 25% sodium hydroxide. Simultaneously, the reaction mixture obtained in step 1) was diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and added to the acid H solution. The pH value was maintained between 1 and 4 by adding 10% by weight sodium hydroxide.

3) 1 mole of 5-nitro-2-aminophenol was diazotized at pH <1 and at a temperature of 0-5 ° C with excess sodium nitrite and hydrochloric acid and then added to the reaction mixture obtained in step 2 ). The pH value was maintained between 3-8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, 0.20-0.30 mol of chromium (III) sulfate was added to the reaction mixture and continued to stir for 1 hour. He

5 dye was precipitated by addition of NaCl and filtered with suction.

Example 26:

The preparation was carried out analogously to the procedure indicated in example 25, in which case in the last step a metallic complexing was not performed.

Similarly to examples 25 and 26, dyes of the general formula A-N = NNapht1 could be obtained

10 N = N-Napht2-N = N-Dk and its metal complexes (= dyes of the general formula I where p = m = 1, P = Napht1, Kk1 = Napht2), where Dk represents a residue derived from the diazo components DK1 to DK9, DK13, DK14, DK26, DK27, DK39 to DK41 and DK58, Napht1 represents one of the bivalent residues II-1, II-3, II-5, II-7, II-9, II-11, II- 13, II15 or II-16, Napht2 represents one of the bivalent residues II-2, II-4, II-6, II-8, II-10, II-12 or II-14 and A means one of residues A1 to A12. The coupling of the residue A-N = N-Napht1-N = N- is carried out in ortho position towards the group

15 amino in Napht2.

Example 27:

image 1

1) 1 mol of p-nitroaniline was dissolved in 21% hydrochloric acid by weight, then diazotized with excess sodium nitrite at pH <1 and at a temperature of 0-5 ° C. Simultaneously 1 mol of H acid was dissolved in sodium hydroxide

20-25% and then the H acid was precipitated by the addition of 21% hydrochloric acid by weight. The H-acid suspension was added to the diazotized p-nitroaniline and the pH value was kept below 2. After 1 hour the reaction was terminated.

2) 1 mol of Cleve-7 acid was dissolved in 25% sodium hydroxide. Simultaneously 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 25-5-5 ° C. To this was added the Cleve-7 acid solution, in which case the pH value was kept below 2.

3) The reaction mixture obtained in step 2) was diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and added to the product obtained in step 1). The pH value was maintained between 5 and 8 by the addition of 10% by weight sodium hydroxide and continued to stir for 1 hour. The dye was precipitated by the addition of NaCl and filtered with suction.

In a manner analogous to example 27, the dyes of the general formula AN = N-Napht1N = NNapht2-N = N-Dk (= dyes of the general formula I where p = m = 1, P = Napht1, Kk1 = can be obtained Napht2), where Dk represents a residue derived from diazo components DK1 to DK83, Napht1 represents one of the bivalent residues II-1, II-3, II-5, II-7, II-9, II-11, II-13 , II-15 or II-16, Napht2 represents one of the bivalent residues 11-2, II-4, II-6, II-8, II-10, II-12 or II-14 and A means one of the residues A1 to A12. The coupling of the residue A-N = N-Napht1

35 N = N- is carried out in ortho position towards the hydroxyl group in Napht2.

image 1

1) 1 mol of acid H was dissolved in 25% sodium hydroxide, diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. 1 mole of resorcinol was dissolved in 50% by weight sodium hydroxide at a pH value> 12. To this solution, the diazotized H-acid was added dropwise over the course of 30 min at a temperature below 10 ° C, in which case the pH value was maintained above 9 by the addition of 10% sodium hydroxide in weight.

2) 1 mole of 4,6-dinitro-2-aminophenol was diazotized at pH <1 and at a temperature of 0-5 ° C with excess sodium nitrite and hydrochloric acid and added to the reaction mixture obtained in the step one). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide.

3) 1 mol of Cleve-7 acid was dissolved in 25% sodium hydroxide. Simultaneously 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and then added to the Cleve-7 acid solution, in in which case the pH value remained below 2.

4) The reaction mixture obtained in step 3) was diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. The reaction mixture obtained in step 2) was added to this reaction mixture. The pH value by adding 10% sodium hydroxide by weight between 3 and 8. After completion of the reaction, 0.40-0.60 mol of iron (III) sulfate was added to the reaction mixture and followed stirring for 1 hour. The dye was precipitated by the addition of NaCl and filtered with suction.

Similarly to example 28a, metallic dye complexes of the general formula AN = NNapht1-N = N-Napht-N = N-Kk-N = N-Dk (= dyes of the general formula XII where p = n = can be obtained 1, P = Napht1, R = Napht2), where Dk represents a residue derived from the diazo components DK1 to DK9, DK13. DK14, DK26, DK27, DK39 to DK41 or DK58, Napht1 represents one of the bivalent residues II-1, II-3, II-5, II-7, II-9, II-11, II-13, II-15 or II16, Napht2 represents one of the bivalent residues II-2, II-4, II-6, II-8, II-10, II-12 or II-14, Kk represents a bivalent residue derived from Kk2, Kk3, Kk49 or Kk50 and A means one of the residues A1 to A12. The coupling of the residue A-N = N-Napht1-N = N- is carried out in an ortho position towards the hydroxyl group in Napht2.

Example 28b:

The reaction was carried out according to the method described in example 28a with the difference, that there was no reaction with iron salts.

In a manner analogous to example 28b, the dyes of the general formula AN = N-Napht1N = NNapht2-N = N-Kk-N = N-Dk (= dyes of the general formula XII where p = n = 1, P can be obtained = Napht1, R = Napht2), where Dk represents one of the diazo components DK1 to DK83 or represents a residue derived from A1 to A12, Napht1 represents one of the bivalent residues II-1, II-3, II-5, II-7 , II-9, II-11, II-13, 11-15 or II-16, Napht2 represents one of the bivalent residues II-2, II-4, II-16, II-8, II-10, II- 12 or II-14, Kk represents a bivalent residue derived from Kk2, Kk3, Kk5, Kk6, Kk14, Kk15, Kk16, Kk49 or Kk50 and A means one of residues A1 to A12. The coupling of the residue A-N = N-Napht1-N = N- is carried out in an ortho position towards the hydroxyl group in Napht2.

image 1

1) 1 mole of 4,6-dinitro-2-aminophenol was diazotized at pH <1 and at a temperature of 0-5 ° C with excess sodium nitrite and hydrochloric acid. 1 mol of resorcinol was dissolved in 50% by weight sodium hydroxide at a pH value> 12 and diazotized 4,6-dinitro-2-aminophenol was added dropwise to this solution within 30 min at a temperature per below 10 ° C, in which case by adding 10% by weight sodium hydroxide the pH value was maintained above 9.

2) 1 mol of acid H was dissolved in 25% sodium hydroxide, diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and added to the reaction mixture obtained in step 1). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide.

3) 1 mol of Cleve-7 acid was dissolved in 25% sodium hydroxide. Simultaneously 1 mol of MSP was suspended and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and a temperature of 0-5 ° C and then added to the Cleve-7 acid solution, in which case the pH value remained below 2.

4) The reaction mixture obtained in step 3) was diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. The reaction mixture obtained in step 2) was added to this reaction mixture. The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, 0.40-0.60 mol of iron (III) sulfate was added to the reaction mixture and continued to stir for 1 hour. The dye was precipitated by the addition of NaCl and filtered with suction.

In a manner analogous to example 29a, the metal complexes of the dyes of the general formula AN = NNapht1-N = N-Napht2-N = N-Kk-N = N-Dk (= dyes of the general formula XII where p = n = 1, P = Napht1, R = Napht2), where Dk represents a residue derived from diazocomponents DK1 to DK9, DK13, DK14, DK26, DK27, DK39 to DK41 or DK58, Napht1 represents one of the bivalent residues II- 1, II-3, II-5, II-7, II-9, II-11, II13, II-15 or II-16, Napht2 represents one of the bivalent residues II-2, II-4, II-6 , II-8, II-10, II-12 or II-14, Kk represents a bivalent residue derived from Kk2, Kk3, Kk49 or Kk50 and A means one of residues A1 to A12. The coupling of the residue A-N = N-Napht1-N = N- is carried out in an ortho position towards the hydroxyl group in Napht2.

Example 29b:

The reaction was carried out according to the method described in example 29a with the difference that no reaction occurred with iron salts.

In a manner analogous to example 29b, the dyes of the general formula AN = N-Napht1N = NNapht2-N = N-Kk-N = N-Dk (= dyes of the general formula XII where p = n = 1, P can be obtained = Napht1, R = Napht2), where Dk represents one of the diazo components DK1 to DK83 or a residue derived from A1 to A12, Napht1 represents one of the bivalent residues II-1, II-3, II-5, II-7, II-9, II-11, II-13, II-15 or II-16, Napht2 represents one of the bivalent residues II-2, II-4, II-6, II-8, II-10, II-12 or II-14, Kk represents a bivalent residue derived from Kk2, Kk3, Kk5, Kk6, Kk14, Kk15, Kk16, Kk49 or Kk50 and A means one of residues A1 to A12. The coupling of the residue A-N = NNapht1-N = N- is carried out in an ortho position towards the hydroxyl group in Napht2.

image 1

1) 1 mole of 4,4-diaminodiphenylsulfamide was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C tetrazotiert. 1 mol of H acid was dissolved in 25% sodium hydroxide and added dropwise to the reaction mixture of tetrazotized 4,4-diaminodiphenylsulfamide. The pH value remained below

5 of 3

2) 1 mol of p-nitroaniline was dissolved in 21% hydrochloric acid by weight, then diazotized with excess sodium nitrite at pH <1 and at a temperature of 0-5 ° C and added to the reaction mixture obtained in step 1). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide.

3) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid to

10 pH <1 and at a temperature of 0-5 ° C. 1 mole of K acid was dissolved in 25% sodium hydroxide and added to the diazotized MSP. The pH value was kept below 2.

4) The product obtained in step 3) was added to the reaction mixture obtained in step 2). The pH value was maintained between 3-8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, the dye was precipitated by addition of NaCl and filtered with suction.

In a manner analogous to example 30, dyes of the general formula Dk1-N = N-Napht1-N = N-TkN = N-Napht2-N = N-Dk2 or their metal complexes (= dyes of general formula IV can be obtained ), where Dk1 and Dk2 respectively represent one of the diazo components DK1 to DK83 or represent a residue derived from A1 to A12, in which case at least one of the residues Dk1 or Dk2 represents a residue of the formula A, Napht1 and Napht2 respectively represent one of the bivalent residues II-2, II-4, II-6, II-8, II-10, II-12 or II-14 and Tk represents a

20 bivalent residue derived from Tk1 to Tk20. The coupling of the residue Dk1-N = N- is carried out in ortho position towards the hydroxyl group in Napht1 and the coupling of the residue Dk2-N = N- is carried out in ortho position towards the amino group in Napht2.

Example 31:

image 1

1 1) 1 mol of p-nitroaniline was dissolved in 21% hydrochloric acid by weight and then diazotized with excess sodium nitrite at pH <1 and at a temperature of 0-5 ° C. To this was added 1-mol of acid H, in which case the pH value was kept below 2.

2) 1 mole of 4,4-diaminodiphenylsulfamide was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and added to the reaction mixture obtained in step 1). The pH value was maintained.

30 between 3 and 8 by adding 10% by weight sodium hydroxide.

3) 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. 1 mole of K acid was dissolved in 25% sodium hydroxide and added to the solution of the diazotized MSP. The pH value was kept below 2.

4) The reaction mixture obtained in step 3) was added to the reaction mixture obtained in step 2). The value

The pH was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, the dye was precipitated by addition of NaCl and filtered with suction.

In a manner analogous to example 31, the dyes of the general formula Dk1-N = N-Napht1-N = NTk-N = N-Napht2-N = N-Dk2 or their metal complexes (= dyes of the general formula IV can be obtained ), where Dk1 and Dk2 respectively represent one of the diazo components DK1 to DK83 or represent a residue derived from A1 to A12, in which case at least one of the residues Dk1 or Dk2 represents a residue of the formula A, Napht1 and Napht2 respectively represent one of the bivalent residues II-2, II-4, II-6, II-8, II-10, II-12 or II-14 and Tk represents a bivalent residue, derived from Tk1 to Tk20. The coupling of the residues Dk1-N = N- and Dk2-N = N- is carried out respectively in an ortho position towards the amino group in Napht1 or Napht2.

Example 32:

image 1

10 1 mol of 4,6-dinitro-2-aminophenol was diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and coupled with 1 mol of acid 4- (β- sulphoethylsulfonyl) pyrazolic-2 (Kk44). The pH value was maintained between 2 and 7. After completion of the coupling, 0.20-0.30 mol of chromium (III) sulfate was added to the reaction mixture and continued to stir for 1 hour. Then the reaction mixture was evaporated at 40 ° C.

In a manner analogous to example 32, the metallic dye complexes of the general formula can be obtained

Dk-N = NPir-A (= dyes of the general formula XIII), where Dk represents a residue derived from diazocomponents DK1 to DK9, DK13, DK14, DK26, DK27, DK39 to DK41 or DK58, Pir represents 5-hydroxy -3-methylpyrazol-1,4-diyl or represents 5-hydroxy-3-carboxypyrazol-1,4-diyl and A means one of residues A1 to A12 which is linked by the Pir nitrogen.

Example 33:

The reaction was carried out according to the method described in Example 32 with the difference that there was no reaction with chromium salts.

In a manner analogous to example 33, the dyes of the general formula Dk-N = N-Pir-A (= dyes of the general formula XIII) can be obtained, where Dk represents a residue derived from the diazo components DK1 to DK83, Pir represents 5 -hydroxy-3-methylpyrazol-1,4-diyl or represents 5-hydroxy-3-carboxypyrazol-1,4-diyl and A means

25 one of the residues A1 to A12, which is linked by the Pir nitrogen.

Example 34a:

image 1

1) 1 mole of 5-nitro-2-aminophenol was diazotized at pH <1 and at a temperature of 0-5 ° C with excess sodium nitrite and hydrochloric acid. 1 mol of resorcinol was dissolved in 50% by weight sodium hydroxide at a pH value> 12 and to this solution was added diazotized 5-nitro-2-aminophenol over 30 min at a temperature below

2) 1 mol of MSP was suspended in ice water, diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C diazotiert, and added to the reaction mixture obtained in the step one). The value

PH 5 was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, 0.40-0.60 mol of iron (III) sulfate was added to the reaction mixture and continued to stir for 1 hour. The dye was precipitated by the addition of NaCl and filtered with suction.

Example 35a:

The reaction was carried out according to the method described according to example 34a with the difference that there was no reaction with 10 iron salts.

Example 36:

image 1

1) 1 mol of MSP was diazotized at pH <1 and a temperature of 0-5 ° C with excess sodium nitrite and hydrochloric acid. 1 mol of resorcinol was dissolved in 50% by weight sodium hydroxide and to this solution the MSP was added dropwise

Diazotized within 30 min at a temperature below 10 ° C, in which case, by adding 10% by weight sodium hydroxide, the pH value was maintained between 3 and 8.

2) 1 mol of 5-nitro-2-aminophenol was suspended in ice water, diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C diazotiert and added to the mixture of reaction obtained in step 1). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After

After the reaction was over, 0.40-0.60 mol of iron (III) sulfate was added to the reaction mixture and continued to stir for 1 hour. The dye was precipitated by the addition of NaCl and filtered with suction.

Example 37:

The reaction was carried out according to the method described in example 36 with the difference that no reaction with iron salts occurred.

In a manner analogous to examples 34a and 36, the metallic dye complexes of the general formula Dk-N = N-Kk-N = NA (= dyes of the general formula I where p = 0 and m = 1) can be obtained, where Dk represents a residue derived from the diazo components DK1 to DK9, DK13, DK14, DK26, DK27, DK39 to DK41 or DK58, Kk represents a bivalent residue derived from Kk2, Kk3, Kk49 or Kk50 and A means one of residues A1 to A12 Examples of these are indicated in table 8.

30 Table 8.

Example No.

Dk Kk TO Metal

34th

DK1 Kk3 A1 Faith

34b

DK2 Kk3 A1 Faith

34c

DK3 Kk3 A1 Faith

34d

DK4 Kk3 A1 Faith

34e

DK4 Kk3 A1 Faith

34f

DK5 Kk3 A1 Faith

34g

DK6 Kk3 A1 Faith

34h

DK7 Kk3 A1 Faith

34i

DK8 Kk3 A1 Faith

34j

DK9 Kk3 A1 Faith

34k

DK13 Kk3 A1 Faith

34l

DK14 Kk3 A1 Faith

34m

DK27 Kk3 A1 Faith

34n

DK39 Kk3 A1 Faith

34th

DK40 Kk3 A1 Faith

34p

DK41 Kk3 A1 Faith

34q

DK58 Kk3 A1 Faith

34r

DK5 Kk49 A1 Faith

34s

DK5 Kk50 A1 Faith

34t

DK5 Kk3 A1 Cr

34u

DK5 Kk49 A1 Co

Example No.

Dk Kk TO Metal

34v

DK5 Kk50 A1 Cr

34z

DK4 Kk3 A3 Faith

34aa

DK5 Kk3 A6 Faith

34ab

DK6 Kk3 A10 Faith

34ac

DK7 Kk3 A11 Faith

In a manner analogous to Examples 35a and 37, the dyes of the general formula Dk-N = N-Kk-N = NA (= dyes of the general formula I where p = 0 and m = 1) can be obtained, where Dk represents a residue derived from diazo components DK1 through DK83, Kk represents a bivalent residue derived from Kk2, Kk3, Kk49 or Kk50 and A means one of residues A1 through A12. Examples of these are indicated in table 9.

Table 9:

Example No.

Dk Kk TO

35th

DK1 Kk3 A1

35b

DK2 Kk3 A1

35c

DK3 Kk3 A1

35d

DK4 Kk3 A1

35e

DK5 Kk3 A1

35f

DK6 Kk3 A1

35g

DK7 Kk3 A1

35h

DK8 Kk3 A1

35i

DK9 Kk3 A1

35j

DK10 KK3 A1

35k

DK12 KK3 A1

35l

DK13 Kk3 A1

35m

DK14 Kk3 A1

35n

DK17 Kk3 A1

35th

DK27 Kk3 A1

Example No.

Dk Kk TO

35p

DK28 Kk3 A1

35q

DK32 Kk3 A1

35r

DK39 Kk3 A1

35s

DK40 Kk3 A1

35t

DK41 Kk3 A1

35u

DK42 Kk3 A1

35v

DK46 Kk3 A1

35z

DK47 Kk3 A1

35aa

DK58 Kk3 A1

35ab

DK5 Kk49 A1

35ac

DK5 Kk50 A1

35ad

DK47 Kk49 A1

35ae

DK47 Kk50 A1

35af

DK4 Kk3 A4

35ag

DK5 Kk3 A7

35ah

DK6 Kk3 A9

35ai

DK7 Kk3 A12

Example 38a:

image 1

Method A:

1) 1 mole of 4,6-dinitro-2-aminophenol was diazotized at pH <1 and a temperature of 0-5 ° C with excess sodium nitrite and hydrochloric acid. 1 mol of resorcinol was dissolved in 50% by weight sodium hydroxide at a pH value> 12 and diazotized 4,6-dinitro-2-aminophenol was added dropwise to this solution within 30 min at a temperature> 10 ° C in which case, by adding 10% by weight sodium hydroxide, the pH value was maintained above 9.

3) 1 mol of p-nitroaniline was dissolved in 21% hydrochloric acid by weight, then diazotized with excess nitrite

5 of sodium at pH <1 and a temperature of 0-5 ° C and added to the reaction mixture obtained in step 2). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, 0.40-0.60 mol of iron (III) sulfate was added to the reaction mixture and continued to stir for 1

h. The dye was precipitated by the addition of NaCl and filtered with suction.

Method B:

10 1) 1 mol of p-nitroaniline was dissolved in 21% hydrochloric acid by weight and then diazotized with excess sodium nitrite at pH <1 and a temperature of 0-5 ° C. 1 mole of resorcinol was dissolved in 50% by weight sodium hydroxide at a pH value> 12. To this solution, the dissolved p-nitroaniline was added dropwise over 30 min at a temperature below 10 ° C, in which case the pH value was maintained above 10% by weight. of 9.

15 2) 1 mol of MSP was suspended in ice water, diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and then added to the reaction mixture obtained in the step one). The pH value was maintained between 3-8 by the addition of 10% by weight sodium hydroxide.

3) 1 mole of 4,6-dinitro-2-aminophenol was diazotized at pH <1 and a temperature of 0-5 ° C with excess sodium nitrite and hydrochloric acid and added to the reaction mixture obtained in the step 2). The pH value was maintained between 3 and

20 8 by adding 10% by weight sodium hydroxide. After completion of the reaction, 0.400.60 mol of iron (III) sulfate was added to the reaction mixture and continued to stir for 1 hour. The dye was precipitated by the addition of NaCl and filtered with suction.

Example 39a:

The reaction was carried out according to the method described in Example 38 with the difference that there was no reaction with iron salts.

Example 40a:

image 1

Method A:

1) 1 mol of p-nitroaniline was dissolved in 21% hydrochloric acid by weight, then diazotized with excess nitrite

30 sodium at pH <1 and at a temperature of 0-5 ° C. 1 mole of resorcinol was dissolved in 50% by weight sodium hydroxide at a pH value> 12. To this solution, the diazotized p-nitroaniline was added dropwise over the course of 30 min at a temperature below 10 ° C, in which case the pH value was maintained by adding 10% by weight sodium hydroxide of 9.

2) 1 mole of 4,6-dinitro-2-aminophenol was diazotized at pH <1 and at a temperature of 0-5 ° C with excess sodium nitrite

35 and hydrochloric acid and then added to the reaction mixture obtained in step 1). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide.

3) 1 mol of MSP was suspended in ice water, diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and added to the reaction mixture obtained in step 2) . The pH value was maintained between 3 and 8 by the addition of 10% sodium hydroxide by weight between 3 and 8. After the end of Method B:

1) 1 mol of MSP was suspended in ice water, diazotized with excess sodium nitrite and hydrochloric acid at

5 pH <1 and at a temperature of 0-5 ° C. 1 mole of resorcinol was dissolved in 50% by weight sodium hydroxide. To this solution, the diazotized MSP was added dropwise over the course of 30 min at a temperature below 10 ° C, in which case the pH value was maintained between 6 and 10 by weight by adding sodium hydroxide by weight. 7.

2) 1 mole of 4,6-dinitro-2-aminophenol was diazotized at pH <1 and at a temperature of 0-5 ° C with excess sodium nitrite and hydrochloric acid and then added to the reaction mixture obtained in the step 1). The pH value is

10 maintained between 3 and 8 by adding 10% by weight sodium hydroxide.

3) 1 mol of p-nitroaniline was dissolved in 21% hydrochloric acid by weight, then diazotized with excess sodium nitrite at pH <1 and at a temperature of 0-5 ° C and added to the reaction mixture obtained in step 2). The pH value was maintained between 3-8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, 0.40-0.60 mol of iron (III) sulfate was added to the reaction mixture and continued to stir for 1

15 hour The dye was precipitated by the addition of NaCl and filtered with suction.

Example 41a:

The reaction was carried out according to the methods described in example 40 with the difference that no reaction occurred with iron salts.

In a manner analogous to examples 38a and 40a, the metal dye complexes of the general formula 20 can be obtained

image 1

(= dyes of the general formula I where p = 0 and m = 2), where Dk1 and Dk2 respectively represent a residue derived from the diazo components DK1 to DK83, in which case at least one of the residues Dk1 or Dk2 represents one of the diazo components DK1 to DK9, DK13, DK14, DK26, DK27, DK39 to DK41 or DK58, Kk represents a

Trivalent derivative derived from Kk2 or Kk3 and A means one of residues A1 to A12. Examples of these are indicated in table 10.

Table 10

Example No.

Dk1 Kk Dk2 TO I

38a

DK1 KK3 DK17 A1 Faith

38b

DK1 KK3 DK5 A1 Faith

38c

DK1 KK3 DK10 A1 Faith

38d

DK2 KK3 DK17 A1 Faith

38e

DK4 KK3 DK17 A1 Cu

Example No.

Dk1 Kk Dk2 TO I

38f

DK4 KK3 DK12 A1 Co

38g

DK4 KK3 DK56 A1 Cr

38h

DK5 KK3 DK9 A1 Faith

38i

DK5 KK3 DK10 A1 Faith

38j

DK5 KK3 DK12 A1 Faith

38k

DK5 KK3 DK17 A1 Faith

38l

DK5 KK3 DK19 A1 Faith

38m

DK5 KK3 DK27 A1 Faith

38n

DK5 KK3 DK28 A1 Faith

38o

DK5 KK3 DK30 A1 Faith

38p

DK5 KK3 DK32 A1 Faith

38q

DK5 KK3 DK35 A1 Faith

38r

DK5 KK3 DK41 A1 Faith

38s

DK5 KK3 DK46 A1 Faith

38t

DK5 KK3 DK47 A1 Faith

38u

DK5 KK3 DK58 A1 Faith

38v

DK5 KK3 DK12 TO 5 Faith

38z

DK5 KK3 DK17 A9 Faith

40th

DK1 KK3 DK17 A1 Faith

40b

DK1 KK3 DK5 A1 Faith

40c

DK1 KK3 DK10 A1 Faith

40d

DK2 KK3 DK17 A1 Faith

40e

DK4 KK3 DK17 A1 Cu

40f

DK14 KK3 DK12 A1 Co

40g

DK4 KK3 DK56 A1 Cr

Example No.

Dk1 Kk Dk2 TO I

40h

DK5 KK3 DK9 A1 Faith

40i

DK5 KK3 DK10 A1 Faith

40j

DK5 KK3 DK12 A1 Faith

40k

DK5 KK3 DK17 A1 Faith

40l

DK5 KK3 DK19 A1 Faith

40m

DK5 KK3 DK27 A1 Faith

40n

DK5 KK3 DK28 A1 Faith

40th

DK5 KK3 DK30 A1 Faith

40p

DK5 KK3 DK32 A1 Faith

40q

DK5 KK3 DK35 A1 Faith

40r

DK5 KK3 DK41 A1 Faith

40s

DK5 KK3 DK46 A1 Faith

40t

DK5 KK3 DK47 A1 Faith

40u

DK5 KK3 DK58 A1 Faith

40v

DK5 KK3 DK12 A4 Faith

40z

DK5 KK3 DK17 A11 Faith

In a manner analogous to examples 39a and 41a, the dyes of the general formula can be obtained

image 1

(= dyes of the general formula I where p = 0 and m = 2), where Dk1 and Dk2 respectively represent a residue derived from the diazo components DK1 to DK83, Kk represents a trivalent residue derived from Kk2, Kk3 or Kk5 and A means one of waste A1 to A12. Examples of these are indicated in table 11.

Table 11:

Example No.

Dk1 Kk Dk2 TO

39a

DK1 KK3 DK17 A1

Example No.

Dk1 Kk Dk2 TO

39b

DK1 KK3 DK5 A1

39c

DK1 KK3 DK10 A1

39d

DK2 KK3 DK17 A1

39e

DK4 KK3 DK17 A1

39f

DK4 KK3 DK12 A1

39g

DK4 KK3 DK56 A1

39h

DK5 KK3 DK9 A1

39i

DK5 KK3 DK10 A1

39j

DK5 KK3 DK12 A1

39k

DK5 KK3 DK17 A1

39l

DK5 KK3 DK19 A1

39m

DK5 KK3 DK27 A1

39n

DK5 KK3 DK28 A1

39o

DK5 KK3 DK30 A1

39p

DK5 KK3 DK32 A1

39q

DK5 KK3 DK35 A1

39r

DK5 KK3 DK41 A1

39s

DK5 KK3 DK46 A1

39t

DK5 KK3 DK47 A1

39u

DK5 KK3 DK58 A1

39v

DK5 KK3 DK12 A7

39z

DK5 KK3 DK17 A12

41st

DK1 KK3 DK17 A1

41b

DK1 KK33 DK5 A1

41c

DK1 KK3 DK10 A1

Example No.

Dk1 Kk Dk2 TO

41d

DK2 KK3 DK17 A1

41e

DK4 KK3 DK17 A1

41f

DK4 KK3 DK12 A1

41g

DK4 KK3 DK56 A1

41h

DK5 KK3 DK9 A1

41i

DK5 KK3 DK10 A1

41j

DK5 KK3 DK12 A1

41k

DK5 KK3 DK17 A1

41l

DK5 KK3 DK19 A1

41m

DK5 KK3 DK27 A1

41n

DK5 KK3 DK28 A1

41st

DK5 KK3 DK30 A1

41p

DK5 KK3 DK32 A1

41q

DK5 KK3 DK35 A1

41r

DK5 KK3 DK41 A1

41s

DK5 KK3 DK46 A1

41t

DK5 KK3 DK47 A1

41u

DK5 KK3 DK58 A1

Example 42a:

image 1

Method A:

1) 1 mol of acid H was dissolved in 25% sodium hydroxide, diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. 1 mole of resorcinol was dissolved in 50% by weight sodium hydroxide at a pH value> 12. To this solution was added dropwise the diazotized acid H within 30 min at a temperature below 10 ° C, in which case the pH value was maintained by adding sodium hydroxide at 10% by weight. of 9.

3) 1 mol of MSP was suspended in ice water, diazotized with excess sodium nitrite and hydrochloric acid at

5 pH <1 and at a temperature of 0-5 ° C and added to the reaction mixture obtained in step 2). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, 0.40-0.60 mol of iron (III) sulfate was added to the reaction mixture and continued to stir for 1 hour. The dye was precipitated by the addition of NaCl and filtered with suction.

Method B:

1 1) 1 mol of acid H was dissolved in 25% sodium hydroxide and acetylated with 1.1-1.5 mol of acetic anhydride.

2) 1 mol of MSP was suspended in ice water and diazotized at pH <1 and at a temperature of 0-5 ° C with excess sodium nitrite and hydrochloric acid and added to the reaction mixture obtained in step 1) . PH value

It was maintained between 4 and 7 by the addition of sodium carbonate. After completion of the coupling, the pH value was adjusted below 1 by the addition of 21% hydrochloric acid by weight and the reaction mixture was

15 heated to 85-95 ° C. in this way the acetyl group dissociated.

3) In the product obtained in step 2) it was diazotized at pH <1 and at a temperature of 0-5 ° C with excess sodium nitrite and hydrochloric acid and added to an aqueous solution of 1 mol of resorcinol. The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide.

4) 1 mole of 5-nitro-2-aminophenol was suspended in ice water, diazotized with excess sodium nitrite and acid

20 hydrochloric at pH <1 and at a temperature of 0-5 ° C and added to the reaction mixture obtained in step 3). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After completion of the reaction, 0.40-0.60 mol of iron (III) sulfate was added to the reaction mixture and continued to stir for 1 hour. The dye was precipitated by the addition of NaCl and filtered with suction.

Example 43a:

The reaction was carried out according to the methods described in example 42a with the difference that a reaction with iron salts did not occur.

Example 44:

image 1

1) 1 mol of Cleve-7 acid was dissolved in 25% sodium hydroxide. Simultaneously 1 mole of was suspended

30 MSP in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and then added to the Cleve-7 acid solution, in which case the value of pH remained below 2.

2) The product obtained in step 1) was diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. The reaction mixture was then added to an aqueous solution of 1 mol of

35 resorcinol. The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide.

3) 1 mol of 5-nitro-2-aminophenol was suspended in ice water, diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and added to the reaction mixture obtained in step 2). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide. After finished

Example 45: The reaction was carried out according to the method described in example 44 with the difference that a reaction with iron salts

Example 46a:

image 1

Method A:

1) 1 mol of MSP was suspended in ice water, diazotized with excess sodium nitrite and hydrochloric acid at

10 pH <1 and at a temperature of 0-5 ° C. 1 mole of resorcinol was dissolved in 50% by weight sodium hydroxide. To this solution, the diazotized MSP was added dropwise over the course of 30 min at a temperature below 10 ° C in which case the pH value between 6 and 8 was maintained by adding 10% by weight sodium hydroxide.

2) 1 mol of acid H was dissolved in 25% sodium hydroxide, diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and added to the reaction mixture obtained in step 1).

The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide.

3) 1 mole of 5-nitro-2-aminophenol was suspended in ice water, then diazotized with excess sodium nitrite at pH <1 and at a temperature of 0-5 ° C and then added to the reaction mixture obtained in step 3). The pH value was maintained by adding 10% sodium hydroxide by weight between 3 and 8. After completion of the reaction, 0.40-0.60 mol of iron (III) sulfate was added to the reaction mixture and kept stirring by

20 1 hour. The dye is precipitated by the addition of NaCl and filtered with suction.

Method B:

1) 1 mol of MSP was suspended in ice water, diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. 1 mole of resorcinol was dissolved in 50% by weight sodium hydroxide. To this the diazotized MSP was added dropwise over the course of 30 min at a temperature below 10 ° C, in which

25 case by adding 10% by weight sodium hydroxide the pH value was maintained between 6 and 8.

2) 1 mol of acid H was dissolved in 25% sodium hydroxide and acetylated with 1.1-1.5 mol of acetic anhydride.

3) 1 mol of 5-nitro-2-aminophenol was suspended in ice water, then diazotized with excess sodium nitrite at pH <1 and at a temperature of 0-5 ° C and added to the reaction mixture obtained in step 2). The pH value was maintained by adding sodium carbonate between 4 and 7. After the coupling was finished, the

30 pH value below 1 by the addition of 21% hydrochloric acid by weight and the reaction mixture was heated to 85-95 ° C, in which case the acetyl group dissociated.

4) The product obtained in step 3) was diazotized at pH <1 and at a temperature of 0-5 ° C with excess sodium nitrite and diazotiert hydrochloric acid and added to the reaction mixture obtained in step 1). The pH value was maintained between 3-8 by the addition of 10% by weight sodium hydroxide. After the end of the reaction,

35 added 0.40-0.60 mol of iron (III) sulfate to the reaction mixture and continued to stir for 1 hour. The dye was precipitated by the addition of NaCl and filtered with suction.

The reaction was carried out according to the methods described in example 46a with the difference that a reaction with iron salts did not occur.

Example 48:

image 1

5 1) 1 Mol of MSP was suspended in ice water, diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. 1 mole of resorcinol was dissolved in 50% by weight sodium hydroxide. To this, the diazotized MSP was added dropwise over the course of 30 min at a temperature below 10 ° C, in which case the pH value between 6 and 8 was maintained by the addition of 10% by weight sodium hydroxide.

2) 1 mole of 5-nitro-2-aminophenol was suspended in ice water, diazotized with excess sodium nitrite and acid

10 hydrochloric acid at pH <1 and a temperature of 0-5 ° C and 25% sodium hydroxide solution of 1 mol of Cleve-7 acid was added, in which case the pH value was kept below 2.

3) The product obtained in step 2) was diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and then added to the reaction mixture obtained in step 1). The pH value was maintained by adding 10% by weight sodium hydroxide between 3-8. After the end of the reaction,

The dye was precipitated by the addition of NaCl and filtered with suction.

In a manner analogous to examples 42a, 44 and 46a, the metallic dye complexes of the general formula Dk1-N = N-Napht-N = N-Kk-N = N-Dk2 (= dyes of the general formula I can be obtained where P = Napht, p = 1 and m = 1), where Dk1 and DK2 either represent one of the diazo components DK1 to DK9, DK13, DK14, DK26, DK27, DK39 to DK41 or DK58 or represent a residue derived from A1 to A12 , in which case at least one of the waste

Dk1 or Dk2 represents a residue of the formula A, Kk represents a bivalent residue derived from Kk2 or Kk3 and Napht is a bivalent residue of the formulas II-1, II-3, II-5, II-7, II-9 , II-11, II-13, II-15 or II-16. Examples of these are indicated in table 12.

Table 12 In a manner analogous to examples 43a, 45, 47a and 48, dyes of the general formula Dk1-N = N-Napht-N = N-Kk-N = N-Dk2 (= dyes of the general formula can be obtained I where P = Napht, p = 1 and m = 1), where Dk1 and DK2 represent one of the diazo components DK1 to DK83 or represent a residue derived from A1 to A12, in which case at least one of the residues Dk1 or Dk2 represents a residue of the formula A, Kk represents a bivalent residue derived from Kk2, Kk3, Kk5, Kk49 or Kk50 and Napht is a bivalent residue of the formulas II-1, II-3, II-5, II-7, II-9 , II-11, II-13, II-15 or II-16. Examples of these are indicated in table 13.

Example No.

Dk1 Napht Kk Dk2 I

42nd

A1 DK44 Kk3 DK1 Faith

42b

A1 DK44 Kk3 DK4 Cu

42c

A1 DK44 Kk3 DK5 Faith

42d

A7 DK44 Kk3 DK5 Faith

42e

A1 DK44 Kk3 DK40 Faith

42f

A1 DK44 Kk3 DK58 Cr

42g

A1 DK57 Kk3 DK5 Faith

Example No.

Dk1 Napht Kk Dk2 I

42h

DK1 DK44 Kk3 A1 Faith

42i

DK2 DK44 Kk3 A1 Faith

42j

DK4 DK44 Kk3 A1 Faith

42k

DK5 DK44 Kk3 A1 Faith

42l

DK27 DK44 Kk3 A1 Faith

42m

DK41 DK44 Kk3 A1 Faith

42n

A3 DK44 Kk3 DK5 Faith

42o

A9 DK44 Kk3 DK40 Faith

46th

DK1 DK44 Kk3 A1 Faith

46b

DK2 DK44 Kk3 A1 Faith

46c

DK4 DK44 Kk3 A1 Faith

46d

DK5 DK44 Kk3 A1 Faith

46e

DK27 DK44 Kk3 A1 Faith

46f

DK41 DK44 Kk3 A1 Faith

46g

A1 DK44 Kk3 DK1 Faith

46h

A1 DK44 Kk3 DK4 Cu

46i

A1 DK44 Kk3 DK5 Faith

46j

A7 DK44 Kk3 DK5 Faith

46k

A1 DK44 Kk3 DK40 Faith

46l

A1 DK44 Kk3 DK58 Cr

46m

A1 DK57 Kk3 DK5 Faith

Example No.

Dk1 Napht Kk Dk2

43rd

A1 DK44 Kk3 DK1

43b

A1 DK44 Kk3 DK4

43c

A1 DK44 Kk3 DK5

43d

A7 DK44 Kk3 DK5

43e

A1 DK44 Kk3 DK9

43f

A1 DK44 Kk3 DK10

43g

A1 DK44 Kk3 DK12

43h

A1 DK44 Kk3 DK28

43i

A1 DK44 Kk3 DK32

43j

A1 DK44 Kk3 DK37

43k

A1 DK44 Kk3 DK40

43l

A1 DK44 Kk3 DK46

43m

A1 DK44 Kk3 DK58

43n

A1 DK57 Kk3 DK5

43rd

DK1 DK44 Kk3 A1

43p

DK2 DK44 Kk3 A1

43q

DK4 DK44 Kk3 A1

43r

DK5 DK44 Kk3 A1

43s

DK8 DK44 Kk3 A1

43t

DK10 DK44 Kk3 A1

43u

DK12 DK44 Kk3 A1

43v

DK17 DK44 Kk3 A1

43z

DK27 DK44 Kk3 A1

43rd

DK28 DK44 Kk3 A1

43ab

DK32 DK44 Kk3 A1

Example No.

Dk1 Napht Kk Dk2

43ac

DK41 DK44 Kk3 A1

43ad

DK46 DK44 Kk3 A1

43ae

DK47 DK44 Kk3 A1

43af

DK28 DK44 Kk3 A3

43ag

DK32 DK45 Kk3 A7

43ah

DK41 DK45 Kk3 A8

43ai

DK46 DK45 Kk3 A11

47th

DK1 DK44 Kk3 A1

47b

A1 DK44 Kk3 DK4

47c

A1 DK44 Kk3 DK5

47d

A7 DK44 Kk3 DK5

47e

A1 DK44 Kk3 DK9

47f

A1 DK44 Kk3 DK10

47g

A1 DK44 Kk3 DK12

47h

A1 DK44 Kk3 DK28

47i

A1 DK44 Kk3 DK32

47j

A1 DK44 Kk3 DK37

47k

A1 DK44 Kk3 DK40

47l

A1 DK44 Kk3 DK46

47m

A1 DK44 Kk3 DK58

47n

A1 DK57 Kk3 DK5

47th

A1 DK44 Kk3 DK1

47p

DK2 DK44 Kk3 A1

47q

DK4 DK44 Kk3 A1

47r

DK5 DK44 Kk3 A1

Example No.

Dk1 Napht Kk Dk2

47s

DK8 DK44 Kk3 A1

47t

DK10 DK44 Kk3 A1

47u

DK12 DK44 Kk3 A1

47v

DK17 DK44 Kk3 A1

47z

DK27 DK44 Kk3 A1

47aa

DK28 DK44 Kk3 A1

47ab

DK32 DK44 Kk3 A1

47ac

DK41 DK44 Kk3 A1

47ad

DK46 DK44 Kk3 A1

47ae

DK47 DK44 Kk3 A1

47af

DK28 DK44 Kk3 A2

47ag

DK32 DK45 Kk3 A6

47ah

DK41 DK45 Kk3 A9

47ai

DK46 DK45 Kk3 A10

Example 49a:

image 1

1) 1 mol of 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and reacted with 1 mol of acid salicylic at a pH value of 5 to 11.

5 2) 1 mol of resorcinol was dissolved in 50% by weight sodium hydroxide at a pH value> 12. To this solution, the reaction product obtained in step 1) was added dropwise over a period of 30 min at a temperature below 10 ° C, in which case by adding 10% by weight sodium hydroxide, the pH value above 9.

3) 1 Mol of MSP was suspended in ice water, diazotized with excess sodium nitrite and hydrochloric acid at

10 pH <1 and at a temperature of 0-5 ° C. The diazotized MSP was then added to the reaction mixture obtained in step 2), in which case by adding 10% by weight sodium hydroxide the pH value was maintained between 5 and 8. After the end of the reaction, added 1 mol of copper (II) sulfate to the reaction mixture and continued stirring for 1 hour at 70 ° C. The dye was precipitated by the addition of NaCl and filtered with suction.

The reaction was carried out according to the method described in example 49a with the difference that a reaction did not occur with copper salts. Example 51:

image4

1) 1 mol 4,4-Diaminobenzanilid was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and reacted with 1 mol of salicylic acid at a pH value of 5-11 .

2) 1 Mol MSP was suspended in ice water, diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C. 1 mole of resorcinol was dissolved in 50% by weight sodium hydroxide. This is

10 the diazotized MSP was added dropwise over a period of 30 min at a temperature below 10 ° C, in which case the pH value was maintained between 6 and 8 by the addition of 10% by weight sodium hydroxide.

3) The product obtained in step 2) was added to the reaction mixture obtained in step 1), in which case the pH value between 5 and 8 was maintained by adding 10% by weight sodium hydroxide. After completion of the reaction, the dye was precipitated by addition of NaCl and filtered with suction.

In a manner analogous to examples 49a, 50a and 51, the dyes of the general formula Kk3N = NTk-N = N-Kk1-N = NA and their metal complexes (= dyes of the general formula XIV) can be obtained, where Kk3 they represent a residue derived from the coupling components Kk1 to Kk48 or Kk51 to Kk67 or represents Dk42 to Dk83, Tk represents a bivalent residue derived from TK1 to Tk20, Kk1 represents a bivalent residue derived from Kk2, Kk3, Kk5, Kk49 or Kk50 and A means one of the residues A1 to A12. Examples of these are indicated in the table

2014.

Table 14: 1) 2 mol of acid H were dissolved in 25% sodium hydroxide, diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and added to a solution 1 mol aqueous of 3,3'dihydroxydiphenylamine. The pH value was maintained by adding 10% by weight sodium hydroxide between 3 and 5.

Example No.

Kk3 Tk Kk1 TO I

49th

Kk1 Tk11 Kk3 A1 Cu

49b

Kk40 Tk11 Kk3 A1 Cu

49c

Dk46 Tk8 Kk3 A1 Cu

50th

DK44 Tk16 Kk3 A1

50b

DK44 Tk18 Kk3 A1

50c

Kk39 Tk18 Kk3 A1

image 1

2) 2 mol MSP were suspended in ice water, diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and added to the reaction mixture obtained in step 1). The pH value was maintained by adding 10% by weight sodium hydroxide between 3-8. After completion of the reaction, the dye was precipitated by addition of NaCl and filtered with suction.

In a manner analogous to example 52a, the dyes of the general formula Dk1-N = NPN = N-Kk1N = NR-N = N-Dk2 and their metal complexes (dyes of the general formula XV) can be obtained, where Dk1 and DK2 they represent one of the diazo components DK1 to DK83 or represent they represent a residue derived from A1 to A12, in which case at least one of the residues Dk1 or Dk2 represents a residue of the formula A, Kk represents a bivalent residue derived from Kk2, Kk3, Kk5, Kk49 or Kk50 and P and R respectively represent a bivalent residue derived from the

15 formulas II-1, II-3, II-5, II-7, II-9, II-11 and II-13. Examples of these are indicated in table 15.

Table 15: 1) 1 mol of MSP was suspended in ice water, diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and added to an alkaline solution of 1 mol of Cleve acid - 7. The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide.

Example No.

Dk1 P Kk1 R Dk2 Metal

52a

A1 DK44 Kk50 DK44 A1

52b

A1 DK44 Kk50 DK44 A1 Cu

52c

A1 DK44 Kk50 DK44 A1 Co

52d

A1 DK44 Kk49 DK44 A1 Cu

52e

A1 DK44 Kk49 DK44 A1 Co

image 1

5 2) 1 mol MSP was suspended in ice water, diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and added to a 1 mol alkaline solution of acid 8- aminonaphthalene-1-sulfonic acid (Dk56). The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide.

3) The product obtained in step 1) was diazotized at pH <1 and at a temperature of 0-5 ° C with excess sodium nitrite and hydrochloric acid and was added over a period of 30 minutes to a 1 mol alkaline solution of 3,3,10 dihydroxydiphenylamine. The pH value was maintained between 3 and 8 by the addition of 10% by weight sodium hydroxide.

4) The product obtained in step 2) was diazotized at pH <1 and at a temperature of 0-5 ° C with excess sodium nitrite and hydrochloric acid and added to the reaction mixture obtained in step 3), in in which case, by adding 10% by weight sodium hydroxide, the pH value was maintained between 5 and 8. After completion of the reaction, the dye was precipitated by the addition of NaCl and filtered with suction.

In a manner analogous to example 53a, the dyes of the general formula Dk1-N = NPN = N-Kk1N = NR-N = N-Dk2 and their metal complexes (dyes of the general formula XV) can be obtained, where Dk1 and DK2 they represent one of the diazo components DK1 to DK83 or represent a residue derived from A1 to A12, in which case at least one of the residues Dk1 or Dk2 represents a residue of the formula A, Kk represents a bivalent residue derived from Kk2, Kk3, Kk5 , Kk49 or Kk50 and P and R respectively represent a bivalent residue of formulas II-15 or II-16 or

20 represents a bivalent residue derived from the diazo components DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK22 to DK27, DK29, DK30, DK33, DK36, DK38, or DK39. Examples of these are indicated in table 16.

Table 16: 1) 2 mol of anthranilic acid was dissolved in sulfuric acid (96%) at a temperature of 70-80 ° C and reacted with 0.50.6 mol of formaldehyde. After 2 hours at 70-80 ° C the reaction mixture was cooled by adding ice to about 0 ° C and the product obtained was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at

Example No.

Dk1 P Kk1 R Dk2 Metal

53a

A1 DK46 Kk50 DK56 A1

53b

A1 DK4 Kk49 DK46 A1 Cu

53c

A1 DK4 Kk49 DK46 A1 Co

53d

A1 DK4 Kk50 DK46 A1 Cu

image 1

5 temperature of 0-5 ° C. 1.8-2.2 mol of resorcinol was dissolved in 50% by weight sodium hydroxide at a pH value> 12 and to this solution the tetrazotized compound was added dropwise over a period of 30 minutes at a temperature below 5 ° C, in which case by adding 10% by weight sodium hydroxide the pH value was maintained above 8.

2) 2 mol MSP was suspended in ice water, diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and

10 at a temperature of 0-5 ° C and added to the reaction mixture obtained in step 1). The pH value was maintained by adding 10% sodium hydroxide by weight between 3 and 8. After the reaction was finished, the reaction solution was heated to 80 ° C and 2 mol of CuSO4 was added. The reaction mixture obtained was then evaporated, in which case the complexed dye was obtained.

Example 55:

The reaction was carried out according to the method described in example 54 with the difference that a reaction with copper salts did not occur.

Example 56:

image 1

1) 2 mol of anthranilic acid was dissolved in sulfuric acid (96%) at a temperature of 70-1), 2 mol of acid

Anthranilic was dissolved in sulfuric acid (96%) at a temperature of 70-80 ° C and reacted with 0.5-0.6 mol of formaldehyde. After 2 hours at 70-80 ° C the reaction mixture was cooled by adding ice to about 0 ° C and the product obtained was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0- 5 ° C

2) 2 mol of MSP was suspended in ice water, diazotized with excess sodium nitrite and hydrochloric acid to

25 pH <1 and at a temperature of 0-5 ° C. 2 mol of resorcinol was dissolved in 50% by weight sodium hydroxide. To this the diazotized MPS was added dropwise over the course of 30 min at a temperature below 10 ° C, in which case by adding 10% by weight sodium hydroxide the pH value was maintained between 6 and 8.

3) The reaction mixture obtained in step 1) was added to the reaction mixture obtained in step 2). The pH value was maintained by adding 10% by weight sodium hydroxide between 3 and 8. After the end of the

The reaction solution was heated to 80 ° C and 2 mol of CuSO4 was added. The reaction mixture obtained was then concentrated to dryness, in which case the complexed dye was obtained.

The reaction was carried out according to the method described in example 56a with the difference that a reaction with copper salts did not occur.

In a manner analogous to examples 54 and 56, the metal complexes of the dyes of the general formula Dk1-N = N-Kk1-N = N-Tk1-N = N-Kk2-N = N-Dk2 (dyes of general formula IV), where Dk1 and DK2

5 represent one of the diazo components DK1 to DK83 or represent a residue derived from A1 to A12, in which case at least one of the residues Dk1 or Dk2 represents a residue of the formula A, Tk1 represents a bivalent residue derived from Tk3, Tk4, Tk8 to Tk11, Tk14, Tk16 or Tk19, and Kk1 and Kk2, independently of each other represent a bivalent residue derived Kk2, Kk3, Kk5, Kk49 or Kk50 or represents a bivalent residue of formulas II-2, II-4, II -6, II-8, II-10, II-12 or II-14.

In a manner analogous to Examples 55 and 57, the dyes of the general formula Dk1-N = NKk1N = N-Tk1-N = N-Kk2-N = N-Dk2 (dyes of the general formula IV) can be obtained, where Dk1 and DK2 represent one of the diazo components DK1 to DK83 or represent a residue derived from A1 to A12, in which case at least one of the residues Dk1 or Dk2 represents a residue of the formula A, Tk1 represents a bivalent residue derived from Tk1 to Tk20, and Kk1 and Kk2 independently of each other represent a bivalent residue derived from Kk2, Kk3, Kk5,

15 Kk49 or Kk50 or represent a bivalent residue of formulas II-2, II-4, II-6, II-8, II-10, II-12 or II-14.

Example 58:

image 1

1) 1 mol of Cleve-7 acid was dissolved in 25% sodium hydroxide. Simultaneously 1 mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of

20-5-5 ° C and then Cleve-7 acid solution was added, in which case the pH value was kept below 2.

2) The product obtained in step 1) was diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 0-5 ° C and then reacted with 1 mol of methanol at a pH value of 3- 8. After completion of the reaction, the dye was precipitated by addition of NaCl and filtered with suction.

In a manner analogous to example 58, the dyes of the general formula AN = N-Napht-N = N-Kk (= dyes of the general formula I where P = Napht, p = 1 and m = 0), where Napht can be obtained represents a residue derived from DK42 to DK59, Kk represents a residue derived from Kk1 to Kk48 or Kk51 to Kk67 and A means one of residues A1 to A12. Examples of these are indicated in table 17.

Table 17: 1 mol of Cleve-7 acid was dissolved in 25% sodium hydroxide. Simultaneously 1 mole of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <1 and at a temperature of 05 ° C and then added to the Cleve-7 acid solution, in which case the pH value was maintained by

Example No.

TO Napht Kk

58th

A1 Dk46 Kk5

58b

A1 Dk46 Kk27

58c

A1 Dk44 Kk27

image 1

5 below 2. After the reaction was over, the dye solution was spray dried.

In a manner analogous to example 59a, the dyes of the general formula AN = N-Kk (= dyes of the general formula I where p = m = 0) can be obtained, where Kk represents a residue derived from Kk1 to Kk48, Kk51 to Kk67 or of DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK21 bis DK27, DK29, DK30, DK33, DK36, DK38, DK39, or Dk42 to Dk83 and A means one of residues A1 to A12 . Depending on the pH value of the reaction, the coupling of the residue A-N = N- can be carried out both in the ortho position towards the hydroxyl group and also in the ortho position towards the amino group in Dk42 to Dk57 and in Dk59. Examples of these are indicated in the table

18.

Table 18:

Example No.

TO Napht

59th

A1 DK47

59b

A1 Kk32

59c

A1 DK44

59d

A1 Kk15

59e

A1 DK42

59f

A7 DK42

59g

A7 DK47

59h

A7 Kk46

59i

A7 DK52

59j

A4 DK52

59k

A4 DK47

Dyeing Procedures:

15 All data should be understood as parts by weight. All data with respect to tanning agents, water-repellent agents, grease impregnating agents and adjuvants refer to usual commercial products (merchandise). The dye data refers to the entire amounts of chemical-organic color components, optionally salts present depending on the production (synthesis salts) and flow conditioners optionally present.

The fixation performance was determined qualitatively by means of HPLC research and quantitatively by means of UV-VIS spectroscopic investigation of the dye immersion liquid. For this purpose, 5 ml samples are taken after dyeing (pH <7), after fixation for 60 min, 120 min, 180 min (pH> 7) and for each immersion liquid in the wash water and the pH is adjust to 3-4 with 1 ml of formic acid solution. The samples were investigated by means of HPLC for the dye and its hydrolysis products. The research was carried out on HPLC Nucleodur C18 Gravity 3, CC70 / 2 and Hypersil 120-5 ODS, CC100 / 2 columns of the Macherey-Nagel company. Acetonitrile / buffer (1.6 g of tetrabutylammonium hydrosulfate, 6 g of dipotassium hydrophosphate trihydrate in 1 L of water) served as eluents.

The color retention determination was made in accordance with the following internationally recognized standards:

Color fastness to sweat: in accordance with Veslic C4260

Color fastness to washing: in accordance with DIN EN ISO 15703

Color fastness to migration: in accordance with DIN EN ISO 15701, as well as 16 hours of storage at 85 ° C at a humidity of 95% under conditions otherwise analogous to those of DIN EN ISO 15701

Rub color fastness: in accordance with DIN EN ISO 105 - X12 (crockmeter, friction with cotton fabric) as well as in accordance with DIN EN ISO 11640 (Vesicle, rub with felt)

Maeser: in accordance with ASTM D 2099

Penetrometer: in accordance with DIN EN ISO 5403

Water vapor permeability: in accordance with DIN EN ISO 14268

Prolonged bending resistance: in accordance with DIN EN ISO 5402

Seam tear test: in accordance with DIN 5331

Tear propagation test: in accordance with DIN EN ISO 3377

Breaking strength: in accordance with DIN EN ISO 3376

Dyeing Procedure 1:

a) A piece of leather of 100 parts by weight of an organically dyed beef leather in a usual manner, of a recess thickness of 1.1 mm was washed at 30 ° C in a barrel filled with 200 parts of water. It was then stained with 150 parts of water, 2 parts of dispersing agent and 5 parts of dye from Example 2d for 60 minutes at pH 4.4 and 30 ° C. Adding 100 parts soda solution to 15% by weight in portions, to fix the dye the pH value between 10.0 and 10.2 was kept batting at 40 ° C for 60 minutes. A 10-minute wash operation followed 6 times in 200 parts of water at 40 ° C. A pH of 4.7 was adjusted by adding 200 parts of water and 0.7 parts of formic acid.

b) The dyed leather in this manner was retanned in a freshly prepared immersion liquid of 100 parts of water, 2 parts of polymeric tanning agent and 2 parts of a natural base grease impregnation liquor for 30 minutes at 35 ° C. Next, 15 parts of a liquid synthetic tanning agent, 6 parts of polymeric tanning, 10 parts of Tara (vegetable tanning) were added to the immersion liquid and beaten 120 minutes. The leather was then impregnated with grease in the same immersion liquid with 8 parts of a fish oil-based grease impregnation liquid and 2 parts of a lecithin-based fat impregnation liquid battling for 2 hours at 35 ° C. Finally it was acidified with 2 parts of concentrated formic acid at pH 3.6 and batted twice for 10 minutes and once for 30 minutes. The dyed, retanned and fat-impregnated leather was further washed with cold water at 15 ° C for 10 minutes and then stretched, dried overnight at room temperature, conditioned, put on stakes and tensioned.

A deep, bright red leather was obtained, which has excellent color fastness to wash, sweat, rub and migration.

Dyeing procedure 2:

a) A piece of leather of 100 parts by weight of a conventionally tanned beef leather of a 1.1 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water. It was then stained with 150 parts of water, 2 parts of dispersing agent and 5 parts of dye from Example 2a for 60 minutes at pH 4.4 and 30 ° C. To fix the dye, adding 15 parts of solid soda in portions, the pH value was maintained at 10.0 by beating at 40 ° C for 60 minutes. A 10-minute washing operation followed, 4 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 0.7 parts of formic acid it was adjusted to a pH of 4.7. The procedure was followed as described in the dyeing procedure 1 in item b).

A deep, bright red leather was obtained, which has excellent color fastness to washing, sweat, rubbing and migration.

Dyeing procedure 3:

a) A piece of leather of 100 parts by weight of an organically tanned beef leather of a 1.1 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of Water. It was then stained with 150 parts of water, 2 parts of dispersing agent and 5 parts of dye from Example 24 for 60 minutes at pH 4.4 and 30 ° C. To fix the dye, adding 100 parts of 15% by weight soda solution in portions, beating at 50 ° C for 60 minutes, the pH value was maintained at 10.0. A 10-minute wash operation was then carried out 4 times in 200 parts of water at 40 ° C. Addition of 200 parts of water and 0.7 parts of formic acid is adjusted to a pH of 4.7. The procedure was followed as in the dyeing procedure 1 in subparagraph b).

A red leather was obtained, with a deep, bright color, which has excellent washing, sweat, rub and migration fastness.

Dyeing procedure 4:

A piece of leather of 100 parts by weight of an organically tanned beef leather of a 1.1 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water . It was then stained with 150 parts of water, 2 parts of a dispersing agent and 5 parts of dye from example 58a for 60 minutes at pH 4.4 and 30 ° C. To fix the dye, adding 100 parts of 15% by weight soda solution by batting at 40 ° C for 90 minutes the pH value was maintained at 10.0. A 10-minute wash operation was then carried out 3 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 0.7 parts of formic acid it was adjusted to a pH of 4.7. The procedure was followed as in the dyeing procedure 1 in subparagraph b).

A red leather was obtained, with a deep, bright color, which has excellent washing, sweat, rub and migration fastness.

Dyeing procedure 5:

A piece of leather of 100 parts by weight of an organically tanned beef leather of a 1.1 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water . It was then stained with 150 parts of water, 2 parts of a dispersing agent and 5 parts of dye from example 58b for 60 minutes at pH 4.4 and 30 ° C. To fix the dye, adding 100 parts of 15% by weight soda solution in portions, beating at 40 ° C for 60 minutes, the pH value was maintained at 10.0. Simultaneously, with the addition of soda solution, 15 parts of Glauber salt were added in 3 portions in total. A 10-minute wash operation was then carried out 5 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 0.7 parts of formic acid it was adjusted to a pH of 4.7. The procedure was followed as described in the dyeing procedure 1 in item b).

A red leather was obtained, with a deep, bright color, which has excellent washing, sweat, rub and migration fastness.

Dyeing procedure 6:

A piece of leather of 100 parts by weight of an organically tanned beef leather of a 1.0 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water . It was then stained with 150 parts of water, 2 parts of a dispersing agent and 5 parts of dye from example 59a for 60 minutes at pH 4.1 and 30 ° C. To fix the dye, adding 100 parts of a borax buffer in portions, batting at 40 ° C for 180 minutes, the pH was maintained in the range of 7.9 and 9.0. A 10-minute wash operation was then carried out 5 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 0.6 parts of acid A red leather was obtained, with a deep color, bright, which has excellent fastness to washing, sweat, rubbing and migration

Dyeing procedure 7:

A piece of leather of 100 parts by weight of an organically tanned beef leather of a 1.0 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water . It was then stained with 150 parts of water, 2 parts of a dispersing agent and 5 parts of dye from example 59e for 60 minutes at pH 4.1 and 30 ° C. By adding only 30 parts of a 15% by weight soda solution, the pH was maintained at 40 ° C at a range of 9.4-9.9 to fix the dye for 180 minutes. A 10-minute wash operation was then carried out 3 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 0.7 parts of formic acid it was adjusted to a pH of 4.5. Then, the procedure was as described in the dyeing procedure 1 literal b).

A red leather was obtained, with a deep, bright color, which has excellent washing, sweat, rub and migration fastness.

Dyeing procedure 8:

A piece of leather of 100 parts by weight of an organically tanned beef leather of a 1.0 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water : It was then stained with 150 parts of water, 2 parts of a dispersing agent and 5 parts of dye from Example 2b for 60 minutes at pH 4.1 and 30 ° C. To fix the dye, adding 100 parts of a borax buffer in portions, batting at 40 ° C for 180 minutes, the pH was maintained in the range of 8.0 and 9.0. Then a 10-minute operation took place 3 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 0.7 parts of formic acid it was adjusted to a pH of 4.5. Then, the procedure was as described in the dyeing procedure 1 literal b).

A deep-colored blue leather was obtained which has excellent washing, sweat, rub and migration fastness.

Dyeing procedure 9:

A piece of leather of 100 parts by weight of an organically tanned beef leather of a 1.0 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water. It was then stained with 150 parts of water, 2 parts of a dispersing agent and 5 parts of dye from Example 2k for 30 minutes at pH 4.2 and 30 ° C. By adding 30 parts of a 15% by weight soda solution once, the pH was maintained at 40 ° C at a range of 9.4-9.9 to fix the dye for 180 minutes. A 10-minute wash operation was then carried out 3 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 0.7 parts of formic acid it was adjusted to a pH of 4.8. Then, the procedure was as described in the dyeing procedure 1 literal b).

A deep-colored blue leather was obtained which has excellent washing, sweat, rub and migration fastness.

Dyeing procedure 10:

A piece of leather of 100 parts by weight of an organically tanned beef leather of a 1.0 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water. It was then stained with 100 parts of water, 2 parts of a dispersing agent and 5 parts of dye from example 11a for 30 minutes at pH 4.2 and 30 ° C. To fix the dye, adding 20 parts of a 15% by weight soda solution batting at 40 ° C for 180 minutes, the pH was maintained in the range of 8.6-9.3. A 10-minute wash operation was then carried out 3 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 0.7 parts of formic acid it was adjusted to a pH of 4.8. The procedure was followed as in the dyeing procedure 1 literal b).

A deep bordeaux color leather was obtained which has excellent washing, sweat, rub and migration fastness.

A piece of leather of 100 parts by weight of an organically tanned beef leather of a 1.0 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water . It was then stained with 150 parts of water, 2 parts of a dispersing agent and 5 parts of dye from Example 12ae for 45 minutes at pH 4.3 and 30 ° C. To fix the dye, adding 40 parts of a 7% sodium bicarbonate solution in portions, batting at 40 ° C for 240 minutes, the pH was maintained in the range of 7.3-8.2. A 10-minute wash operation was then carried out 6 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 1.2 parts of formic acid it was adjusted to a pH of 3.9. The procedure was followed as in the dyeing procedure 1 literal b).

A deep, bright blue leather was obtained, which has excellent wash, sweat, rub and migration fastness.

Dyeing procedure 12:

A piece of leather of 100 parts by weight of an organically tanned beef leather of a 1.0 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water . It was then stained with 150 parts of water, 2 parts of a dispersing agent and 5 parts of dye from example 13c for 30 minutes at pH 4.1 and 30 ° C. To fix, adding 40 parts of a 7% sodium carbonate solution in portions, the pH was adjusted to 7.9-8.1 and beaten for 60 minutes, then in three portions 15 parts of salt were added. Glauber and batted for another 120 minutes at pH 8.1-9.0. A 10-minute wash operation was then carried out 3 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 1.0 parts of formic acid it was adjusted to a pH of 3.8. Then, the procedure was as described in the dyeing procedure 1 literal b).

A dark green leather of deep color was obtained which has excellent fastness to washing, sweat, rubbing and migration.

Dyeing procedure 13:

A piece of leather of 100 parts by weight of an organically tanned beef leather of a 1.0 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water . It was then stained with 150 parts of water, 2 parts of a dispersing agent and 5 parts of dye from Example 12n for 45 minutes at pH 4.2 and 30 ° C. To fix, adding 20 parts of a 15% by weight soda solution in portions, the pH was adjusted between 8.4-9.2 and beaten for 120 minutes. A 10-minute wash operation was then carried out twice in 200 parts of water at 40 ° C. By adding 200 parts of water and 1.1 parts of formic acid it was adjusted to a pH of 3.9. Then, the procedure was as described in the dyeing procedure 1 literal b).

A black leather was obtained which has excellent washing, sweat and migration fastness.

Dyeing Procedure 14:

A piece of leather of 100 parts by weight of an organically tanned beef leather of a 1.0 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water . It was then stained with 150 parts of water, 2 parts of a dispersing agent and 5 parts of dye from example 13i for 60 minutes at pH 4.2 and 30 ° C. Adding portions 21 parts of a 15% by weight soda solution for fixation, the pH was adjusted between 8.8-9.3 and beaten for 180 minutes. A 10-minute wash operation was then carried out 6 times in 200 parts of water at 40 ° C. A pH of 4.5 was adjusted by adding 200 parts of water and 0.7 parts of formic acid. Then, the procedure was as described in the dyeing procedure 1 literal b).

A dark green leather of deep color was obtained which has excellent fastness to washing, sweat, rubbing and migration.

Dyeing procedure 15:

A piece of leather of 100 parts by weight of an organically tanned beef leather of a 1.0 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water. It was then stained with 150 parts of water and 5 parts of dye from Example 59e for 60 minutes at pH 4.1 and 30 ° C. By adding portions of 21 parts of a 15% by weight soda solution for fixation, the pH was adjusted between 8.8-9.3 and a deep, bright red leather was obtained, which has excellent solidity to wash, sweat, rub and migration.

Dyeing procedure 16:

A piece of leather of 100 parts by weight of a chrome-tanned beef leather, of a 1.8 mm recess thickness, was washed in a barrel filled with 200 parts of water and 0.1 parts of formic acid for 10 minutes at 35 ° C and then neutralized in an immersion liquid composed of 100 parts of water, 2 parts of sodium formate, 1 part of sodium acetate, 0.5 parts of sodium bicarbonate and 1 part of a dispersing agent for 120 minutes at 35 ° C. The deadification liquid then had a pH value of 5.0. The leather was then washed with 200 parts of water for 10 minutes at 35 ° C. The leather neutralized in this way was retanned in a freshly prepared immersion liquid of 30 parts of water and 2 parts of a polymeric dye for 30 minutes at 30 ° C. Next, the immersion liquid was mixed with 2 parts of a hydrophobic grease impregnating agent. After a beating time of another 30 minutes, 5 parts of a sulfone tanner and 4 parts of a resin tanner were added and batted for another 60 minutes. Finally, it was acidified with 0.5% formic acid to pH 4.0 and batted once for 10 minutes and once for 30 minutes.

In a dipping liquid prepared from 150 parts of water, 2 parts of a dispersing agent, 5 parts of dye from example 59f and 0.2 parts of sodium bicarbonate, it was stained for 90 minutes at pH 4.8 and 35 ° C . By adding 40 parts of a 15% by weight soda solution for fixation, the pH was adjusted between 9.0-9.3 and for 180 minutes it was batted at 40 ° C. A 10-minute wash operation was then carried out 6 times in 200 parts of water at 40 ° C. A pH of 4.5 was adjusted by adding 200 parts of water and 0.7 parts of formic acid.

In a new immersion liquid composed of 100 parts of water, 4.5 parts of a mixed liquid (base of sulphited fish oil and synthetic oil), 0.5 parts of a liquid based on lanolin the leather is impregnated with grease batting for 40 minutes at 55 ° C. It was then acidified with 1.5 parts of concentrated formic acid to pH 3.5 and batted for 40 minutes. The dyed and grease-impregnated leather was further washed with cold water at 15 ° C for 10 minutes and then stretched, dried overnight at room temperature, conditioned, staked and tensioned.

A deep, bright red leather was obtained, which has excellent wash, sweat, rub and migration fastness.

Dyeing procedure 17:

A piece of leather of 100 parts by weight of a usual tanned beef leather, with a recess thickness of 1.8 mm, was washed in a barrel filled with 200 parts of water and 0.1 part of formic acid per 10 minutes at 35 ° C and then neutralized in an immersion liquid composed of 100 parts of water, 2 parts of sodium formate, 1 part of sodium acetate, 1.5 parts of sodium bicarbonate and 1 part of an agent dispersant for 120 minutes at 35 ° C. Then, the deacidification liquid had a pH value of 6.3. It was then washed with 200 parts of water for 10 minutes at 35 ° C.

In a freshly prepared immersion liquid of 150 parts of water and 5 parts of dye from example 35g, it was stained for 60 minutes at pH 5.6 and 30 ° C. Adding portions 13 parts of a 15% by weight soda solution the pH value of the immersion liquid was adjusted between 8.5-9.1 and batted for 180 minutes at 40 ° C. A 10-minute wash operation was then carried out 3 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 1.5 parts of formic acid it was adjusted to a pH of 4.8. The dyed leather in this manner was retanned in a freshly prepared immersion liquid of 30 Parts of water and 2 parts of a polymeric tanning agent for 30 minutes at 30 ° C. The immersion liquid was then mixed with 2 parts of a water-repellent grease impregnating agent. After a time for batting of another 30 minutes, 5 parts of a sulfone tanner and 4 parts of a resin tanner were added and batted for 60 minutes. Finally, it was acidified with 0.5 part formic acid at pH 4.4 and batted once 10 minutes and once 30 minutes. After a 10-minute wash operation with 100 parts of water the leather was impregnated with grease in a new immersion liquid composed of 100 parts of water, 4.5 parts of a mixed liquid (based on sulphited fish oil and synthetic oil), 0.5 parts of a liquid based on lanolin, batting 40 minutes at 55 ° C. Then 1.5 parts of concentrated formic acid was acidified to pH 3.5 and batted for 40 minutes. The dyed and fat-impregnated leather A deep brown leather was obtained which has excellent wash, sweat, rub and migration fastness.

Dyeing procedure 18:

A piece of leather of 100 parts by weight of a beef leather, tanned in a usual manner, of a recess thickness of 1.8 mm, was washed in a barrel filled with 200 parts of water and 0.1 parts of formic acid for 10 minutes at 35 ° C and then neutralized in an immersion liquid composed of 100 parts of water, 2 parts of sodium formate, 1 part of sodium acetate, 1.5 part of sodium bicarbonate and 1 part of a dispersing agent for 120 minutes at 35 ° C. Then, the deacidification liquid had a pH value of 6.5. It was then washed with 200 parts of water for 10 minutes at 35 ° C.

In a freshly prepared immersion liquid of 150 parts of water and 5 parts of dye from Example 35h, it was stained for 45 minutes at pH 5.9 and 30 ° C. Adding 15 parts of a 15% by weight soda solution in portions, the pH value of the immersion liquid was adjusted between 8.8-9.6 and beaten 120 minutes at 50 ° C. A 10-minute wash operation was then carried out 3 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 0.5 parts of formic acid, a pH of 5.1 was adjusted.

The dyed leather in this manner was retanned in a freshly prepared immersion liquid of 30 parts of water and 2 parts of a polymeric tanning agent for 30 minutes at 30 ° C. The immersion liquid was then mixed with 2 parts of a hydrophobic grease impregnating agent. After a time for batting of another 30 minutes, 5 parts of a sulfone tanner and 4 parts of a resin tanner were added and another 60 minutes were beaten. Finally it was acidified with 1.0 part formic acid at pH 4.1 and batted once for 10 minutes and once for 30 minutes. After a 10-minute wash operation with 200 parts of water, the leather was impregnated with grease in a new immersion liquid composed of 100 parts of water, 4.5 parts of a mixed liquid (based on sulphited fish oil and synthetic oil), 0.5 parts of a lanolin-based liquid batting 40 minutes at 55 ° C. It was then acidified with 1.5 parts of concentrated formic acid at pH 3.3 and batted for 40 minutes. The dyed and grease-impregnated leather was further washed with cold water at 15 ° C for 10 minutes and then stretched, dried overnight at room temperature, conditioned, staked and tensioned.

A dark brown leather of deep color was obtained which has excellent washing, sweat, rub and migration fastness.

 Dyeing Procedure 19:

A piece of leather of 100 parts by weight of a usual tanned beef leather, with a recess thickness of 1.8 mm, was washed in a barrel filled with 200 parts of water and 0.1 part of formic acid per 10 minutes at 35 ° C and then neutralized in an immersion liquid composed of 100 parts of water, 2 parts of sodium formate, 1 part of sodium acetate, 1.5 parts of sodium bicarbonate and 1 part of a dispersing agent for 120 minutes at 35 ° C. The deadification liquid then presented a pH value of 6.6. It was then washed with 200 parts of water for 10 minutes at 35 ° C.

In a freshly prepared immersion liquid of 150 parts of water and 5 parts of dye from example 12a, it was stained for 60 minutes at pH 6.0 and 30 ° C. Adding 18 parts of a 15% by weight soda solution portionwise adjusted the pH value of the immersion liquid between 8.8-9.8. He was then beaten for 120 minutes at 50 ° C. A 10-minute wash operation was then carried out twice in 200 parts of water at 40 ° C. By adding 200 parts of water and 0.5 parts of formic acid it was adjusted to a pH of 5.0.

The dyed leather in this manner was retanned in a freshly prepared immersion liquid of 30 parts of water and 2 parts of a polymeric tanning agent for 30 minutes at 30 ° C. The immersion liquid was then mixed with 2 parts of a water-repellent impregnating agent. After a time for batting of another 30 minutes, 5 parts of a sulfone tanner and 4 parts of a resin tanner were added and beaten for another 60 minutes. Finally it was acidified with 1.0 part formic acid at pH 4.1 and batted once for 10 minutes, once 30 and twice 20 minutes. After a 10-minute wash operation with 200 parts of water, the leather was impregnated with grease in a new immersion liquid composed of 100 parts of water, 4.5 parts of a mixed liquid (based on sulphited fish oil and synthetic oil), 0.5 parts of a lanolin-based liquid batting for 40 minutes at 55 ° C. It was then acidified with 1.5 parts of concentrated formic acid at pH 3.4 and batted for 40 minutes. The dyed and grease-impregnated leather was rinsed with cold water at 15 ° C by 10. A black leather was obtained which has excellent washing, sweat, rub and migration strength.

Dyeing procedure 20:

5 A piece of leather of 100 parts by weight of a beef leather, usually tanned with a recess thickness of 1.8 mm, was washed in a barrel filled with 200 parts of water and 0.1 part of formic acid for 10 minutes at 35 ° C and then neutralized in an immersion liquid composed of 100 parts of water, 2 parts of sodium formate, 1 part of sodium acetate, 1.5 parts of sodium bicarbonate and 1 part of a dispersing agent for 120 minutes at 35 ° C. Then the deadification liquid showed a pH value of 6.4. It was then washed with 200

10 parts of water for 10 minutes at 35 ° C.

In a freshly prepared immersion liquid of 150 parts of water and 4.25 parts of dye from example 17h, it was stained for 90 minutes at pH 5.7 and 30 ° C. Adding 16 parts of a 15% by weight soda solution in portions, the pH value of the immersion liquid was adjusted between 8.6-9.3 and batted for 180 minutes at 50 ° C. A 10-minute wash operation was then carried out 3 times in 200 parts of water at 40 ° C. By adding 200

15 parts of water and 0.7 parts of formic acid was adjusted to a pH of 4.7.

The dyed leather in this manner was retanned in a freshly prepared immersion liquid of 30 parts of water and 2 parts of a polymeric tanning agent for 30 minutes at 30 ° C. The immersion liquid was then mixed with 2 parts of a hydrophobic grease impregnating agent. After a time for batting of another 30 minutes, 5 parts of a sulfone tanner and 4 parts of a resin tanner were added and batted for another 60-20 minutes. Finally it was acidified with 0.5 part formic acid at pH 4.7 and batted once for 10 minutes and once for 30 minutes. After a 10-minute wash operation with 200 parts of water at 40 ° C the leather was impregnated with grease in a new immersion liquid consisting of 100 parts of water, 4.5 parts of a mixed liquid (oil-based fish sulphite and synthetic oil), 0.5 parts of a liquid based on lanolin bathed for 40 minutes at 55 ° C. It was then acidified with 1.5 parts concentrated formic acid at pH 3.7 and batted

25 for 40 minutes. The dyed and grease-impregnated leather was further rinsed with cold water at 15 ° C for 10 minutes and then stretched, dried overnight at room temperature, conditioned, staked and tensioned.

A black leather was obtained which has excellent washing, sweat, rub and migration fastness.

Dyeing procedure 21:

30 A piece of leather of 100 parts by weight of a usual tanned beef leather with a recess thickness of 1.8 mm was washed in a barrel filled with 200 parts of water and 0.1 part of formic acid per 10 minutes at 35 ° C and then neutralized in an immersion liquid composed of 100 parts of water, 2 parts of sodium formate, 1 part of sodium acetate, 1.5 parts of sodium bicarbonate and 1 part of a dispersing agent for 120 minutes at 35 ° C. Then the pH value of the desadification liquid was 6.4. It was then washed with 200

35 parts of water for 10 minutes at 35 ° C.

In a freshly prepared immersion liquid of 150 parts of water and 10 parts of dye from example 25, it was stained for 45 minutes at pH 5.4 and 30 ° C. Adding 20 parts of a 15% by weight soda solution in portions, the pH value of the immersion liquid was adjusted between 8.4-9.1 and beaten for 120 minutes at 50 ° C. A 10-minute wash operation was then carried out twice in 200 parts of water at 40 ° C. By adding 200

40 parts of water and 0.7 parts of formic acid was adjusted to a pH of 4.6.

The dyed leather in this manner was retanned in a freshly prepared immersion liquid of 30 parts of water and 2 parts of a polymeric tanning agent for 30 minutes at 30 ° C. The immersion liquid was then mixed with 2 parts of a hydrophobic grease impregnating agent. After a time for batting of another 30 minutes, 5 parts of a sulfone tanner and 4 parts of a resin tanner were added and batted for another 45 minutes. Finally it was acidified with 0.5 parts of formic acid at pH 4.7 and batted once 10 minutes and once 30 minutes. After a 10-minute wash operation with 200 parts of water at 40 ° C the leather was impregnated with grease in a new immersion liquid composed of 100 parts of water, 4.5 parts of a mixed liquid (oil-based fish sulphite and synthetic oil), 0.5 parts of a liquid based on lanolin bathed for 40 minutes at 55 ° C. It was then acidified with 1.5 parts of concentrated formic acid at pH 3.7 and batted for 50 minutes. The dyed and grease-impregnated leather was also rinsed with cold water at 15 ° C for 15 minutes and at

A deep black leather was obtained which has excellent washing, sweat, rub and migration fastness.

Dyeing procedure 22:

A piece of leather of 100 parts by weight of an organically tanned beef leather of a 1.0 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water . It was then stained with an immersion liquid of 150 parts of water, 2 parts of a dispersing agent and 10 parts of dye from example 32 for 60 minutes at pH 4.3 and 30 ° C. Adding portions 27 parts of a 15% by weight soda solution at 40 ° C in the immersion liquid maintained a pH value in the range of 8.7 and 9.3 and for 180 minutes batting. A 10-minute wash operation was then carried out 3 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 0.7 parts of formic acid it was adjusted to a pH of 4.2. Retanning / impregnation works with grease / mechanics are carried out as in the dyeing procedure 1 literal b).

A deep black leather was obtained which has excellent washing, sweat, rub and migration fastness.

Dyeing procedure 23:

A piece of leather of 100 parts by weight of an organically tanned beef leather of a 1.0 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water . It was then stained with an immersion liquid of 150 parts of water, and 10 parts of dye from example 40b for 60 minutes at pH 4.3 and 30 ° C. Adding portions 27 parts of a 15% by weight soda solution at 40 ° C in the immersion liquid a pH value in the range of 8.7 and 9.3 was adjusted to fix the dye and held for 180 minutes batting. A 10-minute wash operation was then carried out 3 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 0.7 parts of formic acid it was adjusted to a pH of 4.3. Retanning / impregnation of grease / mechanical work was performed as in the dyeing procedure 1 literal b).

A deep brown leather was obtained which has excellent washing, sweat, rub and migration fastness.

Dyeing procedure 24:

A piece of leather of 100 parts by weight of a beef leather, tanned in a usual manner, of a recess thickness of 1.8 mm, was washed in a barrel filled with 200 parts of water and 0.1 parts of formic acid for 10 minutes at 35 ° C and then neutralized in an immersion liquid composed of 100 parts of water, 2 parts of sodium formate, 1 part of sodium acetate, 1.5 parts of sodium bicarbonate and 1 part of a dispersing agent for 120 minutes at 35 ° C. Then, the desadification liquid had a pH value of 6.4. It was then washed with 200 parts of water for 10 minutes at 35 ° C.

In a freshly prepared immersion liquid of 150 parts of water and 4.25 parts of dye from example 42g, it was stained for 60 minutes at pH 6.1 and 30 ° C. Adding portions 23 parts of a 15% by weight soda solution in the immersion liquid was adjusted to a pH value between 8.7-9.5 and batted for 180 minutes at 50 ° C. A 10-minute wash operation was then carried out 4 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 1.0 part of formic acid it was adjusted to a pH of 4.3.

The dyed leather in this manner was retanned in a freshly prepared immersion liquid of 30 parts of water and 2 parts of a polymeric tanning agent for 30 minutes at 30 ° C. The immersion liquid was then mixed with 2 parts of a hydrophobic grease impregnating agent. After a time for batting of another 30 minutes, 5 parts of a sulfone tanner and 4 parts of a resin tanner were added and batted for another 60 minutes. Finally it was acidified with 2.0 parts of formic acid at pH 3.8 and batted once for 10 minutes and three times for 30 minutes. After a 10-minute wash operation with 200 parts of water at 40 ° C the leather was impregnated with grease in a new immersion liquid composed of 100 parts of water, 4.5 parts of a mixed liquid (oil-based fish sulphite and synthetic oil), 0.5 parts of a lanolin-based liquid batting for 40 minutes at 55 ° C. It was then acidified with 1.5 parts of concentrated formic acid at pH 3.3 and batted for 40 minutes. The dyed and grease-impregnated leather was also rinsed with cold water at 15 ° C by a deep brown leather was obtained which has excellent wash, sweat, rub and migration fastness.

Dyeing procedure 25:

A piece of leather of 100 parts by weight of an organically tanned beef leather of a 1.0 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water . It was then stained with an immersion liquid of 150 parts of water and 4.25 parts of dye from example 43a for 60 minutes at pH 4.2 and 30 ° C. Adding 30 parts of a 15% by weight soda solution at 40 ° C in the immersion liquid was adjusted to a pH value in the range of 8.5 and 9.4 and held for 180 minutes while batting. A 10-minute wash operation was then carried out twice in 200 parts of water at 40 ° C. By adding 200 parts of water and 1.4 parts of formic acid it was adjusted to a pH of 4.0. Grease retanning / impregnation / mechanical work was performed as described in the dyeing procedure 1 literal b).

A deep brown leather was obtained which has excellent washing, sweat, rub and migration fastness.

Dyeing procedure 26:

A piece of leather of 100 parts by weight of a beef leather, tanned in a usual way, with a recess thickness of 1.8 mm, was washed in a barrel filled with 200 parts of water and 0.1 part of formic acid for 10 minutes at 35 ° C and then neutralized in an immersion liquid composed of 100 parts of water, 2 parts of sodium formate, 1 part of sodium acetate, 1.5 parts of sodium bicarbonate and 1 part of a dispersing agent for 120 minutes at 35 ° C. The deadification liquid then presented a pH value of 6.2. It was then washed with 200 parts of water for 10 minutes at 35 ° C.

In a freshly prepared immersion liquid of 150 parts of water and 11.5 parts of dye from example 1 c, it was stained for 60 minutes at pH 5.3 and 30 ° C. Adding portions of 28 parts of a 15% by weight soda solution in the immersion liquid was adjusted to a pH value between 8.8-9.3 and batted for 180 minutes at 50 ° C. A 10-minute wash operation was then carried out 3 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 1.0 part of formic acid it was adjusted to a pH of 4.5.

The dyed leather in this manner was retanned in a freshly prepared immersion liquid of 30 parts of water and 2 parts of a polymeric tanning agent for 30 minutes at 30 ° C. The immersion liquid was then mixed with 2 parts of a hydrophobic grease impregnating agent. After a time for batting of another 30 minutes, 5 parts of a sulfone tanner and 4 parts of a resin tanner were added and batted for another 60 minutes. Finally it was acidified with 2.0 parts of formic acid at pH 3.8 and batted once 10 minutes and three times 30 minutes. After a 10-minute wash operation with 200 parts of water at 40 ° C the leather was impregnated with grease in a new immersion liquid consisting of 100 parts of water, 4.5 parts of a mixed liquid (oil-based fish sulphite and synthetic oil), 0.5 parts of a lanolin-based liquid batting for 40 minutes at 55 ° C. It was then acidified with 1.5 parts of concentrated formic acid at pH 4.0 and batted for 40 minutes. The dyed and grease-impregnated leather was further washed with cold water at 15 ° C for 15 minutes and then stretched, subjected to vacuum, dried lying overnight at room temperature, conditioned, staked and tensioned.

A deep black leather was obtained which has excellent washing, sweat, rub and migration fastness.

Dyeing procedure 27:

A piece of leather of 100 parts by weight of a beef leather, tanned in a usual manner, of a recess thickness of 1.8 mm, was washed in a barrel filled with 200 parts of water and 0.1 parts of formic acid for 10 minutes at 35 ° C and then neutralized in an immersion liquid composed of 100 parts of water, 2 parts of sodium formate, 1 part of sodium acetate, 1.5 parts of sodium bicarbonate and 1 part of a dispersing agent for 120 minutes at 35 ° C. Then the deadification liquid had a pH value of 6.2. It was then washed with 200 parts of water for 10 minutes at 35 ° C.

In a freshly prepared immersion liquid of 150 parts of water and 14.3 parts of dye from Example-6c, it was stained for 60 minutes at pH 5.3 and 30 ° C. Adding portions 28 parts of a 15% by weight soda solution in the immersion liquid a pH value between 8.7-9.3 was adjusted and batted for 180 minutes at 50 ° C. A 10-minute wash operation was then carried out 3 times in 200 parts of water at 40 ° C. A pH of 4.6 was adjusted by adding 200 parts of water and 1.0 part of formic acid.

The dyed leather in this manner was retanned in a freshly prepared immersion liquid of 30 parts of water and 2 parts of a polymeric tanning agent for 30 minutes at 30 ° C. The immersion liquid was then mixed with 2 parts of a hydrophobic grease impregnating agent. After a time for batting of another 30 minutes, 5 parts of a sulfone tanner and 4 parts of a resin tanner were added and batted for another 60 minutes. Finally it was acidified with 1.8 parts of formic acid at pH 4.0 and batted once 10 minutes and three times 30 minutes. After a 10-minute wash operation with 200 parts of water at 40 ° C the leather was impregnated with grease in a new immersion liquid consisting of 100 parts of water, 4.5 parts of a mixed liquid (oil-based fish sulphite and synthetic oil), 0.5 parts of a lanolin-based liquid batting for 40 minutes at 55 ° C. It was then acidified with 1.5 parts of concentrated formic acid at pH 3.3 and batted for 40 minutes. The dyed and grease-impregnated leather was further washed with cold water at 15 ° C for 15 minutes and then stretched, subjected to vacuum, dried lying overnight at room temperature, conditioned, staked and tensioned.

A deep black leather was obtained which has excellent washing, sweat, rub and migration fastness.

Dyeing procedure 28:

A piece of leather of 100 parts by weight of an organically tanned beef leather of a 1.0 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water . It was then stained with an immersion liquid of 150 parts of water, 2 parts of a dispersing agent and 11.5 parts of dye from example 6d for 60 minutes at pH 4.3 and 30 ° C. Adding portions of 30 parts of a 15% by weight soda solution at 40 ° C, the pH value was maintained for 180 minutes in the range of 8.8 and 9.2. Then a 10-minute operation took place 3 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 1.0 part of formic acid it was adjusted to a pH of 4.4. Retanning / impregnation of grease / mechanical work is performed as described in the dyeing procedure 1 literal b).

A deep black leather was obtained which has excellent washing, sweat, rub and migration fastness.

Dyeing procedure 29:

A piece of leather of 100 parts by weight of an organically tanned beef leather of a 1.0 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water . It was then stained with 150 parts of water, 2 parts of a dispersing agent and 14.3 parts of dye from Example 9f for 60 minutes at pH 4.3 and 30 ° C. Adding portions of 30 parts of a 15% by weight soda solution at 40 ° C, the pH of the immersion liquid was maintained for 180 minutes in the range of 8.7 and 9.2. A 10-minute wash operation was then carried out 3 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 1.0 part of formic acid it was adjusted to a pH of 4.5. Grease retanning / impregnation / mechanical work was performed as described in the dyeing procedure 1 literal b).

A deep black leather was obtained which has excellent washing, sweat, rub and migration fastness.

Dyeing procedure 30:

A piece of leather of 100 parts by weight of a beef leather, tanned in the usual way, of a recess thickness of 1.0 mm, was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water . It was then stained with an immersion liquid of 150 parts of water and 11.5 parts of dye from Example 1f for 60 minutes at pH 4.3 and 30 ° C. Adding 30 parts of a 15% by weight soda solution to portions at 40 ° C maintained the pH value of the immersion liquid to fix the dye for 180 minutes, batting in the range of 8.8 and 9.4. A 10-minute wash operation was then carried out 3 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 1.0 part of formic acid it was adjusted to a pH of 4.6. Grease retanning / impregnation / mechanical work was performed as described in the dyeing procedure 1 literal b).

Dyeing procedure 31:

A piece of leather of 100 parts by weight of a conventionally tanned beef leather of a 1.0 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water. It was then stained with an immersion liquid of 150 parts of water and 14.3 parts of dye from example 12q for 60 minutes at pH 4.3 and 30 ° C. Adding 30 parts of a 15% soda solution by weight at 40 ° C to fix the dye maintained the pH value of the immersion liquid for 180 minutes, batting in the range of 8.6 and 9.3. A 10-minute wash operation was then carried out 3 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 1.0 parts of formic acid it was adjusted to a pH of 4.6. Grease retanning / impregnation / mechanical work was performed as described in the dyeing procedure 1 literal b).

A deep black leather was obtained which has excellent washing, sweat, rub and migration fastness.

Dyeing procedure 32:

A piece of leather of 100 parts by weight of an organically tanned beef leather of a 1.0 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water. Then in the new immersion liquid of 150 parts of water, 2 parts of a dispersing agent and 8 parts of dye from example 12s the pH was immediately adjusted by adding 30 parts of a 15% by weight soda solution to portions> 8 , 5 and kept batting for 220 minutes at 40 ° C in the range of 8.7 and 9.2 to fix the dye. A 10-minute wash operation was then carried out 3 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 1.0 part of formic acid it was adjusted to a pH of 4.5. Grease retanning / impregnation / mechanical work was performed as described in the dyeing procedure 1 literal b).

A deep black leather was obtained which has excellent washing, sweat, rub and migration fastness.

Dyeing procedure 33:

A piece of leather of 100 parts by weight of a beef leather, tanned in a usual manner, of a recess thickness of 1.8 mm, was washed in a barrel filled with 200 parts of water and 0.1 parts of formic acid for 10 minutes at 35 ° C and then neutralized in an immersion liquid composed of 100 parts of water, 2 parts of sodium formate, 1 part of sodium acetate, 1.5 parts of sodium bicarbonate and 1 part of a dispersing agent for 120 minutes at 35 ° C. Then the deadification liquid had a pH value of 6.4. It was then washed with 200 parts of water for 10 minutes at 35 ° C.

In a freshly prepared immersion liquid of 150 parts of water and 8 parts of dye from example 12t by adding 23 parts of a 15% by weight soda solution in portions, the pH was immediately adjusted to> 8.5 and to fix the dye it was maintained for 240 minutes at 50 ° C, between 8.7-9.5. A 10-minute wash operation was then carried out 4 times in 200 parts of water at 40 ° C. By adding 200 parts of water and 1.1 parts of formic acid it was adjusted to a pH of 4.2.

The dyed leather in this manner was retanned in a freshly prepared immersion liquid of 30 parts of water and 2 parts of a polymeric tanning agent for 30 minutes at 30 ° C. The immersion liquid was then mixed with 2 parts of a hydrophobic grease impregnating agent. After a time for batting of another 30 minutes, 5 parts of a sulfone tanner and 4 parts of a resin tanner were added and batted for another 60 minutes. Finally it was acidified with 2.0 parts of formic acid at pH 3.8 and batted once 10 minutes and three times 30 minutes. After a 10-minute wash operation with 200 parts of water at 40 ° C the leather was impregnated with grease in a new immersion liquid consisting of 100 parts of water, 4.5 parts of a mixed liquid (oil-based fish sulphite and synthetic oil), 0.5 parts of a lanolin-based liquid batting for 40 minutes at 55 ° C. It was then acidified with 1.5 parts of concentrated formic acid at pH 3.3 and batted for 40 minutes. The dyed and grease-impregnated leather was further washed with cold water at 15 ° C for 15 minutes and then stretched, subjected to vacuum, dried lying overnight at room temperature, conditioned, staked and tensioned.

A deep black leather was obtained which has excellent washing, sweat, rub and migration fastness.

A piece of leather of 100 parts by weight of an organically tanned beef leather of a 1.0 mm recess thickness was washed for 20 minutes at 30 ° C in a barrel filled with 200 parts of water . It was then stained with an immersion liquid of 150 parts of water, 2 parts of a dispersing agent and 7 parts of dye from example 12u for 60 minutes at pH 4.3 and 30 ° C. Adding 30 parts of a 15% by weight solution of soda at 40 ° C to fix the dye maintained the pH value of the immersion liquid for 200 minutes, batting in the range of 8.7 and 9.2. After a change of immersion liquid, by adding 200 parts of water and 1.0 parts of formic acid it was adjusted to a pH of 4.5. Grease retanning / impregnation / mechanical work was performed as described in the dyeing procedure 1 literal b).

A deep black leather was obtained which has excellent washing, sweat, rub and migration fastness.

Dyeing Procedure 35:

A piece of leather of 100 parts by weight of a chrome-tanned beef leather, of a 1.8 mm recess thickness, was washed in a barrel filled with 200 parts of water and 0.1 parts of formic acid for 10 minutes at 35 ° C and then neutralized in an immersion liquid composed of 100 parts of water, 2 parts of sodium formate, 1 part of sodium acetate, 1.5 parts of sodium bicarbonate and 1 part of a dispersing agent for 120 minutes at 35 ° C. Then, the deadification liquid had a pH value of 6.4. It was then washed with 200 parts of water for 10 minutes at 35 ° C.

In a freshly prepared immersion liquid of 150 parts of water and 7 parts of dye from example 13n, it was stained for 60 minutes at pH 6.3 and 30 ° C. Adding 23 parts of a 15% by weight soda solution to the portions for fixation, the pH value of the immersion liquid was adjusted between 8.7-9.5 and beaten for 210 minutes at 50 ° C. After the change of immersion liquid by adding 200 parts of water and 1.0 parts of formic acid it was adjusted to a pH of 4.3.

The dyed leather in this manner was retanned in a freshly prepared immersion liquid of 30 parts of water and 2 parts of a polymeric tanning agent for 30 minutes at 30 ° C. The immersion liquid was then mixed with 2 parts of a hydrophobic grease impregnating agent. After a time for batting of another 30 minutes, 5 parts of a sulfone tanner and 4 parts of a resin tanner were added and batted for another 60. Finally it was acidified with 2.0 parts of formic acid at pH 3.8 and batted once 10 minutes and three times 30 minutes. After a 10-minute wash operation with 200 parts of water at 40 ° C the leather was impregnated with grease in a new immersion liquid composed of 100 parts of water, 4.5 parts of a mixed liquid (sulphited oil base of fish and synthetic oil), 0.5 parts of a liquid based on lanolin bathed for 40 minutes at 55 ° C. It was then acidified with 1.5 parts of concentrated formic acid at pH 3.3 and batted for 40 minutes. The dyed and grease-impregnated leather was also rinsed with cold water at 15 ° C for 15 minutes and then stretched, subjected to vacuum, dried lying overnight at room temperature, conditioned, staked and tensioned.

Dyeing Procedure 36:

A piece of leather of 100 parts by weight of a tanned beef leather, in a usual manner, of a recess thickness of 1.8 mm, was washed in a barrel filled with 300 parts of water for 10 minutes at 35 ° C and It was then neutralized in an immersion liquid composed of 100 parts of water, 2 parts of sodium formate, 1 part of sodium acetate and 2.2 parts of sodium bicarbonate for 120 minutes at 40 ° C. The deadification liquid then had a pH value of 7.2. To the deacidification liquid, 10.5 parts of dye 12bj were added and stained for 30 minutes at pH 6.9 and 40 ° C. Adding portions of 8 parts of soda was used to adjust the pH value of the immersion liquid between 9.2 9.7 and beat for 75 minutes at 40 ° C. A 20-minute wash operation was then carried out twice in 300 parts of water at 40 ° C. A pH of 3.9 was adjusted by adding 200 parts of water and 1.2 parts of formic acid.

The dyed leather in this manner was retanned in a freshly prepared immersion liquid of 100 parts of water and 2 parts of a polymeric tanning agent for 30 minutes at 30 ° C. The immersion liquid was then mixed with 2 parts of a hydrophobic grease impregnating agent. After a time for batting of another 30 minutes, 5 parts of a sulfone tanner and 4 parts of a resin tanner were added and batted for another 60 minutes. To the retanning immersion liquid, 4.5 parts of a mixed liquid (based on sulphited fish oil and synthetic oil) and 0.5 parts of a lanolin-based liquid were added and the leather was impregnated with fat batting by 40 minutes at 55 ° C. It was then acidified with 1.6 parts of concentrated formic acid at pH 3.6 and batted for 45 minutes. The dyed and grease-impregnated leather was also washed with 300 parts of cold water to

20 ° C for 10 minutes and then stretched, subjected to vacuum for 1.5 minutes at 70 ° C, dried

hung for a night at room temperature, it was conditioned, staked and stressed. A deep black leather was obtained which has excellent wash, sweat, rub and solidity. migration.

Similarly, the dyes indicated in table 19 were performed: Table 19

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

1st

4 5 black

1 B

eleven 7 black

1 B

26 14.1 black

1 C

4 6.7 black

1d

19 11.3 black

1e

30 6.4 black

1f

19 9.5 black

2nd

35 7.9 black

2b

5 4.7 blue

2 C

6 5.8 blue

2d

9 18.6 black

2e

25 14.6 blue

2f

12 12.4 blue

2 g

3. 4 12.0 Violet

2h

35 7.9 blue

2i

26 18.6 blue

2j

4 14.6 blue

2k

19 12.4 blue

3

30 12.0 Violet

4th

31 6.3 dark brown

5th

3. 4 7.8 Brown

6th

9 17.4 blue

6b

one 5.2 black

6b

16 8.3 black

6c

fifteen 8.8 black

6d

13 8.9 black

6d

17 12.0 black

6e

9 17.4 blue

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

6f

9 17.4 blue

6g

9 17.4 blue

6h

9 17.4 black

7

18 6.7 blue

8

twenty-one 9.2 blue

9a

2 17.1 black

9b

17 11.4 black

9c

14 9.5 black

9c

22 16.7 black

9d

33 15.4 Brown

9e

33 15.4 black

9f

3. 4 4.9 black

9g

2 17.1 black

9h

14 9.5 black

10

24 7.9 blue

11th

27 12.0 bordeaux

11b

twenty-one 10.2 bordeaux

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

12th

3 28 34 21 2.3 8.4 17.9 10.0 black black black black

12b

5 23 32 18 27 33 2.4 8.4 16.9 4.7 10.5 18.7 black black black black black black

12c

6 16 9.8 9.8 dark green dark green

12d

1 29 18.1 4.6 dark green dark green

12e

twenty 3.3 dark green

12f

35 11.7 dark green

12g

7 15.4 dark green

12h

8 24 5.0 5.2 green Green

12i

7 7 17 2.7 15.4 5.1 dark green dark green dark green

12j

4 10 31 2.7 15.4 5.1 black black black

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

12k

12 19 10.0 10.0 black black

12l

fifteen 15.1 green

12m

26 8.8 black

12n

fifteen 15.1 black

120

26 8.8 dark green

12p

13 6.5 black

12q

14 8.3 black

12r

22 15.1 black

12s

one 8.3 black

12t

3 12.0 black

12u

eleven 3.8 black

12v

22 4.7 black

12z

33 9.0 dark green

12aa

13 7.6 dark blue

12ab

6 6.2 dark blue

12ac

2 7.9 dark blue

12ad

7 5.3 dark blue

12ae

9 8.8 blue

12af

8 7.4 black

12ag

4 7.9 black

12ah

14 8.8 black

12ai

5 10.1 black

12aj

2. 3 5.9 black

12ak

17 14.3 black

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

12al

31 13.2 black

12 am

one 19.3 black

12an

4 1.8 black

12th

eleven 5.7 green

12ap

28 3.8 green

12aq

twenty 6.4 green

12ar

13 12.5 black

12th

26 10.5 black

12at

35 7 19 36 7.7 10.2 14.3 3.5 black black black black

12au

fifteen 4.6 black

12av

16 2.3 black

12aw

6 3.1 green

12ax

3. 4 8.6 black

12ay

18 17.3 black

12az

31 2.8 black

12ba

8 5.1 black

12bb

10 6.2 black

12bc

33 11.3 black

12bd

one 7.1 dark green

12be

25 13.7 dark green

12bf

29 18.1 dark green

12bg

twenty-one 4.4 dark green

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

12bh

12 3.5 dark green

12bi

17 6.2 green

12bj

2 2.1 black

12bk

2. 3 3.6 green

12bl

30 5.2 black

12bm

27 8.9 black

12bn

14 5.6 green

12bo

32 3.1 green

12bp

22 14.5 green

12bq

24 9.6 black

12br

9 5.4 black

12bs

7 7.5 black

12bt

5 2.9 black

12bu

3 9.8 black

12bv

19 4.9 black

12bw

8 1.8 black

12bx

10 5.7 black

12by

33 3.8 blue

12bz

one 6.4 blue

12ca

25 12.5 blue

12cb

29 10.5 blue

12cc

twenty-one 7.7 blue

12cd

12 4.6 blue

12ce

17 2.3 blue

12cf

2 3.1 blue

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

12cg

2. 3 8.6 blue

12ch

30 17.3 blue

12ci

27 2.8 blue

12cj

14 5.1 blue

12ck

32 6.2 blue

12cl

22 12.5 blue

12cm

24 10.5 blue

12cn

9 7.7 blue

12co

7 4.6 blue

12cp

5 2.3 blue

12cq

3 3.1 blue

12cr

19 8.6 blue

12cs

35 17.3 blue

12ct

fifteen 2.8 blue

12cu

16 5.1 blue

12cv

6 6.2 blue

12cw

3. 4 11.3 bau

12cx

18 7.1 blue

12cy

31 13.7 blue

12cz

4 18.1 blue

12th

eleven 4.4 blue

12db

28 3.5 blue

12dc

twenty 6.2 blue

12dd

13 2.1 blue

12 of

26 3.6 green

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

12df

35 5.2 green

12dg

fifteen 8.9 black

12dh

16 5.6 black

12di

6 3.1 black

12dj

25 14.5 black

12dk

29 9.6 black

12dl

twenty-one 5.4 green

12dm

12 7.5 green

12dn

17 2.9 green

12th

2 9.8 black

12dp

2. 3 4.9 black

12dq

30 1.8 black

12dr

27 5.7 black

12ds

14 3.8 black

12dt

32 6.4 black

12du

22 12.5 black

12dv

24 10.5 black

12dw

9 7.7 blue

12dx

7 4.6 blue

12dy

5 2.3 blue

12dz

3 3.1 blue

12ea

19 8.6 blue

12eb

35 17.3 blue

12ec

fifteen 2.8 blue

12ed

16 5.1 blue

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

12ee

6 6.2 blue

12ef

14 5.6 blue

12eg

32 3.1 blue

12eh

22 14.5 blue

12ei

24 9.6 blue

12ej

9 5.4 blue

12ek

7 7.5 blue

12el

5 2.9 blue

12em

3 1.8 blue

12in

19 5.7 blue

12o

35 3.8 blue

12ep

fifteen 6.4 blue

12eq

16 12.5 blue

12th

6 10.5 blue

12es

3. 4 7.7 blue

12et

18 4.6 blue

12eu

31 2.3 blue

12ev

4 3.1 blue

12ew

eleven 8.6 blue

12ex

28 17.3 blue

12ey

twenty 2.8 blue

12th

13 5.1 blue

12fa

fifteen 6.2 blue

12fb

16 11.3 blue

12fc

6 7.1 blue

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

12fd

14 13.7 blue

12fe

32 18.1 blue

12ff

22 7.7 blue

12fg

24 4.6 green

12fh

9 2.3 green

12fi

7 3.1 black

12fj

5 8.6 black

12fk

3 17.3 black

12fl

19 2.8 black

12fm

3. 4 5.1 black

12fn

18 6.2 green

12fo

31 5.6 green

12fp

4 3.1 green

12fq

eleven 14.5 black

12fr

28 9.6 black

12fs

twenty 5.4 black

12ft

13 8.2 black

12fu

fifteen 1.9 black

12fv

16 2.6 black

12fw

6 14.3 black

12fx

5 6.7 black

12fy

one 5.9 blue

12fz

14 3.2 blue

12ga

36 4.6 blue

12gb

fifteen 17.9 blue

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

12gc

27 6.8 blue

12gd

4 2.4 blue

12ge

twenty 10.1 black

12gf.

9 6.6 black

12gg

3 7.5 black

12gh

33 3.5 black

12gi

fifteen 11.2 black

12gj

7 8.6 black

12gk

eleven 3.6 blue

12gl

2 19 blue

12gm

4 10.9 blue

12gn

8 5.6 blue

12go

fifteen 6.1 blue

12gp

16 4.8 blue

12gq

7 3.1 black

12gr

13 9.9 black

12gs

twenty-one 12.6 black

12t

30 13.5 black

12gu

36 14.8 black

12gv

25 2.8 black

12gw

15 29 15.1 4.8 black black

12gz

26 8.8 black

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

12ha

15 8 15.1 5.5 black black

12hb

26 11 8.8 6.1 black black

12hc

13 24 6.5 11.2 black black

12hd

14 35 8.3 4.1 black black

12he

22 16 15.1 7.5 black black

12hf

1 33 8.3 4.6 black black

12hh

3 27 12.0 6.1 black black

12hi

eleven 3.8 black

12hj

22 4.7 black

12hk

33 9.0 black

12hl

13 7.6 black

12hm

6 6.2 black

12hn

2 7.9 black

12ho

7 5.3 black

12hp

9 8.8 black

12hq

8 7.4 black

12hr

4 7.9 black

12hs

14 8.8 black

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

12ht

5 10.1 blue

12hu

2. 3 5.9 blue

12hv

17 14.3 blue

12hw

31 13.2 black

13th

2 6 11 17 2.3 8.4 17.9 10.0 black black black black

13b

9 25 21 21 21 2.4 8.4 4.7 10.5 18.7 black black black black black

13c

25 11.0 dark green

13d

17 10.8 dark green

13e

30 17.0 dark green

13f

3. 4 11.5 dark green

13g

7 11.2 dark green

13h

3 24 8.4 8.4 black black

13i

16 8.4 dark green

13j

27 11.4 black

13k

10 10 6.6 13.2 black black

131

12 15.1 green

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

13m

fifteen 8.8 black

13n

fifteen 8.8 black

130

one 8.2 dark green

13p

19 2.9 black

13q

twenty-one 4,5 black

13r

4 6.7 black

13s

twenty 15.0 black

13t

5 4.6 black

13u

17 6.7 black

13v

19 8.2 black

13z

8 2.9 dark green

13aa

9 4,5 dark blue

13ab

10 6.7 dark blue

13ac

eleven 7.7 dark blue

13ad

18 9.1 dark blue

13ae

16 8.3 blue

13af

14 5.9 black

13ag

fifteen 11.0 black

13ah

14 8.8 black

13ai

6 10.9 black

13aj

7 11.1 dark blue

13ak

fifteen 9.7 dark blue

13al

12 8.4 dark green

13am

13 7.6 black

13an

2. 3 5.9 black

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

13th

17 14.3 black

13ap

31 13.2 black

13aq

one 19.3 black

13ar

4 1.8 black

13th

eleven 5.7 green

13at

28 3.8 green

13au

twenty 6.4 green

13av

13 12.5 black

13aw

26 10.5 black

13ax

35 7.7 black

13ay

fifteen 4.6 black

13az

16 2.3 black

13ba

6 3.1 black

13bb

3. 4 8.6 black

13bc

18 17.3 black

13bd

31 2.8 black

13be

8 5.1 black

13bf

10 6.2 black

13bg

33 11.3 black

13bh

one 7.1 dark green

13bi

25 13.7 dark green

13bj

29 18.1 dark green

13bk

twenty-one 4.4 dark green

13bt

12 3.5 dark green

13bm

17 6.2 dark green

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

13bn

2 2.1 black

13bo

2. 3 3.6 dark green

13bp

30 5.2 green

13bq

27 8.9 black

13br

14 5.6 green

13bs

32 3.1 green

13bt

22 14.5 green

13bu

24 9.6 black

13bv

9 5.4 black

13bw

7 7.5 black

13bx

5 2.9 black

13by

3 9.8 black

13bz

19 4.9 black

13ca

8 1.8 black

13cb

10 5.7 black

13cc

33 3.8 blue

13cd

one 6.4 blue

13ce

25 12.5 blue

13cf

29 10.5 blue

13cg

twenty-one 7.7 blue

13ch

12 4.6 blue

13ci

17 2.3 blue

13cj

2 3.1 blue

13ck

2. 3 8.6 blue

13cl

30 17.3 blue

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

13cm

27 2.8 blue

13cn

14 5.1 blue

13co

32 6.2 blue

13cp

22 12.5 blue

13cq

24 10.5 blue

13cr

9 7.7 blue

13cs

7 4.6 blue

13ct

5 2.3 blue

13cu

3 3.1 blue

13cv

19 8.6 blue

13cw

35 17.3 blue

13cx

fifteen 2.8 blue

13cy

16 5.1 blue

13cz

6 6.2 blue

13th

3. 4 11.3 blue

13db

18 7.1 blue

13dc

31 13.7 blue

13dd

4 18.1 blue

13 of

eleven 4.4 blue

13df

28 3.5 blue

13dg

twenty 6.2 blue

13dh

13 2.1 green

13di

26 3.6 green

13dj

35 5.2 black

13dk

fifteen 8.9 black

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

13dl

16 5.6 black

13dm

6 3.1 black

13dn

25 14.5 black

13th

29 9.6 green

13dp

twenty-one 5.4 green

13dq

12 7.5 green

13dr

17 2.9 black

13ds

2 9.8 black

13dt

2. 3 4.9 black

13du

30 1.8 black

13dv

27 5.7 black

13dw

14 3.8 black

13dx

32 6.4 black

13dy

22 12.5 black

13dz

24 10.5 blue

13ea

9 7.7 blue

13eb

7 4.6 blue

13ec

5 2.3 blue

13ed

3 3.1 blue

13ee

19 8.6 blue

13ef

35 17.3 blue

13eg

fifteen 2.8 blue

13eh

16 5.1 blue

13ei

6 6.2 blue

13ej

14 5.6 blue

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

13ek

32 3.1 blue

13el

22 14.5 blue

13em

24 9.6 blue

13in

9 5.4 blue

13o

7 7.5 blue

13ep

5 2.9 blue

13eq

3 1.8 blue

13th

19 5.7 blue

13es

35 3.8 blue

13et

fifteen 6.4 blue

13eu

16 12.5 blue

13ev

6 10.5 blue

13ew

3. 4 7.7 blue

13ex

18 4.6 blue

13ey

31 2.3 blue

13th

4 3.1 blue

13fa

eleven 8.6 blue

13fb

28 17.3 blue

13fc

twenty 2.8 blue

13fd

13 5.1 blue

13fe

fifteen 6.2 blue

13ff

16 11.3 blue

13fg

6 7.1 blue

13fh

14 13.7 blue

13fi

32 18.1 blue

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

13fj

22 7.7 green

13fk

24 4.6 green

13fl

9 2.3 black

13fm

7 3.1 black

13fn

5 8.6 Black

13fo

3 17.3 black

13fp

19 2.8 black

13fq

3. 4 5.1 green

13fr

18 6.2 green

13fs

31 5.6 green

13ft

4 3.1 black

13fu

eleven 14.5 black

13fv

28 9.6 black

13fw

twenty 5.4 black

13fx

13 8.2 black

13fy

eleven 8.6 black

13fz

28 17.3 black

13ga

twenty 2.8 black

13gb

one 5.9 blue

13gc

14 3.2 blue

13gd

36 4.6 blue

13ge

fifteen 17.9 blue

13gf

27 6.8 blue

13gg

4 2.4 blue

13gh

twenty 10.1 black

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

13gi

9 6.6 black

13gj

3 7.5 black

13gk

33 3.5 black

13gl

fifteen 11.2 black

13gm

7 8.6 black

13gn

eleven 3.6 blue

13go

2 19 blue

13gp

4 10.9 blue

13gq

8 5.6 blue

13gr

fifteen 6.1 blue

13gs

16 4.8 blue

13gt

7 3.1 black

13gr

13 9.9 black

13gs

twenty-one 12.6 black

13gt

30 13.5 black

13gu

36 14.8 black

13gv

25 2.8 black

13gw

fifteen 15.1 black

29

4.8 black

13gz

26 8.8 black

13ha

15 8 15.1 5.5 black black

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

13hb

26 11 8.8 6.1 black black

13hc

13 24 6.5 11.2 black black

13hd

14 35 8.3 4.1 black black

13he

22 16 15.1 7.5 black black

13hf

1 33 8.3 4.6 black black

13hh

3 27 12.0 6.1 black black

13hi

eleven 3.8 black

13hj

22 4.7 black

13hk

33 9.0 black

13hl

13 7.6 black

13hm

6 6.2 black

13hn

2 7.9 black

13ho

7 5.3 black

13hp

9 8.8 black

13hq

8 7.4 black

13hr

4 7.9 black

13hs

14 8.8 black

13ht

5 10.1 blue

13hu

2. 3 5.9 blue

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

13hv

17 14.3 blue

13hw

31 13.2 black

14

2 6.9 black

fifteen

3 3.9 black

16th

8 10.0 green

16b

22 7.3 black

16c

16 10.0 black

16d

24 10.9 dark green

16e

30 11.1 dark green

16f

28 11.1 green

16g

2. 3 12.4 black

4pm

31 12.4 black

16i

26 12.4 black

16j

fifteen 3.6 dark blue

16k

27 12.3 dark blue

17th

13 8.4 green

17b

28 14.4 black

17c

32 14.4 black

17d

35 12.4 dark green

17e

3. 4 8.4 dark green

17f

33 14.4 green

17g

4 4 19 19 3.4 13.6 3.4 13.6 black black black black

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

17h

18 5.8 black

17i

35 19.8 black

17j

17 9.7 green

17k

14 7.6 dark blue

171

26 17.3 dark blue

18

16 8.6 dark green

19

fifteen 6.8 dark green

twenty

31 5.9 dark green

twenty-one

29 3.9 dark green

22

30 10.0 dark green

2. 3

22 7.3 blue

24

twenty-one 10.0 black

25

18 7.3 black

26

13 8.2 Brown

27

3. 4 11.1 Brown

28th

33 8.4 Brown

28b

32 7.6 Brown

29th

eleven 6.9 Brown

29b

2 10.9 Brown

30

one 11.1 blue

31

5 8.8 blue

32

4 10.4 black

33

12 11.2 black

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

34th

28 28 28 4.2 8.4 16.8 brown brown brown

34b

21 21 21 4.2 8.4 16.8 dark brown dark brown dark brown

34c

5 8.8 Brown

34d

4 10.4 Brown

34e

12 11.2 Brown

34f

9 18 10.2 10.2 brown brown

34g

5 7 24 14.4 7.7 14.4 brown brown brown

34h

7 5.5 Brown

34i

13 7.7 dark brown

34j

29 7.7 dark brown

34k

eleven 9.2 Brown

341

fifteen 4.9 Brown

34m

9 7.0 Brown

34n

8 6.3 Brown

34th

32 11.1 Brown

34p

14 13.1 dark brown

34q

12 12.5 dark brown

34r

13 7.8 Brown

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

34s

27 8.4 Brown

34t

eleven 7.7 dark brown

34u

18 9.1 light brown

34v

16 8.3 dark brown

34z

7 4.6 Brown

34aa

14 5.7 Brown

34ab

twenty-one 18.6 Brown

34ac

28 12.2 Brown

35th

14 5.9 Brown

35b

1 1 1 4.2 8.4 16.8 dark brown dark brown dark brown

35c

6 8.1 dark brown

35d

19 5.4 light brown

35e

2 2 2 27 7.2 14.4 20 7.2 vermilion vermilion vermilion vermilion

27 27

14.4 20 vermilion vermilion

35f

33 14.4 Brown

35g

26 12.4 Brown

35h

31 9.4 dark brown

35i

3. 4 7.9 Brown

35j

fifteen 8.8 Brown

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

35k

27 6.3 Brown

35l

22 8.8 Brown

35m

18 8.9 Brown

35n

12 5.7 light brown

35th

26 8.2 Brown

35p

24 3.9 Brown

35q

29 6.4 Brown

35r

18 5.7 Brown

35s

30 30 26 26 4.1 17.6 4.1 17.6 brown brown brown brown

35t

28 7.4 Brown

35u

25 8.9 dark brown

35v

24 4.7 light brown

35z

eleven 4.7 light brown

35aa

2. 3 8.8 dark brown

35ab

eleven 16.6 light brown

35ac

12 6.8 Brown

35ad

14 6.8 Brown

35ae

twenty 7.4 Brown

35af

3. 4 4.8 Brown

35ag

33 4.8 Brown

35ah

18 4.2 Brown

35ai

29 17.9 Brown

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

36

10 7.4 Brown

37

16 7.4 Brown

38a

twenty 7.4 Brown

38b

3 8.8 Brown

38c

9 16.6 Brown

38d

7 15.4 Brown

38e

6 5.6 roasted yellow

38f

4 5.2 light brown

38g

12 13.3 dark brown

38h

10 35 5.6 5.6 brown brown

38i

25 16.6 Brown

38j

33 15.4 Brown

38k

3. 4 4.9 Brown

381

24 7.9 Brown

38m

27 12.0 Brown

38n

31 10.0 Brown

38o

26 7.7 Brown

38p

31 9.2 Brown

38q

3. 4 4.9 Brown

38r

fifteen 7.0 Brown

38s

27 12.4 Brown

38t

22 9.4 Brown

38u

18 7.9 Brown

38v

17 11.3 Brown

38z

3 18.2 Brown

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

39a

12 8.8 Brown

39b

26 6.3 Brown

39c

2. 3 5.6 Brown

39d

3 8.8 Brown

39e

3. 4 6.4 Brown

39f

12 6.4 Brown

39g

4 5.6 Brown

39h

7 4.4 Brown

39i

8 13.3 Brown

39j

5 20 10.6 10.6 brown brown

39k

14 10.2 Brown

391

17 10.2 Brown

39m

3. 4 14.6 Brown

39n

fifteen 7.3 Brown

39o

19 7.3 Brown

39p

17 11.0 Brown

39q

eleven 9.2 Brown

39r

fifteen 4.9 Brown

39s

9 7.0 Brown

39t

8 6.3 Brown

39u

32 11.1 Brown

39v

18 7.4 Brown

39z

16 11.0 Brown

40th

10 7.4 Brown

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

40b

twenty 7.4 Brown

40c

13 8.8 Brown

40d

16 8.4 Brown

40e

17 8.0 roasted yellow

40f

twenty-one 8.8 light brown

40g

25 8.9 dark brown

40h

24 4.7 Brown

40i

eleven 7.3 Brown

40j

12 4.7 Brown

40k

24 24 24 4.2 8.4 16.8 brown brown brown

401

29 16.8 Brown

40m

25 12.4 Brown

40n

16 14.1 Brown

40th

3. 4 8.6 Brown

40p

one 12.0 Brown

40q

28 4.2 Brown

40r

22 8.6 Brown

40s

24 9.0 Brown

40t

27 9.0 Brown

40u

eleven 5.9 Brown

40v

2 12.7 Brown

40z

twenty-one 4,5 Brown

41st

13 8.8 Brown

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

41b

9 8.6 Brown

41c

twenty-one 9.0 Brown

41d

32 8.8 Brown

41 e

30 6.2 Brown

41f

33 8.6 Brown

41 g

24 9.0 Brown

41h

29 7.4 Brown

41i

9 9 9 4.2 8.4 16.8 brown brown brown

41j

30 16.8 Brown

41k

fifteen 12.4 Brown

411

14 12.4 Brown

41m

17 14.0 Brown

41n

18 9.8 Brown

41st

27 4.2 Brown

41p

24 12.1 Brown

41q

27 12.4 Brown

41r

eleven 12.4 Brown

41s

13 11.8 Brown

41t

9 14.2 Brown

41u

10 14.0 Brown

42nd

12 2.4 Brown

42b

25 4.6 Brown

42c

16 6.8 dark brown

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

42d

31 8.7 Brown

42e

17 19 8.8 8.8 brown brown

42f

32 8.6 dark brown

42g

25 9.0 Brown

42h

14 11.0 Brown

42i

33 8.6 Brown

42j

24 9.0 Brown

42k

16 16 8.8 16.8 brown brown

421

10 14.0 Brown

42m

12 2.4 Brown

42n

4 15.0 Brown

42o

2. 3 18.6 Brown

43rd

25 4.6 Brown

43b

16 6.8 Brown

43c

31 8.7 Brown

43d

8 4.4 Brown

43e

5 4.6 Brown

43f

29 5.4 Brown

43g

32 10.8 Brown

43h

11 33 14.1 14.4 brown brown

43i

17 12.2 Brown

43j

19 12.2 Brown

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

43k

7 11.0 Brown

431

9 12.2 Brown

43m

5 11.0 Brown

43n

22 22 8.8 16.8 brown brown

43rd

28 2.4 green

43p

3. 4 4.6 green

43q

twenty-one 4.8 green

43r

twenty 8.7 green

43s

18 18 6.9 15.1 Green Green

43t

fifteen 12.2 green brown

43u

25 8.7 green

43v

one 11.0 Brown

43z

26 5.4 green

43rd

14 5.4 green

43ab

2 11.1 green

43ac

13 10.0 green

43ad

27 12.7 Brown

43ae

30 16.8 Brown

43af

eleven 5.4 green

43ag

24 11.9 green

43ah

2. 3 10.5 green

43ai

29 2.7 Brown

44

fifteen 12.4 Brown

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

Four. Five

14 12.4 Brown

46th

17 14.0 olive green

46b

18 9.8 green

46c

10 8.8 green

46d

twenty-one 7.4 green

46e

32 7.4 green

46f

13 8.2 green

46g

4 7.4 Brown

48h

fifteen 5.6 light brown

46i

twenty-one 7.4 Brown

46j

32 7.4 Brown

46k

26 5.6 Brown

46l

2. 3 12.1 dark brown

46m

12 14.6 Brown

47th

6 6.8 green

47b

24 8.7 Brown

47c

eleven 8.7 Brown

47d

28 2.4 Brown

47e

3. 4 4.6 Brown

47f

16 10.6 Brown

47g

24 10.6 Brown

47h

3. 4 4.8 Brown

47i

33 4.8 Brown

47j

18 4.2 Brown

47k

29 17.9 Brown

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

47l

one 11.0 Brown

47m

10 8.8 Brown

47n

one 11.0 Brown

47th

16 10.6 Brown

47p

24 10.6 green

47q

2 11.1 green

47r

19 10.1 green

47s

10 8.8 green

47t

twenty 8.8 green

47u

16 10.6 green

47v

24 10.6 green

47z

10 8.8 green

47aa

28 2.4 green

47ab

3. 4 4.6 green

47ac

10 8.8 green

47ad

28 2.4 green

47ae

3. 4 4.6 green

47af

9 4.8 green

47ag

32 12.6 green

47ah

7 11.6 green

47ai

twenty 7.8 green

48

2. 3 12.0 Brown

49th

16 10.6 Brown

49b

24 10.6 Brown

49c

28 10.4 Brown

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

50th

33 4.8 russet

50b

31 16.4 rust red

50c

29 17.9 russet

51

30 12.0 roasted yellow

52a

2. 3 7.8 Brown

52b

2. 3 7.8 Brown

52c

30 14.4 Brown

52d

19 7.8 Brown

52e

22 7.8 Brown

53a

27 7.8 Brown

53b

9 6.6 Brown

53c

twenty-one 6.6 Brown

53d

14 10.2 Brown

54

17 10.2 Brown

55

3. 4 14.6 Brown

56

fifteen 7.3 Brown

57

19 7.3 Brown

58th

17 11.0 black

58b

eleven 9.2 black

58c

fifteen 4.9 black

59th

9 7.0 black

59b

8 6.3 bordeaux

59c

32 11.1 black

59d

10 7.4 gelb

59e

twenty 7.4 black

Coloring example No.

Dyeing Procedure No. Parts by weight (%) Leather color

59f

13 8.8 black

59g

16 8.4 black

59h

17 8.0 roasted yellow

59i

twenty-one 8.8 black

59j

25 8.9 black

59k

24 8.8 beige

Hereinafter the process of the invention is exemplified in greater detail by means of formulations of articles for preparing dyed leather for the most important segments of articles of footwear, clothing,

5 cars, gloves and furniture. The process of the invention is not limited, however, to these 5 leather segments; for example, according to the process of the invention it is also possible to produce leather for wallets and reptile leather for accessories.

In the following article formulations all data in parts should be understood as parts by weight. All data refers to merchandise. The data regarding the dye refers to the total amount of

10 chemical-organic, colored components of the salts optionally present depending on the production (synthesis salts) and optionally present flow conditioners. In the article formulations the following abbreviations were used for the chemical products of the wet-end process.

Main ingredients of commercially used fat impregnating agents (F):

F1: aqueous emulsion of vegetable oils and sulphited fish oils.

F2: aqueous preparation based on sodium salt of an anionic vinyl polymer and a non-ionic surfactant (ethoxylated oleic acid).

F3: aqueous preparation based on modified fatty acids.

F4: aqueous preparation based on synthetic oils and esters of phosphoric acid and ethoxylated alcohols containing fatty alcohol sulfonates and butyldiglycol.

20 F5: aqueous preparation based on bisulphited fish oils (sodium salts) and the hydrolysates of sulfochlorinated oils of paraffin, ethoxylated isotridecanol.

F6: aqueous preparation based on the sodium salts of sulphonated vegetable oils and modified synthetic oils and polymer.

F7: aqueous preparation based on sulfated fatty acid esters.

25 F8: aqueous preparation based on non-ionic surfactants, sulphited oils (sodium salt).

F9: Mixture of surfactants based on paraffin sulphonate, alkyl phosphate and monoalkyl sulfate in the form of a preparation of ammonium salts in solvent / water.

Main ingredients of commercial water repellent (H):

H1: aqueous preparation based on paraffins, functionalized polysiloxanes, Na salt of oleoylsarcosine.

H3: aqueous preparation based on paraffins and anionic surfactants. H4 aqueous preparation based on functionalized polysiloxanes and an emulsifying system H5: aqueous preparation based on silicone modified with a salt of a vinyl polymer. H6: aqueous preparation based on polysiloxane functionalized with anionic surfactants. H7: aqueous preparation based on functionalized polysiloxane. H8: aqueous preparation based on paraffins and sodium salts of anionic surfactants. The concept "mixture" hereafter used in the case of re-tanning agents and adjuvants may mean so much that the

mixing is prepared by mixing the components at room temperature and normal pressure, as well as mixing at elevated temperatures and pressures for short to longer periods of time. Main ingredients of usual commercial retanning ingredients (G):

G1: Condensation product of phenolsulfonic acid, formaldehyde and aniline in the form of sodium salt. G2: Aqueous preparation of the sodium salt of a condensation product of phenolsulfonic acid, formaldehyde and aniline.

G3: Aqueous preparation of a mixture of a sodium / ammonium salt of a condensation product of phenolsulfonic acid, formaldehyde, melamine, urea, and aniline with an amphoteric copolymer based on acrylic acid and a basic monomer.

G4: aqueous preparation of the ammonium salt of a condensation product of phenol, phenolsulfonic acid and

formaldehyde. G5: Sodium salt of a condensation product based on dihydroxydiphenylsulfone, phenolsulfonic acid, urea and formaldehyde.

G6: aqueous solution of a sodium / ammonium salt of a condensation product based on dihydroxydiphenylsulfone,

Phenolsulfonic acid, urea and formaldehyde. G7: High molecular weight condensation product based on dihydroxydiphenylsulfone, phenolsulfonic acid, urea and formaldehyde in the form of sodium salt.

G8: Aqueous preparation based on a mixture of the sodium / ammonium salt of a low molecular weight condensation product based on dihydroxydiphenylsulfone, urea and formaldehyde with a low molecular weight condensation product of diphenylsulfone with formaldehyde.

G9: Fatty tanning agent based on a modified paraffin (C16-C34 alkyl sulfochloride). G10: Aqueous preparation based on a copolymer of acrylic acid with acrylonitrile and an amine. G11: Mixture of a condensate of naphthalene sulfonic acid-melamine with hydroxymethanesulfonate and urea. G12: 24% by weight solution of glutardialdehyde in water. G13: 50% by weight solution of glutardialdehyde in water. G14: Preparation containing solvent, aqueous, based on a polymeric tanning agent based on aldehyde (product of

condensation of formaldehyde and glutardialdehyde). G15: Aqueous preparation based on a copolymer of acrylic acid with acrylonitrile.

G16: Aqueous preparation based on low molecular weight polymeric acrylic acid (Mn <8000, average in

number). G17: Aqueous preparation based on a polymeric acrylic acid of high molecular weight (Mn> 40000, average in number).

G18: Aqueous preparation based on polymeric methacrylic acid.

G19: Aqueous preparation of a copolymer of maleic acid and styrene

G20: Chrome synthane (mixture of a condensation product based on an aromatic oligosulfone and a preparation

chrome) G21: Tara. G22: Mimosa. G23: Chestnuts. G24: Weakly masked chrome tanning with a Cr2O3 content of 24% by weight and a basicity of

40% G25: liquid tetrakis (hydroxymethyl) phosphoniumchloride and sulfate preparation G26: 4,4-dimethyl-1,3-oxazolidine. G27: 1-aza-3,7-dioxybicyclo-5-ethyl [3.3.0] octane. G28: Mixing a urea and formal condensation polyproduct with a condensation polyproduct a

Phenol and formaldehyde base. G29; 30% by weight aqueous formaldehyde solution. G30: Mixture of mineral tanning agents based on aluminum hydroxide in an amount of 14% by weight (calculated

as Al2O3) and 3% by weight of chromium salt (calculated as Cr2O3)

[0378] Main ingredients of commercially common adjuvants (HM):

HM1: Mixture of hydroxymethanesulfonate with the sodium salt of a condensation product of naphthalene sulfonic acid, urea and formaldehyde.

HM2: Mixture of ethoxylated alkylamines (C16-C18).

HM3: aqueous preparation of a partially hydrolyzed, weakly cationic poly-N-vinylformamide.

HM4: aqueous preparation of an anionically modified copolymer.

HM5: Hydroxymethylated urea.

HM6: A mixture based on aromatic sulfonic acids such as sodium salt, phenol, formaldehyde and urea.

HM7: aqueous preparation of a cationic polycondensate containing amino groups.

The determination of solidity was made in accordance with the following internationally recognized standards:

Sweat resistance: in accordance with Veslic C4260

Wash fastness: in accordance with DIN EN ISO 15703 Rub solidity: in accordance with DIN EN ISO 105 - X12 (Crockmeter, rub with cotton fabric) as well as in accordance with DIN EN ISO 11640 (Veslic, rub with felt)

5 Maeser: in accordance with ASTM D 2099

Penetrometer: in accordance with DIN EN ISO 5403

Water vapor impermeability: in accordance with DIN EN ISO 14268

Prolonged bending resistance: in accordance with DIN EN ISO 5402

Stitch tear test: in accordance with DIN 5331

10 Weiterreißversuch tear test: in accordance with DIN EN ISO 3377

Breaking strength: in accordance with DIN EN ISO 3376

A Top leather shoe formulations:

Top leather formulation of footwear 1:

A piece of leather of 100 parts by weight of a usual tanned beef leather with a recess thickness of 2.0

15 mm was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and then in an immersion liquid composed of 150 parts of water, 2 parts of sodium formate and 1 part of sodium acetate and batted for 5 minutes at 40 ° C, then 2 parts of sodium bicarbonate were added and neutralized for 10 minutes at 40 ° C. Then, the deadification liquid had a pH value of 7.3. To the deacidification liquid 4.6 parts of dye 1e were added and stained 30 minutes at pH 6.8 and 40 ° C. Adding portions in total 6

20 parts of sodium carbonate, for fixation, the pH value of the immersion liquid was adjusted between 9.2-9.6 and beaten for 60 minutes at 40 ° C. After changing the immersion liquid, it was washed twice respectively with 300 parts of water in total for 30 minutes. In an immersion liquid of 300 parts of water, adding a total of 0.5 parts of formic acid in portions within 30 minutes was adjusted to a pH of 6.5.

The dyed leather in this way was retanned in a freshly prepared immersion liquid of 200 parts of water and

25 5 parts of the hydrophobic agent that impregnates grease and cures H5 for 20 minutes at 40 ° C. by adding 0.5 parts of formic acid over the course of 20 minutes it was adjusted to a pH value of 5.0. With 3 parts of the polymeric tanning G15 it was retanned for 30 minutes at 40 ° C. The immersion liquid was then mixed with a mixture of 5 parts of the water-repellent agent H2 and 0.3 parts of the adjuvant HM 4. After a time for batting of 60 more minutes, by adding portions of a total of 2.5 parts of formic acid, in the

After 60 minutes, it was acidified to a pH value of 3.7. In a freshly prepared immersion liquid of 150 parts of water and 0.5 parts of formic acid, it was beaten 10 minutes at 30 ° C. It was then re-chromed by adding 5 parts of G 24 chrome fume for 90 minutes. A pH value of 3.6 was obtained. Finally, it was washed twice respectively in 300 parts of water respectively 10 minutes at 30 ° C.

The dyed, retanned and hydrophobicized leather in this manner was stored overnight on supports, then

35 stretched, subjected to vacuum at 60 ° C for 3 minutes, dried overnight at room temperature, conditioned, staked and dried under vacuum at 60 ° C for 2 minutes.

A hydrophobic leather was obtained for the upper part of the footwear with excellent color fastness to washing, sweat, migration and rubbing. Similarly, leather can be produced for the upper part of the shoe dyed with one of the dyes of examples 1a to 59k.

40 Formulation of the upper leather of footwear 2:

A piece of leather of 100 parts by weight of a usual tanned beef leather, with a recess thickness of 2.0 mm, was washed in a 200-part immersion liquid for 10 minutes at 35 ° C and then in an immersion liquid composed of 150 parts of water, 2 parts of sodium formate and 1 part of sodium acetate, beaten for 5 minutes at 40 ° C, then 2 parts of sodium bicarbonate were added and neutralized for 10 minutes at 40 ° C. Then the deadification liquid had a pH value of 7.3. To the deacidification liquid 7.5 parts of dye 2f were added and stained for 30 minutes at pH 6.8 and 40 ° C. Adding a total of 8 parts of sodium carbonate in portions for fixation, the pH value of the immersion liquid was adjusted between 9.2-9.6 and beaten for 60 minutes at 40 ° C. After changing the immersion liquid, it was washed twice respectively with 300 parts of water in total for 30 minutes. In an immersion liquid of 300 parts of water, in total adding a total of 0.5 parts of formic acid in portions within 30 minutes was adjusted to a pH of 6.5.

The dyed leather in this manner was retanned in a freshly prepared immersion liquid of 200 parts of water and 5 parts of the water-impregnating agent that impregnates grease and cures H5 for 20 minutes at 40 ° C. By adding 0.5 parts of formic acid over the course of 20 minutes it was adjusted to a pH value of 5.0. With 3 parts of the polymeric tanning G15 it was retanned for 20 minutes at 40 ° C. Then, 5 parts of G1 retannant were added to the immersion liquid and batted for an additional 30 minutes. The immersion liquid was then mixed with a mixture of 6 parts of the H2 water repellent agent and 0.3 parts of the HM4 adjuvant. After a time for batting of 60 more minutes, adding in portions in total 2.5 parts of formic acid over the course of 60 minutes, it was acidified to a pH value of 3.6. In a freshly prepared immersion liquid of 150 parts of water and 0.5 parts of formic acid, it was beaten for 10 minutes at 30 ° C. It was then re-chromed by adding 5 parts of G24 chrome tanning agent for 90 minutes. A pH value of 3.6 was obtained. In the end it was washed twice respectively in 300 parts of water respectively for 10 minutes at 30 ° C.

The dyed, retanned and hydrophobicized leather was thus stored on supports for one night, then stretched, subjected to vacuum at 60 ° C for 3 minutes, dried lying overnight at room temperature, conditioned, conditioned. staked and dried under vacuum at 60 ° C for 2 minutes.

A leather was obtained for the upper part of footwear with excellent solidity to wash, sweat, migration and rub.

Similarly, a top shoe leather can be produced, dyed with one of the dyes of examples 1a to 59k, hydrophobicized.

Formulation of the upper leather of footwear 3:

A piece of leather of 100 parts by weight of a usual tanned beef leather, with a recess thickness of 2.0 mm, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and then in an immersion liquid composed of 150 parts of water, 2 parts of sodium formate and 1 part of sodium acetate, beaten for 5 minutes at 40 ° C, then 2 parts of sodium bicarbonate were added and neutralized for 10 minutes at 40 ° C. Then the deacidification liquid had a pH value of 7.3. 5.1 parts of dye 3 were added to the deacidification liquid and stained for 30 minutes at pH 6.8 and 40 ° C. Adding a total of 6 parts of sodium carbonate for fixation, the pH value of the immersion liquid was adjusted between 9.2-9.6 and batted for 60 minutes at 40 ° C. After changing the immersion liquid, it was washed twice respectively with 300 parts of water in total for 30 minutes. In an immersion liquid of 300 parts of water, adding a total of 0.5 parts of formic acid in portions, within 30 minutes, it was adjusted to a pH of 6.5.

The dyed leather in this manner was retanned in a freshly prepared immersion liquid of 200 parts of water and 5 parts of the water-impregnating agent that impregnates grease and cures H5 for 20 minutes at 40 ° C. By adding 0.5 parts of formic acid over the course of 20 minutes it was adjusted to a pH value of 5.0. With 3 parts of the polymeric tanning G15 it was retanned for 20 minutes at 40 ° C. Then, 5 parts of G11 retannant were added to the immersion liquid and it was beaten for another 30 minutes. The immersion liquid was then mixed with a mixture of 6 parts of the H2 water repellent agent and 0.3 parts of the HM4 adjuvant. After a time for batting of 60 more minutes, adding in portions in total 2.5 parts of formic acid, over the course of 60 minutes, it was acidified to a pH value of 3; 6. In a freshly prepared immersion liquid of 150 parts of water and 0.5 parts of formic acid, it was beaten for 10 minutes at 30 ° C. It was then re-chromed by adding 5 parts of G24 chrome tanning agent for 90 minutes. A pH value of 3.7 was obtained. In the end, it was washed twice respectively in 300 parts of water respectively for 10 minutes at 30 ° C.

The dyed, retanned and hydrophobicized leather was thus stored on supports for one night, then stretched, subjected to vacuum at 60 ° C for 3 minutes, dried lying overnight at room temperature, conditioned, conditioned. staked and dried under vacuum at 60 ° C for 2 minutes.

A superior leather of footwear was obtained, hydrophobicized, with excellent color fastness to washing, sweat, migration and rubbing. Similarly, a superior hunting leather, dyed with one of the dyes of examples 1a to 59k, hydrophobicized can be produced.

A piece of leather of 100 parts by weight of an organically tanned beef leather in a usual manner, of a recess thickness of 1.3-1.4 mm, was washed in an immersion liquid of 300 parts of water for 15 minutes at 30 ° C and then in a freshly prepared immersion liquid of 100 parts of water and 1.5 parts of sodium formate, beaten for 10 minutes at 35 ° C. The immersion liquid had a pH value of 4.2-4.6. To the immersion liquid 8.5 parts of 4d dye were added and stained for 60 minutes at pH 5.5 and 35 ° C. Adding a total of 3 parts of sodium bicarbonate in portions over the course of 20 minutes was adjusted to a pH value of 7.3-7.8. For fixation by adding 8 parts of sodium carbonate in portions, the pH value of the immersion liquid was adjusted between 9.2-9.6 and beaten for 60 minutes at 35 ° C. After changing the immersion liquid, it was washed twice respectively with 300 parts of water and 1.5 parts of HM3 in total for 50 minutes at 40 ° C. In an immersion liquid of 200 parts of water, adding in total 2 parts of formic acid, within 70 minutes at 40 ° C it was adjusted to a pH of 4.3-4.6.

The dyed leather in this manner was retanned in a freshly prepared immersion liquid of 100 parts of water, 6 parts of polymeric tanning G18 and 1.5 parts of the water-repellent agent F6 for 30 minutes at 35 ° C. After the addition of 10 parts of G18 retanning and a 60 minute batting time to complete the tanning, 10 parts of G22 vegetable tanning and 10 parts of G4 retanning were added and batted for 60 minutes at 35 ° C. To the immersion liquid 5.5 parts of F6 fat impregnating agent were added and fat was impregnated for 90 minutes at 35 ° C. For the fixation of the hydrophobic agent, after adding 100 parts of hot water at 40 ° C and a time for batting of 20 minutes, the pH value was adjusted to 3.5 over the course of 50 minutes by adding formic acid . It was then rinsed for 15 minutes. The dyed, retanned and grease-impregnated leather was thus stored on supports for one night, then stretched, subjected to vacuum at 45 ° C for 4 minutes, dried hanging overnight at room temperature, conditioned , it staked and dried under vacuum.

We obtained a top leather of wet white shoes (wetwhite) with excellent color fastness to wash, sweat, migration and rub. Similarly, wet-white leather can be produced, dyed with one of the dyes of examples 1a to 59k.

Formulation of the top leather of footwear 5:

A piece of leather of 100 parts by weight of an organically tanned beef leather in a usual manner, of a recess thickness of 1.3 - 1.4 mm, was washed in an immersion liquid of 300 parts of water for 15 minutes at 30 ° C and then bathed in a freshly prepared immersion liquid of 100 parts of water and 1.5 parts of sodium formate for 10 minutes at 35 ° C. The immersion liquid had a pH value of 4.2-4.6. To the immersion liquid, 10 parts of dye 5b were added and stained for 60 minutes at pH 5.5 and 35 ° C. Adding a total of 3 parts of sodium bicarbonate in portions, within a period of 20 minutes it was adjusted to a pH value of 7.3-7.8. For fixation, the pH value of the immersion liquid was adjusted, adding 9 parts in total portions of sodium carbonate, between 9.2-9.6 and for 60 minutes it was batted at 35 ° C. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes at 40 ° C. In an immersion liquid of 200 parts of water, adding a total of 2 parts of formic acid in portions, over 70 minutes, at 40 ° C it was adjusted to a pH of 4.3-4.6.

The dyed leather was thus retanned in a freshly prepared immersion liquid of 100 parts of water, 6 parts of G18 polymeric tanning agent and 1.5 parts of F6 grease impregnating agent for 30 minutes at 35 ° C. After adding 10 parts of G18 retanning and a 60 minute batting time to complete the tanning, 10 parts of G22 vegetable tanning and 10 parts of G4 retanning were added and banded for 60 minutes at 35 ° C. To the immersion liquid 5.5 parts of agent for impregnating F6 fat were added and fat was impregnated for 90 minutes at 35 ° C. For the fixation of the hydrophobic agent, after adding 100 parts of hot water at 40 ° C and a time for batting of 20 minutes, over the course of 50 minutes, by adding formic acid, it was adjusted to a pH value of 3.5. It was then rinsed for 15 minutes.

The dyed, retanned and fat-impregnated leather was thus stored on supports for one night, then stretched, subjected to vacuum at 45 ° C for 4 minutes, dried lying overnight at room temperature, conditioned , it staked and dried under vacuum.

We obtained a top leather of wet white shoes (wetwhite) with excellent color fastness to wash, sweat, migration and rub. Similarly, a wet white leather upper shoe can be produced, dyed with one of the dyes of examples 1 to 59k.

A piece of leather of 100 parts by weight of a usual tanned beef leather, with a recess thickness of 1.8 mm, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and It was then poured into an immersion liquid composed of 150 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then 1.5 parts of sodium bicarbonate were added and neutralized for 10 minutes at 40 ° C. After adding 1.5 more parts of sodium bicarbonate and 3 parts of HM4, it was beaten for an additional 15 minutes. Then the deadification liquid had a pH value of 7.6. To the deacidification liquid 9 parts of dye 6c were added and stained for 90 minutes at pH 7.2 and 40 ° C. Adding a total of 8 parts of sodium carbonate, for fixation, the pH value of the immersion liquid was adjusted between 9.3-9.9 and batted for 60 minutes at 40 ° C. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In an immersion liquid of 200 parts of water, by adding to portions of a total of 2 parts of formic acid, within 60 minutes, it was adjusted to a pH of 4.5.

The dyed leather was thus retanned in a freshly prepared immersion liquid of 80 parts of water and 4 parts of G15 polymeric tanning agent for 30 minutes at 45 ° C. After adding 5 parts of vegetable tanning G22 and 3 parts of tanning resin G11, it was beaten for an additional 40 minutes. To impregnate grease, the immersion liquid was then mixed with a mixture of 6 parts of the water repellent agent H1 and 0.4 parts of the adjuvant HM4. After a time for batting of 90 minutes more 70 parts of hot water were added at 60 ° C, beaten for 10 minutes and then adding in portions in total 5 parts of formic acid over the course of 60 minutes it was acidified to a value pH 3.4. After a 10-minute wash with 200 parts of water at 30 ° C, they were bathed in a freshly prepared immersion liquid of 200 parts of water, 1 part of H6 water repellent agent and 0.2 parts of H4 adjuvant for 20 minutes at 30 ° C. Then, by adding 4 parts of G 24 chrome tanning agent it was re-chromed overnight. The pH value of the immersion liquid was 3.4. In the end it was washed twice respectively in 200 parts of water respectively for 10 minutes at 30 ° C.

The dyed, retanned and hydrophobicized leather was stored on supports for one night, then stretched, subjected to vacuum at 50 ° C for 6 minutes, dried lying overnight at room temperature, conditioned, staked 50 ° C for 2 minutes dried under vacuum.

A superior leather of footwear was obtained, hydrophobicized, with excellent color fastness to washing, sweat, migration and rubbing. Similarly, a top shoe leather, hydrophobicized, dyed with one of the dyes of examples 1a to 59k can be produced.

Formulation of the upper leather of footwear 7:

A piece of leather of 100 parts by weight of a usual tanned beef leather, with a recess thickness of 1.8 mm, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and It was then bathed in an immersion liquid composed of 150 parts of water and 1.5 parts of sodium formate was bathed for 5 minutes at 40 ° C, then 1.5 parts of sodium bicarbonate were added and neutralized for 10 minutes at 40 ° C. After adding 1.5 more parts of sodium bicarbonate and 3 parts of HM4, it was beaten for an additional 15 minutes. Then the deadification liquid had a pH value of 7.6. To the deacidification liquid 11.5 parts of dye 7 were added and stained for 90 minutes at pH 7.2 and 40 ° C. Adding a total of 10 parts of sodium carbonate in portions, for fixing the pH value of the immersion liquid was adjusted between 9.3-9.9 and beaten for 60 minutes at 40 ° C. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In an immersion liquid of 200 parts of water, adding a total of 2 parts of formic acid in portions over the course of 60 minutes, it was adjusted to a pH of 4.6.

The dyed leather was thus retanned in a freshly prepared immersion liquid of 80 parts of water and 4 parts of G15 polymeric tanning agent for 30 minutes at 45 ° C. After adding 5 parts of vegetable tanning G22 and 3 parts of resin tanning G11, it was beaten for 40 more minutes. To impregnate grease, the immersion liquid was then mixed with a mixture of 6 parts of the water repellent agent H1 and 0.4 parts of the adjuvant HM4. After a time for batting of 90 minutes more 70 parts of hot water were added at 60 ° C, it was beaten for 10 minutes and then adding in portions in total 5 parts of formic acid over the course of 60 minutes it was acidified to a value pH of 3.3. After a 10-minute wash with 200 parts of water at 30 ° C, it was transferred into a freshly prepared immersion liquid of 100 parts of water and 3 parts of G24 retanning overnight at 30 ° C. After washing for 10 minutes in 200 parts of water at 30 ° C in a freshly prepared immersion liquid of 100 parts of water and 2 parts of H6 hydrophobic agent, beaten for 20 minutes at 30 ° C. Then, by adding 3 parts of G 24 chrome tanning agent, it was fixed for 90 minutes. The pH value of the immersion liquid was 3.4. In the end it was washed twice respectively in 200 parts of water, respectively for 10 minutes at 30 ° C.

A superior leather of footwear was obtained, hydrophobicized, with excellent color fastness to washing, sweat, migration and rubbing. Similarly, a top shoe leather, hydrophobic, dyed with one of the dyes of Examples 1 to 59k, can be prepared.

Formulation of the upper leather of footwear 8:

A piece of leather of 100 parts by weight of a usual tanned beef leather, with a recess thickness of 1.8 mm, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and Then, they were bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then, within 20 minutes, a total of 3 parts of bicarbonate were added to portions in total of sodium and a neutralization pH value of 7.7 was reached. After adding 1.5 parts of HM2, it was beaten for 5 minutes at 40 ° C and then 6.5 parts of dye 8 were added to the deacidifying liquid and stained for 40 minutes at pH 7.5 and 40 ° C. Adding in total 7.1 parts of sodium carbonate for fixation, the pH value of the immersion liquid was adjusted between 9.2-9.6 and batted at 40 ° C for 90 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In an immersion liquid of 200 parts of water, adding a total of 2 parts of formic acid in portions over the course of 90 minutes was adjusted to a pH of 4.3.

The dyed leather was thus retanned in a freshly prepared immersion liquid of 80 parts of water and 3 parts of G15 polymeric tanning agent at 45 ° C for 40 minutes. By adding 3 parts of G1 retanning, 3 parts of G22 vegetable tanning and 3 parts of G11 resin tanning, it was retanned for 60 minutes at 45 ° C. After adding 70 parts of hot water at 60 ° C, it was beaten for 20 minutes at 60 ° C and after adding 2.5 parts of agent for impregnating fat F7 and 2.5 parts of agent for impregnating fat F4 was impregnated with fat for 60 minutes at 60 ° C. Adding a total of 4 parts of formic acid in portions, within 60 minutes it was acidified to a pH value of 3.5. It was then washed for 15 minutes.

The dyed leather, retanned and impregnated with grease in this way was stored overnight on supports, then stretched, at 60 ° C for 2 minutes it was subjected to vacuum, dried lying overnight at room temperature, conditioned , staked and at 60 ° C for 2 minutes dried under vacuum.

A superior shoe leather with excellent color fastness to wash, sweat, migration and rub was obtained. Similarly, a top shoe leather dyed with one of the dyes of examples 1a to 59k can be produced.

Formulation of the upper leather of shoes 9:

A piece of leather of 100 parts by weight of a tanned beef leather in a usual manner, of a 1.8 mm recess thickness, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and then it was bathed in a freshly prepared immersion liquid of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then, within 20 minutes, a total of 3 parts of bicarbonate were added to portions in total of sodium and a neutralization pH value of 7.7 was achieved. After adding 1.5 parts of HM2, it was beaten for 5 minutes at 40 ° C and then 4 parts of dye 9b were added to the acidification liquid and stained for 40 minutes at pH 7.5 and at 40 ° C. Adding a total of 5 parts of sodium carbonate in portions, for fixing the pH value of the immersion liquid was adjusted between 9.2-9.6 and beaten at 40 ° C for 90 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In an immersion liquid of 200 parts of water, adding a total of 2 parts of formic acid in portions, within 90 minutes, it was adjusted to a pH of 4.3.

The dyed leather was thus retanned in a freshly prepared immersion liquid of 80 parts of water and 3 parts of G17 polymeric tanning agent at 45 ° C for 40 minutes. By adding 3 parts of G7 retanning, 2 parts of G22 vegetable tanning, 2 parts of G23 vegetable tanning and 3 parts of G11 resin tanning, it was retanned for 60 minutes at 45 ° C. After adding 70 parts of hot water at 60 ° C, it was beaten for 20 minutes at 60 ° C and after adding 2.5 parts of agent for impregnating fat F7 and 2.5 parts of agent for impregnating fat F4 was impregnated with fat for 60 minutes at 60 ° C. Adding a total of 4 parts of formic acid in portions, within 60 minutes, was acidified to a pH value of 3.5. It was then rinsed for 15 minutes.

A superior shoe leather with excellent color fastness to wash, sweat, migration and rub was obtained. Similarly, a top shoe leather dyed with one of the dyes of examples 1a to 59k can be produced.

Formulation of top shoe leather 10:

A piece of leather of 100 parts by weight of a usual tanned beef leather, with a recess thickness of 1.8 mm, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and Then, in an immersion liquid of 100 parts of water and 1.5 parts of sodium formate, it was beaten for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH of 7.7 was achieved. After adding 1.5 parts of HM2, 6.9 parts of dye 10 were added to the acidification liquid for 5 minutes and then stained for 40 minutes at pH 7.5 and 40 ° C. Adding a total of 7.2 parts of sodium carbonate for fixation was used to fix the pH value of the immersion liquid between 9.2-9.6 and beat at 40 ° C for 90 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In an immersion liquid of 200 parts of water adding a total of 2 parts of formic acid in portions over the course of 90 minutes was adjusted to a pH of 4.3.

The dyed leather was thus retanned in a freshly prepared immersion liquid of 80 parts of water and 5 parts of G18 polymeric tanning agent at 45 ° C for 40 minutes. By adding 3 parts of retanning G1, 2 parts of vegetable tanning G22 and 4 parts of polymeric tanning G10, it was retanned for 60 minutes at 45 ° C. After adding 70 parts of hot water at 60 ° C, it was beaten for 20 minutes at 60 ° C and after adding 4.5 parts of agent for impregnating fat F5 and 0.5 parts of agent for impregnating fat F8 was impregnated with fat for 60 minutes at 60 ° C. Adding a total of 4 parts of formic acid in portions over the course of 60 minutes was acidified to a pH value of 3.5. It was then rinsed cold for 15 minutes.

The dyed leather, retanned and impregnated with grease in this way was stored overnight on supports, then stretched, at 60 ° C for 2 minutes it was subjected to vacuum, dried lying overnight at room temperature, conditioned , staked and at 60 ° C for 2 minutes dried under vacuum.

A superior shoe leather with excellent color fastness to wash, sweat, migration and rub was obtained. Similarly, a top shoe leather dyed with one of the dyes of examples 1a to 59k can be produced.

Formulation of upper shoe leather 11:

A piece of leather of 100 parts by weight of a chrome-tanned beef leather in a usual manner, of a recess thickness of 1.8 mm, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of bicarbonate were added to portions in total of sodium and a neutralization pH value of 7.7 was achieved. After adding 1.5 parts of HM2, it was beaten for 5 minutes at 40 ° C and then 9 parts of dye 11b were added to the deacidification liquid and stained for 40 minutes at pH 7.5 and 40 ° C. Adding a total of 9.5 parts of sodium carbonate to the portions for fixation, the pH value of the immersion liquid was adjusted between 9.2-9.6 and beaten at 40 ° C for 90 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In a dipping liquid of 200 parts of water, adding a total of 2 parts of formic acid in portions over the course of 90 minutes a pH of 4.3 was adjusted.

The dyed leather was thus retanned in a freshly prepared immersion liquid of 80 parts of water, 1.5 parts of G13 retanning and 2.5 parts of G16 polymeric tanning agent at 45 ° C for 40 minutes. By adding 3 parts of G1 retanning, 3 parts of G22 vegetable tanning and 3 parts of G11 resin tanning, it was retanned for 60 minutes at 45 ° C. After adding 70 parts hot water at 60 ° C, it was beaten for 20 minutes at 60 ° C and after adding 4.5 parts of agent for impregnating fat F5 and 0.5 parts of agent for impregnating fat F8 was impregnated with fat by 60 minutes at 60 ° C. Adding a total of 4 parts of formic acid in portions over the course of 60 minutes was acidified to a pH value of 3.5. It was then washed cold for 15 minutes.

A superior shoe leather with excellent color fastness to wash, sweat, migration and rub was obtained. Similarly, a top shoe leather dyed with one of the dyes of examples 1a to 59k can be produced.

Formulation of upper shoe leather 12:

A piece of leather of 100 parts by weight of a usual tanned beef leather, with a recess thickness of 1.8 mm, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and It was then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.7 was reached. After adding 1.5 parts of HM2, it was beaten for 5 minutes at 40 ° C and then 8.5 parts of dye 12d were added to the deacidification liquid and stained for 40 minutes at pH 7.5 and 40 ° C. Adding a total of 9 parts of sodium carbonate for fixation, the pH value of the immersion liquid was adjusted between 9.2-9.6 and beaten at 40 ° C for 90 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In an immersion liquid of 200 parts of water adding a total of 2 parts of formic acid in portions over the course of 90 minutes was adjusted to a pH of 4.3.

The dyed leather was thus retanned in a freshly prepared immersion liquid of 80 parts of water, 1.5 parts of G13 retanning and 2.5 parts of G16 polymeric tanning agent at 45 ° C for 40 minutes. By adding 8 parts of G2 retanning, 3 parts of G19 polymeric tanning and 3 parts of G11 resin tanning, 60 minutes were retanned at 45 ° C. After adding 70 parts of hot water at 60 ° C, it was beaten for 20 minutes at 60 ° C and after adding 4.5 parts of agent for impregnating fat F5 and 0.5 parts of agent for impregnating fat F8 was impregnated with fat for 60 minutes at 60 ° C. Adding a total of 4 parts of formic acid in portions over the course of 60 minutes was acidified to a pH value of 3.5. It was then rinsed cold for 15 minutes.

The dyed leather, retanned and impregnated with grease in this way was stored overnight on supports, then stretched, at 60 ° C for 2 minutes it was subjected to vacuum, dried lying overnight at room temperature, conditioned , staked and at 60 ° C for 2 minutes dried under vacuum.

A superior shoe leather with excellent color fastness to wash, sweat, migration and rub was obtained. Similarly, a top shoe leather dyed with one of the dyes of examples 1a to 59k can be produced.

Formulation of the upper leather of footwear 13:

A piece of leather of 100 parts by weight of a usual tanned beef leather, with a recess thickness of 1.8 mm, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and It was then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.7 was achieved. After adding 1.5 parts of HM2, it was beaten for 5 minutes at 40 ° C and then 8 parts of 12at dye were added to the deacidification liquid and stained for 40 minutes at pH 7.5 and 40 ° C. Adding a total of 9 parts of sodium carbonate in portions, the pH value of the immersion liquid was adjusted between 9.2-9.6 for fixation and batted at 40 ° C for 90 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water, in total for 60 minutes. In a dipping liquid of 200 parts of water, adding a total of 2 parts of formic acid in portions over the course of 90 minutes, a pH of 4.3 was adjusted.

The dyed leather in this manner was retanned in a freshly prepared immersion liquid of 80 parts of water, 1 part of G13 retanning and 3 parts of G16 polymeric tanning agent at 45 ° C for 40 minutes. By adding 1.5 parts of HM4 adjuvant, 3 parts of polymeric tanning G19 and 3 parts of polymeric tanning G10, it was retanned for 60 minutes at 45 ° C. After adding 70 parts of hot water at 60 ° C, it was beaten for 20 minutes at 60 ° C and after adding 1.5 parts of agent for impregnating fat F2 and 3.5 parts of water repellent agent H3 was impregnated with fat by 60 minutes at 60 ° C. Adding a total of 4 parts of formic acid in portions was acidified over a period of 60 minutes at a pH value of 3.5. It was then rinsed cold for 10 minutes.

A superior shoe leather with excellent color fastness to wash, sweat, migration and rub was obtained. Similarly, a top shoe leather dyed with one of the dyes of examples 1a to 59k can be produced.

Formulation of upper shoe leather 14:

A piece of leather of 100 parts by weight of a usual tanned beef leather, of a thickness of 1.3 mm recess, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and It was then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.7 was achieved. After adding 1.5 parts of HM2, it was beaten for 5 minutes at 40 ° C and then to the deacidifying liquid 8 parts of 12bx dye were added and stained for 40 minutes at pH 7.5 and 40 ° C. Adding a total of 8.5 parts of sodium carbonate in portions, the pH value of the immersion liquid was adjusted between 9.2-9.6 for fixation and batted at 40 ° C for 90 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In an immersion liquid of 200 parts of water, adding a total of 2 parts of formic acid in portions over the course of 90 minutes was adjusted to a pH of 4.3.

The dyed leather in this way was bathed in a freshly prepared immersion liquid of 80 parts of water and 1 part of G13 retanning for 10 minutes. By adding 4 parts of chrome tanner G24, 2 parts of retanning G1, 1 part of fat impregnating agent F1 was retanned for 40 minutes at 35 ° C. Then 1 part of sodium formiatop was added and batted for 20 min. After adding 0.3 parts of sodium bicarbonate, it was retanned for an additional 90 minutes. After washing for 10 minutes at 35 ° C in 300 parts of water, it was neutralized in a new immersion liquid of 100 parts of water and 1.5 parts of sodium formate at 35 ° C for 10 minutes. 0.5 parts of sodium bicarbonate were added to the neutralization liquid and batted for 30 minutes. After retanning 30 minutes with 5 parts of G18 polymeric tanning to complete the tanning, 5 parts of G5 retanning and 3 parts of G1 retanning were added. After a time for batting of 40 minutes the immersion liquid was diluted with 100 parts hot water at 60 ° C and batted for 10 minutes at 60 ° C. After adding 3.5 parts of agent to impregnate F1 grease and 3.5 parts of hydrophobic agent H3, it was impregnated with grease for 60 minutes at 60 ° C. Adding a total of 4 parts of formic acid in portions over the course of 60 minutes was acidified to a pH value of 3.5. It was then rinsed cold for 10 minutes.

The dyed leather, retanned and impregnated with grease in this way was stored overnight on supports, then stretched, at 60 ° C for 2 minutes it was subjected to vacuum, dried lying overnight at room temperature, conditioned , staked and at 60 ° C for 2 minutes dried under vacuum.

A superior leather of Softy footwear was obtained with excellent color fastness to wash, sweat, migration and rub. Similarly, a top leather of Softy shoes dyed with one of the dyes of examples 1a bis 59k can be produced.

Formulation of the upper leather of shoes 15:

A piece of leather of 100 parts by weight of a usual tanned beef leather, with a thickness of 1.3 mm recess, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and then it was bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.7 was reached. After adding 1.5 parts of HM2, it was beaten for 5 minutes at 40 ° C and then to the deacidification liquid 8 parts of mixed 12gz dye were added and stained for 40 minutes at pH 7.5 and 40 ° C. Adding a total of 8.5 parts of sodium carbonate in portions, the pH value of the immersion liquid was adjusted between 9.2-9.6 for fixation and batted at 40 ° C for 90 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In a immersion liquid of 200 parts of water adding a total of 2 parts of formic acid in portions over the course of 90 minutes a pH of 4.3 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 80 parts of water and 1.5 parts of G14 retanning for 10 minutes. By adding 6 parts of G20 chromium sintane and 1 part of F1 grease impregnating agent, it was retanned for 40 minutes at 35 ° C. Then 1 part of sodium formate was added and batted for 20 min. After adding 0.3 parts of sodium bicarbonate, it was retanned for an additional 90 minutes. After washing for 10 minutes at 35 ° C in 300 parts of water, it was neutralized in a new immersion liquid of 100 parts of water and 1.5 parts of sodium formate at 35 ° C for 10 minutes. 0.5 parts of sodium bicarbonate were added to the neutralization liquid and batted for 30 minutes. Nach of retanning for 30 minutes with 6 parts of polymeric tanning G18 to complete the tanning were added 6 parts of G5 retanning and 6 parts of G3 retanning. After a time for batting of 40 minutes, the immersion liquid was diluted with 100 parts of hot water at 60 ° C and batted for 10 minutes at 60 ° C. After adding 3.5 parts of agent to impregnate F1 grease and 3.5 parts of hydrophobic agent H3, it was impregnated with grease for 60 minutes at 60 ° C. Adding a total of 4 parts of formic acid in portions over the course of 60 minutes was acidified to a pH value of 3.5. It was then rinsed cold for 10 minutes.

The dyed, retanned and fat-impregnated leather was stored in this way for one night on supports, then stretched, at 60 ° C for 2 minutes under vacuum, dried on a night at room temperature, conditioned. , staked and at 60 ° C for 2 minutes dried under vacuum.

A superior leather of Softy footwear was obtained with excellent color fastness to wash, sweat, migration and rub. Similarly, a top leather of Softy shoes dyed with one of the dyes of examples 1a bis 59k can be produced.

Formulation of upper shoe leather 16:

A piece of leather of 100 parts by weight of a tanned beef leather in a usual manner, of a 1.8 mm recess thickness, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and then it was bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.4 was reached. After adding 1.5 parts of HM2, it was beaten for 5 minutes at 40 ° C and then 7 parts of mixed 12hf dye were added to the deacidification liquid and stained for 40 minutes at pH 7.5 and 40 ° C. Adding a total of 8 parts of sodium carbonate in portions, the pH value of the immersion liquid was adjusted between 9.2-9.6 for fixation and batted at 40 ° C for 90 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In an immersion liquid of 200 parts of water, adding a total of 4 parts of formic acid in portions, over a period of 90 minutes, it was adjusted to a pH of 3.7.

The dyed leather was thus retanned in a freshly prepared immersion liquid of 80 parts of water, 1.5 parts of G13 aldehyde frit and 6 parts of G18 polymeric tanner for 40 minutes at 45 ° C. Then 8 parts of G2 retanning, 2 parts of G19 polymeric tanning and 3 parts of G11 resin tanning were added and the tanning was completed in 60 min at 45 ° C. The immersion liquid was then diluted with 70 parts of hot water at 60 ° C and batted for 20 minutes at 60 ° C. After adding 6.5 parts of agent to impregnate F1 grease and 3.5 parts of agent to impregnate fat F3 was impregnated with fat for 60 minutes at 60 ° C. Adding a total of 4 parts of formic acid in portions, within 60 minutes it was acidified to a pH value of 3.5. It was then rinsed cold for 10 minutes.

The dyed leather, retanned and impregnated with grease in this way was stored overnight on supports, then stretched, at 60 ° C for 2 minutes it was subjected to vacuum, dried lying overnight at room temperature, conditioned , staked and at 60 ° C for 2 minutes dried under vacuum.

A superior leather of Softy footwear was obtained with excellent color fastness to wash, sweat, migration and rub. Similarly, a top leather of Softy shoes dyed with one of the dyes of examples 1a to 59k can be produced.

Formulation of the upper leather of footwear 17:

A piece of leather of 100 parts by weight of a tanned beef leather in a usual manner, with a thickness of 1.5 mm recess, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and It was then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.6 was reached. To the deacidification liquid were added 9 parts of mixed dye 12 hr and stained for 30 minutes at pH 7.5 and 40 ° C. Adding a total of 9 parts of solid sodium carbonate in portions, the pH value of the immersion liquid was adjusted between 9.2-9.6 for fixation and batted at 40 ° C for 90 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In an immersion liquid of 200 parts of water, by adding a total of 4 parts of formic acid, within a period of 90 minutes it was adjusted to a pH of 3.5.

The leather dyed in this way in a freshly prepared immersion liquid of 100 parts of water and 4 parts of G12 aldehyde fuming was bathed for 10 minutes at 35 ° C. Then 6 parts of G24 chrome tanning agent and 2 parts of G1 retanning were added and retanned for 50 minutes at 35 ° C. Then 1 part of sodium formate was added to the immersion liquid and allowed to bat for 10 minutes. After adding 1.5 parts of the agent to impregnate F1 fats, they were beaten for 90 min at 35 ° C. The immersion liquid was purged and washed once with 300 parts of water at 45 ° C for 10 minutes.

Then, in a freshly prepared immersion liquid of 70 parts of water and 2 parts of hydrophobic agent H3 was previously impregnated with grease for 15 minutes at 45 ° C. Then 2 parts of sodium formate, 1 part of sodium bicarbonate and 3 parts of HM4 adjuvant were added and batted for 30 minutes. To the neutralization liquid were added 12 parts of G6 retanning, after batting 10 minutes 2 parts of polymeric tanning-G19 were added and retanning for 50 more minutes. To the retanning liquid, 4 parts of F4 grease impregnating agent, 4 parts of F1 grease impregnating agent and 2 parts of F6 grease impregnating agent were added and fat was impregnated for 60 minutes at 45 ° C. Adding a total of 4 parts of formic acid in portions, within 60 minutes it was acidified to a pH value of 3.5. The immersion liquid was then purged and washed cold for 5 minutes.

The dyed leather, retanned and impregnated with grease in this way was stored overnight on supports, then stretched, at 55 ° C for 1 minute it was subjected to vacuum, dried lying overnight at room temperature, conditioned , staked, batted dry for one night and dried on tensioning rack.

A superior leather of footwear with dry batting pints with dry felting pints and excellent color fastness to washing, sweat, migration and rubbing was obtained. Similarly, a top shoe leather can be produced, with dry batting pints, dyed with one of the dyes of examples 1a to 59k.

Formulation of the upper leather of footwear 18:

A piece of leather of 100 parts by weight of a usual tanned beef leather, of a 2.1 mm recess thickness, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and It was then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.6 was reached. 7.5 parts of dye 13b were added to the deacidification liquid and stained for 30 minutes at pH 7.5 and 40 ° C. Adding a total of 8 parts of sodium carbonate in portions, for fixing the pH value of the immersion liquid was adjusted between 9.2-9.6 and was beaten at 40 ° C for 75 minutes. After changing the immersion liquid, it was washed twice respectively with 300 parts of water in total for 60 minutes.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 80 parts of water and 3 parts of G12 aldehyde pellet for 30 minutes at 45 ° C. Then 5 parts of G5 retannant were added and retanned for 30 minutes at 45 ° C. Then, 1 part of the agent for impregnating F1 fat and 1 part of the agent for impregnating F4 fat was added to the immersion liquid and it was previously impregnated with fat for 40 minutes at 45 ° C. 70 parts of hot water were then added at 55 ° C and batted for 20 minutes at 55 ° C. Adding 1.5 parts of formic acid in portions, within a period of 55 minutes it was adjusted to a pH value of 5.0. The immersion liquid was purged and washed once with 300 parts of water at 45 ° C for 10 minutes.

Next, they were bathed in a freshly prepared immersion liquid of 100 parts of water and 2 parts of H3 hydrophobic agent for 15 minutes at 45 ° C. Then 2 parts of polymeric tanning G19 were added. After batting for 15 minutes, 2 parts of polymeric tanning G15 were added and retanned for an additional 30 minutes. To the retanning liquid 2.5 parts of fat impregnating agent F1, 2.5 parts of fat impregnating agent F4, 1 part of fat impregnating agent F3 and 1 part of fat impregnating agent F2 were added and fat was impregnated for 60 minutes at 45 ° C. Adding a total of 4 parts of formic acid in portions, within a period of 60 minutes it was adjusted to a pH value of 3.5. The immersion liquid was then purged and the leather was rinsed cold for 5 minutes.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, stretched wet and dried at 40 ° C, conditioned, staked, batted at night. Dry and dried on tensioning frame.

A superior leather of Floater footwear was obtained with excellent color fastness to washing, sweat, migration and rubbing. Similarly, a top leather of Floater shoes dyed with one of the dyes of examples 1a to 59k can be produced.

A piece of leather of 100 parts by weight of a usual tanned beef leather, of a 2.1 mm recess thickness, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and Then, in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate, it was beaten for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions. and adjusted to a neutralization pH value of 7.7. 5.9 parts of dye 13ae were added to the deacidification liquid and stained for 40 minutes at pH 7.5 and 40 ° C. adding a total of 6.5 parts of sodium carbonate to portions, for fixing the pH heat of the immersion liquid was adjusted between 9.2-9.6 and batted at 40 ° C for 90 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In an immersion liquid of 200 parts of water, adding a total of 4 parts of formic acid in portions within 60 minutes was adjusted to a pH of 3.6.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 80 parts of water and 1 part of G13 aldehyde tanner and 3 parts of G16 polymeric tanner for 60 minutes at 45 ° C. Then 0.5 parts of sodium bicarbonate were added, after a time of 30 minutes to batan, 5 parts of G18 polymeric tanning agent were added and retanned for 30 minutes at 45 ° C. Subsequently, 0.8 parts of HM5 adjuvant, 3 parts of polymeric tanning G17 and 2 parts of polymeric tanning G19 were added to the immersion liquid and tanning was completed for 60 minutes at 45 ° C. Then 70 parts of water were added and batted for 10 minutes at 60 ° C. 2.5 parts of F6 grease impregnating agent, 1.5 parts of H3 hydrophobicizing agent and 1.5 parts of F2 fat impregnating agent were added to the retanning liquid and fat was impregnated for 60 minutes at 45 ° C. Then adding 4 parts of formic acid in portions over the course of 60 minutes was adjusted to a pH value of 3.5. Then the immersion liquid was purged and rinsed cold briefly.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, at 60 ° C for 2 minutes under vacuum, dried hanging at room temperature, conditioned, staked and at 60 ° C for 2 minutes it was dried under vacuum.

A top shoe leather based on pure polymer with excellent color fastness to wash, sweat, migration and rub was obtained. Similarly, a top shoe leather based on pure polymer dyed with one of the dyes of examples 1a to 59k can be produced.

Formulation of top shoe leather 20:

A piece of leather of 100 parts by weight of a usual tanned beef leather, with a recess thickness of 2.0 mm, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and Then, in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate, it was beaten for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions. and a neutralization pH value of 7.8 was adjusted. To the deacidification liquid 4.8 parts of dye 13dt were added and 35 minutes were stained at pH 7.6 and 40 ° C. Adding a total of 6 parts of sodium carbonate in portions, the pH value of the immersion liquid was adjusted between 9.4-9.9 for fixation and batted at 40 ° C for 60 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In an immersion liquid of 200 parts of water, adding a total of 2 parts of formic acid in portions within 60 minutes was adjusted to a pH of 4.3.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 80 parts of water and 1.5 parts of H3 hydrophobic agent for 20 minutes. Then 5 parts of G18 polymeric tanning agent were added, after batting for 40 minutes an addition of 1 part of HM5 adjuvant and 5 parts of G18 polymeric tanning agent was made. After batting for an additional 30 minutes at 45 ° C, 3 parts of G19 polymeric tanning agent were added and retanned for 60 minutes at 45 ° C. Then 70 parts of water were added and batted for 10 minutes at 60 ° C. To the retanning liquid 2.5 parts of agent for impregnating fat F6, 0.5 parts of water repellent agent H3 and 1.5 parts of agent for impregnating fat F2 were added and fat was impregnated for 60 minutes at 60 ° C. Then, adding 4 parts of formic acid in portions, within a period of 60 minutes it was adjusted to a pH value of 3.4. Then the immersion liquid was purged and rinsed briefly in cold.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, at 60 ° C for 2 minutes under vacuum, dried hanging at room temperature, conditioned, staked and at 60 ° C for 2 minutes it was dried under vacuum.

A top shoe leather based on pure polymer with excellent color fastness to wash, sweat, migration and rub was obtained. Similarly, a top shoe leather based on pure polymer can be produced, dyed with one of the dyes of examples 1a to 59k.

A piece of leather of 100 parts by weight of a usual tanned beef leather, with a recess thickness of 2.2 mm, was washed in a dipping liquid of 200 parts of water for 10 minutes at 35 ° C and Then, in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate, it was beaten for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions. and a neutralization pH value of 7.8 was adjusted. To the deacidification liquid 7.7 parts of mixed dye 13hb were added and stained for 35 minutes at pH 7.6 and 40 ° C. Adding a total of 8 parts of sodium carbonate in portions, the pH of the immersion liquid was adjusted between 9.5 and 10.0 for fixation and batted at 40 ° C for 55 minutes. After changing the immersion liquid, it was washed twice respectively with 300 parts of water in total for 60 minutes. In an immersion liquid of 200 parts of water, adding in total 2 parts portions of formic acid, within 60 minutes it was adjusted to a pH of 4.4.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 80 parts of water and 1.5 parts of H3 hydrophobic agent for 15 minutes. Next, 5 parts of G18 polymeric tanning agent were added, after batting for 40 minutes an addition of 1 part of HM5 adjuvant, 3 parts of polymeric tanning G17, 3 parts of vegetable tanning G23 and 2 parts of tanning G11 were made. After batting an additional 30 minutes at 45 ° C, 3 parts of G19 polymeric tanning agent were added and retanned for 60 minutes at 45 ° C. Then 70 parts of water were added and batted for 10 minutes at 60 ° C. To the retanning liquid 2.5 parts of agent for impregnating fat f7 and 2 parts of agent for impregnating fat F4 were added and impregnated for 60 minutes at 60 ° C. Then, adding 4 parts of formic acid in portions over the course of 60 minutes, it was adjusted to a pH value of 3.5. Then the immersion liquid was purged and the leather was briefly rinsed cold.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, at 60 ° C for 2 minutes under vacuum, dried hanging at room temperature, conditioned, staked and at 60 ° C for 2 minutes it was dried under vacuum.

A superior shoe leather with excellent color fastness to wash, sweat, migration and rub was obtained. Similarly, a top shoe leather dyed with one of the dyes of examples 1a to 59k can be produced.

Formulation of the upper leather of footwear 22:

A piece of leather of 100 parts by weight of a tanned beef leather in a usual manner, of a recess thickness of 1.9 mm, was washed in a dipping liquid of 200 parts of water for 10 minutes at 35 ° C and It was then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.8 was adjusted. To the deacidification liquid, 10.5 parts of 13hp mixed dye were added and stained for 20 minutes at pH 7.6 and 40 ° C. Adding a total of 9 parts of sodium carbonate in portions, for fixing the pH value of the immersion liquid was adjusted between 9.5 -10.0 and batted at 40 ° C for 70 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In a dipping liquid of 200 parts of water, adding 2 parts of formic acid in portions over the course of 60 minutes, a pH of 4.3 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 80 parts of water and 3 parts of G19 polymeric tanning agent for 5 minutes. Subsequently, 6 parts of G2 retannant were added, after a time of 30 minutes to batan, an addition of 5 parts of polymeric tanning G18, 3 parts of polymeric tanning G19 and 4 parts of retanning G2 were made. After batting for an additional 60 minutes at 45 ° C, 70 parts of water were added and beaten for 20 minutes at 65 ° C. To the retanning liquid, 3 parts of F1 grease impregnating agent and 2 parts of F2 grease impregnating agent were added and fat was impregnated for 60 minutes at 65 ° C. Then, adding 4 parts of formic acid in portions over the course of 60 minutes a pH value of 3.6 was adjusted. Then the immersion liquid was purged and the leather was briefly rinsed cold.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, at 55 ° C for 4 minutes under vacuum, dried hanging at room temperature, conditioned, staked and at 55 ° C for 3 minutes it was dried under vacuum, polished with 220 sandpaper for nubuck, dusted and dried in tensioning frame.

A leather upper directly from nubuck footwear was obtained with excellent color fastness to washing, sweat, migration and rubbing. Similarly, a top shoe leather, directly nubuck, can be produced dyed with one of the dyes of examples 1a to 59k.

A piece of leather of 100 parts by weight of a beef leather, usually tanned, of a recess thickness of 2.0 mm, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 20 minutes, a total of 3 parts of bicarbonate were added to portions in total of sodium and a neutralization pH value of 7.6 was set. To the deacidification liquid, 6.1 parts of 13hw mixed dye were added and stained for 15 minutes at pH 7.5 and 40 ° C. Adding a total of 8 parts of sodium carbonate in portions, the pH value of the immersion liquid was adjusted between 9.2-9.6 for fixation and batted at 40 ° C for 90 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In an immersion liquid of 200 parts of water, adding a total of 2 parts of formic acid in portions, within 60 minutes, it was adjusted to a pH of 4.2.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 80 parts of water and 1 part of G13 aldehyde tanning agent for 3 minutes. After adding 3 parts of polymeric tanning G19, it was beaten for 30 more minutes. Then 0.8 parts of sodium bicarbonate were added. After a time of 30 minutes to batan, 3 parts of water repellent agent H5 were added, after 30 more minutes of batting it was retanned with 5 parts of G18 polymeric tanning agent for 30 minutes. To the retanning liquid, 5 parts of water repellent agent H1 and 0.5 parts of adjuvant HM4 were added and fat was impregnated for 60 minutes at 45 ° C. Then 70 parts of water were added and batted for 20 minutes at 65 ° C. Then, adding 4 parts of formic acid in portions over the course of 60 minutes a pH value of 3.5 was adjusted. Then the immersion liquid was purged. The leather was bathed in a freshly prepared immersion liquid of 150 parts of water and 0.5 parts of formic acid for 10 minutes at 30 ° C. By adding 5 parts of G24 chrome tanning the hydrophobicization was set for 90 minutes at 30 ° C. It was then washed once with 300 parts of water for 10 minutes and then bathed in an immersion liquid of 300 parts of water and 0.2 parts of formic acid for 10 minutes. After purging the immersion liquid, it was rinsed briefly in cold.

The dyed, retanned and hydrophobicized leather was thus stored overnight on supports, then stretched, at 55 ° C for 4 minutes under vacuum, dried hanging at room temperature, conditioned, staked and 55 ° C for 3 minutes dried under vacuum, polished with 220 er sandpaper for nubuck, dusted and dried in tensioning frame.

An upper shoe leather was obtained, directly hydrophobic nubuck with excellent color fastness to washing, sweat, migration and rubbing. In an analogous manner, a top leather of dyed footwear, directly hydrophobic nubuck, dyed with one of the dyes of examples 1a to 59k can be produced.

Formulation of the upper shoe leather 24:

A piece of leather of 100 parts by weight of a tanned beef leather in a usual manner, of a 1.8 mm recess thickness, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and then it was bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.5 was set. 9.2 parts of dye 14 were added to the deacidification liquid and stained 25 minutes at pH 7.5 and 40 ° C. Adding a total of 9 parts of sodium carbonate in portions, for fixing the pH value of the immersion liquid was adjusted between 9.2-9.6 and batted at 40 ° C for 50 minutes. After changing the immersion liquid, it was washed twice respectively with 300 parts of water in total for 60 minutes. In an immersion liquid of 200 parts of water, adding a total of 2 parts of formic acid in portions within 60 minutes was adjusted to a pH of 4.3.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 80 parts of water and 3 parts of G19 polymeric tanning agent for 15 minutes. Then 2 parts of hydrophobic agent H1 were added. After a 15-minute batting time, it was retanned after adding 5 parts of G18 polymeric tanning agent, 3 parts of G1 retanning and 1 part of G19 polymeric tanning agent for 30 minutes. To the retanning liquid, 4 parts of water repellent agent H1 and 0.3 parts of adjuvant HM4 were added and impregnated with grease for 60 minutes at 45 ° C. Then 70 parts of water were added and batted for 20 minutes at 65 ° C. Then, adding 4 parts of formic acid in portions, a pH value of 3.5 was adjusted over 60 minutes. Then the immersion liquid was purged. The leather was bathed in a freshly prepared immersion liquid of 150 parts of water and 0.5 parts of formic acid for 10 minutes at 30 ° C. Adding 5 parts of G24 chrome tanner, the hydrophobicization was set for 90 minutes at 30 ° C. It was then washed once with 300 parts of water for 10 minutes and then bathed in an immersion liquid of 300 parts of water and 0.2 parts of formic acid for 10 minutes. After purging the immersion liquid, it was rinsed briefly in cold.

The dyed, retanned and hydrophobicized leather was thus stored overnight on supports, then stretched, at 55 ° C for 4 minutes under vacuum, dried hanging at room temperature, conditioned, staked and 55 ° C for 3 minutes, dried under vacuum, polished with 220 er sandpaper for nubuck, dusted and dried in tensioning frame.

A superior shoe leather, directly hydrophobic nubuck, with excellent color fastness to washing, sweat, migration and rubbing was obtained. In an analogous manner, a top leather of dyed footwear, directly hydrophobic nubuck, dyed with one of the dyes of examples 1a to 59k can be produced.

Formulation of the upper leather of footwear 25:

A piece of leather of 100 parts by weight of a usual tanned beef leather, with a recess thickness of 1.8 mm, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and It was then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.5 was adjusted. 6.8 parts of dye 15 were added to the deacidification liquid and stained 30 minutes at pH 7.5 and 40 ° C. Adding a total of 8 parts of sodium carbonate in portions, the pH value of the immersion liquid was adjusted between 9.2-9.6 for fixation and batted at 40 ° C for 90 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In a dipping liquid of 200 parts of water, adding a total of 5 parts of formic acid in portions over the course of 90 minutes a pH of 3.0 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 80 parts of water and 0.4 parts of formic acid for 10 min. Then 1 part of G14 retannant was added and batted for 30 minutes. Then 4 parts of G24 chrome tanning and 2 parts of G28 retanning were added. After a time of 30 minutes to batan, 0.5 parts of sodium formate were added and rechromated for 60 minutes. 100 parts of water were added to the immersion liquid and batted for one night. The immersion liquid was then purged. The leather was bathed in a freshly prepared immersion liquid of 80 parts of water, 1.5 parts of sodium formate and 0.5 parts of sodium bicarbonate for 30 minutes at 30 ° C. Then 2 parts of polymeric tanning G19 were added. After batting for 15 minutes, 2 parts of H1 hydrophobic agent were added and batted for 15 minutes. After adding 5 parts of G18 polymeric tanning and batting for 30 minutes, 4 parts of G28 retanning and 3 parts of G11 retanning were added to complete the tanning and retanning for 30 more minutes. To the retanning liquid, 4 parts of water repellent agent H1 and 0.3 parts of adjuvant HM4 were added and impregnated with grease for 60 minutes. Then, 70 parts of water were added to the immersion liquid and beaten at 65 ° C for 20 minutes. Over the course of 45 minutes, adding 3.5 parts of formic acid in total portions, a pH value of 3.5 in the immersion liquid was adjusted. The leather was bathed in a freshly prepared immersion liquid of 150 parts of water and 0.5 parts of formic acid for 10 minutes at 30 ° C. By adding 5 parts of G24 chrome tanner, hydrophobicization was set for 90 minutes at 30 ° C. It was then washed once with 300 parts of water for 10 minutes and then bathed in an immersion liquid of 300 parts of water and 0.2 parts of formic acid for 10 minutes. After purging the immersion liquid, it was washed cold briefly.

The dyed, retanned and hydrophobicized leather was thus stored overnight on supports, then stretched, at 55 ° C for 4 minutes under vacuum, dried hanging at room temperature, conditioned, staked and 55 ° C for 3 minutes, dried under vacuum, polished with 220 er sandpaper for nubuck, dusted and dried in tensioning frame.

A superior shoe leather, directly hydrophobic nubuck, with excellent color fastness to washing, sweat, migration and rubbing was obtained. Similarly, a superior leather of shoes can be produced. Directly hydrophobic nubuck, dyed with one of the dyes of examples 1a to 59k.

Formulation of upper shoe leather 26:

A piece of leather of 100 parts by weight of a tanned beef leather in a usual manner, of a recess thickness of 1.9 mm, was washed in a dipping liquid of 200 parts of water for 10 minutes at 35 ° C and Then, in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate, it was beaten for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions. and a neutralization pH value of 7.6 was adjusted. To the deacidification liquid, 8.8 parts of dye 16i were added and stained for 40 minutes at pH 7.5 and 40 ° C. Adding a total of 8 parts of sodium carbonate in portions, the pH value of the immersion liquid was adjusted between 9.1-9.7 for fixation and batted at 40 ° C for 60 minutes. After changing the immersion liquid, it was washed twice respectively with 300 parts of water in. The dyed leather was thus bathed in a freshly prepared immersion liquid of 80 parts of water and 1 part of G14 retanning for 5 minutes. Then, 2 parts of G19 polymeric tanning agent were added, after 5 minutes of batting time the addition of 5 parts of G18 polymeric tanning agent was made. After 40 more minutes of batting at 45 ° C, 3 parts of vegetable tanning G22 and 3 parts of G28 retanning were added and retanned for 60 minutes at 45 ° C. Then 70 parts of water were added and batted for 10 minutes at 60 ° C. To the retanning liquid 2.5 parts of agent for impregnating F1 grease and 2.5 parts of hydrophobic agent H3 were added and fat was impregnated for 60 minutes at 50 ° C. Then, adding 4 parts of formic acid in portions over the course of 60 minutes, a pH value of 3.5 was adjusted. Then the immersion liquid was purged and the leather was briefly rinsed cold.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, at 55 ° C for 4 minutes under vacuum, dried hanging at room temperature, conditioned, staked and at 55 ° C for 3 minutes it was dried under vacuum, polished with 220 er sandpaper for nubuck, dusted and dried in tensioning frame. A superior shoe leather, directly hydrophobic nubuck, with excellent color fastness to washing, sweat, migration and rubbing was obtained. Similarly, a top shoe leather can be produced, directly hydrophobic nubuck, dyed with one of the dyes of examples 1a to 59k.

Formulation of the upper leather of footwear 27:

A piece of leather of 100 parts by weight of a tanned beef leather in a usual manner, of a thickness of 1.9 mm, was washed in a dipping liquid of 200 parts of water for 10 minutes at 35 ° C and then in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate, it was beaten for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.6 eingestellt was adjusted. To the deacidification liquid 9 parts of dye 17b were added and stained for 40 minutes at pH 7.5 and 40 ° C. Adding a total of 9.5 parts of sodium carbonate in portions, the pH value of the immersion liquid was adjusted between 9.2-9.8 for fixation and batted at 40 ° C for 60 minutes. After changing the immersion liquid, it was washed twice respectively with 300 parts of water in total for 60 minutes. A pH of 4.3 was adjusted in an immersion liquid of 200 parts of water and 2 parts of formic acid.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 80 parts of water and 1 part of G14 retanning for 5 minutes at 45 ° C. Then 2 parts of G19 polymeric tanning agent were added, after batting for 15 minutes the addition of 5 parts of G18 polymeric tanning agent was made. After batting an additional 40 minutes at 45 ° C, 4 parts of G28 resin tanning and 4 parts of G11 resin tanning were added and retanned for 60 minutes at 45 ° C. Then 70 parts of water were added and batted for 10 minutes at 60 ° C. 2.5 parts of F1 fat impregnating agent and 2.5 parts of H3 hydrophobic agent were added to the retanning liquid and fat was impregnated for 60 minutes at 55 ° C. Then, adding 4 parts of formic acid in portions over the course of 60 minutes, a pH value of 3.5 was adjusted. Then the immersion liquid was purged and the leather was briefly rinsed cold.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, at 55 ° C for 4 minutes under vacuum, dried hanging at room temperature, conditioned, staked and at 55 ° C for 3 minutes it was dried under vacuum, polished with 220 er sandpaper for nubuck, dusted and dried in tensioning frame.

A superior shoe leather, directly nubuck, was obtained with excellent color fastness when washing, sweat, migration and rubbing. Similarly, a top shoe leather, directly nubuck, can be produced dyed with one of the dyes of examples 1a to 59k.

Formulation of upper shoe leather 28:

A piece of leather of 100 parts by weight of a tanned beef leather in a usual manner, of a recess thickness of 1.9 mm, was washed in a dipping liquid of 200 parts of water for 10 minutes at 35 ° C and It was then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.6 was adjusted. 5 parts of dye 19 were added to the deacidification liquid and stained 30 minutes at pH 7.5 and 40 ° C. Adding a total of 6.5 parts of sodium carbonate in portions, for fixing the pH value of the immersion liquid was adjusted between 9.2-9.8 and beaten at 40 ° C for 65 minutes.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 80 parts of water and 1 part of G14 retanning for 5 minutes at 45 ° C. Then 2 parts of G19 polymeric tanning agent were added, after batting for 15 minutes the addition of 5 parts of G18 polymeric tanning agent was made. After batting for an additional 40 minutes at 45 ° C, 2 parts of vegetable tanning G22 and 4 parts of tanning resin G28 were added and retanned for 60 minutes at 45 ° C. Then 70 parts of water were added and batted for 10 minutes at 60 ° C. To the retanning liquid 2.5 parts of agent for impregnating F1 grease and 2.5 parts of hydrophobic agent H3 were added and fat was impregnated for 60 minutes at 60 ° C. Then, adding 4 parts of formic acid in portions, over a period of 50 minutes, a pH value of 3.5 was adjusted. Then the immersion liquid was purged and rinsed briefly in cold.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, at 55 ° C for 4 minutes under vacuum, dried hanging at room temperature, conditioned, staked and at 55 ° C for 3 minutes it was dried under vacuum, dried with 220 er sandpaper for nubuck, dusted and dried in tensioning frame.

A superior shoe leather, directly nubuck, was obtained with excellent color fastness when washing, sweat, migration and rubbing. Similarly, a top shoe leather, directly nubuck, can be produced dyed with one of the dyes of examples 1a to 59k.

Formulation of upper shoe leather 29:

A piece of leather of 100 parts by weight of a tanned beef leather in a usual manner, of a recess thickness of 1.9 mm, was washed in a dipping liquid of 200 parts of water for 10 minutes at 35 ° C and It was then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.6 was adjusted. 7.1 parts of dye 22 were added to the deacidification liquid and stained for 40 minutes at pH 7.5 and 40 ° C. Adding a total of 8 parts of sodium carbonate in portions, for fixing the pH value of the immersion liquid was adjusted between 9.2-9.8 and batted at 40 ° C for 60 minutes. After changing the immersion liquid, it was washed twice respectively with 300 parts of water in total for 60 minutes. In a immersion liquid of 200 parts of water adding a total of 3 parts of formic acid in portions over the course of 60 minutes a pH of 3.9 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 80 parts of water and 2 parts of G29 retanning for 20 minutes at 45 ° C. Then 2 parts of G19 polymeric tanning agent were added, after batting for 15 minutes the addition of 5 parts of G18 polymeric tanning agent was made. After batting for an additional 40 minutes at 45 ° C, 4 parts of G28 resin tanning and 4 parts of G11 resin tanning were added and retanned for 60 minutes at 45 ° C. Then 70 parts of water were added and batted for 10 minutes at 60 ° C. To the retanning liquid 2.5 parts of agent for impregnating F1 grease and 2.5 parts of hydrophobic agent H3 were added and fat was impregnated for 60 minutes at 55 ° C. Then, adding 4 parts of formic acid in portions, a pH value of 3.5 was adjusted over 60 minutes. Then the immersion liquid was purged and the leather was briefly rinsed cold.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, 55 ° C for 4 minutes under vacuum, dried hanging at room temperature, conditioned, already staked 55 ° C for 3 minutes, dried under vacuum, polished with 220 er sandpaper for nubuck, dusted and dried in tensioning frame.

A superior shoe leather, directly nubuck, was obtained with excellent color fastness when washing, sweat, migration and rubbing. Similarly, a top shoe leather, directly nubuck, can be produced dyed with one of the dyes of examples 1a to 59k.

Formulation of the upper leather of footwear 30:

A piece of leather of 100 parts by weight of a usual tanned beef leather, with a recess thickness of 2.0 mm, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and It was then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then, within 20 minutes a total of 3 parts of baking soda were added to portions Sodium and 8 parts of sodium carbonate were added to portions in total, the pH value of the immersion liquid was adjusted between 9.2-9.8 for fixation and batted at 40 ° C for 60 minutes. After changing the immersion liquid, it was washed twice respectively with 300 parts of water in total for 60 minutes. In a immersion liquid of 200 parts of water, dosing a total of 4 parts of formic acid over a period of 60 minutes, a pH of 4.0 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 80 parts of water and 3 parts of G25 retanning for 35 minutes at 45 ° C. Then 2 parts of G19 polymeric tanning agent were added, after batting for 15 minutes the addition of 5 parts of G18 polymeric tanning agent was made. After batting for 40 minutes at 45 ° C, 4 parts of G28 resin tanning and 4 parts of G11 resin tanning were added and retanned for 60 minutes at 45 ° C. Then 70 parts of water were added and batted for 10 minutes at 60 ° C. To the retanning liquid 2.5 parts of agent for impregnating F1 grease and 2.5 parts of hydrophobic agent H3 were added and fat was impregnated for 60 minutes at 55 ° C. Then, adding 4 parts of formic acid in portions, a pH value of 3.5 was adjusted over 60 minutes. Then the immersion liquid was purged and rinsed briefly in cold.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, at 55 ° C for 4 minutes under vacuum, dried hanging at room temperature, conditioned, staked and at 55 ° C for 3 minutes it was dried under vacuum, polished with 220 er sandpaper for nubuck, dusted and dried in tensioning frame.

A superior shoe leather, directly nubuck, was obtained with excellent color fastness when washing, sweat, migration and rubbing. Similarly, a top shoe leather, directly nubuck, can be produced dyed with one of the dyes of examples 1a to 59k.

Formulation of the upper leather of footwear 31:

A piece of leather of 100 parts by weight of a usual tanned beef leather, with a recess thickness of 2.0 mm, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and Then, they were bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of baking soda were added to portions. sodium and a neutralization pH value of 7.7 was adjusted. To the deacidification liquid, 4.9 parts of dye 28a were added and stained for 30 minutes at pH 7.5 and 40 ° C. Adding a total of 6.8 parts of sodium carbonate in portions, for fixing the pH value of the immersion liquid was adjusted between 9.5-10.0 and was battered at 40 ° C for 60 minutes. After changing the immersion liquid, it was washed twice respectively with 300 parts of water in total for 60 minutes. In a dipping liquid of 200 parts of water, adding a total of 1.5 parts of formic acid in portions over the course of 50 minutes, a pH of 5.5 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 80 parts of water and 5 parts of H5 hydrophobic agent for 20 minutes at 45 ° C. Next, 5 parts of G18 polymeric tanning agent were added, after a time of batting of 40 minutes the addition of 5 parts of water repellent agent H1 and 0.3 parts of adjuvant HM4 was made. After impregnating with grease for 60 minutes at 45 ° C 70 parts of water were added and beaten for 10 minutes at 60 ° C. Then, adding 4 parts of formic acid in portions over the course of 60 minutes, a pH value of 3.5 was adjusted. The immersion liquid was then purged and in a freshly prepared immersion liquid of 150 parts of water and 0.5 parts of formic acid was beaten for 5 minutes. After adding 5 parts of chrome tanning G24 it was fixed for 90 minutes. In the end it was rinsed twice with 300 parts of water for respectively 10 minutes at 30 ° C.

The dyed, retanned and hydrophobicized leather was thus stored overnight on supports, then stretched, at 55 ° C for 4 minutes under vacuum, dried hanging at room temperature, conditioned, staked and 55 ° C for 2 minutes dried under vacuum.

A leather was obtained for the upper part of footwear with excellent solidity to wash, sweat, migration and rub. Similarly, a hydrophobic footwear upper leather can be produced, dyed with one of the dyes of examples 1a to 59k.

A piece of leather of 100 parts by weight of a tanned beef leather in a usual manner, of a recess thickness of 1.9 mm, was washed in a dipping liquid of 200 parts of water for 10 minutes at 35 ° C and It was then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.7 was adjusted. To the deacidification liquid, 9.1 parts of dye 30 were added and stained for 40 minutes at pH 7.6 and 40 ° C. Adding a total of 9.2 parts of solid sodium carbonate in portions, for fixing the pH value of the immersion liquid was adjusted between 9.3-9.8 and beaten at 40 ° C for 60 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In a dipping liquid of 150 parts of water, adding a total of 2 parts of formic acid in portions over the course of 50 minutes, a pH of 4.3 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 80 parts of water, 1.5 parts of G13 retanning and 2 parts of G19 polymeric tanning agent for 40 minutes at 45 ° C. Then 0.7 parts of sodium bicarbonate were added and after batting for 20 minutes a pH value of 5.5 was obtained. Then 3 parts of water repellent agent H1 and 0.2 parts of adjuvant HM4 were added and batted 20 minutes. After adding 6 parts of polymeric tanning G18, it was retanned for an additional 30 minutes. To impregnate fat, 5 parts of H1 water repellent agent and 0.3 parts of HM4 adjuvant were added and batted for 60 minutes. Next, 70 parts of water were added. After batting for 10 minutes at 60 ° C, adding 4 parts of formic acid in portions over the course of 60 minutes a pH value of 3.5 was adjusted. The immersion liquid was then purged and in a freshly prepared immersion liquid of 150 parts of water and 0.5 parts of formic acid was beaten for 5 minutes. After adding 5 parts of chrome tanning G24 it was fixed for 90 minutes. At the end it was washed twice with 300 parts of water respectively for 10 minutes at 30 ° C.

The dyed, retanned and hydrophobicized leather was thus stored overnight on supports, then stretched, at 55 ° C for 4 minutes under vacuum, dried hanging at room temperature, conditioned, staked and 55 ° C for 2 minutes dried under vacuum.

A soft leather upper of Softy hydrophobic footwear was obtained, with excellent color fastness to wash, sweat, migration and rub. Similarly, a top shoe leather, softy hydrophobicized, can be produced dyed with one of the dyes of examples 1a to 59k.

Formulation of upper shoe leather 33:

A piece of leather of 100 parts by weight of a chrome-tanned beef leather in a usual manner, of a recess thickness of 2.0 mm, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of bicarbonate were added to portions in total of sodium and a neutralization pH value of 7.7 was adjusted. To the deacidification liquid, 9.9 parts of dye 32 were added and stained for 40 minutes at pH 7.6 and 40 ° C. Adding a total of 10.0 parts of sodium carbonate in portions, the pH value of the immersion liquid was adjusted between 9.2-9.7 for fixation and batted at 40 ° C for 60 minutes. After changing the immersion liquid, it was washed twice respectively with 300 parts of water in total for 60 minutes. In a dipping liquid of 200 parts of water, adding a total of 1.5 parts of formic acid in portions over the course of 50 minutes, a pH of 5.4 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 80 parts of water and 3 parts of G19 polymeric tanning agent for 15 minutes at 45 ° C. Then 1.5 parts of hydrophobic agent H1 were added and batted for 15 minutes. After adding 5 parts of polymeric tanning G18, it was tanned for an additional 30 minutes. Then 2 parts of vegetable tanning G22, 2 parts of retanning G1, 2 parts of tanning resin G28 and 3 parts of G11 equating were added and batting for 30 minutes. To impregnate fat, 4.5 parts of H1 water repellent agent and 0.3 parts of HM4 adjuvant were added and batted for 60 minutes. Next, 70 parts of water were added. After batting for 10 minutes at 60 ° C, adding 4 parts of formic acid in portions over the course of 50 minutes, a pH value of 3.5 was adjusted. The immersion liquid was then purged and bathed in a freshly prepared immersion liquid of 150 parts of water and 0.5 parts of formic acid for 10 minutes. After adding 5 parts of chrome tanning G24 it was fixed for 90 minutes. It was then washed once with 300 parts of water for 10 minutes at 30 ° C and once with an immersion liquid of 300 parts of water and 0.2 parts of formic acid. In the end the leather was rinsed briefly.

The dyed, retanned and hydrophobicized leather was thus stored overnight on supports, then stretched, at 55 ° C for 4 minutes under vacuum, dried hanging at room temperature, conditioned, staked and 55 ° C for 2 minutes dried under vacuum.

A leather was obtained for the upper part of footwear with excellent solidity to wash, sweat, migration and rub. Similarly, a top shoe leather, hydrophobicized, dyed with one of the dyes of examples 1a bis 59k can be produced.

Formulation of upper shoe leather 34:

A piece of leather of 100 parts by weight of a chrome tanned beef leather in a usual manner, of a recess thickness of 1.8-2.0 mm, was washed in a dipping liquid of 200 parts of water for 10 minutes at 35 ° C and then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then added in a portion of 25 parts in total 3 parts of sodium bicarbonate and a neutralization pH value of 7.7 was adjusted. 6.8 parts of 34p dye were added to the deacidification liquid and stained for 40 minutes at pH 7.6 and 40 ° C. Adding a total of 7.5 parts of sodium carbonate in portions, the pH value of the immersion liquid was adjusted between 9.2-9.6 for fixation and batted at 40 ° C for 90 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In a dipping liquid of 200 parts of water, adding a total of 2 parts of formic acid in portions over the course of 60 minutes a pH of 4.3 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 80 parts of water, 1 part of G14 retanning and 2 parts of G19 polymeric tanning agent for 40 minutes at 45 ° C. Then 0.8 parts of sodium bicarbonate were added and a pH of 5.6 was reached. Next, 3 parts of H5 water repellent and 0.15 parts of HM4 were added and batted for 20 minutes. After adding 5 parts of G18 polymeric tanner, it was retanned for an additional 30 minutes. Then, 2 parts of G1 retanning, 2 parts of vegetable tanning G22 and 2 parts of tanning resin G28 were added and batted for 30 minutes. To impregnate grease, 5 parts of water repellent agent H1 and 0.15 parts of adjuvant HM4 were added and batted for 60 minutes. Next, 70 parts of water were added. After a time of batting of 10 minutes at 60 ° C, adding 4 parts of formic acid in portions over the course of 40 minutes a pH value of 3.5 was adjusted. The immersion liquid was then purged and in a freshly prepared immersion liquid of 150 parts of water and 0.5 parts of formic acid for 10 minutes. After adding 5 parts of chrome tanning G24 it was fixed for 90 minutes. It was then washed once with 300 parts of water for 10 minutes at 30 ° C and once with an immersion liquid of 300 parts of water and 0.2 parts of formic acid for 10 minutes at 30 ° C. In the end the leather was rinsed briefly.

The dyed, retanned and hydrophobicized leather was thus stored overnight on supports, then stretched, at 55 ° C for 4 minutes under vacuum, dried hanging at room temperature, conditioned, staked and 55 ° C for 2 minutes dried under vacuum.

A leather was obtained for the upper part of footwear with excellent solidity to wash, sweat, migration and rub. Similarly, a top shoe leather, hydrophobicized, dyed with one of the dyes of examples 1a to 59k can be produced.

Formulation of upper shoe leather 35:

A piece of leather of 100 parts by weight of a usual tanned beef leather, with a recess thickness of 1.8 mm, was washed in an immersion liquid of 300 parts of water for 10 minutes at 30 ° C and then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and adjusted a neutralization pH value of 7.7. 8.1 parts of dye 36 were added to the deacidification liquid and stained for 50 minutes at pH 7.6 and 40 ° C. Adding a total of 8.7 parts of sodium carbonate in portions, the pH value of the immersion liquid was adjusted between 9.2-9.8 for fixation and batted at 40 ° C for 60 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In a immersion liquid of 150 parts of water adding a total of 1.5 parts of formic acid in portions over the course of 60 minutes a pH of 5.3 was adjusted.

The leather dyed in this way in a freshly prepared immersion liquid of 100 parts of water and 3 parts of H5 hydrophobic agent is previously impregnated with grease for 20 minutes. Then 5 parts of G18 polymeric tanning agent were added and batted for 40 minutes. After adding 3 parts of polymeric tanning agent G16 it was retanned for an additional 30 minutes. Then 2 parts of polymeric tanning G19 were added and the tanning was completed for 30 minutes. To the retanning liquid, 5 parts of water repellent agent H1 and 0.5 parts of adjuvant HM4 were added and impregnated with grease for 60 minutes. Subsequently, 100 parts of water were added. After a time of batting of 10 minutes at 60 ° C, adding 4 parts of formic acid in portions over the course of 55 minutes a pH value of 3.5 was adjusted. The immersion liquid was then purged and bathed in a freshly prepared immersion liquid of 120 parts of water and 0.5 parts of formic acid for 10 minutes. After adding 5 parts of chrome tanning G24 it was fixed for 90 minutes. It was then washed twice respectively with 300 parts of water for 10 minutes at 30 ° C.

The dyed, retanned and hydrophobicized leather was thus stored overnight on supports, then stretched, at 55 ° C for 4 minutes under vacuum, dried hanging at room temperature, conditioned, staked and 55 ° C for 3 minutes dried under vacuum.

A superior leather of hydrophobic footwear was obtained, based on pure polymer, with excellent color fastness to wash, sweat, migration and rub. Similarly, a top shoe leather, hydrophobicized, based on pure polymer, dyed with one of the dyes of examples 1a to 59k can be produced.

Formulation of upper shoe leather 36:

A piece of leather of 100 parts by weight of a tanned leather of usual way, of a thickness of recess 1.8 mm, was washed in an immersion liquid of 300 parts of water for 10 minutes at 30 ° C and then it was bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.7 was adjusted. 5.7 parts of dye 35v were added to the deacidification liquid and stained for 50 minutes at pH 7.6 and 40 ° C. Adding a total of 6.5 parts of sodium carbonate in portions, for fixing the pH value of the immersion liquid was adjusted between 9.2-9.6 and beaten at 40 ° C for 60 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In a immersion liquid of 150 parts of water, adding a total of 1.5 parts of formic acid in portions over the course of 60 minutes a pH of 5.3 was adjusted.

The leather dyed in this way in a freshly prepared immersion liquid of 100 parts of water and 2 parts of H5 hydrophobic agent was previously impregnated for 20 minutes. Then 5 parts of G18 polymeric tanning agent were added and batted for 40 minutes. After adding 3 parts of G1 retanning it was retanned for 30 more minutes. Then 2 parts of vegetable tanning G22 were added and the tannery was completed for 30 minutes. To the retanning liquid, 5 parts of water repellent agent H1 and 0.5 parts of adjuvant HM4 were added for 60 minutes. Subsequently, 100 parts of water were added. After a time of batting of 10 minutes at 60 ° C, adding 4 parts of formic acid in portions over the course of 55 minutes a pH value of 3.5 was adjusted. The immersion liquid was then purged and in a freshly prepared immersion liquid of 120 parts of water and 0.5 parts of formic acid was bathed for 10 minutes. After adding 5 parts of chrome tanning G24 it was fixed for 90 minutes. It was then washed twice respectively with 300 parts of water for 10 minutes at 30 ° C.

The dyed, retanned and hydrophobicized leather was thus stored overnight on supports, then stretched, at 55 ° C for 4 minutes under vacuum, dried hanging at room temperature, conditioned, staked and 55 ° C for 3 minutes dried under vacuum.

A leather was obtained for the upper part of footwear with excellent solidity to wash, sweat, migration and rub. Similarly, a top shoe leather, hydrophobicized, dyed with one of the dyes of examples 1a to 59k can be produced.

Formulation of upper shoe leather 37:

A piece of leather of 100 parts by weight of a chrome-tanned beef leather, of a 1.8 mm recess thickness, was washed in an immersion liquid of 300 parts of water for 10 minutes to 30 ° C and then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of portions were added sodium bicarbonate and a neutralization pH value of 7.7 was adjusted. To the deacidification liquid 7.8 parts of 38o dye were added and stained for 50 minutes at pH 7.6 and 40 ° C. Adding a total of 8.1 parts of sodium carbonate in portions, for fixing the pH value of the immersion liquid was adjusted between 9.2-9.6 and beaten at 40 ° C for 60 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In a dipping liquid of 150 parts of water, adding a total of 2 parts of formic acid in portions over the course of 60 minutes a pH of 4.5 was adjusted.

The leather dyed in this way in a freshly prepared immersion liquid of 100 parts of water, 1.5 parts of G14 retanning, 1.5 parts of G16 polymeric tanning and 1.5 parts of G19 retanning 40 minutes lang was batted. After adding 2 parts of vegetable tanning G22 and 3 parts of G28 retanning, the tanning was completed for 60 minutes. To the retanning liquid, 6 parts of water repellent agent H1 and 0.5 parts of adjuvant HM4 were added and impregnated with grease for 90 minutes. Subsequently, 100 parts of water were added. After a time of batting of 10 minutes at 60 ° C by adding 4 parts of formic acid in portions over the course of 50 minutes a pH value of 3.5 was adjusted. Then the immersion liquid was purged and in an immersion liquid prepared again from 120 parts of water and 0.5 parts of formic acid was bathed for 5 minutes. After adding 5 parts of chrome tanning G24 it was fixed for 90 minutes. It was then washed twice respectively with 300 parts of water for 10 minutes at 30 ° C.

The dyed, retanned and hydrophobicized leather was thus stored overnight on supports, then stretched, at 55 ° C for 4 minutes under vacuum, at room temperature dried hung, conditioned, staked and stacked. ° C for 3 minutes dried under vacuum.

A leather was obtained for the upper part of footwear with excellent solidity to wash, sweat, migration and rub. Similarly, a top shoe leather, hydrophobicized, dyed with one of the dyes of examples 1a bis 59k can be produced.

Formulation of upper shoe leather 38:

A piece of leather of 100 parts by weight of a usual tanned beef leather, with a recess thickness of 2.0 mm, was washed in an immersion liquid of 200 parts of water 10 minutes at 35 ° C and then it was bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.6 was adjusted. 9.2 parts of dye 40d were added to the deacidification liquid and stained for 40 minutes at pH 7.5 and 40 ° C. Adding a total of 9.3 parts of sodium carbonate for fixation, the pH value of the immersion liquid was adjusted between 9.2-9.8 and beaten at 40 ° C for 60 minutes. After changing the immersion liquid, it was washed twice respectively with 300 parts of water in total for 60 minutes. In a dipping liquid of 200 parts of water, adding a total of 3.5 parts of formic acid in portions over the course of 60 minutes a pH of 3.8 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 80 parts of water and 3 parts of G26 retanning for 60 minutes at 45 ° C. Then 2 parts of G19 polymeric tanning agent were added, after batting for 15 minutes the addition of 5 parts of G18 polymeric tanning agent was made. After batting for an additional 40 minutes at 45 ° C, 4 parts of G28 resin tanning and 4 parts of G11 resin tanning were added and retanned for 60 minutes 45 ° C. Then 70 parts of water were added and batted for 10 minutes at 60 ° C. To the retanning liquid 2.5 parts of agent for impregnating F1 grease and 2.5 parts of hydrophobic agent H3 were added and fat was impregnated for 60 minutes at 55 ° C. Then, adding 4 parts of formic acid in portions over the course of 60 minutes a pH value of 3.5 was adjusted. Then the immersion liquid was purged and the leather was briefly rinsed cold.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, at 55 ° C for 4 minutes under vacuum, at room temperature dried hung, conditioned, staked and at 55 ° C for 3 minutes it was dried under vacuum, dried with 220 er sandpaper for nubuck, dusted and dried in tensioning frame.

A leather upper directly from nubuck footwear was obtained with excellent color fastness to washing, sweat, migration and rubbing. Similarly, a superior nubuck shoe leather can be produced, dyed with one of the dyes of examples 1a to 59k.

Formulation of the upper leather of footwear 39:

A piece of leather of 100 parts by weight of a usual tanned beef leather, of a 2.1 mm recess thickness, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 ° C and It was then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.6 was adjusted. To the deacidification liquid 8 parts of dye 391 were added and stained for 40 minutes at pH 7.5 and 40 ° C. Adding a total of 8.6 parts of sodium carbonate in portions, for fixing the pH value of the immersion liquid was adjusted between 9.2-9.8 and beaten at 40 ° C for 60 minutes. After changing the immersion liquid, it was washed twice respectively with 300 parts of water in. The dyed leather was thus bathed in a freshly prepared immersion liquid of 80 parts of water and 3.5 parts of G27 retanning for 50 minutes. 45 ° C Then 2 parts of G19 polymeric tanning agent were added, after batting for 15 minutes the addition of 5 parts of G18 polymeric tanning agent was made. After batting for an additional 40 minutes at 45 ° C, 4 parts of G28 resin tanning and 4 parts of G11 resin tanning were added and retanned for 60 minutes at 45 ° C. Then 70 parts of water were added and batted for 10 minutes at 60 ° C. To the retanning liquid 2.5 parts of agent for impregnating F1 grease and 2.5 parts of hydrophobic agent H3 were added and fat was impregnated for 60 minutes at 55 ° C. Then, adding 4 parts of formic acid in portions over the course of 60 minutes a pH value of 3.5 was adjusted. Then the immersion liquid was purged and the leather was briefly rinsed cold.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, at 55 ° C for 4 minutes under vacuum, at room temperature dried hung, conditioned, staked and at 55 ° C for 3 minutes it was dried under vacuum, polished with 220 er sandpaper for nubuck, dusted and dried in tensioning frame.

A superior shoe leather, directly nubuck, was obtained with excellent color fastness when washing, sweat, migration and rubbing. Similarly, a top shoe leather, directly nubuck, can be produced dyed with one of the dyes of examples 1a to 59k.

Formulation of upper shoe leather 40:

A piece of leather of 100 parts by weight of a tanned leather of usual way, of a thickness of recess 1.8 mm, was washed in an immersion liquid of 300 parts of water for 10 minutes at 30 ° C and then In an immersion liquid composed of 100 parts of water, 1.5 parts of tanning G1 and 1 part of HM7 adjuvant was battered for 60 minutes at 40 ° C. Subsequently, 1.5 parts of sodium formate were added to the immersion liquid and 30 min at 40 ° C. Then, in the course of 25 minutes, a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.6 was adjusted. To the deacidification liquid 8.0 parts of dye 13ae were added and stained for 45 minutes at pH 7.0 and 40 ° C. Adding a total of 7.5 parts of sodium carbonate in portions, for fixing the pH value of the immersion liquid was adjusted between 9.2-9.5 and beaten at 40 ° C for 60 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In a dipping liquid of 200 parts of water, adding a total of 4 parts of formic acid in portions over the course of 60 minutes, a pH of 3.6 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 80 parts of water and 1 part of G13 aldehyde tanner and 3 parts of G16 polymeric tanner for 60 minutes at 45 ° C. Then 0.5 parts of sodium bicarbonate were added, after a time of 30 minutes to batan, 5 parts of G18 polymeric tanning agent were added and retanned for an additional 30 minutes at 45 ° C. Subsequently, 0.8 parts of HM5 adjuvant, 3 parts of polymeric tanning G17 and 2 parts of polymeric tanning G19 were added to the immersion liquid and tanning was completed for 60 minutes at 45 ° C. Then 70 parts of water were added and batted for 10 minutes at 60 ° C. To the retanning liquid 2.5 parts of agent for impregnating fat F6, 1.5 parts of water repellent agent H3 and 1.5 parts of agent for impregnating fat F2 were added and fat was impregnated for 60 minutes at 45 ° C. Then adding 4 parts of formic acid in portions over the course of 60 minutes a pH value of 3.5 was adjusted. Then the immersion liquid was purged and the leather was briefly rinsed cold.

The dyed leather, retanned and impregnated with grease in this way was stored overnight on supports, then the corners were cut, at 60 ° C for 2 minutes it was subjected to vacuum, at room temperature it was dried hung, conditioned, staked and at 60 ° C for 2 minutes dried under vacuum.

A superior shoe leather with excellent color fastness to wash, sweat, migration and rub was obtained. Similarly, a top shoe leather dyed with one of the dyes of examples 1a to 59k can be produced.

Leather formulation for furniture 1:

A piece of leather of 100 parts by weight of a tanned beef leather in a usual way, of a recess thickness of 1.1 mm, was washed in an immersion liquid of 300 parts of water for 10 minutes at 30 ° C and It was then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 35 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.8 was adjusted. Then 1.5 HM2 parts were added and batted for 5 minutes. To the deacidification liquid, 10.5 parts of dye 41 c were added and stained for 30 minutes at pH 7.3 and 35 ° C. Then 0.5 parts sodium bicarbonate were added and batted for 60 minutes. Adding a total of 9.5 parts of sodium carbonate in portions, for fixing the pH value of the immersion liquid was adjusted between 9.3-9.5 and beaten at 35 ° C for 60 minutes. After changing the immersion liquid, it was washed twice respectively with 300 parts of water in total for 60 minutes at 40 ° C. In a dipping liquid of 200 parts of water, adding a total of 3 parts of formic acid in portions over a period of 60 minutes, a pH of 3.7 was adjusted.

The dyed leather in this way was bathed in a freshly prepared immersion liquid of 150 parts of water and 2 parts of G13 retanning for 60 minutes at 45 ° C. Then 2 parts of G18 polymeric tanning agent were added. After batting for 60 minutes, 1.5 parts of sodium bicarbonate were added. After batting for 20 minutes at 45 ° C, 2 parts of F1 fat impregnating agent and 0.2 parts of HM4 adjuvant were added and fat was previously impregnated for 20 minutes. To the immersion liquid, 5 parts of G5 retanning, 3 parts of vegetable tanning G22 and 2 parts of tanning resin G11 were added and retanned for 60 minutes. To the retanning liquid, 7 parts of F1 grease impregnating agent and 3 parts of F6 grease impregnating agent were added and fat was impregnated for 60 minutes at 45 ° C. Then, adding 5 parts of formic acid in portions over the course of 45 minutes a pH value of 3.5 was adjusted. Then the immersion liquid was purged and the leather was briefly rinsed cold.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, stretched wet and dried on a tensioning frame, conditioned, staked and batted dry.

Furniture leather was obtained with excellent color fastness to wash, sweat, migration and rub. Similarly, a stained furniture leather can be produced with one of the dyes of examples 1a to 59k.

Leather formulation for furniture 2:

A piece of leather of 100 parts by weight of an organically tanned beef leather in a usual manner, of a recess thickness of 1.0-1.1 mm, was washed in a 300-part immersion liquid of water for 15 minutes at 30 ° C and then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 10 minutes at 35 ° C. The immersion liquid had a pH value of 4.2-4.6. To the immersion liquid 8.7 parts of dye 42g were added and stained for 40 minutes at pH 5.5 and 35 ° C. Adding a total of 3 parts of sodium bicarbonate in portions over the course of 20 minutes a pH value of 7.3-7.8 was adjusted. For the fixation, the pH value of the immersion liquid was adjusted by adding 9 parts of sodium carbonate in total between 9.2-9.6 and batted for 60 minutes at 35 ° C. After changing the immersion liquid, it was washed twice with an immersion liquid respectively of 300 parts of water and 1.5 parts of HM3 adjuvant in total for 60 minutes at 40 ° C. In a dipping liquid of 200 parts of water, adding in total 2 parts of formic acid in the course of 60 minutes at 40 ° C, a pH of 4.3-4.6 was adjusted.

The leather dyed in this way in a freshly prepared immersion liquid of 100 parts of water, 3 parts of G18 polymeric tanning agent and 1.5 parts of F6 grease impregnating agent was retanned for 30 minutes at 35 ° C. Next, 6 parts of G18 polymeric tanning and 10 parts of G18 retanning were added and batted for 60 minutes at 35 ° C. After adding 1.5 parts of agent to impregnate F6 fat and batting for 30 minutes, 6 parts of G18 polymeric tanning agent and 10 parts of G8 retanning were added and retanned for 60 minutes at 35 ° C. To the retanning liquid, 10 parts of the agent for impregnating F6 fat were added and fat was impregnated for 60 minutes at 35 ° C. For the fixation of the hydrophobic agent, after adding 100 parts of hot water at 45 ° C and after a time to batt of 20 minutes, a pH value of 3.5 was adjusted over the course of 50 minutes by the addition of formic acid . Then 300 parts of water was washed for 15 minutes.

The dyed, retanned and fat-impregnated leather was thus stored on supports for one night, then stretched, stretched wet, dried on a tensioning frame, conditioned, staked, batted dry and tensioned .

A wet white leather (wet-white) was obtained for furniture with excellent color fastness to washing, sweat, migration and rubbing. Similarly, a wet-white furniture leather can be produced, dyed with one of the dyes of examples 1a to 59k.

A piece of leather of 100 parts by weight of an organically tanned beef leather in a usual manner, of a recess thickness of 1.0-1.1 mm, was washed in a 300-part immersion liquid of water for 15 minutes at 30 ° C and then in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate, beaten for 10 minutes at 35 ° C. The immersion liquid had a pH value of 4.4. To the immersion liquid 7.5 parts of dye 46e were added and stained for 45 minutes at pH 5.3 and 35 ° C. Adding a total of 3 parts of sodium bicarbonate in portions, a pH value of 7.3-7.8 was adjusted within 20 minutes. For fixation, the pH value of the immersion liquid was adjusted between 9.5 -10.0, adding 8 parts of sodium carbonate in total portions and beaten for 60 minutes at 35 ° C. After changing the immersion liquid, it was washed three times with an immersion liquid respectively of 300 parts of water in total for 60 minutes at 40 ° C. In a dipping liquid of 200 parts of water, adding a total of 1.5 parts of formic acid in portions over the course of 60 minutes at 40 ° C, a pH of 4.7-5.0 was adjusted.

The dyed leather was thus retanned in a freshly prepared immersion liquid of 50 parts of water, 15 parts of H5 hydrophobic agent and 15 parts of G18 polymeric tanning agent for 90 minutes at 35 ° C. Then 8 parts of H5 hydrophobic agent and 6 parts of F6 grease impregnating agent were added and fat was impregnated for 150 minutes at 35 ° C. Then 100 parts of hot water were added at 45 ° C and beaten for 10 minutes. Then, over the course of 40 minutes by adding 3 parts of formic acid, a pH value of 3.5 was adjusted. In the end he rinsed briefly with water.

The dyed, retanned and grease-impregnated leather was thus stored on supports for one night, then stretched, stretched wet, dried on a tensioning rack, conditioned, staked, batted dry for one night , staked and stressed.

A leather of wet-white furniture based on pure polymer with excellent color fastness to washing, sweat, migration and rubbing was obtained. Similarly, a wet-white furniture leather of dyed footwear with one of the dyes of examples 1a to 59k can be produced.

Leather formulation for furniture 4:

A piece of leather of 100 parts by weight of a tanned beef leather in a usual way, of a recess thickness of 1.1 mm, was washed in an immersion liquid of 300 parts of water for 10 minutes at 30 ° C and It was then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 35 ° C, then within 30 minutes a total of 4 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.7 was adjusted. Then 1.5 parts of HM2 were added and batted for 5 minutes. To the deacidification liquid 9 parts of 43ag dye were added and stained for 30 minutes at pH 7.4 and 35 ° C. Then 0.5 parts of sodium bicarbonate were added and beaten for 60 minutes at pH 7.5. Adding a total of 9.8 parts of sodium carbonate in portions, the pH value of the immersion liquid was adjusted between 9.3-9.8 for fixation and beaten at 35 ° C for 60 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes at 40 ° C. In a immersion liquid of 200 parts of water adding a total of 1.8 parts of formic acid in portions over the course of 60 minutes a pH of 4.6 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 150 parts of water and 6 parts of G18 retanning for 40 minutes at 45 ° C. The pH value of the immersion liquid was 5.0. After adding 0.8 parts of sodium bicarbonate and batting for 20 minutes, a pH value of the immersion liquid of 6.9 was achieved. Two parts of F1 fat impregnating agent and 0.2 parts of HM4 adjuvant were added to the retanning liquid and fat was previously impregnated for 20 minutes at 45 ° C. To the immersion liquid, 3 parts of G5 retanning, 3 parts of G22 vegetable tanning and 2 parts of G11 resin tanning were added and retanned for 60 minutes. To the retanning liquid, 7 parts of F1 grease impregnating agent and 3 parts of F6 grease impregnating agent were added and fat was impregnated for 60 minutes at 45 ° C. Then, adding 5 parts of formic acid in portions over the course of 45 minutes, a pH value of 3.5 was adjusted. Then the immersion liquid was purged and the leather was rinsed cold briefly.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, stretched wet and dried on a tensioning frame, conditioned, staked and batted dry.

Furniture leather was obtained with excellent color fastness to wash, sweat, migration and rub. Similarly, a stained furniture leather can be produced with one of the dyes of examples 1a to 59k.

A piece of leather of 100 parts by weight of a tanned beef leather in a usual way, of a recess thickness of 1.1 mm, was washed in an immersion liquid of 300 parts of water for 10 minutes at 30 ° C and It was then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 35 ° C, then within 30 minutes a total of 4 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.7 was adjusted. Then 1.5 parts of HM2 were added and batted for 5 minutes. To the deacidification liquid 8 parts of 47ac dye were added and stained for 30 minutes at pH 7.5 and 35 ° C. Then 0.5 parts of sodium carbonate were added and beaten for 60 minutes at pH 7.6. Adding a total of 9 parts of sodium carbonate in portions, the pH value of the immersion liquid was adjusted between 9.5-9.9 for fixation and beaten at 35 ° C for 60 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes at 40 ° C. In a dipping liquid of 200 parts of water, adding a total of 3.0 parts of formic acid in portions over the course of 60 minutes, a pH of 3.7 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 150 parts of water and 1 part of G13 retanning for 60 minutes at 45 ° C. Then 6 parts of G18 polymeric tanning agent were added and retanned for 40 minutes at 45 ° C. The pH value of the immersion liquid was 4.2. After adding 1.5 parts of sodium bicarbonate and batting for 20 minutes, the immersion liquid of pH 6.2 was reached. Two parts of F1 fat impregnating agent and 0.2 parts of HM4 adjuvant were added to the retanning liquid and fat was impregnated for 20 minutes at 45 ° C. To the immersion liquid, 3 parts of G5 retanning, 3 parts of G22 vegetable tanning and 2 parts of G11 resin tanning were added and retanned for 60 minutes. To the retanning liquid, 7 parts of F1 grease impregnating agent and 3 parts of F6 grease impregnating agent were added and fat was impregnated for 60 minutes at 45 ° C. The pH value of the immersion liquid was 5.6. Then, adding 5 parts of formic acid in portions over the course of 45 minutes, a pH value of 3.5 was adjusted. Then the immersion liquid was purged and the leather was briefly rinsed cold.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, stretched wet and dried on a tensioning frame, conditioned, staked and batted dry.

A leather for furniture with excellent color fastness to washing, sweat, migration and rubbing was obtained. Similarly, a furniture leather dyed with one of the dyes of examples 1a to 59k can be produced.

Leather formulation for furniture 6:

A piece of leather of 100 parts by weight of a usual tanned beef leather, of a 1.1 mm recess thickness, was washed in an immersion liquid of 300 parts of water for 10 minutes at 30 ° C and then in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate, it was beaten for 5 minutes at 35 ° C, then within 4 minutes a total of 4 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.7 was adjusted. Then 1.5 parts of HM2 were added and batted for 5 minutes. To the deacidification liquid 7 parts of dye 49b and 30 minutes were added at pH 7.5 and stained at 35 ° C. Then 0.5 parts of sodium bicarbonate were added and beaten for 60 minutes at pH 7.6. Adding a total of 8 parts of sodium carbonate in portions, for fixing the pH value of the immersion liquid was adjusted between 9.5-9.9 and batted at 35 ° C for 60 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes at 40 ° C. In a dipping liquid of 200 parts of water, adding a total of 3.0 parts of formic acid in portions over the course of 60 minutes, a pH of 3.7 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 150 parts of water and 1 part of G13 retanning for 40 minutes at 45 ° C. Then 6 parts of G18 polymeric tanning agent were added and retanned for 40 minutes at 45 ° C. The pH value of the immersion liquid was 4.2. Then 1 part of sodium bicarbonate was added and batted for 20 minutes. To the retanning liquid were added 2 parts of agent to impregnate F1 fat and was previously impregnated with fat for 20 minutes at 45 ° C. To the immersion liquid 10 parts of G3 retannant were added and batted for 90 minutes. The grease was then impregnated with 6 parts of F1 grease impregnating agent and 2 parts of F6 grease impregnating agent for 60 minutes at 45 ° C. Adding 5 parts of formic acid in portions over the course of 45 minutes a pH value of 3.5 was adjusted. Then the immersion liquid was purged and the leather was briefly rinsed cold.

A leather for furniture with excellent color fastness to washing, sweat, migration and rubbing was obtained. Similarly, a furniture leather dyed with one of the dyes of examples 1a to 59k can be produced.

Leather formulation for furniture 7:

A piece of leather of 100 parts by weight of a tanned beef leather in a usual way, of a recess thickness of 1.1 mm, was washed in an immersion liquid of 300 parts of water for 10 minutes at 30 ° C and Then, in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate, it was beaten for 5 minutes at 35 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions. and a neutralization pH value of 7.6 was adjusted. To the deacidification liquid 5.5 parts of dye 52e were added and stained for 40 minutes at pH 7.5 and 35 ° C. Adding a total of 7 parts of sodium carbonate for fixation, the pH value of the immersion liquid was adjusted between 9.2-9.6 and beaten at 35 ° C for 60 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes at 40 ° C. In a dipping liquid of 150 parts of water, adding a total of 2.0 parts of formic acid in portions over the course of 60 minutes, a pH of 5.2 was adjusted.

The leather dyed in this way in a freshly prepared immersion liquid of 100 parts of water, 3 parts of polymeric tanning G18 and 1.5 parts of polymeric tanning G19 was battered for 20 minutes at 45 ° C. To the retanning liquid, 1 part of the agent for impregnating fat f6 and 0.5 parts of the agent for impregnating fat F2 were added and fat was previously impregnated for 20 minutes at 45 ° C. To the immersion liquid, 3 parts of polymeric tanning G18, 6 parts of G8 retanning and 2 parts of vegetable tanning G22 were added and retanned for 60 minutes. The grease was then impregnated with 6 parts of F6 grease impregnating agent, 2 parts of F2 grease impregnating agent and 1 part of F3 grease impregnating agent for 60 minutes at 45 ° C. After adding 100 parts of water and batting for 10 minutes, adding 4 parts of formic acid in portions within 45 minutes, a pH value of 3.5 was adjusted. Then the immersion liquid was purged and the leather was briefly rinsed cold.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, stretched wet and dried on a tensioning frame, conditioned, staked and batted dry.

A leather for furniture with excellent color fastness to washing, sweat, migration and rubbing was obtained. Similarly, a furniture leather dyed with one of the dyes of examples 1a to 59k can be produced.

Leather formulation for furniture 8:

A piece of leather of 100 parts by weight of a tanned beef leather in a usual way, of a recess thickness of 1.1 mm, was washed in an immersion liquid of 300 parts of water for 10 minutes at 30 ° C and then in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate, it was beaten for 5 minutes at 35 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.6 was adjusted. To the deacidification liquid 6 parts of dye 53b were added and stained for 50 minutes at pH 7.5 and 35 ° C. Adding a total of 7 parts of solid sodium carbonate in portions, the pH value of the immersion liquid was adjusted between 9.5 and 10.0 for fixing, and beaten at 35 ° C for 60 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes at 40 ° C. In a dipping liquid of 150 parts of water and 2.2 parts of formic acid, a pH of 4.9 was adjusted over 60 minutes.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 100 parts of water and 2 parts of G14 retanning for 30 minutes. Then 5 parts of G18 polymeric tanning agent were added and retanned for 40 minutes at 45 ° C. To the retanning liquid, 2 parts of agent for impregnating fat F6 and 1 part of agent for impregnating fat F2 were added and fat was previously impregnated for 20 minutes at 45 ° C. To the immersion liquid 6 parts of G2 retanning, 2 parts of G22 vegetable tanning and 2 parts of G28 resin tanning were added and retanned for 60 minutes. The grease was then impregnated with 8 parts of F6 grease impregnating agent, 2 parts of F2 grease impregnating agent and 1 part of F3 grease impregnating agent for 60 minutes at 45 ° C. After adding 100 parts of water and batting for 10 minutes, adding portions. The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, stretched, wet and dried. Tensioning rack, conditioned, staked and batted dry.

A leather for furniture with excellent color fastness to washing, sweat, migration and rubbing was obtained. Similarly, a furniture leather dyed with one of the dyes of examples 1a to 59k can be produced.

Leather formulation for furniture 9:

A piece of leather of 100 parts by weight of a tanned beef leather in a usual way, of a recess thickness of 1.1 mm, was washed in an immersion liquid of 300 parts of water for 10 minutes at 30 ° C and then in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate, it was beaten for 5 minutes at 35 ° C, then within 3 minutes a total of 3 parts of sodium bicarbonate were added to portions and a neutralization pH value of 7.8 was adjusted. 5.7 parts of dye 58b were added to the deacidification liquid and stained for 60 minutes at pH 7.7 and 35 ° C. Adding a total of 9 parts of sodium carbonate in portions, the pH of the immersion liquid was adjusted between 9.5 and 10.0 for fixing, and was beaten at 35 ° C for 60 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes at 40 ° C. In a dipping liquid of 150 parts of water, adding a total of 2.3 parts of formic acid in portions over the course of 60 minutes a pH of 5.0 was adjusted.

The leather dyed in this way in a freshly prepared immersion liquid of 100 parts of water and 2 parts of G14 retanning was bathed for 30 minutes. Then 6 parts of G18 polymeric tanning agent were added and retanned for 40 minutes at 45 ° C. To the retanning liquid were added 2 parts of agent to impregnate F1 fat and was previously impregnated with fat for 20 minutes at 45 ° C. To the immersion liquid 4 parts of G3 retanning and 2 parts of G22 vegetable tanning were added and batted for 60 minutes. After adding 2 parts of polymeric tanning G19, it was retanned for an additional 20 minutes. Next, 6 parts of the agent for impregnating F1 grease, 4 parts of the agent for impregnating fat F6 and 1 part of the agent for impregnating fat F3 were added to the retanning liquid and fat was impregnated for 60 minutes at 45 ° C. After adding 100 parts of water and batting for 10 minutes, adding 4 parts of formic acid in portions over the course of 45 minutes, a pH value of 3.5 was adjusted. Then the immersion liquid was purged and the leather was briefly rinsed cold.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, stretched wet and dried on a tensioning frame, conditioned, staked and batted dry.

A leather for furniture with excellent color fastness to washing, sweat, migration and rubbing was obtained. Similarly, a furniture leather dyed with one of the dyes of examples 1a to 59k can be produced.

Leather formulation for car 1:

A piece of leather of 100 parts by weight of a tanned beef leather in a usual manner, with a recess thickness of 1.21.3 mm, was washed in an immersion liquid of 300 parts of water for 10 minutes at 30 ° C and then in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate, it was beaten for 5 minutes at 35 ° C, then within 3 minutes a total of 3 parts of bicarbonate were added to portions in total of sodium and a neutralization pH value of 7.8 was adjusted. Then 1.5 parts of HM2 were added and batted 5 minutes. To the deacidification liquid 4.7 parts of dye 59d were added and stained for 30 minutes at pH 7.3 and 35 ° C. Then 0.5 parts of sodium bicarbonate were added and beaten for 60 minutes at pH 7.4. Adding a total of 5 parts of sodium carbonate in portions, for fixing the pH value of the immersion liquid was adjusted between 9.4-9.8 and beaten at 35 ° C for 80 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes at 40 ° C. In a dipping liquid of 200 parts of water, adding a total of 3 parts of formic acid in portions over a period of 60 minutes, a pH of 3.7 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 150 parts of water and 1.5 parts of G13 retanning for 60 minutes at 45 ° C. Then 8 parts of G18 polymeric tanning agent were added and retanned 40 minutes at 45 ° C. After adding 1.5 parts of sodium bicarbonate and batting for 20 minutes, fat was previously impregnated with 2 parts of F1 grease impregnating agent and 0.2 parts of HM4 adjuvant for 20 minutes at 45 ° C. To the immersion liquid, 4 parts of G5 retanning, 4 parts of G21 vegetable tanning and 2 parts of G11 resin tanning were added and retanned for 60 minutes. To the retanning liquid, 7 parts of F1 grease impregnating agent and 3 parts of F6 grease impregnating agent were added and fat was impregnated for 60 minutes at 45 ° C. Then, adding 5 parts of formic acid in portions over the course of 45 minutes, a pH value of 3.5 was adjusted. Then the immersion liquid was purged and the leather was rinsed cold briefly.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, stretched wet and dried on a tensioning frame, conditioned, staked and batted dry.

A car leather with excellent color fastness to wash, sweat, migration and rub was obtained. In an analogous manner a car leather dyed with one of the dyes of examples 1a to 59k can be produced.

Leather formulation for car 2:

A piece of leather of 100 parts by weight of an organically tanned beef leather in a usual manner, of a recess thickness of 1.1-1.2 mm, was washed in an immersion liquid of 300 parts of water for 15 minutes at 30 ° C and then 100 parts of water and 1.5 parts of sodium formate were bathed in an immersion liquid for 10 minutes at 35 ° C. The immersion liquid had a pH value of 4.4. 7.2 parts of dye 56 were added to the immersion liquid and it was quenched for 60 minutes at pH 4.5 and 35 ° C. Adding a total of 3 parts of sodium bicarbonate in portions, a pH value of 7.1-7.6 was adjusted within 20 minutes. For fixing, the pH value of the immersion liquid was adjusted between 9.6-9.7, adding 8 parts of sodium carbonate in portions and batting for 90 minutes at 35 ° C. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes at 40 ° C. In a dipping liquid of 300 parts of water, adding a total of 2 parts of formic acid in portions over a period of 60 minutes at 40 ° C, a pH of 4.2 was adjusted.

The leather dyed in this way in a freshly prepared immersion liquid of 100 parts of water and 5 parts of G18 polymer tanning was bathed for 10 minutes at 35 ° C. Next, 1 part of the F6 fat impregnating agent and 0.5 parts of the F2 fat impregnating agent were added and the fat was previously impregnated for 20 minutes at 35 ° C. After adding 5 parts of polymeric tanning G18 and 10 parts of G8 retanning, it was retanned for 60 minutes. To the retanning liquid, 1 part of F6 fat impregnating agent and 0.5 part of F2 fat impregnating agent were added and fat was impregnated for 30 minutes at 35 ° C. Then the tanning was completed for 90 minutes with 5 parts of G18 polymeric tanning and 10 parts of G8 retanning. After adding 8 parts of agent for impregnating fat F6 and 2 parts of agent for impregnating fat F2 was impregnated with fat for 60 minutes at 35 ° C. For fixation, after adding 100 parts of hot water at 45 ° C and batting for 20 minutes over the course of 60 minutes, a pH value of 3.5 was adjusted by adding 3 parts of formic acid. The leather was then washed 15 minutes with 300 parts of water.

The dyed, retanned and grease-impregnated leather was thus stored on supports for one night, then stretched, dried on a tensioning rack, conditioned, staked, dried, and dried on a tensioning rack. .

A wet-white car leather was obtained with excellent color fastness to wash, sweat, migration and rub. Similarly, a wet-white car leather can be produced, dyed with one of the dyes of examples 1a to 59k.

Leather formulation for car 3:

A piece of leather of 100 parts by weight of an organically tanned beef leather in a usual manner, of a 1.1-1.2 mm recess thickness, was washed in an immersion liquid of 300 parts of water for 15 minutes at 30 ° C and then in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate, batted for 10 minutes at 35 ° C. The immersion liquid had a pH value of 4.4. To the immersion liquid 3.5 parts of dye 54 were added and stained for 40 minutes at pH 4.5 and 35 ° C. Adding a total of 3 parts of sodium bicarbonate in portions, a pH value of 7.6 was adjusted over 20 minutes. For the fixation, the pH value of the immersion liquid was adjusted between 9.6-9.7, adding in total 5 parts of sodium carbonate and beaten for 90 minutes at 35 ° C. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes at 40 ° C. In an immersion liquid of 200 The dyed leather in this manner was retanned in a freshly prepared immersion liquid of 50 parts of water, 15 parts of H5 hydrophobic agent and 15 parts of G18 polymeric tanning agent for 90 minutes at 35 ° C. Then, 4 parts of H5 hydrophobicizing agent, 6 parts of F6 grease impregnating agent and 4 parts of F2 grease impregnating agent were added to the retanning liquid and fat was impregnated for 150 minutes at 35 ° C. For fixing, after adding 100 parts of hot water at 45 ° C and batting for 10 minutes, adding 4 parts of formic acid in portions over the course of 60 minutes a pH value of 3.5 was adjusted. The leather was then washed for 15 minutes with 300 parts of water.

The dyed, retanned and grease-impregnated leather was thus stored on supports for one night, then stretched, dried on a tensioning frame, conditioned, staked, dried for a night, staked and dried on tensioning frame.

A wet-white car leather based on pure polymer with excellent color fastness to washing, sweat, migration and rubbing was obtained. Similarly, a wetwhite car leather can be produced, dyed with one of the dyes of examples 1a to 59k.

Leather formulation for car 4:

A piece of leather of 100 parts by weight of a tanned leather of usual way, of a thickness of 1,11,2 mm recess, was washed in an immersion liquid of 300 parts of water for 10 minutes at 30 ° C and then in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate, it was beaten for 5 minutes at 35 ° C, then within 30 minutes a total of 3.5 parts were added to portions of sodium bicarbonate and a neutralization pH value of 7.6 was set. 5.2 parts of dye 51 were added to the deacidification liquid and stained 30 minutes at pH 7.5 and 35 ° C. Then 0.5 parts of sodium bicarbonate were added and batted 60 minutes at pH 7.6. Adding a total of 7 parts of sodium carbonate in portions, for fixing the pH value of the immersion liquid was adjusted between 9.3-9.9 and beaten at 35 ° C for 60 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes at 40 ° C. In a dipping liquid of 200 parts of water, adding a total of 3.5 parts of formic acid in portions over the course of 60 minutes, a pH of 3.5 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 150 parts of water and 3 parts of G12 retanning for 10 minutes at 45 ° C. After adding 1.5 parts of agent to impregnate F1 fat, it was previously impregnated with fat for 50 minutes at 45 ° C. Then 0.5 parts of sodium bicarbonate were added and beaten for 30 minutes. To the immersion liquid, 5 parts of G18 polymeric tanning agent and 1.5 parts of F1 grease impregnating agent were added and batted for 40 minutes. To the retanning liquid 1.5 parts of agent for impregnating F1 grease and 1.5 parts of agent for impregnating fat F2 were added and fat was impregnated for 20 minutes at 45 ° C. Then the addition of 8 parts of retanning G6, 8 parts of retanning G8 and 2 parts of polymeric tanning G19 was made. After a time of batting of 60 more minutes, 3 parts of F1 fat impregnating agent, 1.5 parts of F6 fat impregnating agent and 1.5 parts of F2 fat impregnating agent were added and fat was impregnated for 90 minutes at 45 ° C. Then, adding 3.5 parts of formic acid in portions, a pH value of 3.5 was adjusted within 50 minutes. Then the immersion liquid was purged and the leather was washed with 300 parts of water for 15 minutes.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, stretched wet and dried on a tensioning frame, conditioned, staked and batted dry.

A car leather with excellent color fastness to wash, sweat, migration and rub was obtained. In an analogous manner, a car leather can be obtained, dyed with one of the dyes of examples 1a to 59k.

Leather formulation for car 5:

A piece of leather of 100 parts by weight of a tanned leather of usual way, of a thickness of 1.1-1.2 mm recess, was washed in an immersion liquid of 300 parts of water for 10 minutes to 30 ° C and then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 35 ° C, then within 30 minutes they were added to portions in total 3.5 portions of sodium bicarbonate and a neutralization pH value of 7.5 was set. 4.7 parts of dye 48 were added to the deacidification liquid and stained for 30 minutes at pH 7.5 and 35 ° C. Then 0.5 parts of sodium bicarbonate were added and beaten for 60 minutes at pH 7.6. Adding a total of 6 parts of solid sodium carbonate in portions, for fixing the pH value of the immersion liquid was adjusted between 9.3-9.9 and beaten at 35 ° C for 60 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes at 40 ° C. In a immersion liquid of 200 parts of water adding a total of 1.5 parts of formic acid in portions over the course of 60 minutes a pH of 5.5 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 120 parts of water and 6 parts of G18 polymeric tanning agent for 5 minutes at 45 ° C. Then 2 parts of polymeric tanning G19 were added. After batting for another 5 minutes, 1.5 parts of the agent to impregnate F1 fat were added and batted for 30 minutes at 45 ° C. Next, 1.5 parts of the F1 fat impregnating agent and 1 part of the F2 fat impregnating agent were added and the fat was previously impregnated for an additional 20 minutes. To the immersion liquid, 4 parts of G18 polymeric tanning agent were added and batted for 20 minutes. Then the addition of 8 parts of G6 retanning and 8 parts of G8 retanning was made. After a time for batting of 40 more minutes, 1 part of polymeric tanning G19 was added and the tanning was completed for 20 minutes. To the retanning liquid 6 parts of agent for impregnating F1 fat and 2 parts of agent for impregnating fat F2 were added and fat was impregnated for 90 minutes at 45 ° C. Then, adding 3.5 parts of formic acid in portions, a pH value of 3.5 was adjusted over 45 minutes. Then the immersion liquid was purged and the leather was washed 300 parts of water for 15 minutes washed.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, stretched wet and dried on a tensioning frame, conditioned, staked and batted dry.

A car leather with excellent color fastness to wash, sweat, migration and rub was obtained. Similarly, a car leather dyed with one of the dyes of examples 1a to 59k can be produced.

Leather formulation for clothing 1:

A piece of leather of 100 parts by weight of a chrome-tanned sheepskin in the usual manner, of a recess thickness of 0.7 mm, was washed in an immersion liquid of 300 parts of water for 10 minutes at 35 ° C and then bathed in an immersion liquid composed of 150 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 20 minutes a total of 3 parts of portions were added sodium bicarbonate. Next, 3 parts of HM4 adjuvant were added and batted for 10 minutes. The pH of the immersion liquid was 7.7. To the deacidification liquid 9 parts of dye 44 were added and stained for 40 minutes at pH 7.4 and 40 ° C. Adding a total of 10 parts of sodium carbonate in portions, the pH value of the immersion liquid was adjusted between 9.6-9.8 for fixation and batted at 40 ° C for 60 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes at 40 ° C. In a dipping liquid of 150 parts of water, adding a total of 4 parts of formic acid in portions over the course of 55 minutes, a pH of 3.6 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 150 parts of water and 2 parts of G14 retanning for 40 minutes at 45 ° C. Then 2 parts of sodium formate were added. After batting for 20 more minutes, 2 parts of sodium bicarbonate were added and batted for 20 minutes at 45 ° C. The pH of the immersion liquid was 5.2. To the immersion liquid, 8 parts of G3 retanning and 2 parts of G11 retanning were added and beaten for 40 minutes. Then the addition of 6 parts of F1 grease impregnating agent, 4 parts of F3 grease impregnating agent and 1 part of H7 hydrophobic agent was made. After a 20 minute batting time, 4 parts of polymeric tanning G10 were added and batted for 20 minutes. Subsequently, 6 parts of F1 grease impregnating agent, 4 parts of F3 grease impregnating agent and 1 part of H7 hydrophobic agent were added. After impregnating with fat for an additional 40 minutes, adding 5 parts of formic acid in portions over the course of 45 minutes, a pH value of 3.5 was adjusted. Then the immersion liquid was purged and the leather was washed with 300 parts of water for 15 minutes.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, dried, hung, conditioned, staked, batted dry and dried on a tension frame.

A garment leather was obtained with excellent color fastness to wash, sweat, migration and rub. Similarly, a leather for garment dyed with one of the dyes of examples 1a to 59k can be produced.

A piece of leather of 100 parts by weight of a tanned beef leather in a usual manner, with a recess thickness of 0.8-0.9 mm, was washed in an immersion liquid of 200 parts of water for 10 minutes at 35 minutes. ° C and then bathed in an immersion liquid composed of 100 parts of water and 1.5 parts of sodium formate for 5 minutes at 40 ° C, then within 25 minutes they were added to portions in total 3.2 portions of sodium bicarbonate and a neutralization pH value of 7.6 was set. To the deacidification liquid 8 parts of mixed 12hu dye were added and tanned for 40 minutes at pH 7.5 and 40 ° C. Adding a total of 8.7 parts of sodium carbonate for fixation, the pH value of the immersion liquid was adjusted between 9.6-9.8 and batted at 40 ° C for 90 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes. In a dipping liquid of 200 parts of water, adding a total of 5 parts of formic acid in portions over the course of 60 minutes, a pH of 3.3 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 100 parts of water and 3 parts of G12 retanning for 10 minutes at 30 ° C. After adding 4 parts of G24 chrome tanning agent and 1.5 parts of HM6 adjuvant, it was retanned with chromium for 50 minutes at 30 ° C. Then 1 part of sodium formate was added and batted for 90 minutes. After adding 100 parts of water it was re-chromed for one night. The immersion liquid was then purged and washed with 300 parts of water for 10 minutes at 45 ° C. In a freshly prepared immersion liquid of 100 parts of water, 1.5 parts of H5 hydrophobic agent was beaten for 20 minutes at 45 ° C. Next, 5 parts of G18 polymeric tanning agent were added, after 2 batting time the addition of 2 parts of G5 retanning was made. After retanning for an additional 30 minutes, 2 parts of G19 polymeric tanning agent were added, beaten 10 minutes and then 5 parts of G5 retanning agent were added. After retanning for an additional 60 minutes, 4 parts of water repellent agent H8, 6 parts of water repellent H2, 7 parts of water repellent H7 and 0.8 parts of adjuvant HM4 were added and impregnated with grease for 60 minutes at 45 ° C. 100 parts of water were then added and batted for 10 minutes at 60 ° C. Then, adding 4 parts of formic acid in portions over the course of 45 minutes, a pH value of 3.5 was adjusted. Then the immersion liquid was purged and in a new immersion liquid prepared from 300 parts of water and 0.15 parts of formic acid was washed for 15 minutes. In an immersion liquid prepared again from 150 parts of water, 2 parts of H7 water repellent agent and 0.2 parts of HM4 adjuvant was beaten for 20 minutes at 30 ° C. After adding 5 parts of the mineral tanning G30 it was fixed for 90 minutes. At the end it was washed once with an immersion liquid of 300 parts of water and 0.2 parts of formic acid and once with an immersion liquid of 300 parts of water and 0.1 parts of formic acid respectively for 10 minutes at 30 ° C

The dyed, retanned and hydrophobicized leather was thus stored overnight on supports, then stretched out, stretched wet and dried on a tensioning frame, conditioned, staked, batted dry and dried on a frame of tensioning.

A leather for motorcycle clothing was obtained with excellent color fastness to wash, sweat, migration and rub. Similarly, a leather for motorcycle clothing can be produced, dyed with one of the dyes of examples 1a to 59k.

Formulation for leather gloves 1:

A piece of leather of 100 parts by weight of a chrome tanned goat leather in the usual manner, of a 0.5-0.7 mm recess thickness, was washed in an immersion liquid of 300 parts of water per 10 minutes at 30 ° C and then bathed in an immersion liquid composed of 120 parts of water and 1.5 parts of sodium formate for 5 minutes at 35 ° C, then within 30 minutes they were added to portions in total 3.1 parts of baking soda. Then 3 parts of HM2 adjuvant were added and batted for 5 minutes. The pH of the immersion liquid was 7.8. To the deacidification liquid, 10 parts of mixed 13hi dye were added and stained for 40 minutes at pH 7.4 and 35 ° C. Adding a total of 9 parts of sodium carbonate in portions, for fixing the pH value of the immersion liquid was adjusted between 9.6-9.8 and was beaten at 35 ° C for 90 minutes. After changing the immersion liquid, it was washed twice with an immersion liquid respectively of 300 parts of water and 1.5 parts of HM3 adjuvant in total for 50 minutes at 40 ° C. In a dipping liquid of 200 parts of water, adding a total of 3 parts of formic acid in portions over a period of 60 minutes, a pH of 3.4 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 150 parts of water and 1.5 parts of G13 retanning for 60 minutes at 40 ° C. Then 1.5 parts of sodium formate were added. After batting for another 20 minutes, 1 part of sodium bicarbonate was added and batted for 30 minutes at 40 ° C. To the immersion liquid, 6 parts of G18 polymeric tanning agent were added and batted for 40 minutes. Then 6 parts of G3 retannant were added and retanned for 30 minutes. Next, 5 parts of hydrophobic agent H3, 2 parts of polymeric tanning agent G19, 10 parts of retanning G9, 4 parts of agent for impregnating fat F9 and 1 part of sodium carbonate were added and retanned for 120 minutes. Adding 3.5 parts of formic acid in portions over the course of 45 minutes a pH value of 3.5 was adjusted. Next, 3 parts of H4 hydrophobic agent were added and batted for 20 minutes. Then the immersion liquid was purged and the leather was washed twice with an immersion liquid respectively of 300 parts of water and 0.2 parts of formic acid 15 minutes.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, stretched wet and dried on a tensioning frame, conditioned, staked and batted dry.

A leather for gloves with excellent color fastness to wash, sweat, migration and rub was obtained. Similarly, a dyed glove leather can be prepared with one of the dyes of examples 1a s 59k.

Leather formulation for gloves 2:

A piece of leather of 100 parts by weight of a chrome tanned goat leather in a usual manner, of a 0.5-0.7 mm recess thickness, was washed in an immersion liquid of 300 parts of water per 10 minutes at 30 ° C and then in an immersion liquid composed of 120 parts of water and 1.5 parts of sodium formate, beaten for 5 minutes at 35 ° C, then within 30 minutes they were added to portions in total 3.1 parts of baking soda. Then 3 parts of HM2 adjuvant were added and batted for 5 minutes. The pH of the immersion liquid was 7.8. To the deacidification liquid 8 parts of mixed 13gz dye were added and stained for 40 minutes at pH 7.4 and 35 ° C. Adding a total of 8 parts of solid sodium carbonate in portions, the pH value of the immersion liquid was adjusted between 9.6-9.8 and fixed at 90 ° C for 90 minutes. After changing the immersion liquid, it was washed twice with an immersion liquid respectively of 300 parts of water and 1.5 parts of HM3 adjuvant in total for 50 minutes at 40 ° C. In a dipping liquid of 200 parts of water, adding a total of 1.3 parts of formic acid in portions over the course of 60 minutes a pH of 5.8 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 150 parts of water and 4 parts of H3 hydrophobic agent for 20 minutes. Then 8 parts of G18 polymeric tanning agent were added and retanned for 40 minutes. Then 8 parts of G2 retannant were added and batted for 30 minutes at 40 ° C. Then, 4 parts of H3 water repellent agent, 0.5 parts of HM4 adjuvant, 8 parts of G9 retanning agent, 3 parts of F9 grease impregnating agent and 0.8 parts of sodium carbonate were added and retanned for 120 minutes. Adding 3.5 parts of formic acid in portions, a pH value of 3.5 was adjusted over 35 minutes. Next, 3 parts of H7 water repellent agent and 3 parts of HM4 adjuvant were added and batted for 20 minutes. Then the immersion liquid was purged and the leather was washed twice with an immersion liquid respectively of 300 parts of water and 0.2 parts of formic acid for 15 minutes.

The dyed, retanned and fat-impregnated leather was thus stored overnight on supports, then stretched, stretched wet and dried on a tensioning frame, conditioned, staked and batted dry.

A leather for gloves with excellent color fastness to wash, sweat, migration and rub was obtained. Similarly, leather for gloves can be produced, dyed with one of the dyes of examples 1a to 59k.

Leather formulation for gloves 3:

A piece of leather of 100 parts by weight of a chrome tanned goat leather in the usual manner, of a 0.5-0.7 mm recess thickness, was washed in an immersion liquid of 300 parts of water per 10 minutes at 30 ° C and then in an immersion liquid composed of 120 parts of water and 1.5 parts of sodium formate, beaten for 5 minutes at 35 ° C, then within 30 minutes they were added to portions in total 3.1 parts of baking soda. Then 3 parts of HM2 adjuvant were added and batted for 5 minutes. The pH of the immersion liquid was 7.8. To the deacidification liquid 8.2 parts of mixed 12hb dye were added and stained for 40 minutes at pH 7.4 and 35 ° C. Adding a total of 8 parts of solid sodium carbonate in portions, for fixing the pH value of the immersion liquid was adjusted between 9.6-9.8 and batted at 35 ° C for 90 minutes. After changing the immersion liquid, it was washed three times respectively with 300 parts of water in total for 60 minutes at 40 ° C. In a dipping liquid of 200 parts of water, adding a total of 1.2 parts of formic acid in portions over the course of 60 minutes, a pH of 5.7 was adjusted.

The dyed leather in this manner was bathed in a freshly prepared immersion liquid of 100 parts of water, 1 part of water repellent H1 and 0.2 parts of HM4 adjuvant was batted for 20 minutes. Then 10 parts of H5 hydrophobic agent were added and batted for 5 minutes. Then 10 parts of G18 polymeric tanning agent were added and retanned for 55 minutes. 5 parts of agent were added to the retanning liquid

5 water repellent H5, 8 parts water repellent agent H1 and 0.8 parts adjuvant HM4 and for 120 minutes it was impregnated with grease. After adding 100 parts of water and batting for a time of 20 minutes, adding 4 parts of formic acid in portions over the course of 50 minutes, a pH value of 3.5 was adjusted. Then the immersion liquid was purged and the leather was washed twice with an immersion liquid respectively of 300 parts of water and 0.2 parts of formic acid for 15 minutes.

10 The dyed, retanned and grease-soaked leather was thus stored overnight on supports, then stretched, stretched wet and dried on a tensioning frame, conditioned, staked and batted dry.

A glove leather, hydrophobicized, based on pure polymer, with excellent color fastness to washing, sweat, migration and rubbing was obtained. Similarly, a dyed glove leather can be produced with one of

15 the dyes of examples 1a to 59k.

Claims (18)

1. Method for dyeing leather with at least one F dye, which has at least one group of the formula A: image 1 activated in alkaline conditions, where ---- means the bond to the dye molecule, 5 X represents a residue that attracts electrons, k represents 1, 2 or 3, n means 0 or 1, and B represents a group CH = CH2 or a group CH2-CH2-Q, where Q represents a dissociable group under conditions alkaline, which comprises treating the leather with an aqueous immersion liquid, which contains at least one dye F, at a pH value of 7; 5 to 11. 2. Method according to claim 1, in which case at least one of the residues X in the formula A represents a group SO3H. 3. A method according to claim 1 or 2, wherein B in formula A represents CH = CH2, a CH2-CH2-O-SO3H group or a CH2-CH2-O-C (O) CH3 group.

Four.

Method according to one of the preceding claims, wherein group A is linked to the dye molecule by a group -NH- or -N = N-.

5.

Method according to claim 4, in which case the dye F is selected from the dyes of the phthalocyanine series, anthraquinone dyes, azocolorants, formazan dyes, dioxazine dyes, dyes

20 of actidine, xanthene dyes, polyimotine dyes, stilbene dyes, sulfur dyes and triarylmethane dyes.

6.

Method according to one of the preceding claims, wherein n is = 0.

7.

Method according to claim 6, wherein residue A is selected from the following residues A1 to A12:

image 1 image 1 5 Method according to one of the preceding claims, wherein the dye F is selected from the dyes of the general formulas I to XV: Dk1-N = N- [PN = N-] pKk1 [-N = N-Dk2] m ( I) Dk1-N = N-Napht1 [-N = N-Tk1] r [-N = N-Kk1] k [-N = N-Dk2] n (II) 10 Dk1-N = N-Napht1-N = N-Tk1-N = N-Kk1-N = N-Tk2-N = N-Napht2-N = N-Dk2 (III) Dk1-N = N-Kk1-N = N-Tk1-N = N-Kk2- N = N-Dk2 (IV) Dk1-N = N- [PN = N-] pNapht1 [-N = N- R] r-NH-Tr1-NH-Dk2 (V) Dk1-N = NP-NH-Tr1 -NH-RN = N-Dk2 (VI) Dk1-N = N-Napht1-N = N-Tk1-N = NP-NH-Tr1-NH-Dk2 (VII) Dk1-N = N-Napht1-NH-Tr1-NH-P-NH-Tr2-NH-Napht2-N = N-Dk2 (VIII) Dk1-N = N-Napht1-NH-Tr1-NH-Tk1-NH -Tr2-NH-Napht2-N = N-Dk2 (IX) Dk1-N = N-Kk1-N = N-Tk1-NH-Tr1-NH-Dk2 (XI) Dk1-N = N- [P-N = N-] pR-N = N-Kk1 [-N = N-Dk2] n (XII) Dk1-N = N-Pir-A (XIII) 5 Kk3-N = N-Tk1-N = N-Kk1-N = N-A (XIV) Dk1-N = N-P-N = N-Kk1-N = N-R-N = N-Dk2 (XV) where: k, n, p and r independently of each other represent 0 or 1 stehen, in which case k + n + r in formula II is = 1, 2 or 3; 10 m means 0, 1 or 2; Dk1, Dk2, independently of one another, represent a residue derived from an aromatic amine or means a group of the formula A, in which case in formulas I-XII and XV, respectively, at least one of the residues Dk1 or Dk2 represents a residue of the formula A Kk1, Kk2, independently of each other, represent a mono-, bi- or trivalent aromatic residue, 15 derived from benzene, naphthalene, pyrazole, quinoline, diphenylamine, diphenylmethane, pyrimidine, pyridine or diphenyl ether, which may optionally have one or more of the following residues as substituents: SO3H, COOH, CN, CONH2, OH, NH2, NO2, halogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, C1-C4 carboxy-alkyl, C1-C4 alkoxy, C1-C4 alkyl-amino, dialkyl-C1C4-amino, C1-C4 alkyl aminocarbonyl, dialkyl-C1-C4-aminocarbonyl, alkyl-C1-C4-carbonylamino, N- (C1-C4-carbonyl) -N- (C1-C4-carbonyl) amino, C1-C4-aminocarbonyloxy, dialkyl-C1C4-aminocarbonyloxy, C1-C4-alkylcarbonylamino, dialkyl- C1-C4-aminocarbonylamino, phenylaminocarbonyloxy, phenylaminocarbonylamino, alkoxy-C1-C4-carbonylamino, C1-C4-hydroxy-C1-C4alkylamino, carboxy-alkyl-C1-C4-amino, phenylcarbonylamino, alkyl-C1-C4-sulfonyl, hydroxy- C1-C4-sulfonyl alkyl, C1-C4-aminosulfonyl alkyl, C1-C4-sulfonylamino, phenylsulfonyl, phenylsulfonylamino, Formamide, a residue of the formula SO2NR56R57, wherein R56 and R57 independently of one another represent hydrogen, C1-C4 alkyl, formyl, C1-C4 alkylcarbonyl, C1-C4 alkyl oxycarbonyl, NH2-CO or alkyl -C1-C4-aminocarbonyl, C1-C4-aminosulfonylamino, di-C1-C4-amino sulfonylamino, phenylsulfonylamino, which may have one or two substituents on the phenyl ring, selected from C1-C4 alkyl, C1 alkoxy -C4 or halogen, or heterocyclic of 30 5 or 6 members, which is optionally substituted by 1, 2 or 3 of the following residues: OH, halogen, C1-C4 alkyl or phenyl, in which case the 5-membered aromatic heterocyclyl optionally has a group in the nitrogen optionally phenyl or a naphthyl group, which may optionally have one or two of the following residues: OH, SO3H, C1-C4 alkyl, and / or C1-C4 alkoxy; Kk3 represents a monovalent residue derived from benzene, pyrimidine, pyridine or naphthalene, which 35 optionally has 1 or 2 hydroxysulfonyl groups and optionally 1, 2 or 3 more substituents, selected from SO3H, COOH, CN, -CONH2, OH, NH2, NO2, halogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, carboxy -C1-C4 alkyl, C1-C4 alkoxy, C1-C4-alkyl-alkyl, C1-C4-alkyl-alkyl, C1-C4-alkylcarbonyl, dialkyl-C1-C4-aminocarbonyl, C1-C4-carbonylamino , N- (C1-C4-carbonyl) -N- (C1-C4-alkyl-carbonyl) amino, C1-C4-aminocarbonyloxy, dialkyl-C1 C4-aminocarbonyloxy, alkyl-C1-C4-aminocarbonylamino, dialkyl-C1-C4-aminocarbonylamino, phenylaminocarbonyloxy, phenylaminocarbonylamino, C1-C4-alkoxycarbonylamino, hydroxy-C1-C4-C1-C4 alkyl-amino, carboxy-C1-alkyl -C4-amino, phenylcarbonylamino, alkyl-C1-C4-sulfonyl, hydroxy-C1-C4-sulfonyl, alkyl-C1-C4-aminosulfonyl, alkyl-C1-C4-sulfonylamino, phenylsulfonyl, phenylsulfonylamino, formamide, a residue of the formula SO2NF56F57, where R56 and R57 independently of each other 45 represent hydrogen, C1-C4 alkyl, formyl, C1-C4 alkylcarbonyl, C1-C4 alkyl oxycarbonyl, NH2-CO or C1-C4 alkyl aminocarbonyl, C1-C4 alkyl-aminosulfonylamino, di- C1-C4 alkyl amino sulfonylamino, phenylsulfonylamino, which may have one or more substituents on the phenyl ring, selected from C1-C4 alkyl, C1-C4 alkoxy or halogen, or 5- or 6-membered heterocyclyl, which is substituted optionally for 1, 2 or 3 of the following wastes: OH, 50 halogen, C1-C4 alkyl or phenyl, in which case the 5-membered aromatic heterocyclyl has Tk1, Tk2, independently of one another, represent a bivalent aromatic residue that is derived from benzene, diphenylamine, diphenyl, diphenyl methane, 2-phenylbenzimidazole, phenylsulfonylbenzene, phenylamino sulfonylbenzene, stilbene or phenylaminocarbonylbenzene, which may optionally have one or more of the following residues as substituents: SO3H, COOH, OH, NH2, NO2, halogen, C1-C4 alkyl; L, M, P and R, independently of one another, represent a bivalent aromatic residue that is derived from benzene or naphthalene, which may optionally have one or more, for example 1, 2, 3, 4 or 5 of the following residues as Substituents: SO3H, COOH, CN, CONH2, OH, NH2, NO2, halogen, C1-C4 alkyl, hydroxy C1-C4 alkyl, carboxy-C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkyl, dialkyl-C1-C4-amino, alkyl-C1-C4-aminocarbonyl, dialkyl-C1-C4-aminocarbonyl, alkyl-C1C4-carbonylamino, N- (alkyl-C1-C4-carbonyl) -N- (C1-C4 alkyl -carbonyl) amino, alkyl-C1-C4-aminocarbonyloxy, dialkyl-C1-C4-aminocarbonyloxy, alkyl-C1-C4-aminocarbonylamino, dialkyl-C1-C4aminocarbonylamino, phenylaminocarbonyloxy, phenylaminocarbonylamino, C1-C4-alkoxylamino, C1-C4-hydroxy -C1-C4-amino-alkyl, carboxy-C1-C4-alkyl-amino, phenylcarbonylamino, C1-C4-alkyl sulfonyl, hydroxy-C1-C4-sulfonyl, C1-C4-alkyl-aminosulfonyl, C1-C4-alkyl -sulfonylamino, phenylsulfonyl, phenylsulfonyl Mino, formamide, a residue of the formula SO2NR56R57, where R56 and R57, independently of one another, represent hydrogen, C1-C4 alkyl, formyl, C1-C4 alkylcarbonyl, C1-C4 alkyl-oxycarbonyl, NH2-CO or alkyl-C1-C4-aminocarbonyl, alkyl-C1-C4aminosulfonylamino, di-C1-C4-aminosulfonylamino, phenylsulfonylamino, which may have one or two substituents on the phenyl ring selected from C1-C4 alkyl, C1- alkoxy C4 or halogen, 5 or 6 heterocyclyl, which may be optionally substituted by 1, 2 or 3 of the following residues: OH, halogen, C1-C4 alkyl or phenyl, in which case the 5-membered aromatic heterocyclyl optionally has the nitrogen a phenyl or naphthyl group which may optionally have one or two of the following residues: -OH, SO3H, C1-C4 alkyl, and / or C1-C4 alkoxy; Napht1, Napht2, independently of one another, represent a bivalent naphthalene-derived residue having 1 or 2 hydroxysulfonyl groups and may optionally have 1, 2 or 3 more substituents more selected from OH, NH2, C1-C4-amino alkyl, dialkyl -C1-C4-amino, alkyl-C1-C4-sulfonylamino, phenylsulfonylamino, 4-methylphenylsulfonylamino, alkyl-C1-C4-aminosulfonyl, di-alkyl-C1-C4aminosulfonyl, phenylaminosulfonyl, 4-methylphenylaminosulfonyl and NHC (O) Rx residues, where Rx represents hydrogen, C1-C4 alkyl, maleinyl or phenyl; Pyr represents pyrazole-1,4-diyl, which is linked with the nitrogen atom to group A and optionally has one or two substituents that are selected from halogen, C1-C4 alkyl, hydroxy or C1-C4 alkoxy; Tr1, Tr2, independently of one another, represent a 1,3,5-triazine-2,4-diyl residue, which optionally also has a halogen atom, a methyl group or a methoxy group as substituents, and metal complexes of these dyes.

9.

Method according to one of the preceding claims, in which case the leather is first treated with the aqueous immersion liquid containing at least one dye F, at a pH value in the range of 3 to 6.5 and then a value is adjusted pH of at least 7.5 in the immersion liquid.

10.

Method according to one of claims 1 to 7, in which case the dyeing is carried out as a one-stage method.

eleven.

Method according to one of the preceding claims, in which case the dyeing is carried out before retanning.

12.

Method according to one of the preceding claims, in which case the dyeing is carried out at temperatures in the range of 10 to 60 ° C.

13.

Use of colorants F, as defined in claim 1, having at least one of the alkaline activatable groups of the formula A, and of their mixtures for dyeing leather at pH 7.5 to 11.

14.

Dyes F of the general formulas IIa, IIIa or IVa

Dk1-N = N-Napht1-N = N-Tk1- [N = N-Kk1] k-N = N-Dk2 (IIa) Dk1-N = N-Napht1-N = N-Tk1-N = N-Kk1-N = N-Tk2-N = N-Napht2-N = N-Dk2 (IIIa) Dk1-N = N-Napht1-N = N-Tk1-N = N-Napht2-N = N-Dk2 (IVa) 5 where Dk1, Dk2, Napht1, Napht2 and Kk1 have previously mentioned meanings, k represents 0 or 1, and where Tk1 and Tk2, independently of one another, represents a bivalent residue, derived from diphenyl, diphenylmethane, 2-phenylbenzimidazole, phenylsulfonylbenzene, phenylaminosulfonylbenzene, diphenylamine, stilbene or phenylaminocarbonylbenzene, which may optionally have one or more of the following residues: , COOH, OH, NH2, NO2, halogen, C1-C4 alkyl, in which case Tk1 in formula IIa no 10 represents a residue derived from diphenylamine, if k is = 0, and in which case one or both residues Dk1 and Dk2 represent a residue of the formula A, as defined in claim 1. 15. F colorants of the general formula IIb, A-N = N-Napht1-N = N-Tk1-N = N-Kk1- [N = N-Dk2] n (IIb) where A, Dk2, Napht1 and Kk1 have the previously named meanings, n represents 0 or 1, and where Tk1 15 represents a bivalent residue, derived from diphenyl, diphenylmethane, 2-phenylbenzimidazole, phenylsulfonylbenzene, phenylaminosulfonylbenzene, diphenylamine, stilbene or phenylaminocarbono optionally you can have one or several of the following residues: SO3H, COOH, OH, NH2, NO2, halogen, C1-C4 alkyl, in which case Tk1 does not represent a residue derived from diphenylamine, if n is = 0, and in which case the residue Dk2 It also represents a residue of the formula A, as defined in claim 1. 16. Dyes according to claim 14 or 15, wherein Tk1 and / or Tk2 in formulas IIa, IIb, IIIa or IVa represents a residue of the general formula image 1 where they represent the links to the azo groups. 17. Dyes according to one of claims 14 to 16, wherein Napht1 and / or Napth2 represents a bivalent residue 25 of the general formula, image 1 where R1 and R2 independently of each other mean hydrogen, OH, NH2 or NHC (O) R3, where R3 represents hydrogen, C1-C4 alkyl, maleinyl or phenyl, and at least one of the residues R1 and R2 is different from hydrogen ,  ---- represents the links to the azo groups, s and t represent 0 or 1 and the sum s + t has the value 1 or 2. 18. Dyes according to one of claims 14 to 17, wherein one or both residues Dk1 and Dk2 represents one of residues A1 to A12 defined in claim 7.

19.

Dyed leather that can be obtained by a dyeing method according to one of claims 1 to 12.

twenty.

Leather according to claim 19, for the segments of gloves, footwear, cars, clothing or furniture.