GB2208393A - Leather dyeing pre-and post-treatment - Google Patents

Leather dyeing pre-and post-treatment Download PDF

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Publication number
GB2208393A
GB2208393A GB8818608A GB8818608A GB2208393A GB 2208393 A GB2208393 A GB 2208393A GB 8818608 A GB8818608 A GB 8818608A GB 8818608 A GB8818608 A GB 8818608A GB 2208393 A GB2208393 A GB 2208393A
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Prior art keywords
product
leather
process according
acid
mixture
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GB8818608D0 (en
GB2208393B (en
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Michel Dien
Willi Egli
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Sandoz AG
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Sandoz AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D06P5/04—After-treatment with organic compounds
    • D06P5/08—After-treatment with organic compounds macromolecular
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/32—Material containing basic nitrogen containing amide groups leather skins
    • D06P3/3206—Material containing basic nitrogen containing amide groups leather skins using acid dyes

Abstract

The dyeing or printing of leather with anionic metal-complexed monoazo and/or monoazomethine dyes is preceded and/or followed by treatment with a product (P) or a mixture of products (P) or an acid addition product thereof, product (P) being a polymer obtainable by reaction of ( alpha ) a mono-functional or poly-functional amine containing one or more amino groups of the group consisting of primary, secondary and tertiary amino groups with (???) cyanamide, dicyanodiamide, guanidine or biguanide or a mixture in which up to 50 mole percent of the cyanamide, dicyanodiamide, guanidine or biguanide are replaced by a di-carboxylic acid or a mono- or diester thereof with cleavage of ammonia or a further reaction product thereof with reactant ( gamma ) selected from the group consisting of:   1) (???1) a N-methylol derivative of a urea, a melamine, a guanamine, a triazine, a urone, a urethane or an acid amide,   2) (???2) an epihalohydrin or an epihalohydrin precursor,   3) (???3) formaldehyde or a formaldehyde yielding product,   4) ( gamma 2) followed by (???1)

Description

1 1 - Case 150-5193 r) z_208393 Dyeing and printing of leather The
invention provides a process for the dyeing or printing of leather with anionic metal complex dyes wherein the metal complex dyes are metal complexes of metallizable mono-azo dyes or metallizable monoazomethine dyes or both metallizable monoazo and monoazomethine dyes and before the application of the dye or after the a pplication of the dye or both before and after the application of the dye the leather is treated with a product (P) or a mixture of products (P) or an acid addition product thereof, the product (P) being a polymer obtainable by reaction of (cc) a mono-functional or poly-functional amine containing one or more amino groups of the group consisting of primary, secondary and tertiary amino groups with cyanamide, dicyanodiamide, guanidine or biguanide or a mixture in which up to 50 mole percent of the cyanamide, dicyanodiamide, guanidine or biguanide are replaced by a di-carboxylic acid or a mono or diester thereof with cleavage of ammonia or a further reaction product thereof with reactant (y) selected from the group consisting of: 1) (yl) a N-methylol derivative of a urea, a melamine, a guanamine, a triazine, a urone, a urethane or an acid amide, 2) (Y2) an epihalohydrin or an epihalohydrin precursor, 3) (Y3) formaldehyde or a formaldehyde-yielding product, 4) (Y2) followed by (yl) and 5) (y3) followed by (yl).
t Case 150-5193 If desired a subsequent cross-linking of N-methylol compounds may be carried out in the presence of a catalyst K.
Any kind of tanned leather commonly used as a substrate for dyeing from aqueous media may be used for the process of the invention, particularly grain leather (e.g. nappa from sheep, goat or cow and box leather from calf or cow), suede leather (e.g. velours from sheep, goat or calf and hunting leather), split velours (e.g. from cow or calf skin), buckskin and nubuk leather; further also wool-bearing skins and furs (e.g. fur- bearing suede leather). The leather may have been tanned by any usual tanning method, in particular vegetable, mineral, synthetic or combined tanned (e.g. chrome tanned, zirconyl tanned, aluminium tanned or semichrome tanned). If desired, the leather may also be retanned and/or fatted; for retanning, there may be used any tanning agent conventionally employed for retanning, e.g. mineral, vegetable or synthetic tanning agents [e.g. chromium, zirconyl or aluminium derivatives, oak, quebracho, chestnut or mimosa extract, aromatic syntans, copolymers of (meth)acrylic acid compounds or urealformaldehyde resins].
A fatting step may, if desired, be carried out before, and/or after the treatment with the product (P). For fatting there may be used conventional fatting agents (in particular fat-liquoring agents), preferably from aqueous medium. Such fatting agents include animal, vegetable or mineral fats, oils, resins or waxes and/or their chemical modification products, e.g. hydrogenation, oxydation, saponification, trans-esterification or sulphonation products of animal or vegetable fats and oils, or chlorination and/or sulphonation products of mineral fats or oils, and synthetic fatting agents; neutralization agents may also be employed. For fat-liquoring there are preferably employed aqueous fat- liquor emulsions, in which the fat-liquor is emulsified by means of an emulsifier and/or by chemical modification. Fatting agents and emulsifiers are described e.g. in F. Stather "Gerbereichemie und Gerbereitechnologie", t, k Akademie-Verlag, Berlin, 1967, 4th edition. By the term 'Isulphonationl' for the fatting agents, there is meant generally the introduction of a sulpho group, including also the formation of a sulphato group (= 11sulphating11) and the introduction of a sulpho group by reaction with a sulphite or S02 (= "sulphiting").
The leathers may be of various thicknesses, thus there may be used very thin leathers such as bookbinders' leather or glove leather (nappa), leather of medium thickness such as shoe upper leather, garment leather and leather for handbags, or also thick leathers such as shoe sole leather, furniture leather, leather for suitcases, for belts and for sport articles; hair-bearing leathers and furs may also be used.
A pretreatment with the product (P) may also be carried out in the presence of a fatting agent.
The leather employed for the treatment with the product (P) may advantageously have been previously treated with conventional leathertreating agents. These leather treating agents may, hwever, also be used after a pre-treatment with a product (P) or for the treatment of a dyed leather that has been after-treated with a product (P). 20 The leather that has been pre-treated with a product (P) may be intermediately dried before the dyeing or printing or may be used in the wet state for dyeing or printing. Similarly a dyed or printed leather may be intermediately dried and then treated with a product (P) or may be used in the wet state for after-treatment with the 25 product (P). Preferred metal complex dyes for the dyeing process of the invention contain at least one hydrosolubilizing acid group or sulphonic acid amide group, more preferably 2-8 and in particular 2-4 of such hydrosolubilizing groups in the molecule. The molecular weight of 30 the metal complex dyes is preferably of at least 800. The dyes are preferably in the form of their 1:1- or 1:2-metal complexes, in C.se 150-5193 particular chromium, cobalt, iron or copper complexes, pr:ncipally in the form of 1:2-cobalt or -iron complexes, 1:1-copper ctmplexes and 1:2- chromium complexes optionally in admixture with the corresponding 1:1- chromium complexes. Of the above, the cobalt and:--hromium complexes are preferred.
The dyes to be used according to the process of the invention are advantageously 1:2-metal complex dyes which preferably correspond To the formula A-N - Z-El 1 1 1 (co),, X Me (CO),., X 1 1 1 D-N Z-E -v.
(I) wherein each Z independently is nitrogen or a CE-group, each A and D independently is a radical of a compound of the benzene or naphthalene series containing a hydroxy or carboxy group in ortho position to the azo or azomethine group, each B and E independently signifies the radical of a coupling component when Z is nitrogen, X being in ortho or a- position to the azo group, or the radical of an o-hydroxyaldehyde when Z is the group CH, each X independently signifies oxygen or a group of formula -NR- , R being hydrogen or Cl-4-alkyl, He signifies chromium or cobalt, each Y independently is a group of formula -S03H, -COON or -P03B2, p signifies 1 or 2 and n signifies a number from 1-6.
The dyes are of anionic nature and are preferably used in the form of their salts, in particular alkaline metal salts, principally lithium, potassium or sodium salts, or ammonium salts. Ammonium 1 1 Case 150-5193 salts include also salts of organic amines, e.g. such that are substituted with Cl-6-alkyl or hydroxy-C2-6-alkyl groups.
The dyes of formula (1) may be symmetrical or asymmetrical 1:2-azo complexes or 1:2-azomethine complexes or 1:2-complexes that contain one azo and one azomethine dye bound to the metal.
X is preferably oxygen.
When n is a number > 1 the groups Y may have the same significance or different significances., i.e. the dyes may contain sulphonic acid groups and/or carboxylic acid groups and/or phosphonic acid groups. Preferably, however, all the symbols Y signify the sulpho group.
In the dyes of formula (I) p is preferably 1 and n is preferably 1-3, more preferably 2.
Preferably the metal-complex dyes of formula (I) contain 24-40 carbon atoms.
The molecular weight of the 1:2-metal-complex dyes of formula (I) is preferably in the range of 800-1000 (calculated as the free acid).
The radicals A and D may contain one or more carboxylic acid, phosphonic acid or sulphonic acid groups and also be further substituted, in particular with C1-4-alkyl or -alkoxy, chloro or nitro. /I COtf=T-OH /I CO)-p OH Suitable diazo components A-NH2 and D-NH2 include: anthranilic acid, 4- or 5-sulphoanthranilic acid, 2-amino-l-hydroxybenzene, 4-chloroand 4,6-dichloro-2-amino-l-hydroxybenzene, 4- or 5-nitro2-amino-l-hydroxybenzene, 4-chloro- or 4-methyl-6-nitro-2-amino-lhydroxybenzene, 4-chloro4-nitro-2-amino-l-hydroxybenzene, 4-cyano2-amino-l-hydroxybenzene, 4methoxy-2-amino-l-hydroxybenzene, 4-methoxy-5-chloro-2-amino-lhydroxybenzene, 4-methyl-2-amino-l-hydroxybenzene, 4-chloro-S-nitro-2amino-l-hydroxybenzene, 3,4,6-trichloro- Case 150-5193 2-amino-l-hydroxybenzene, 4,6-dinitro-2-amino-l-hydroxybenzene, 2-amino-lhydroxybenzene-4- or 5-sulphonic acid, 4-nitro-2-aminolhydroxybenzene-6sulphonic acid, 5-nitro- or 6-nitro-2-amino-l-hydroxybenzene-4-sulfonic acid, 6-chloro-2-amino-l-hydroxybenzene-4sulphonic acid, 4-chloro-2-aminol-hydroxybenzene-6-sulphonic acid, 1-amino-2-hydroxynaphthalene-4sulphonic acid, 1-amino-2-hydroxy-6nitronaphthalene-4-sulphonic acid, 2amino-l-hydroxybenzene-4,6-disulphonic acid or 1-amino-2-hydroxybenzene-4sulphonic acid amide.
is F When A and D are radicals of the benzene series they are preferably the radical of a 1-hydroxy-2-amino-benzene which is unsubstituted or is substituted by one or more substituents selected from the group consisting of nitro, sulpho, chloro, methyl and methoxy, of which nitro, chloro and sulpho are preferred, more preferably the radical of a 1hydroxy-2-amino-benzene, bearing a nitro group or a chlorine atom in the 4- or 5-position, or the radical of a 1-hydroxy-2-aminobenzene bearing a nitro group or chlorine atom in the 4-position and a sulpho-group in the 6-position, or the radical of a 1-hydroxy-2amino-benzene bearing a sulphogroup in the 4-position and a nitro group or a chlorine atom in the 6position.
When A and D independently are radicals of the naphthalene series, they are preferably radicals of 1-amino-2-hydroxynaphthalene-4-sulphonic acid or 1-amino-2-hydroxy-6-nitronaphthalene-4-sulphonic acid.
When B and E independently are radicals of coupling components they are preferably derived from a coupling component selected from the group consisting of:
hydroxy- and/or amino-group-containing benzenes (wherein the amino group may optionally be acylated), particularly phenols that couple in orthoposition and may be substituted with low molecular alkyl or alkoxy, amino or acylamino, acylamino signifying Cl-4-alkanoylamino, CI-4alkylsulphonyl-amino, CI-4-alko- Case 150-5193 xycarbonyl-amino, aroyl-amino or arylsulphonyl-amino, resorcinol or m- phenylene-diamine which is unsubstituted or substituted in the 4-position with sulpho, chloro, methyl or methoxy; is naphthols which may be further substituted with C1-4-alkyl or -alkoxy, chloro, amino, acylamino or sulpho, acylamino having the same significance as indicated above, unsubstituted naphthols and sulpho- naphthols being preferred, in particular 0--naphthol; 5-pyrazolones or 5-amino-pyrazoles that bear in the 1-position a phenyl or naphthyl radical, which may be unsubstituted or substituted with chloro, nitro, Cl-4-alkyl or -alkoxy or-sulpho, and in the 3-position a Cl-4-alkyl group, in particular methyl; acetoacetic acid amides, acetoacetic anilides and benzoylacetic acid anilides, in which the anilide-nucleus is either unsubstituted or substituted with chloro, Cl-4-alkyl or -alkoxy or sulpho; 6hydroxy-3-cyano or 6-hydroxy-3-carbamoyl-4-alkyl-2-pyridones, the 1position of which is substituted by optionally further substituted Cl-4alkyl, e.g. methyl, isopropyl, f3--hydroxy-ethyl, 0-aminoethyl or yisopropoxy-propyl, or by unsubstituted phenyl, the alkyl in the 4position being preferably a Cl-4-alkyl, in particular methyl.
Representative examples of these coupling components are: 2-naphthol, 1,3or 1,5-dihydroxy-naphthalene, l-naphthol, 1-acetylamino7-naphthol, 1propionylamino-7-naphthol, 1-carbomethoxyamino-7-naphthol, 1carboethoxyamino-7-naphthol, 1-carbopropoxyamino-7-naphthol, 6-acetyl-2naphthol, 2-naphthol-3-, -4-, -5-, -6-, -7- or -8-sulphonic acid, lnaphthol-3-, -4- or -5-sulphonic acid, l-naphthol-3,6disulphonic acid, lnaphthol-4,8-disulphonic acid, 1naphthol-3,8disulphonic acid, 2-naphthol3,6-disulphonic acid, 4-methyl-l-naph- Case 150-5193 thol, 4-methoxy-l-naphthol, 4-acetyl-l-naphthol, 5,8-dichloro-lnaphthol, 5-chloro-l-naphthol, 2-naphthylamine, 2-naphthylamine-lsulphonic acid, lnaphthylamine-4- or 5-sulphonic acid, 2-aminonaphthalene-6- or -5sulphonic acid, 1-phenyl-3-methylpyrazole-5-on, 1-phenyl-5pyrazolone-3carboxylic acid amide, 1-(21-, 31- or 41-methylphenyl)-3-methylpyrazol-5one, 1-(21-, 31- or 41-sulphophenyl)3-methylpyrazol-5-one, 1-(21-chloroSt-sulphophenyl)-3-methylpyrazol-5-one, 1-(21- or 41-methoxyphenyl)-3methylpyrazole-5-one, 1-(2f-, 31- or 41-chlorophenyl)-3-methylpyrazole-5one, 1-(21-, 3for 41-nitrophenyl)-3-methylpyrazol-5-one, 1-(21,51- or 31, 47-dichlorophenyl)-3-methylpyrazol-5-one, 1-(21,51-dichloro-41sulphophenyl)-3-phenylpyrazole-5-one, 1-(21-, 31- or 41-sulphophenyl)3methyl-5-aminopyrazole, 1-(21-chloro-51-sulphophenyl)-3-methylSaminopyrazole, acetoacetic acid anilide, acetoacetic acid anilide2-, -3oder -4-sulphonic acid, acetoacetic acid-o-anisidide, acetoacetic acid-otoluidide, acetoacetic acid-o-chloroanilide, acetoacetic acid-m-xylidide, tetralol, 4-methylphenol, 3-dialkylaminophenol, in particular 3dimethylamino- and 3-diethylaminophenol, 4-butylphenol, 4-amylphenol, in particular 4-t.amylphenol, 2-isopropyl-4-methylphenol, 2- or 3acetylamino-4-methylphenol, 2-methoxycarbonylamino-4-methoxyphenol, 2ethoxycarbonylamino-4-methylphenol, 3,4-dimethylphenol, 1-ethyl-3-cyano-4methyl-6-hydroxypyridone, 1-methyl3-cyano-4-methyl-6-hydroxypyridone and 1-phenyl-3-carbamoyl-4-methyl-6-hydroxypyridone.
Preferably B and E represent each the radical of a coupling component which is unsubstituted 2-naphthol, 2-naphthol substituted with a sulpho group, unsubstituted 1-phenyl-3-methyl-S-pyrazolone, unsubstituted acetoacetic acid anilide or 1-phenyl-3-methyl-S-pyrazolone or acetoacetic acid anilide, in which the phenyl ring is substituted with Cl-4-alkyl, Cl4-alkoxy, chloro or sulpho.
Yhen Z represents the group CH the corresponding radical B or E represents the radical of an o-hydroxyaldehyde, preferably the radical of an o-hydroxy benzaldehyde or o-hydroxy-naphthaldehyde.
Suitable aldehydes include: 2hydroxy-l-naphthaldehyde, 1-hydroxy2naphthaldehyde, 2-hydroxy-benzaldehyde, 3- and 5-methyl-2hydroxybenzaldehyde, 3,5-dimethyl-2-hydroxybenzaldehyde, 5-butyl-2benzaldehyde, 5-chloro- or 5-bromo-2-hydroxybenzaldehyde, 3-chloro-2hydroxybenzaldehyde, 3,5-dichloro2-hydroxybenzaldehyde, 5-sulpho2hydroxybenzaldehyde, 3-methyl-S-chloro-2-hydroxybenzaldehyde, 5(phenylazo)-2-hydroxybenzaldehyde, 5-(21-, 31- or 41-sulphophenylazo)-2hydroxybenzaldehyde or 5-(61-sulphonaphthyl-ll-azo)-2-hydroxybenzaldehyde.
Preferably the 1:2-metal complexes'contain two sulpho groups (Y sulpho, n = 2).
1:2-Metal complexes of monoazo compounds with two sulpho groups per metal complex molecule, in particular with one sulpho group in each azo complexant are particularly preferred. Most preferred are the following dyes:
(a) yellow dyes of the formula - (D cl 0 - N=N- C MO 3 5 % C-CH 3 0 0 / CO 0 9 0 \ IC-CH c 3 MO 34-N=N C-Nil-@ 0 (M; M (D (b) red dyes of the formula Y Y CH 3 - N Y 3 N=N 1 N - 1 C f r Y 4 0 Y N -NN N Y 4 Y Y CH 3 0 (III), m 0 in which at the ring A' one of Y1, Y2 and Y3 signifies chlorine, one signifies hydrogen and one signifies the group -S03M, or Y1 and Y2 together with the vicinal carbon atoms to which they are linked form a condensed benzo ring and Y3 signifies a group -S03M in para position to the azo group and Y4 signifies hydrogen or chlorine; (c) blue dyes of the formula 0 0 0 0 MO 3 5 4 N N C 1 r 0 0 0 MO 5 0 0 3 -f 0 0 m e (IV); 4 Case 150-5193 (d) brown dyes which are mixed 1:2-chromium complexes of monoazo dyesof the formulae OH OR MO 3 5 0 - N=N 0 0 0 X 1 is H Z1 0 so 3 m N and N=N - 1 0 2 W' Z3 CH 3 - N Z2 (V) (VI) 1 wherein X, signifies hydrogen or -N02, Z1 signifies hydrogen, chloro or methyl and Z2 and Z3 signify each hydrogen or chlorine, the purely asymmetrical complex representing at least mole % of the mixed complex; (e) black dyes which are chromium complexes of the monoazo dyes of the formula (V) in which X, signifies -N02; in the formula (II) to (V1) M signifying hydrogen or a cation.
In the dyes (a) the chlorine atom in the diazo component is preferably in para-position to the oxygen and the sulpho group is preferably in orthoposition to the oxygen.
Of the dyes (b) the ones are preferred in which Y4 is hydrogen, in particular bordeaux red dyes, in which Y1 and Y2 together with the carbon atoms to which they are linked form a condensed benzo ring and Y3 is a sulpho group in para-position to the azo group, and medium red dyes in which Y1 is chlorine, Y2 is hydrogen and Y3 is a sulpho group in ortho position to the oxygen.
Case 150-5193 In the dyes (d) X, is preferably the nitro-group and at least two of the symbols Z1, Z2 and Z3 signify hydrogen, more preferably all three symbols Z1, Z2 and Z3 signify hydrogen. The nitro group in formula (VI) is preferably in para-position to the hydroxy group; the sulpho group in formula (VI) may be in any of the positions ortho, meta or para to the pyrazolone ring and is more preferably in para position.
M may be any cation conventional in sulpho group-containing metal complexes, preferably unsubstituted or substituted ammonium (in particular ammonium substituted with CI-4-alkyl and/or with 0-hydroXY-C2- 3-alkyl, preferably mono-, di- or tri-ethanol- or -isopropanolammonium) or alkali metal (lithium, sodium, potassium), of which potassium and in particular sodium are preferred.
These dyes are known or may be produced in known manner, e.g. by metallisation of the corresponding metallisable mono-azo compounds.
They may be used in the form as has been synthetised and if necessary purified or, preferably, be blended with conventional blending agents (in particular with inorganic salts, preferably sodium carbonate, sulphate or chloride, with non-electrolyte blending agents, preferably dextrine and/or urea and optionally, for the production of granular or liquid forms, with corresponding suitable additives). The dyes may be used in any conventional form, e.g. as powder, liquid compositions or granules; for the production of especially electrolyte-poor compositions the dyes may be purified e.g. by dialysis before any blending with non-electrolyte blending agents.
The products (P) that are used in the process of the invention may be produced in conventional manner. The reaction of (a) with (0) is carried out without any addition of water or of any other organic solvents and at temperatures > 50% more preferably in the range of 60-2000C, in particular of 80-180C and with cleavage of ammonia). The molar ratio (cc)1(0) is advantageously in the range of 0.7511.25 1 Case 150-5193 to 1.25/0.75, preferably 1/1, component (0) being employed preferably in amounts of 0.1 to 1 moles per mole of reactive NH or NH2 group in (a). Preferably the reaction is carried out in the presence of a catalyst (Kj) which is advantageously a metal compound of a metal of the third or preferably second group of the periodic system of elements (principally aluminium, barium, magnesium or zinc). The metal compound is advantageously a hydrosoluble salt of a low molecular acid, preferably a mineral acid, in particular a chloride, especially zinc chloride. The catalyst (Kj) may also be an inorganic base or a heterocyclic base which is advantageously an amino-substituted pyridine, preferably a pyridine substituted by a tertiary amino group, in particular a dialkylamino group; the dialkylamino is preferably di-(Cl-4-alkyl)amino, more preferably dimethylamino; the most preferred heterocyclic base is 4-dimethylamino- pyridine. Of the above-mentioned catalysts the metal salts are preferred. (KI is advantageously employed in amounts of 0.01 to 10% by weight, referred to the sum [((z) + (0)], the metal salts being employed preferably in amounts of 0.1 to 5% by weight, in particular 0.2 to 1% by weight and the heterocycles being employed in amounts of 0.1 to 7% by weight, in particular 4.5 to 5.5% by weight.
The reaction takes place with ammonia-cleavage and is suitably carried out until the ammonia development extinguishes. Advantageously the reaction is carried on until the product contains at least one free hydrogen atom bound to a nitrogen atom in the molecule.
The obtained product may if desired be protonated with an acid, preferably a mineral acid, more preferably hydrochloric acid or sulphuric acid, to the corresponding acid addition product or be further reacted with (y) and then be protonated if desired.
A preferred polymer product (P) of the reaction of (a) with (0) is in particular the reaction product of a monoamine of the formula NERR or a polyamine of the formula RRN--4Zr-X2)r-ZI-NRR Case 150-5193 (VII) (Viii) wherein each R independently signifies hydrogen, Cl-4-alkyl or Cl-4-alkyl substituted with hydroxy, Cl-4-alkoxy, phenyl or cyano t is a number from 0 to 100 each Z1 independently signifies a Cl-4-alkylene or hydroxyalkylene radical and each X2 signifes -0-, -S- or -NR- the amine of formula (VIII) containing at least one reactive NH or NH2 group.
In the amines of formula (VIII) R signifies preferably hydrogen, t is preferably a number from 0 to 4, X2 signifies -NH- or -NCH3 and each Z1 signifies C2-4-alkylene.
Particularly preferred amines of the formula (VIII) are diethylenetriamine, triethylenetetraamine, tetraethylene-pentaamine, 3-(2aminoethyl)-aminopropylamine, dipropylenetriamine or N,N-bis-(3aminopropyl)-methylamine.
Component (0) is most preferably dicyanodiamide.
Compounds of the kind (P), their acid addition products and their production are described e.g. in german published patent applications DE 35 25 104 A1 (corresponding to GB 2 163 760 A) and DE 32 16 913 Al (corresponding to GB 2 099 007 A) and in PCT published patent application WO 81/02423 (corresponding to GB 2 070 006 B); the content of these patent specifications (before all, of DE 35 25 104 Al) is incorporated herein by reference, in particular
11 - is - Case 150-5193 with regard to the production of the compounds (P) and their acid addition products, the employed starting materials, catalysts and acids, the production parameters and.reaction conditions and the obtained products.
Before dyeing or printing the leather may be pre-treated with products (P) (optionally in the form of their acid addition products) and dyeing or printing may then be carried out in conventional way, but according to a preferred feature, the treatment with the products (P) (optionally in the form of their acid addition products) is carried out after dyeing or printing.
In the pre-treatment of the undyed and unprinted leather or in the aftertreatment of the dyed or printed leather, the product (P) (calculated as 100% active substance) is used in amounts in the range of 0.2 to 5% by weight, preferably 0.4 to 3% by weight, referred to the dry weight of the leather, or in amounts of 0.1 to 2.5% by weight, preferably 0.2 to 1.5% by weight, referred to the wet weight of the substrate. The pre-treatment of the leather with a product (P) is carried out advantageously in the pH range of 3 to 6, more preferably 4.5 to 5.0; the after-treatment with a product (P) of the dyed or printed leather is advantageously carried out at a pH in the range of 3 to 5, preferably 3 to 4.
The pre-treatment and after-treatment with product (P) is preferably carried out for 10-45 minutes.
The dyeing may be carried out under conventional conditions, preferably at temperatures in the range of 25-70'C and at pH values in the range of 3 to 9, more preferably 4 to 8. optionally in the presence of conventional dyeing assistants, e.g. of a dye-substantive uptake assistant, such as a highly oxyethylated and optionally quaternated fatty amine or fatty aminoalkylamine. After dyeing the pH of the dye bath is advantageously lowered, preferably to values in the pH-range Case 150-5193 of 3 to 5, more preferably 3.3 to 4; a fatting may advantageously be carried out subsequently to the dyeing.
The after-treatment of the dyeing with product (P) may take place in the same bath in which the dyeing has been carried out, advantageously at acidic pH-conditions, preferably in the range of pH 3 to pH 5, more preferably at pH-values < 4, in particular at pH 3.3 to 4. The aftertreatment agent (P) is conveniently added to the dye bath which after the dyeing (if a fatting agent has been added, also after the addition of a fatting agent) has been acidified advantageously to pH-values < 4, in particular to pH values in the range of 3.3 to 4.
The after-treatment may, however, also be carried out in a separate fresh bath, advantageously after having lowered the pH of the dye bath and then having drained off the dye bath. The pH of the fresh bath may range in any suitable scope, e.g. between pH 3 and pH 8, preferably in the pH- range of 3 to 6.5, depending on the pH of the employed product (P); a further acid addition in the fresh bath is in general not required since in this case the leather, when adding the fresh bath, is still soaked with the previous bath which is preferably acidic of pH < 4.
The after-treatment is advantageously carried out in the same temperature range as the dyeing, any fatting and any lowering of the pH value by acid addition, preferably at temperatures in the range of 25-700C, more preferably 35-60C for leather and 25-550C for woolbearing skins.
The treated leathers may then be finished in conventional way.
By the process of the invention, there may be achieved a good buildup of the dyes on the leather and deep shades. The obtained dyeings are distinguished by their good fastnesses, principally light-fastnesses and wet-fastnesses, in particular fastness to sweat, to sea- water and to lake-water and their good shade-stability.
In the following Examples parts and percentages are by weight; the temperatures are indicated in degrees Celsius.
The percent indications refer to the dry weight of the substrates, if there is not clearly meant a concentration of a solution or dispersion. The products are employed in commercial form, the dye quantities are referred to the active substance.
Example 1 (drum-dyeing) Chrome-tanned intermediately dried nappa from sheep is wetted back with 600% of water and 1% of 25% ammonia for 60 minutes at 50. The bath is then drained off and a fresh bath of 500% of water at 55, 1% of 25% ammonia, 0.8% of vegetable fatty acids which are partially esterified with methyl (fatting agent) and 1.5% of the red dye of formula cl N=N NaO 3 -CO C r 0.
0 NaO 3 0 _N=N - cl H3C N HIC (D Na(D (III I) are added and dyeing is carried out for 50 minutes at 55. 1% of 85% formic acid are then added and after 15 minutes further 0.8% of the dye of formula (IIII) are added and dyeing is continued for further 1 - 18 - Case 150-5193 minutes at 55. 2% of 85% formic acid are then added and the treatment is continued for further 40 minutes and the bath is then drained off. 600% of water at 50C and 3% of the aqueous reaction product of dicyanodiamide and diethylenetriamine (molar ratio 1/1) in the form of the sulphate according to Example 1 of German published Patent Specification DE 35 25 104 A1 (corresponding to GB 21 63 760 A) but of 55% concentration are then added and the after-treatment is carried out for 30 minutes at 50C. The bath is then drained off and the leather is rinsed for 5 minutes in a running water of 251C. The bath is then drained off, the leather is drained, dried and mechanically finished as conventional.
MR Example 2 to 6 The process of Example 1 is repeated with the difference that in place of the red dye of formula (III') the following dyes are employed:
Example 2: the yellow dye of formula - (D 0 cl % C-NH_@) 0 N=N-Cl % c -CH NaO S 9 1 / 3 3 0 1 0 (ii,) NaO 0 0 3 C-CH 3 0 NIN - c C-NH-CO n Example 3: the bordeaux-red dye of formula 1 1 0 H 3 c aCS 0 N7N \ 1 N N 0 Na03 0 -N=N t - - N 0 H3C Example 4:
(D 0 N-CO the blue dye of formula 0 0 Nao 0 N=N 0 41- 3 0 0 NaO 5 0 N=N- 03 -f 0 0 G Na G) Na E) Case 150-5193 (III-) (IV') - Example 5: the black dye of formula 0 2 - (D 0 0 NaO S 0 - N=N 0 3 C1r 0 1 0 Na%S_ 0 N=N_ 0 0 - t 0 02N Na (D Case 150-5193 W) Example 6: the brown 1:2-chromium mixed complex of the mono-azo dyes of the formulae NaO 3 S0 - 0 02 in molar ratio 1/1.
OH OH - 0 0 (vf F) and Example 7 (drum-dyeing) 02 H HO N -S03Na 0 N=N H 3 (VI') Chrome-synthetically tanned and intermediately dried lamb-leather for gloves is wetted back with 1000% of water at 50, 3% of 25% ammonia and 0. 3% of the addition product of 10 moles of ethylene TI oxyde to 1 mole of di-t-butyl phenol for 60 minutes. The bath is drained off and the leather is washed for 10 minutes with 800% of water at 50'. The bath is then drained off. 900% of water at 500, 2% of 25% ammonia and 3% of vegetable fatty acids that are partially esterified with methyl (fatting agent) are added and after 15 minutes of rotation 2.4% of the blue dye of formula (IV') are added in 3 portions and at intervals of 10 minutes. 30 minutes after the third dye-addition 5% of 85% formic acid are added also in 3 portions at intervals of 10 minutes (pH = 3.5). 30 minutes after the third acid-addition the bath is drained off. 600% of water at 50 and 3% of the aqueous condensation-product of dicyanodiamide and diethylenetriamine (molar ratio 1/1) in the form of the sulphate according to Example 1 of DE 35 25 104 Al (corresponding to GB 2 163 760 A) but of 55% concentration are added and after 30 minutes rotation the bath is drained off. After washing for 10 minutes with 800% of water at 25 the bath is drained off, the leather is drained, dryed and mechanically finished as conventional.
Examples 8 to 12 The procedure of Example 7 is repeated with the difference that in place of the blue of formula (IV') the following dyes are added:
Example 8: the yellow dye of formula (M) Example 9: the bordeaux-red dye of formula (III") Example 10: the red dye of formula (III,) Example 11: the black dye of formula (V') Example 12: the brown 1:2-chromium complex dye of the monoazo dyes of formulae a OH OH Nao 3 S 0 - N=N 0 0 0 07 Case 150-5193 H HO N -&SO0a 0 N=N 0 ? 2 H 3 -N (vf e) and (VII) in the molar ratio 1/1.
The obtained dyes are level intense and brilliant with optimum penetration and fastnesses, in particular wet-fastnesses 1

Claims (13)

  1. Claims is Case 150-5193 A process for the dyeing or printing of leather
    with anionic metal complex dyes wherein the metal complex dyes are metal complexes of metallizable mono-azo dyes or metallizable monoazomethine dyes or both metallizable monoazo and monoazomethine dyes and before the application of the dye or after the application of the dye or both before and after the application of the dye the leather is treated.with a product (P) or a mixture of products (P) or an acid addition product thereof, the product (P) being a polymer obtainable by reaction of (a) a mono-functional or poly-functional amine containing one or more amino groups of the group consisting of primary, secondary and tertiary amino groups wi th (0) cyanamide, dicyanodiamide, guanidine or biguanide or a mixture in which up to 50 mole percent of the cyanamide, dicyanodiamide, guanidine or biguanide are replaced by a di-carboxylic acid or a mono or diester thereof with cleavage of ammonia or a further reaction product thereof with reactant (y) selected from the group consisting of: 1) (yl) a N-methylol derivative of a urea, a melamine, a guanamine, a triazine, a urone, a urethane or an acid amide, 2) (Y2) an epihalohydrin or an epihalohydrin precursor, 3) (Y3) formaldehyde or a formaldehyde yielding product, 4) (Y2) followed by (yl) and 5) (Y3) followed by (yl).
  2. 2. A process according to claim 1, wherein the product of the reaction of (a) with (0) is a product obtainable from the reaction in the presence of a catalyst (K,).
    Case 150-5193
  3. 3. A process according to claim 1 or 2, wherein (P) is the product of the reaction of (a) with (0) and with (y) the reaction product of (a) with (0) containing at least one free hydrogen-atom bound to a nitrogen atom.
  4. 4. A process according to any of claims 1 to 3 wherein the product (P), a mixture of such products (P) or an acid addition product thereof is used in amounts of 0.2% to 5% by weight (calculated as 100% non-protonated active substance) referred to the dry weight of the leather substrate.
  5. 5. A process according to any of claims 1 to 3, wherein the product (P), a mixture of such products (P) or an acid adduct thereof is used in amounts of 0.1 to 2.5% by weight (calculated as 100% non-protonated active substance), referred to the wet weight of the leather substrate.
  6. 6. A process according to any of claims 1 to 5, wherein the leather is pre-treated with a product (P), a mixture of such products (P) or an acid addition product thereof at a pH in the range of 3 to 6, or is aftertreated after the dyeing with a product (P), a mixture of such products (P) or an acid addition product thereof at a pH in the range of 3 to 5.
  7. 7. A process according to any of claims 1 to 6, wherein the pretreatment or the after-treatment is carried out during 10 to 45 minutes.
  8. 8. A process according to any of claims 1 to 7, wherein the metal complex dyes are sulpho group-containing 1:2-metal complexes of monoazo complexants.
  9. 9. A process according to any of claims 1 to 8, wherein the leather is fatted before the treatment with a product (P), a mixture of such products (P) or an acid addition product thereof.
    f 1 i 1 - 25 - Case 150-5193 1
  10. 10. A process according to claim 9, wherein the leather is aftertreated with the product (P), a mixture of such products (P) or an acid addition product thereof, after the dyeing and a fatting is carried out'after the dyeing and before the after-treatment.
  11. 11. Leather, whenever treated by a process according to any of claims 1 to 10.
  12. 12. A process according to any of claims 1 to 10, as hereinbefore described and as specifically disclosed in any of Examples 1 to 12.
  13. 13. Leather according to claim 11, whenever treated by a process according to any of claims 1 to 10, as hereinbefore described and as specifically disclosed in any of Examples 1 to 12.
    PUbllshed 1988 at The Patent Office. State HousC, 6671 High Hollborn. London WC1R 4TP Purther copies inay be obtained froin. The Patent Office.
    - -- ---- 1 ---
GB8818608A 1987-08-08 1988-08-05 Dyeing and printing of leather Expired - Lifetime GB2208393B (en)

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IT (1) IT1224686B (en)

Cited By (2)

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US5152801A (en) * 1989-12-11 1992-10-06 Ciba-Geigy Corporation Process for dyeing leather with an aqueous bath containing sulfonated carbon black and black anionic dye
US20200399491A1 (en) * 2019-06-19 2020-12-24 Seiko Epson Corporation Aqueous ink composition for ink jet textile printing and textile printing method

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Publication number Priority date Publication date Assignee Title
CA2141646C (en) 1994-02-04 2001-11-06 Nobuyuki Kuwabara Leather coloring process, leather coloring apparatus, and colored leather produced by such process
GR1004726B (en) 2001-12-07 2004-11-22 Μαρια Κοκκου Method for the embossed impression of sketches on leather surfaces and leather products made by applying the method
NL2026818B1 (en) * 2020-11-04 2022-06-24 Stahl Int B V Composition and process for leather dyeing with polycarbodiimides and dyes

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GB2163760A (en) * 1984-07-21 1986-03-05 Sandoz Ltd Cationic polycondensate fixing agents

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EP0061998B1 (en) * 1981-03-23 1985-04-03 Ciba-Geigy Ag Use of 1:2-chrome or cobalt complex dyes for dyeing leather or furs
DE3264505D1 (en) * 1981-03-23 1985-08-08 Ciba Geigy Ag Use of 1:2-chrome or cobalt complex dyes for dyeing leather or furs
US4452602A (en) * 1981-03-23 1984-06-05 Puentener Alois Process for dyeing leather with mixtures of dyes
US4453942A (en) * 1981-12-21 1984-06-12 Ciba-Geigy Corporation Use of 1:2 cobalt complex dyes for dyeing leather or furs
US4507124A (en) * 1982-07-02 1985-03-26 Ciba-Geigy Corporation 1:2 Metal complexes of azomethine dyes having arylazo groups
DE3481634D1 (en) * 1984-01-03 1990-04-19 Sandoz Ag DYEING AND PRINTING FIBERS.
DE3566915D1 (en) * 1984-11-09 1989-01-26 Ciba Geigy Ag Process for improving the light fastness of dyed leathers

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5152801A (en) * 1989-12-11 1992-10-06 Ciba-Geigy Corporation Process for dyeing leather with an aqueous bath containing sulfonated carbon black and black anionic dye
US20200399491A1 (en) * 2019-06-19 2020-12-24 Seiko Epson Corporation Aqueous ink composition for ink jet textile printing and textile printing method

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IT8848229A0 (en) 1988-07-26
GB8818608D0 (en) 1988-09-07
JPH01139882A (en) 1989-06-01
CH677943A5 (en) 1991-07-15
FR2619130B1 (en) 1990-05-25
GB2208393B (en) 1991-03-13
IT1224686B (en) 1990-10-18
US5002586A (en) 1991-03-26
FR2619130A1 (en) 1989-02-10

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