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Patent US4411665 - Dyeing process using alkoxylated fatty amines and polyamines as reserving agents - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsThe invention relates to a wet-on-wet dyeing process comprising (A) impregnating the substrate with an acid dyeing liquor containing an anionic dye having a K'pH6 -value≧5 (B) applying locally to the substrate at room temperature, a liquor or paste containing an alkoxylated fatty amine or polyamine...http://www.google.com/patents/US4411665?utm_source=gb-gplus-sharePatent US4411665 - Dyeing process using alkoxylated fatty amines and polyamines as reserving agentsAdvanced Patent SearchTry the new Google Patents, with machine-classified Google Scholar results, and Japanese and South Korean patents.Publication numberUS4411665 APublication typeGrantApplication numberUS 06/277,860Publication dateOct 25, 1983Filing dateJun 26, 1981Priority dateFeb 6, 1979Fee statusPaidAlso published asDE3003192A1, DE3003192C2, US4285691, WO1980001577A1Publication number06277860, 277860, US 4411665 A, US 4411665A, US-A-4411665, US4411665 A, US4411665AInventorsHermann Egli, Emil EngelerOriginal AssigneeSandoz Ltd.Export CitationBiBTeX, EndNote, RefManPatent Citations (5), Non-Patent Citations (1), Referenced by (8), Classifications (19), Legal Events (5) External Links: USPTO, USPTO Assignment, EspacenetDyeing process using alkoxylated fatty amines and polyamines as reserving agents
US 4411665 AAbstract
The invention relates to a wet-on-wet dyeing process comprising
(A) impregnating the substrate with an acid dyeing liquor containing an anionic dye having a K'pH6 -value≧5
(B) applying locally to the substrate at room temperature, a liquor or paste containing an alkoxylated fatty amine or polyamine having affinity for anionic dyes with a K'pH6 -value≧5, said step (B) being carried out directly after or directly before said step (A), and
1. In a wet-on-wet process for dyeing an anionic dyeable substrate with reserve effects, the improvement which comprises applying to at least one common area of the substrate, in one step, an acid dyeing liquor containing an anionic dye having a K'pH6 -value≧5, and in a separate step, an alkoxylated fatty amine or polyamine having affinity for anionic dyes with a K'pH6 -value≧5, there being no rinsing or drying of the substrate between said steps.
2. A process for dyeing an anionic dyeable substrate with reserve effects, which process comprises(A) impregnating the substrate with an acid dyeing liquor containing an anionic dye having a K'pH6 -value≧5 (B) applying locally to the substrate at room temperature, a liquor or paste containing an alkoxylated fatty amine or polyamine having affinity for anionic dyes with a K'pH6 -value≧5, said step (B) being carried out directly after or directly before said step (A), and the dyeing liquor of step (A) and the liquor or paste of step (B) being applied to at least one common area of the substrate, and (C) subsequently submitting the substrate to a heat treatment to effect fixation of the dye. 3. A process according to claim 2 wherein step (A) is a ground dyeing or printing of the whole area of the substrate.
5. A process according to claim 2 wherein the anionic dye applied in step (A) has a K'pH6 -value≧6.
9. A process according to claim 2 wherein the liquor or paste applied in step (B) contains an alkoxylated fatty amine or polyamine of formula I ##STR4## wherein R is (C10-24)alkyl or (C10-24)alkenylX1 is --CO-- or a direct bond in each (A--O)x, (A--O)y and (A--O)z chain A is, independently, --CH2 CH2 -- or ##STR5## each n is, independently, 2 or 3 m is O or an integer from 1 to 6, and each x, y or z is a numeral from 1 to 100 the sum x+y+z being from 10 to 102,in the form of a free base, acid addition salt quaternary ammonium salt or mixture thereof, or mixtures of such compounds differing from one another by virtue of the significance of R. 10. A process according to claim 9 wherein the liquor or paste applied in step (B) contains an alkoxylated fatty amine or polyamine of formula Ia ##STR6## wherein A, X1, x, y, z and n are as stated in claim 9, andR' is (C12-24)alkyl or (C12-24)alkenyl. 11. A process according to claim 9 wherein, in the compound of formula IR is (C12-24)alkyl or (C12-24)alkenyl, n is 3 when m is 1 and is 2 when m exceeds 1 and the sum of x+y+z is 15 to 80. 12. A process according to claim 9 wherein the compound of formula I is the product of the addition of 15 to 80 mols of ethylene oxide to aminopropyl-tallow amine or to tallow fatty acid amidopropylamine.
16. A process according to claim 14 wherein the anionic dye applied in step (A) has a K'pH6 -value≧6 and is an acid dye bearing at least two sulpho groups or a metal complex dye containing at least one sulpho group and, in the compound of formula I, R is (C12-24)alkyl or (C12-24)alkenyl, n is 3 when m is 1 and is 2 when m exceeds 1, and the sum of x+y+z is 15 to 80.
18. A process according to claim 14 wherein the liquor or paste applied in step (B) contains in addition to the alkoxylated fatty amine or polyamine, a disperse or anionic dye or a mixture thereof or an anionic optical brightening agent, said anionic dye or anionic optical brightening agent having a K'pH6 -value≦5 and at least one unit lower than the K'pH6 -value of the anionic dye used in step (A), and said dye(s) or optical brightening agent applied in step (B) being also fixed by the heat treatment of step (C).
19. A process according to claim 18 wherein the anionic dye applied in step (A) has a K'pH6 -value≧6 and is an acid dye bearing at least two sulpho groups or a metal complex dye containing at least one sulpho group and the liquor or paste applied in step (B) contains an anionic dye selected from the group consisting of non-metalized acid and direct dyes containing a maximum of one sulpho group and metal complex dyes free from sulpho groups, and, in the compound of formula I, R is (C12-24)alkyl or (C12-24)alkenyl, n is 3 when m is 1 and is 2 when m exceeds 1, and the sum of x+y+z is 15 to 80.
23. A process according to claim 2 wherein the liquor or paste applied in step (B) contains, in addition to the alkoxylated fatty amine or polyamine, a disperse or anionic dye or a mixture thereof or an anionic optical brightening agent, said anionic dye or anionic optical brightening agent having a K'pH6 -value≦5 and at least one unit lower than the K'pH6 -value of the anionic dye used in step (A), and said dye(s) or optical brightening agent applied in step (B) being also fixed by the heat treatment of step (C).
24. A process according to claim 23 wherein the liquor or paste applied in step (B) contains, in addition to the alkoxylated fatty amine or polyamine, an acid dye having a K'pH6 -value 2 to 6 units lower than the K'pH6 -value of the anionic dye applied in step (A).
28. A process according to claim 2, comprising(B) applying locally to the substrate at room temperature a liquor or paste containing an alkoxylated fatty amine or polyamine having affinity for anionic dyes with a K'pH6 -value≧5, (A) directly thereafter impregnating the locally treated substrate with an acid dyeing liquor containing an anionic dye having a K'pH6 -value≧5, and (C) subsequently submitting the substrate to a heat treatment to effect fixation of the dye. 29. A process according to claim 2 wherein the amine or polyamine applied in step (B) is cationic or amphoteric and is free from fiber-reactive groups.
According to a further aspect of the invention, the liquor or paste of step (B) may contain, in addition to the alkoxylated fatty amine or polyamine, a disperse or anionic dye or a mixture thereof or an anionic optical brightening agent, provided that the anionic dye or anionic optical brightening agent has a K'pH6 -value≦5 which is at least one unit lower than the K'pH6 -value of the anionic dye used in step (A). As it will be appreciated, the dyes or optical brightening agent applied in step (B) are also fixed by the heat treatment of step (C).
The K'pH6 -value represents the combinability value of an anionic dye experimentally assessed at pH 6 in the presence of a cationic compound; this value is usually employed to indicate the combination capacity of anionic dyes [See G.B. Pat. No. 1,489,456;Otten H. G., Bayer Farbenrevue, 21, 32 (1972); and Beckmann W., Hoffmann F. and Otten H. G., Melliand Textilber. 6, 641 (1973)]. The K'-value is a specific dyestuff characteristic which provides a practical indication of the behaviour in dyeing of an anionic dye in relation with its combination capacity. This value usually may vary from 1 to 10.
The K'pH6 -value of the anionic dyes may be assessed according to the following test method with reference to a standard anionic dye whose K'pH6 -value is known:
Nylon yarn (Du Pont, type 846) is introduced at a goods to liquor ratio of 1:40 in a dyebath at 40° and pH 6. This dyebath contains demineralized water, a standard anionic dye and the dye to be tested in an amount corresponding for each dye respectively to the amount sufficient to obtain a standard dyeing of
The dyebath is then heated from 40° to 100° C. at a rate of 1° C./min. The dye concentration in the dyebath is determined spectrophotometrically every 5 min (or 2.5 min when the dye builds up quickly) and calculated with a computer. The K'pH6 -value of the dye to be tested is then calculated according to the method indicated by Atherton E., Downey D. A. and Peters R. H. in J.S.D.C., 74, 242 (1958).
Step (A) is a ground dyeing or printing of the substrate, preferably on the whole area. The expression "ground dyeing or printing" refers only to the application of the dye onto the substrate but does not include the fixation of the dye. Step (A) may be carried out at room temperature according to known methods, e.g. padding, pouring, slop-padding, printing, etc. Suitable anionic dyes for the ground dyeing or printing are those having a K'pH6 -value≧5, preferably≧6. Preferred anionic dyes are acid dyes containing two or more sulpho groups and metal complex dyes containing at least one sulpho group. More preferred anionic dyes are 1:2 or 1:1 chromium or cobalt complexes, particularly of azo or azomethine dye, containing one or two sulpho groups. Such dyes are known from the Colour Index. Particularly preferred anionic dyes are e.g. C.I. Acid Yellow 235, 218, Acid Orange 168, Acid Red 399, 263, 128, Acid Violet 128, Acid Blue 296, 247, 80, Acid Green 106, Acid Brown 289, 298, 363, Acid Black 218.
In step (B), the substrate is locally treated, in controlled form or at random, with a liquor or a paste containing an alkoxylated fatty amine or polyamine having affinity for anionic dyes with a K'pH6 -value≧5. The affinity of the amine for anionic dyes with a K'pH6 ≧5 may be assessed e.g. by the following test method:
(a) 0.2 ml of an aqueous solution of a standard anionic dye (1 part dye per 100 parts water), having a K'pH6 -value≧5 are added to 5 ml of demineralized water.
A drop of each solution (a) and (b) is deposited on a thin layer chromatography plate. After drying at room temperature, the spot of the solution (a) is coloured on the whole diffusion surface whereas the spot of the solution (b) containing the amine having affinity for anionic dyes with a K'pH6 -value≧5 is coloured in the center and comprises a substantially colourless and relatively wide diffusion edge.
Preferred cationic reserving agents according to the invention are those of formula I ##STR1## wherein R is (C10-24)alkyl or (C10-24)alkenyl
X1 is --CO-- or a direct bond
in each (A--O)x, (A--O)y and (A--O)z chain A is, independently, --CH2 CH2 -- or ##STR2## each n is, independently, 2 or 3 m is O or an integer from 1 to 6, and
R is preferably (C12-24)alkyl or (C12-24)alkenyl. R may be for example dodecyl, hexadecyl, octadecyl, octadecadienyl, arachinyl, behenyl, the mixture of alkyl groups present in soya fatty acid or tallow fatty acid, etc. . .
Preferably the sum x+y+z corresponding to the total number of ethylene-oxy units, propylene-oxy units or mixture thereof is from 15 to 80, more preferably from 30 to 40. The (AO)x,y,z chains are preferably made up of ethylene-oxy units or ethylene-oxy and propylene-oxy blocks, more preferably of ethylene-oxy units.
The alkoxylated amine or polyamine, particularly the compounds of formula I, may be used in the form of an acid addition salt, quaternary ammonium salt or mixtures thereof. Preferred acid addition salt forms are those derived from hydrogen haloacids, for example from hydrochloric acid. Preferred quaternary ammonium salt forms are those bearing on the quaternized nitrogen atom a (C1-4)alkyl or aryl-(C1-4)alkyl group, especially methyl or benzyl. Suitable anions of the quaternary ammonium salts are e.g. halogenide, preferably chloride, or sulfate ions.
A preferred class of reserving agents of formula I is the one constituted by compounds of formula Ia ##STR3## wherein A, X1, x, y, z and n are as defined above, and
R' is (C12-24)alkyl or (C12-24)alkenyl
When bi- or multi-coloured effects are desired, the reserving paste or liquor locally applied in step (B) may contain, in addition to the reserving agent, also an anionic dye, a disperse dye or a mixture thereof or an anionic optical brightening agent, provided that the anionic dye or anionic optical brightening agent has a K'pH6 -value≧5 which is at least one unit lower than the K'pH6 -value of the anionic dye used in step (A). Depending on the final pattern which is desired, it may be possible to apply one or more of such pastes or liquors, either simultaneously or one after the other. For example, a paste containing the reserving agent alone and one or more liquors or pastes comprising the reserving agent together with a disperse dye or one or more anionic dyes of the specified type may be applied locally either directly before or directly after step (A).
Suitable dyes or optical brightening agents for the local colouration are those whose build-up or fixation behaviour is not adversely affected either by the reserving agent or the application conditions. Suitable anionic dyes are those having preferably a K'pH6 -value<5, more preferably 2 to 6 units lower than the K'pH6 -value of the anionic dye applied in step (A). Preferred anionic dyes of this type are non metallized acid and direct dyes containing no more than one sulpho group and metal complex dyes free from sulpho groups, more preferably acid dyes, particularly levelling dyes. Such anionic dyes and the disperse dyes which may be used are known from the Colour Index. Anionic dyes are preferred for the local colouration. Examples of preferred anionic dyes include C.I. Acid Yellow 196, 132, 151, Orange 156, 67, Blue 288, 40, 278, Red 299.
Subsequent to the latter of steps (A) and (B), the substrate is submitted to a heat treatment to effect fixation of the dye applied in step (A) and optionally in step (B) or, if used, of the brightening agent. Fixation can be achieved by known methods depending on the dyestuff or agent used, preferably with saturated steam at a temperature from 100° to 105° C. The heat treatment in step (C) is carried out for 2 to 20, preferably 5 to 10 minutes.
The K'pH6 -values indicated in the following examples have been assessed in the presence of the ethoxylated cationic levelling agent of Example 1 of U.S. Pat. No. 2,967,755.
A tufted carpet of polyamide 66 is impregnated with a padding liquor containing, per 1000 parts
6 parts dyestuff C.I. Acid Brown 298 (K'pH6 -value=6)
The carpet is treated afterwards for 10 minutes in saturated steam at 100° and then rinsed. A brown dyed carpet with a white pattern is obtained.
A tufted polyamide carpet is padded with a liquor as described in Example 1 and then treated with drops of a liquor containing, per 1000 parts
3 parts dyestuff C.I. Acid Orange 156 (K'pH6 -value=2,5)
The carpet is subsequently treated for 10 minutes in saturated steam at 100° and then rinsed.
Knitted goods of polyamide 6 carpet yarn are impregnated at a pick-up of 100% with a padding liquor as described in Example 1 but replacing 6 parts of dyestuff C.I. Acid Brown 298 by 16 parts of dyestuff C.I. Acid Green 106. Subsequently, a printing paste containing, per 1000 parts
3 parts dyestuff Acid Blue 40 (K'pH6 -value=2)
is printed on the impregnated substrate by a printing screen. Then the substrate is treated for 10 minutes in saturated steam at 100°.
By following the procedure of example 1, 2 or 3, but replacing the ethoxylated tallowaminopropylamine by the optionally quaternized addition product of 1 mol of
Knitted goods of polyamide 6 carpet yarn are impregnated with a padding liquor containing, per 1000 parts
12 parts dyestuff C. I. Acid Green 106 (K'pH6 -value=8,5)
2.8 parts dyestuff C.I. Acid Yellow 151 (K'pH6 -value=3)
2 parts dyestuff C.I. Acid Yellow 127 (K'pH6 -value=3,5)
2.8 parts dyestuff C.I. Acid Orange 127 (K'pH6 -value=3,5)
The material is subsequently treated for 10 minutes in saturated steam at 100° and then rinsed.
Proceeding in a manner analogous to Example 5 but replacing for the ground dyeing the 12 parts of dyestuff C.I. Acid Green 106 by a mixture of 2.2 parts of dyestuff C.I. Acid Brown 298, 0.7 parts of dyestuff C.I. Acid Green 106 and 8.24 parts of dyestuff C.I. Acid Blue 80 (K'pH6 -value=9), and for the local printing the mixture of C.I. Acid Yellow 151, C.I. Acid Yellow 127 and C.I. Acid Orange 127 by a mixture of 2 parts of dyestuff C.I. Acid Orange 156 (K'pH6 -value=2.5) and 0.4 parts of dyestuff C.I. Acid Blue 40 (K'pH6 -value=2), similar good results are obtained.
A nylon carpet is padded to a pick up of 60% with an aqueous liquor containing, per 1000 parts, 5 parts of a commercially available wetting agent based on an ethoxylated higher alcohol and 1 part of a commercially available thickening agent (guar gum). The resulting carpet is then printed on a flatbed printer with two pastes having the following composition per 1000 parts:
______________________________________          K'pH6                Paste I   Paste II______________________________________dyestuff C.I. Acid Yellow 151            3-3.5   0.075  part 0.06 partdyestuff C.I. Acid Red 217            4.5     0.05   part 0.17 partdyestuff C.I. Acid Blue 288            2.5     0.30   part 0.02 parttallow-aminopropylamineethoxylated with 30 mols ethyl-ene oxide                10     parts                                10   partscommercially available wettingagent based on an ethylene-oxide/propylene oxide additionproduct                  1      part 1    partcommercially availablethickening agent         8      parts                                8    partstrisodium phosphate      1,5    parts                                1,5  partsEach paste has a pH from7.5 to 8.0______________________________________
The pH of the paste is from 7.5 to 8.0.
0.025 part of dyestuff C.I. Acid Yellow 235 (K'pH6 =6)
1 part of dyestuff C.I. Acid Blue 296 (K'pH6 =7)
monosodium phosphate so that the liquor has a pH from 5.5 to 6.0.
The resulting carpet is finally steamed for 6 minutes at 100° C. in a horizontal steamer.
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS2963513 *Sep 21, 1956Dec 6, 1960Ciba LtdPolyglycol ether derivativesUS2967755 *Jan 30, 1958Jan 10, 1961Sandoz LtdLeveling and stripping agentsUS3074774 *Oct 16, 1959Jan 22, 1963Arkansas Company IncDischarge printing pastes and methods of application involving sameUS3591325 *Apr 25, 1969Jul 6, 1971Arkansas Co IncProducts and process for removing organic pigments and dyes from dyed and printed natural and synthetic textile materialsUS3627475 *May 12, 1969Dec 14, 1971Sandoz LtdLevelling agents for and process for colouring a fibrous natural polyamide with reactive dyes* Cited by examinerNon-Patent CitationsReference1 *Atherton, E., Jour. of the Soc. of Dyers and Colorists, vol. 74, No. 4, p. 242, (1958).* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS4894065 *Mar 3, 1988Jan 16, 1990Sandoz Ltd.Method for producing wool dyeings of improved levelness and dye mixtures useful therefor: parameters for combination capacity and compensation of variable affinity for wool from root to tip of fiberUS5356445 *Sep 24, 1993Oct 18, 1994Ciba-Geigy CorporationProcess for dyeing natural or synthetic polyamide fibre material with dye mixturesUS5364417 *Nov 16, 1992Nov 15, 1994Milliken Research CorporationMethod of dyeing nylon fiber with acid dye: sullfamic acidUS5403358 *Sep 21, 1992Apr 4, 1995Imperial Chemical Industries PlcInk jet printing process and pretreatment composition containing a quaternary ammonium compoundUS5443598 *Jun 17, 1992Aug 22, 1995Sandoz Ltd.Dyeing assistants and their useUS5769904 *May 27, 1997Jun 23, 1998Ciba Specialty Chemicals CorporationProcess for the production of resists or multicolor effects on natural and synthetic polyamide fibre materialsUS7014699Feb 26, 2002Mar 21, 2006Clariant GmbhOxalkylation products produced from epoxides and amines and their use in pigment preparationsUS20040116562 *Feb 26, 2002Jun 17, 2004Winter Martin AlexanderOxalkylation products produced from epoxides and amines and their use in pigment preparations* Cited by examinerClassifications U.S. Classification8/455, 8/457, 8/478, 8/463International ClassificationD06P5/12, C22B3/38, D06P1/607Cooperative ClassificationC22B3/0071, D06P5/12, C22B3/0068, D06P1/6076, C22B3/0077, Y02P10/234, Y10S534/01European ClassificationC22B3/00D2M2P2B20, C22B3/00D2M2P2B12R, D06P5/12, C22B3/00D2M2P2D, D06P1/607DLegal EventsDateCodeEventDescriptionMar 7, 1983ASAssignmentOwner name: SANDOZ LTD.AKA SANDOZ AG,4002 BASLE,SWITZERLAND AFree format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:EGLI, HERMANN;ENGELER, EMIL;REEL/FRAME:004101/0655Effective date: 19810619Owner name: FIDELITY UNION TRUST COMPANY,Free format text: ASSIGNS ENTIRE INTEREST. SUBJECT TO CONDITIONS SET FORTH IN SAID TRUST OF MAY 4, 1955;ASSIGNOR:SANDOZ LTD.;REEL/FRAME:004101/0666Effective date: 19820823Owner name: FIDELITY UNION TRUST COMPANY,NEW JERSEYFree format text: ASSIGNS ENTIRE INTEREST. SUBJECT TO CONDITIONS SET FORTH IN SAID TRUST OF MAY 4, 1955;ASSIGNOR:SANDOZ LTD.;REEL/FRAME:004101/0666Effective date: 19820823Apr 20, 1987FPAYFee paymentYear of fee payment: 4Nov 7, 1990FPAYFee paymentYear of fee payment: 8Apr 24, 1995FPAYFee paymentYear of fee payment: 12Aug 19, 1996ASAssignmentOwner name: CLARIANT FINANCE (BVI) LIMITED, VIRGIN ISLANDS, BRFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:SANDOZ LTD.;REEL/FRAME:008178/0144Effective date: 19960805RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services