CA1187654A

CA1187654A - Process for improving the fastness of dyeings with basic dyes on cellulose substrates

Info

Publication number: CA1187654A
Application number: CA000405574A
Authority: CA
Inventors: Helmut Moser; Tibor Robinson
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1981-06-22
Filing date: 1982-06-21
Publication date: 1985-05-28
Also published as: ES8307953A1; NL8202475A; ES513322A0; US4439208A; FR2508068A1; AU8507482A; GB2100760A; GB2100760B; BR8203625A; IT8248676A0; FR2508068B1; IT1189301B

Abstract

IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS

Abstract of the Disclosure The fastness properties of basic dyeings on cellulosic substrates are improved by treating the substrate with a fixing agent comprising a precondensate or mixture of A) the reaction product of an amine with cyanamide, di-cyandiamide, guanidine or biguanidine or B) a quaternary polyalkylene polyamine with C) formaldehyde and/or D) an N-methylol compound optionally together with E) a catalyst, e.g. MgCl2.
The fixing agents are normally applied as an aftertreatment, with a subsequent heat-curing step.

Description

~ i!37~

PROCESS FOR IMPROVING THE FASTNESS OF DYEINGS WITH BASIC
DYES ON CELLULOSE SUBSTRATES

This invention relates to a textile treatment process for improving fastness properties, in particular the light and wash fastness properties of dyeings and printings on hydroxy group-containing substrates with basic dyestuffs.
The Invention provides a process for producing fast dyeings and printings on a hydroxy group-containing substratP by applying a ~ basic dyestuff to the substrate and treating the substrate either 10: subsequently or simultaneously with a fixing agent comprising a pre-condensate or mixture of either A) the product of reacting a mono- or polyfunctional primary or secondary amine with cyanamide, dicyandi-amide (DCDA), guanidine or biguanidine, whereby up to ; 15 50 mole % of the cyanamide, DCDA, guanidine or biguani-dine may be replaced with a dicarboxylic acid or a mono-: or di-ester thereoF, said product A) containing reactive:
: hydrogen atoms bound to nitrogen, or B) a quaternary polyalkylene polyamine haYing recurring units of formula II' ..
, ~ I

, ~18i765~

- 2 - 1 50-4568 CH2-- CH --CH~

where R1 is Cl 4alkyl, m' is 20-30~ and ~ is an anion with C) formaldehyde or a formaldehye precursor andlor D) an N-methylol derivative of a urea, melamine, guanamine, triazinone, urone, carbamate or acid amide, optionally together with E) a catalyst for the crosslinking of N-methylol compounds of the type D) above, and preferably carrying out a subsequent heat-curing step.
Preferred fixing agents comprise precondensates or mixtures of A) with D), B) with D) and A) with C), optionally together with D). Preferably catalyst E) is also present. Preferred fixing agents comprise precondensates, that is, reaction products which remain water-soluble and non-gelled, and are capable of further crosslinking.
- .
The substrate may be treated with the basic dyestuff simul-taneously with the fixing agent~ i.e. in the same bath for an exhaust or padding process, or in the same printing paste for a printing process. Alternatively the fixing agent may be applied as an aftertreatment to the already dyed or printed substrate. In both cases the fixing agent may already conta;n the catalyst E) or the catalyst may be applied separately in a subsequent step. Where the fixing agent contains a precondensate and a catalyst, the catalyst may be added before, during or after the reaction which gives rise to the precondensate, but preferably this reaction takes place in the presence of the catalyst.
Component A) is preferably the reaction product of a poly-functional amine of formula I

,., ~

~: L8~5~ -

- 3 - 150-4568 RRN ~- Z - X ~ ~ - NRR
in which each R independently is hydrogen or a C1_10alkyl group unsubstituted or monosubstituted with hydroxy, C1_4alkoxy ~r cyano, n is a number from 0 to lûO
Z, or each Z independently when n > 0, is C1 4alkylene or hydroxyalkylene and X, or each X independently when n ~ 1, is -0-, -S- or -NR- where R is as defined above, provided ~hat the amine of formula I contains at least one reactive -NH~ or -NH2 group, with cyanamide, DCDA, guanidine or biguanidine~ particularly DC~A.
R is preferably hydrogen or C~ 4alkyl or hydroxyalkyl, more preferably each R is hydrogen. n is preferably a number from û
to 30, which may be non-integral representing an average value.
More preferably n is an integer from 1 to 6. Z is preferably a 1,2-ethyiene, 1,3-propylene or 1,3-(2-hydroxypropylene3group, X is preferably -NR-9 most preferably -NH-.
Particularly preferred am;nes arQ diethylene triam;ne, triethylene tetramine, tetraethylenepentamine, 2-aminoethyl-3-aminopropylamine, dipropylenetriamine or N,N-bis-(3-aminopropyl)-methylamine Particularly preferred components A) are the reaction products of DCDA with diethylenetriamine or triethylene tetramine.
Components A) are known, and their preparation and their reaction with N-methylol compounds D) to form precondensates are described in published British Patent Applicat;on No. 2070D06A, ~n component A), up to 50% mole, preferab1y up to 20~ mole of the DCDA or other reagent to be reacted wi~h the amine may be replaced by a dicarboxylic acid or a mono- or di-ester thereof.
Suitable acids include adipic acid, oxalic acid and terephtha7ic acid, for example in the for~m o~ their dimethyl esters.

i;54

4 150-4568 Preferred compounds of cDmponent B) have recurring units of the formula II -- Rl A~3 - ~ - CH2 - CH - Xl ~ II
R1 R2 ~ m where R1 is C~ 4alky1, R2 is H

X i --Nb~ X , - CH2 - or - CH2-CH2 -~.~
and X~ is -CH2C~2-OC~2CH2- or -(~H2)b-where m is a number between 7 and 75 b is 1 to 5 and A~ is an anion.
Preferably the compounds of component B) have recurring units f formula II' _ ~ _ _ _ ~ A CH2 ~ CH - CH2 - II' R1 OH _ m' where R1 is Cl_qalkyl, preferably methyl m' is 20-30, preferably on average about 25.
Component B) is known and may be prepared according ts known methods, ~or e~ample by react;on of an N,N'-tetraalkylalkylene-diamine with a dichloroalkane, or of a secondary amine with anepihalohydrin, as described in British Patent No. 1 396 195.
Components B) and their reaction w;th N-methylol compounds D) to form precondensates are described in published British Patent - Application No.Z 084 597A, 76S~

- 5 - 15~-4~68 The reaction of cQmponent A) with formaldehyde or a precursor thereof (e.g. paraformaldehyde~ C) i5 preferably carried out in an aqueQus medium at a temperature from 20-60DC, preferably 40-50C
and at a pH~> 4, pre~erably bet~een 7 and 11. The formaldehyde may be added in the form of a concentrated (e.g. 37%) aqueous solution.
Preferred mole ratios of comp~nent A) to formaldehyde are in the range 1:2-1~6, based on the number of moles of amine originally present.
Suitable N-methylol derivatives (component D) are generally those N~methylol compounds which are known as cross-linking agents for cellulose fibres, and are used to impart a crease-resistant finish to cellulose fabrics. The compounds may contain free N-methylol ~roups ~N-CH20H, or these may be etherified. Preferred ether derivatives are the lower alkyl ethers having 1 to 4 carbon atoms in the alkyl groups.
Examples of suitable N-methylol comp~unds are N,N'-dimethylol-urea, N,N'-dimethylolurea dimPthyl ether, ~,N'-tetramethylolacetylene-diurea,.N,N'.dimethylolpropyleneurea, 4,5-dihydroxy-N,N'-dimethylol-ethyleneurea, 4,5-dihydroxy-N,N'-dimethylolethyleneurea dimethyl ether, N,N'-dimethylol 5-hydroxypropyleneurea, N,N'-dimethylol-4-met.hoxy-- 5,5-dimethylpropyleneurea, N,N'-dimethylolethyleneurea, methoxymethyl- melamine, dimethylolalkandioldiurethanes, N,N'-dimethylol-5-alkyl-hexahydro-1,3,5-triazin-2-ones, N,N'-dimethylolurone and dimethylol~
carbamates, These compounds can be used either alone or as mixtures.
Particularly suitable are hydrolysis-resistant reactive resin precursors, for example N,N'-dimethylol-495-dihydroxy- or 4,5-dimethoxy ethyleneurea, N,N'-dimethylol-4-methoxy-5,5-d;methyl-propyleneurea and N,N'-dimethylol c~rbamates, optionally in ether-ified form. Preferred ether forms are the methyl and ethyl ether 3~ derivativPs.
Suitable catalysts E) are described in British Patent Applicatiuns 2070006A and 2084597A.

7~

- 6 - 150-456~

Preferred catalysts are the nitrates, sulphates, chlorides and dihydr~gen orthophosphates of aluminium, magnesium or zinc, more preferably of magnesium, particularly magnesium chloride~
optionally together with an alkali metal sulphate9 particularly sodium sulphate.
When A) or B) is used with D) in the absence of formaldehyde C), the preferred weight ratios of A) or 3) to D? and catalyst E) lie in the range 1:0.625-22:0.025-6, preferably in the range 1:1.75-7.5:
0.25-1.5, based on the dry weight of ac~ive components. When N-methylol compound D) is present together with a precondensate of A) and formaldehyde C~, ;t is preferably present to the extent of 50-200% of the weight of A) ~ C). The amount of catalyst used is then preferably about 7.5-12.5X by weight of the dry weight of D).
The hydroxy ~roup-containing substrate is preferably a cellulosic fibrous substrate comprising natural or regenerated ce`llulose, particularly cotton and viscose rayon, alone or ~ixed with synthetic fibres. The substrate may be dyed or printed with basic dyestuffs by any conventional methods, for example dyeing may be carried out by exhaust methods or by padding followed by thenmo-fixation or cold dwell fixation.
When the fixing agent i5 to be used as an aftertreatment agent,it is applied to a substrate on which the dyeing or printing process including any necessary fixation step, has been completed.
The substrate may be dry, or may still be damp, provided that it is not so wet that it is incapable of further pick-up. The aftertreatment agent is applied tb the substrate in aqueous solution by dipping, spraying, foam application, padding or other conventional application techniques. The pre~erred appl;cation method ;s by padding at room temperature.
For application by padding, the quantities in which the product according to the invention is applied to the substrate depend largely upon the depth of the dyeing which is to be fixed. For dyeings of 1J1 standard depth on cotton the quantities used are 30-200 9/1 ~f the padding liquor when applied at a pick-up of 70-~nox

- 7 - 150-456 of the dry weight of the goods. Preferably the quantity is 70-140 9/
for co~ton, in order ~o obtain a wash-resistant improvement in wet fastness together with adequate crease resis~ance, and 100-200 9/1 for regenerated cellulose. For application to mixtures of cellulose fibres and synthetic fibres, the quantity to be applied is calculated on the basis of the cellulose content of the substrate.
The padding liquor may contain further auxiliaries such as stiffening agents, softening agents, agents to improve the rubbing or breaking strength, soil-release products, hydrophobic agents and others proYided that these are capable of forming stable aqueous solution when mixed with the product according to the invention.
When the fixing agent is applied simultaneously with the dyestuff, it may he added ~o the padding liquor in the same quantities as indicated above. When application is by exhaust, then ~hen a long liquor to goods ratio ( ~ 1û:1) is used the concentration of fixin~
agent in the liquor is preferably 1 10 9/l, more preferably 2-5 9/l, while for short liquor processes quantities of up to 20 or even lD0 9/1 may be necessary. (All ~leights are based on the dry weight of active components.) In simultaneous application from an exhaust Z bath, a subsequent heat curing step may not be necessary.
&enerally, however, there will be a final heat curing step such as is conventional for resin treatment based on compounds of type D). The substrate may for example be dried at 70-120C and finally crosslinked at a temperature of 130-180C for 2 to 8 minutes, or alternatively simultaneously dried and crosslinked by heat treat-ment at 100-200~C, preferably 140-180C for 5 seconds to 8 minutes depending on the temperature. A preferred process involves heating the padded substrate to 170-180C for 30 seconds to 1 minute.
By basic dyestuffs are meant those containing one or more groups selected from protonatable amino groups; cationic groups, e.g.
quaternary ammonium groups; an~ cycloîrnmonium groups, i.e. unsa~urated nitrogen-containing heterocyclic groups. Such heterocyclic groups may form part of the chromophoric system, or may be jo;ned to the .

8~7~

chrom~ph~re directly or via a bridging group. The basic dyestuffs may be mono- or polyazo dyes~ and may be metal-free or may be 1:1 or 1:2 complexes with metals, e.g. Cu, Cr, Co, ~i, Zn, Fe and Mn.
Basic dyes may also be of the anthraquinone, diphenyl- or triphenyl-methane, styryl, az~methine, hydrazone, nitro, phthalocyanine,naphthoquin~ne or quinophthalone types.
They arP predominantly dyestuffs which contain one or more protonatable amino or quaternary ammDnium groups bound directly or via a bridging group to a carbocyclic or heterocyclic aromatic nucleus.
Azo dyestuffs containing an acetoacetyl-alkyl-or -arylamide coupling component are also relevant. Protonatable groups include primary, secondary and tertiary amino groups, particularly alkylam;no groups, as well as cyclic amines such as morpholine, piperidine, pvrrolidine, piperazine or aziridine.
As a rule, basic dyestuffs ~re free of su~lphonic acid yroups, and are used primarily for dyeing and printing of cellulose, including cotton and paper, but also of polyacrylonitrile, leather or acid-modified polyamide or polyester. There are however basic dyestuffs which contain sulphonic acid groups as well as basic groups, for example basic phthalocyanine dyestuffs or, for example dyestuffs such as disclosed in the claims and examples of US Patent 4 273 7û7, British Patent Application No.208~734 A and European Patent Application No. 51 041. These dyestuffs may also be used in the process of the invention.
In principle any basic dyestuff~ includ;ng any of those listed in the Color Index under C~I. Basic Dyes, e.g. C.I. Basic Red 27, may be used in the process of this invention. Suitable basic dyestuffs, for example, include those described and claimed in any of the following:
German Patents 1 011 396, 1 014 519, 1 444 715, 1 444 716, 2 054 697;
German Published Applicati~ns (DOS) 2 543 009, 2 061 9~4 2 809 6Dl;

37~i54

- 9 150-456~
French Patents 1 495 2~2, 1 541 429, 1 563 323~ 2 000 639;
- British Patents 576 270, 1 088 611, 1 185 791, 1 273 748, 1 547 gO0, 1 568 767;
Belgian Patents 553 773, 633 447;
Swiss Patents 464 392, 53~ 773, 546 269, 547 337, 554 398, 554 399, 560 241, 563 430;
European Patent Application 41 040.
Preferred dyestuffs are those having a molecular weight (in cationic or protonated fonm without metal ions3 of from 400 to 1200, preferably 450 to 1000, more preferably 500-9509 and which give à degree of exhaustion (ratio between dyestuff exhausted and dyestuff originally in the dyeba~h) on merce~ised cotton in a standard depth dyeing from an electrolyte~free dyebath at a go~ds to liquor ratio of 1:2D, a~ter 90 minutes at the boil, of from SD to 100X, preferably 70-100~, more preferably 80-100%, particularly 90-100~. The /1 standard.depth is defined according tD DI~ standard 54 000 or IS0 standard RIOS/I, 1959, part 1.
Such conditions are met by the majority of the dyestuffs disclosed and claimed in German published patent applications 2 000 639 and ? 548 009, British Patents 576 270, 1 185 791 and 1 547 90D, ~S Patent 4 273 707, French Patent 1 495 232, European Patent ~pplications 41 040 and 51 041, and British Published Patent Application 2081734 A . Further suitable dyestuffs are those o~ formula:

. ~ - N = N - C - A - X - A - C - N = N - C

; / ~ \ ~ (Y Z)n C - A1 A2 C R3 ~3 ~ C ~ A2 Al :
_ :

in metal-free or in 2:1 meta11ised form .
. :

7~S~

- 10 - 150-4568 in which each Y independently is a direct bond or a (Cl 4) alkylene group or a bridging group of the formula - CO - NH - (CH2)m-- NH - C0 - (CH2) or - S02 - N - (CH2)m where the above substituents, marked with a star, are attached to the group Z by the carbon atom:
which is starred, in which m is 1, 2, 3 or 4 and R4 is hydrogen or Cl 4alky1, each Rl independently is an aromatic or a.heterocyclic diazo or coupling component group;
X is a bridging group or a direct bond, n is at least 2;
e~ch Z independently is -N(CH3)2, --N IC~3) 3 A~ CH3) 2 ' ~ A~ N ICH3~ 2 ~3 CH2-CH2-OH ~cE~2)m ~H2 H (CH3)p N (CH3) 2 A~3 or ~ CH3~ 2 A
(1H2) m~N~CH3 6CH23 m_N lCH3~ 2 in which p is 09 1 or 2 and m is as defined above and A~3 is a convent;onal non-chromophoric anion, and either 1) each A is - C - NH ~ (a) and ~76S4~

- 11 - 150-4568 each R3 independently is (Cl_4)alkyl;
or 2) each A together with R3 and the ethylene group to which A and R3 are attached, forms the group (b) ~ (b) and the aromatic rings in groups (a) and (b) independently, can be substituted by one or two groups selected from halogen, (Cl 4)alkyl and (Cl 4)alkoxy and Al and A2, for compounds of formula I in metal complex form, form the group -O-Me-O- where Me is copper, cobalt, iron, nickel, manganese or ~inc, and for metal-free compounds each A2 independently is hydrogen, C1_4alkoxy or -OH
and Al is -OH
with the proviso that, when the compound of formula I is in metal-free form, each A and R3 form the group b) above and Rl is a l-phenyl pyrazole, the phenyl group of which is substituted by one group -Y-Z where Y and Z are as defined above.
In this published patent application, the dyestuffs of formulae III, IV, V and VI, together with the Examples, are of particular importance.
Dyeings and print;ngs with basic dyestuffs often show inade-quate wash fastness. The dyestuff which is bound to the surface of the cellulose fibres is largely removed from the fibres by repeated washings, and bleeding of the dyestuff into the wash liquid can cause partial readsorption onto undyed cellulose material.
There have been many attempts to overcome these disadvantag~s, ~IL157~S9L

but the problem with all previously used methods is that although improved fastness is indeed attained, the results are only temporary.

Treatment of dyed or printed cellulose substrates according to the invention gives improved wet fastness properties, particularly fastness to ~Yashing, including washing under alkaline or acid conditions at temperatures of 40-90C, particularly at 60C and above. For example, repeated 30 minute ~0C washings with a wash liquor containing 5 g/l soap and 2 9/1 soda at a goDds to 1 j9UDr 1Q ratio of 1:50 are readily withstood.
This improvement in wet fastness is obtained without loss of light fastness; indeed light fastness properties may actually be improved.
At the same time a resin f;nish is imparted to the cellulose fibres which gives reduced swelling in aqueous or alkaline media and hence more rapid drying, improved dimensional stability and higher crease resistance.
The following Examples, in wh;ch a11 parts and percentages are by ~leight and all temperatures in degrees Centigrade, illustrate the invention.

.. ,,' Preparation of fixing agents A) 1D3 Parts diethylene triamine and 84 parts DCDA are heated at 110~.
As so~n as this temperature is reached an exothermic reaction takes place and amm~nia escapes. The temperature is slowly raised to 16D~
and kept there for ab~ut 6 hours until no more amm~nia is released.
The amount of ammonia is about 34 parts. The liquid reaction product is pou~ed onto a flat metal pan and ground to a powder after it is col ~ . ' 69.3 Parts of this powder is added slowly to 81 parts water lû at 35 stirring const~ntly. Then 53.4 parts of 44.6% sulphuric acid are added simultaneously with 45.0 parts of ice so that the temperature does not rise above 4B-50. Afterwards a further 69.3 parts of the powder are added, and once again neutralized with 78.8 parts of 44.6% sulphuric acid and 45.0 parts of ice s~ that the temperature stays under 50~. The yellow solution which has a pH of 7.5 i~ then spray-dried, to give a white powder.
18.3 Parts DCDA and 362.6 parts of a 50% soluti~n of dimethyl-~ldihydroxyethyleneurea are stirred together and diluted w;th 147.2 parts water. 54.3 Parts magnesium chloride hexahydrate are added, 2~ then 72.6 parts of the above spray dried product, and the mixture is stirred at 30 until all solids have dissolved to give a soluti~n of approx. pH 4.~. The mixture is then heated to 70 over 45 minutes, held for 1~/2 hours at 70-74~ and coolPd to g;ve a clear stable yellow solution.
B)~ he reaction product of epichlorohydrin an~ iimethylam;ne is reacted with dimethyl~ldihydroxyethyleneurea and magnesîum chloride as described in Examples 1 3 of Br;tish Patent Application No.
2 084 ~97.
E) The reaction product of 1,2-bis(dimethylamino)ethane and 2,2'-dichlor~diethyl ether is reacted w;th dimethylold;hydroxyethylene-urea and magnesium chloride as described in Example 4 of British Patent Applicatisn N~. 2 ~84 597.

... - ~ . , ~ . . .
~. ~ ., . ,. ; . . . . . . . . .

765~

F) 103 Parts diethylene triamine and 84 parts DCDA are heated to 110. At this temperature an exothermic reaction ~egins and ammonia is evolved. The temperature is allowed to rise to 150D, then held at 160 for 6 hours to complete the reaction. Finally the reaction product is cooled until it solidifies, then pulver-ized.
156 Parts of this powder are suspended in 400 parts by volume of water and the mixture warmed to 80-90; the powder gradually dissolves, to gi~e a solution having a pH value of about 11. A~ter cooling ~o 50, 343 parts of a 35% aqueous formaldehyde solution are added dropwise. The reaction mixture is stirred for a fur~her 2 hours at 50 then cooled to room temperature and neutralized with hydrochloric acid, to give g3D
parts of a clear yellow solution containing about 30% dry weight of a precondensate of diethylenetriaminejDCDA with formaldehyde.
G)-I~ The preparation of product F) is repeated, but with the pH
adjusted by addition of hydrochloPic acid to 8, 6 or 4 respectively, before addition of formaldehyde.
J)~K~ The solid reaction product of diethylene triamine and DCDA is ?0~ prepared as described above under F). Two lots of 90 parts of this powder are each dissolved in 330 parts by volume of water and reacted at pH 11 with 227 parts and 3~0 parts respectively of 35X
aqueous forinaldehyde.
Examele 1 .
A ootton fabric is dyed by conventional methods with the dyestuff of Example 42 of British Patent Application 2 076 4?13 in metal-free form. The dyed fabric is padded with a solution eon-taining 100 g/l of fixing agent A), and squeezed out to a pickup of BOX. The impregnated fabric is shock dried on a tens;on frame at 175-180 s~ch that the condensation time after drying is apprDxi-nately 30-45 seconds.
The resulting yellow dye;ng shows good wet-, wash- and light-~,. ., .; ~ - , - 15 - 150-456~

fastness, which is retained after repeated 60 washings~ and even after washing at the bDil. At the same time the crease resistance is improved and the s~elling of the cellulose fibres is reduced.
Examples 2-5 Example 1 is repeated using cotton fabric dyed with the phthalocyanine dyestuff of British Patent l 185 791, and aftertreating with fixing agents B)-E). Dyeings with good fastness properties are obtained.
Example 6 lD A cotton fabric is dyed with the dyestuff of Example 68 of European Patent Application 51 041, rinsed and dried. The dyed fabric is padded with a liquor containing 30 9/l fixing agent F) (as lOOb active material), 50 gJl dimethyloldihydroxyethyleneurea and 15 9~1 MgCl2 6H20, and adjusted to pH 4 with acetic acid; then squeezed nut to 80~ pickup. The fabric is shock dried at 180 on a tension frame, ~he condensation time being about 30-45 seconds.
The fixed dyeing has excellent wash- and light-fastness.
Examples 7-lO
Example 6 is repeated using fixing agents G)-K~. Similar good results are obtained.
Example ll _ _ A cotton fabric is dyed with the dyestuff of Example 80 of European Patent Application 51 041, rinsed and dried. The procedure of Example 6 is repeated on this dyeing, except that the padding liquor contains 50 g/l of fixing agent F)~ 15 g/l MgCl~ 6H20 and no N-methylol compound. The fixed dyeing has excellent wash- and liyht fastness.
Example 12 . . .
The dyed fabric of Example 11 is padded at 80X pickup with a solution containing 7D g/l (as 100~ active substance) of fixing 6~i~

agent F) and 15 g/l MgC12 6H20. The i~pregnated fabric is dried to 2-4~ residual moisture then condensed for 60 seconds at 180.
G~od fastness properties are obtained.

Example 13 . _ .
A cotton fabric is dyed by the exhaust process from an aqueous bath containing the dyestuff of Exarnple 1 of British Patent 1 547 90D, 4D 9/1 of fixing agent A and 0.25 9/1 80~ acetic acid. Dyeing is carried out at the boil for approx. 90 minutes, until a 2~ dyeing i5 obtained. The fabric is rinsed and dried, giving a dyeing of improved wash and light fastness.
Example 14 A 100~ rayon fabric is dyed according to Example 13, but using 80 9/l of ~ixing agent B inste`ad of 40 9/1 of A, a 3% dyeing being obtained. The dyed fabric is rinsed and dried to give a dyeing of improved wash and light fastness.

.:

'. :
-- . .

, '' ' -

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for producing fast dyeings and printings on a hydroxy group-containing substrate by applying a basic dyestuff to the substrate and treating the substrate either subsequently or simultaneously with a fixing agent comprising a precondensate or mixture of either A) the product of reacting a mono- or polyfunctional primary or secondary amine with cyanamide, dicyandiamide (DCDA), guanidine or biguanidine; whereby up to 50 mole % of the cyanamide, DCDA, guanidine or biguanide may be replaced with a dicarboxylic acid or a mono- or di-ester thereof, said product A) containing reactive hydrogen atoms bound to nitrogen, or B) a quaternary polyalkylene polyamine having recurring units of formula II' II' where R1 is C1-4alkyl, m' is 20-30; and A? is an anion with C) formaldehyde or a formaldehyde precursor and/or D) an N-methylol derivative of a urea, melamine, guanamine, triazinone, urone, carbamate or acid amide.

2. A process according to Claim 1 in which the substrate is treated with the fixing agent subseqently to the dyeing or printing step.

3. A process according to Claim 1 in which the fixing agent comprises a precondensate or mixture of A) with D), B) with D), A) with C), or A) with C) together with D).

4. A process according to Claim 1 in which the fixing agent also contains E) a catalyst for the cross-linking of N-methylol compounds of the type D) above.

5. A process according to Claim 1 in which component A) is the reaction product of a polyfunctional amine of formula I
I
in which each R independently is hydrogen or a C1-10alkyl group unsubstituted or monosubstituted with hydroxy, C1-4alkoxy or cyano, n is a number from 0 to 100 Z, or each Z independently when n > 0, is C1-4alkylene or hydroxyalkylene and X, or each X independently when n > 1, is -O-, -S- or -NR- where R is as defined above, provided that the amine of formula I contains at least one reactive -NH- or -NH2 group, with cyanamide, DCDA, guanidine or biguanidine.

6. A process according to Claim 5 in which component A) is the reaction product of DCDA with diethylene triamine or triethylene tetramine.

7. A process according to Claim 1 in which component D) is selected from N,N'-dimethylol-4,5-dihydroxy- or 4,5-dimethoxyethylene-urea, N,N'-dimethylol-4-methoxy-5,5-dimethylpropyleneurea, N,N'-diemthylol carbamates and their methyl and ethyl ethers.

8. A process according to Claim 4 in which catalyst E) is magnesium chloride.

9. A process according to Claim 3 in which the fixing agent comprises a precondensate of components A) and D).

10. A process according to Claim 9 in which the precondensate is formed in the presence of catalyst E).

11. A process according to Claim 10 in which component A) is the reaction product of diethylene triamine with DCDA, component D) is N,N'-dimethyloldihydroxyethylene urea and component E) is magnesium chloride.

12. A process according to Claim 3 in which the fixing agent comprises a precondensate of components B) and D).

13. A process according to Claim 12 in which the precondensate is formed in the presence of catalyst E).

14. A process according to Claim 4 in which the weight ratios of A) or B) to D) and catalyst E) lie in the range 1:0.625-22:0.625-6.

15. A process according to Claim 3 in which the fixing agent comprises a precondensate of components A) and C).

16. A process according to Claim 15 in which the mole ratio of component A) to formaldehyde C) is in the range 1:2-6, based on the number of moles of amine originally present in A).

17. A process according to Claim 1 in which the basic dyestuff has a molecular weight (in cationic or protonated form without metal ions) of from 400 to 1200 and gives a degree of exhaustion on mer-cerised cotton in a 1/1 standard depth dyeing from an electrolyte-free dyebath at a goods to liquor ratio of 1:20, after 90 minutes at the boil, of from 50-100%.

18. A process according to Claim 1 in which the substrate is subjected to a final heat-curing step.

19. A dyebath containing a basic dyestuff and from 1-100 g/1 of a fixing agent as defined in Claim 1.