US2940812A - New textile treatment process - Google Patents

Description

United States Patent 2,940,812 Patented June 14, 1.960

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2,940,812 NEW TEXTILE rnnxrrmnr PROCESS Ronald Leonard Denyer and Harry Rose Hadfield, Manchester, England, assignors to Imperial Chemical Industries, Limited, London, England, a corporation of Great Britain No Drawing. Filed Nov. 18, 1957, Ser. No. 696,966 Claims priority, application Great Britain Nov. 21, 19 57 Claims. (Cl. 829) invention relates to a textile treatment process and more particularly it relates to a process for the colouration of textile materials comprising protein or artificial fibres in shades having extremely good -fastness to wet treatments.

It 'has previously been proposed to improve the fastness to wet treatments of textile materials which have been dyed with a dyestuff containing at least one reactive hydrogen atom, by treating the dyed textile material with a heterocyclic substance containing in the heterocyclic ring at least one grouping of the formula In particular there has been described the treatment of a -dyed textile material with an aqueous emulsion of a solution of cyanuric chloride or 2:4:6-trichloroquinazoline in benzene and carbon tetrachloride.

The previously described processes however are-difiicult to apply in practice because of the toxic hazard involved in the use of these organic solvents. Furthermore the fastness to wet treatment of textile materials so treated is usually uneven.

It has now been found that the textile materials hereinafter defined, especially those made from protein or synthetic protein fibres, may be coloured satisfactorily in shades having a high fastness to wet treatments when there are used in the colouration process dyestufis containing a reactive amino group as hereinafter defined and the treatment with the dyestuff is carried out in conjunction with a treatment with an aqueous solution of a water soluble heterocyclic compound containing at least one halogenotriazine ring, or the like, thus eliminating the toxic hazards of the previously described processes and giving a uniform improvement in fastness to wet treatments.

For the purpose of this invention, a reactive amino group is one which contains a hydrogen atom which is readily replaced 'by treating the dyestufi with cyanuric chloride at C. in aqueous medium.

Suitable dyestuffs include, for example, Naphthalene Dark Green A (Colour Index No. 20495), 'Solochrome Yellow 2GN (Colour Index No. 14045), Duranol Brillia'nt Blue CB (Colour Index No. 64500), 1:8-dihydroxy- 4:5-diaminoanthraquinone-2:7-disulphonic acid, Solochrome Brown EB (Colour Index No. 20110), Chlorazol Black BH (Colour Index No. 22590), Chlorazol Brown MP "(Colour Index No. 22311), Chlorazol'Sky Blue FF (Colour Index No. 24410), Ultralan Orange R (Colour Index No. 18870), p-aminophenylazosalicyclic acid and :the chromium complex of 3:5-dinitro-2:4'-diamino-2- hydroxyazobenzened'-sulphonic acid.

The Colour Index numbers are those given in the second edition of the Colour Index, published jointly in l957fby the Society of Dyers and Colourists and the American Association of Textile Chemists and Colorists.

The textile materials treated in the process of the invention are those obtained from natural protein and artifically-produced fibres, for example wool, silk, ethers and me'rcapto compounds esters of cellulose, especially cellulose acetate, polyamides for example nylon, polyacrylonitrile and its co-polymers and polyvinylalcohol.

According to the present invention, therefore, there is provided a process for the treatment of textile materials as hereinbefore defined which comprises treating the textile material with an aqueous solution of a water soluble heterocyclic compound containing at least once the grouping of the formula -N=C(halogen) in the ring, and with a dyestufi containing at least one reactive amino group as hereinbefore defined.

Suitable water soluble heterocyclic compounds for use in the above process may be obtained for example by interaction of a poly-halogeno heterocyclic compound such as a trihalogenopyrimidine or a cyanuric halide, especially cyanuric chloride, with a compound which contains at least one water-solubilising group, for example sulphonic acid, carboxylic acid, or sulphate or phosphate ester group (or salts thereof) and which also contains at least one grouping, for example hydroxyl, thiol or amino, known to be capable of interaction with the halogen 'of the heterocyclic compound.

Especially suitable compounds for use in the process of the invention may be obtained by interaction of a cyanuric halide, preferably the chloride, with a primary or secondary amine containing at least one water-solubilising group, under conditions such that at least one halogen atom or preferably two halogen atoms, remain attached to the triazine ring. Suitable conditions for such reactions are well known from the literature.

Thus, there "may be used the primary and secondary condensation products of cyanuric chloride and such amines as 1-nap'hthylamine-5- and -7-sulphonic acids, 2'- naphthylamine-6- and -7-sulphonic acids, 2-methylaminonaphthalene-6-sulphonic acid, benzidine disulphonic acid, p-aminophenyl-beta-hydroxy ethyl ether sulphuric ester, 2-naphthylamine-l:6-, -4:8, -5:7- and -6:8-disulphonic acids, l-naphthylamine-4:6:S-trisulphonic acid, sulphanilic acid, 3-amino-5-sulpho-2-hydroxybenzoic acid, pphenylene diamine sulphonic acid, orthanilic acid, metanilic acid, m-phenylene diamine-4-sulphonic acid, amino methane phosphoric acid, m-aminophenyl trimethylammonium bromide, p-aminobenzoic acid, taurine, N-methylta'urine, N-phenylglycine, 4:4-diaminostilbene-2:2'-disulphonic acid, and 2-amino-8-naphthol-6-sulphonic acid. There may also be used the primary and secondary condensation products of cyanun'c chlorideand hydroxy and especially 2-thionaphthol-6-sulphonic acid. The following list names typical examples of heterocyclic compounds which may be used:

'4- (2 4-dichloro-'s-triazinylamino)benzene sulphonic acid, *3-(2'2'4' dichloro -s triazinylamino)-2-hydroxy-5-sulphobenz'oic'acid,

- usedf techniques.

, 2-chloro-4 6-di(6-sulpho-2'-naphthoxyj -s-triazine,

2-chloro-4:6-di(carboxymethylthio)s-triazine, 2-chloro-4: 6-di(4-sulphoanilino) -s-triazine, 2-chloro-4:6-di(6'-sulpho2-naphthylthio) -s-triazine,

2-(2-chloro 4-methoxy-6'-triazinylamino)naphthalene-6:

' 8-dis'ulphonic acid,

2-(2-chloro-4'-anilino 6 triazinylamino)naphthalene- 4:8-disulphonic acid, and in particular, .6-(2'z4' dichloro s triazinylamino) naphthalene-Z-sulphonicacid, j V V 2 2 4-,bis(2' :4-dichloro-s-triazinylamino)benzene sulphonic 2 -bis (2' 5 '-dichloro-s-triazinylamino)benzene sulphonic acid. 7

starting materials just mentioned. There may also be 3-(2':4'-dichloro-s-triazinylammo)benzene sulphonic acid, 7

ethylene oxide with fatty alcohols and phenols, sulphonated fatty alcohols and sulphonated oils, solution aids such as urea and thiodiglycol and thickening agents such as gum arabic, starch, gum tragacanth and preferably sodium alginate. I

When the dyestutf or heterocyclic compound used in the process contains a metal-complex forming system such as a o-hydroxy carboxylic acid or a o:o-diliydroxyazobenz ene grouping, the new process may advantageously incorporate a treatment with a metal-yielding agent such as copper sulphate, cobalt sulphate, nickel sulphate, ferrous sulphate or chromium acetate, in order toiirnprove the fastness to light of the resultant colourations. The (2':4-dichloro-s-triazinyl)derivative of 3- amino-2-hydroxy-5-sulphobenzoic acid is particularly useful so that this treatment may be carried out.

The textile materials coloured by the new process are advantageously scouredin soap or detergent solutions, in order to improve still further the fastness to washing. The'process of the invention enables protein,.and artificial textile materi lsto be coloured in a wide variety of shades having far greater fastness to washing than the shades obtainable from the same dyestuffs by the commonly-used techniques.

However the heterocyclic compounds are not limited in use to the colourless compounds obtained from the used a coloured heterocyclic compound containing'two groups of the type.-N=C(halogen)- thereby obtaining heavy secondary or tertiary shades having good fastness .to washing. Such shades with good washing fastness cannot .at'present be easily obtained with dyestufis at present commercially available which either contain an-am'ino group or one or more groups of the type +N=C(halogen). The'particular shades of dyestufi and. coloured heterocyclic compound used should be chosen in accordance with the commonly accepted methods' of mixingdyestufis having primary or secondary shades in order to obtain secondary or tertiary shades.

,Suitable coloured heterocyclic compounds for example of the azo, anthraquinone, nitro and phthalocyanine series are described in British specifications Nos. 209,723,

298,484, 772,030, 774,925, 775,308, 780,591, 781,930, 785,120, and 785,222; and in Belgian specifications Nos. 552,910, 556,092, 557,162 and 558,390.

When it is desired to colour the entire surface of the material, the dyestufi, especially if it is a dyestufl having .poor affinity for'the material being coloured, such as a disperse dyestufi on wool or an acid dyestufi on cellulose acetate, may be applied by padding the textile material in an aqueous solution or suspensionof the dyestufi. Dyestuffs of the type commonly used for dyeing the textile material may be applied by the commonly- For the local colouration of the textile material the dyestufi may be applied from a thickened a printing paste. V

The water-soluble heterocyclic compound may be applied by padding the textile material in an aqueous solution of the heterocyclic compound'in a pretreatment 'or after-treatment step and may be added'to the'dyebath or printing paste containing the dyestuif. The pretreatment or aftertreatment step may alternatively comprise a treatment in a neutral or slightly acid solution of the heterocyclic compound at a temperature 'of between 50 and100" C. for a period of between 10.and ''minutes.

' r The solutions, suspensions and printing :pastes containing dyestufi and/ or heterocyclic compound may also contain the adjuvants commonly used in dyeing and pad-. ding solutions and suspensions and textile printing pastes. Such adjuvants include for example, migration inhibitors sucha's ethers'ofcellulose, sodium chloride and .sodium sulphate, wetting agents suchascondensates of "or; nylon isused in place ofthewool. a

The invention is illustrated but not limited by the Example 1 100 parts of nylon fabric are treated for 1 hourat 90 C. in 4,000 parts of water containing 5 parts of sodium 2-(2':4-dichloro-s-triazinylamino-)naphthalene- 6-sulphonate and 4 parts of aqueous formic acid. The fabric is then rinsed in cold water and treated for 30 minutes at 60 C. in 4,000 parts of water containing 2 parts of sodium carbonate, the fabric is' then treated 'for 5 minutes at 60 C. in 4,000 parts of water containing 8 parts of soap and then rinsed 'in'cold water and dried. A printing paste is made up of the following composition:

for 30 minutes at atmospheric pressure, rinsed in water 'andwashed for 10. minutes at 60 C. in 4,000 parts of water containing 8 parts of soap, and dried.

- The blue print obtained possesses higher fastness to washing than a print obtained using the above print paste on untreated nylon, r j

Example 2' e A printing paste is'made by mixing together 10 parts of Duranol Brilliant Blue CB200 paste fine, 10 parts of urea and 20 parts of water, then adding a'solution of 1 'part of sodium 2-(2':4'-dichloro-s-triazinylamino)naphthalene-6-sulphonatein 24 parts of water and finally 35 parts of a 5% solution of sodium alginate.

The printing pastevis applied to wool and the Wool is then dried, steamed for 1 0 minutes,-rinsed in cold water, treated for 10 minutes at 60- C. in a 0.3% aqueous solution of a detergent mixture'consisting of sulphated fatty alcohol and alkyl phenols condensed with ethylene oxide, rinsed again and dried. I" v i Blue prints areobtained which are strong'er than those obtained from a printing paste from whichthe sodium 2- (2' 4' -dichlorotriazinylamino) naphthalene-fi-sulphonate hasbeenomitted.

Similar results are obtained if chlorinated wool, silk Example 3 Silk cloth is padded in a 5% aqueous solution of sodium 2-(2':4-dichloro-satriaziny1amino)naphthalene-6- sulphonate and the cloth is squeezed through rollers to remove excess liquid and is then dried. The cloth is then padded in a 0.5% aqueous suspension of Duranol Brilliant Blue CB and squeezed and dried. It is then acidrsteamed (suspended in a vessel containing steam and the vapour of acetic acid) for 15 minutes.

The blue dyeing so obtained is superior in washing fastness to a dyeing of similar depth of Duranol Brilliant Blue CB on silk which has not had the pretreatment step described above.

A similar effect is obtained if nylon cloth or acetate rayon cloth is used in place of the silk.

Example 4 If in the method described in Example 3, the sodium 2 (2'z4 dichloro s triazinylamino)naphthalene 6 sulphonate is replaced by the dyestufif described in Example 1 of United Kingdom specification No. 774,925, the silk and nylon cloths are dyed green shades having very good fastness to washing.

Example 5 20 parts of silk are immersed in 1200 parts of water containing 1 part of sodium 2 (2.:4' dichloro s triazinylaminohaphthalene 6 sulphonate, 1 part of Durangl Brilliant Blue CB and 0.6 part of oleyl sodium sulp ate.

The bath is heated to 65 C. and held at this temperature for 20 minutes. 0.1 part of 85 formic acid is added and the bath is heated to 95 C. 0.7 part of 85% formic acid is added and the treatment is continued for 1 hour at 95 C.

The fastness to washing of the blue dyeing so obtained is much superior to one carried out without the addition of the sodium 2 (2'z4' dichloro s tn'azinylamino)- naphthalene 6 sulphonate.

Nylon can be dyed in similar manner, except that the bath is first heated to 85 C. instead of 65 C. A similar efiect is obtained if the formic acid is added to the bath before heating. A weaker dyeing is obtained, but the fastness to washing is again superior to a dyeing carried out without adding the sodium 2 (2'14' dichloro s triazinylamino)naphthalene 6 sulphonate.

Example 6 If the sodium 2 (2'z4 dichloro s triazinylamino)- naphthalene 6 sulphonate used in Example 5 is replaced by the dyestufi described in Example 1 of United Kingdom specification No. 774,925, the cloth, silk or nylon as the case may be, is dyed a green shade of very good fastness to washing.

Example 7 20 parts of cellulose acetate are immersed in 1200 parts of water containing 1 part of 4 (2'z4 dichloro s triazinylamino)phenoxy beta ethyl sodium sulphate, 1 part of Duranol Brilliant Blue CB and 0.6 part of oleyl sodium sulphate and the bath is heated to 85 C. After 30 minutes, 8 parts of sodium chloride are added and the treatment is continued for 45 minutes.

A pale blue dyeing is obtained, having superior fastness to Washing and somewhat redder in shade than a dyeing carried out Without the addition of the 4 (2':4 dichloro s triazinylamino)phenoxy beta ethyl sodium sulphate.

If in place of this compound there is used the dyestufr' described in Example 1 of United Kingdom specification No. 774,925 a similar improvement in washing fastness is obtained.

Example 8 A printing paste is made up by mixing together 10 parts of Duranol Brilliant Blue CB, 42 parts of water, 40 parts of a 5% aqueous solution of sodium alginate, 5 parts of 50% aqueous ethanol, 2 parts of a wetting agent consisting of an aqueous emulsion of sulphonated sperm oil and pine oil, and 1 part of sodium m-nitrobenzene sulphonate.

This paste is applied to continuous filament nylon twill fabric by roller and the print is dried and steamed for 30 minutes. The fabric is padded in a solution containing 5% of sodium 2 (2':4' dichloro s triazinylamino)- naphthalene 6 sulphonate and 2% of the wetting agent mentioned above, squeezed between rollers so that it retains only its own weight of solution, and is then dried at 100 C. by contact with the surface of a steam-heated drum.

The nylon is then steamed for 10 minutes, rinsed, washed, and rinsed again and dried as described in Example 1. The blue print obtained has better fastness to washing than a print which has not been aftertreated in the sodium 2 (2:4' dichloro s triazinylamino)naph'- thalene 6 sulphonate. I

If cellulose acetate sateen fabric is used in place of the nylon, a similar efiect is obtained.

Example 9 100 parts of nylon are immersed in 4000 parts of water at 95 C, containing 4 parts of cetyl sodium sulphate and 2 parts of tetraminoanthraquinone. After 30 minutes the nylon is rinsed and treated for 30 minutes in 4000 parts of water at 95 C. containing 4 parts of formic acid and 2 parts of the product obtained by interacts equimoleclflar propor n o sodium p y m fi-sulphonate and cyanuric chloride. The nylon is then soaped for 5 minutes at 85 C. in a bath containing an alkaline detergent. A blue dyeing of excellent Wet fastness is obtained.

If the soaping treatment is omitted in the above example, a similar result is obtained.

Example 10 The process described in Example 9 is repeated, using 1 part of the dye formed by coupling diazotised p-nitroaniline with aniline in place of the tetraminoanthraquinone. A reddish yellow dyeing of excellent wet fastness results.

Other dyestuffs which may be used in place of the tetraminoanthraquinone are 4 amino 4' dimethylaminoazobenzene, 4 (4' aminophenylazo 1 amino-naphthalene, and 4:4 diamino 5 dimethoxy 2 methylazobenzene (all of which give yellow shades), 1:4 diamino 2 methoxyanthraquinone (which gives a red shade), 5 nitro 1:4 diaminoanthraquinone, 1:4:5 triaminoanthraquinone and 1:4 diaminoanthraquinone (all of which give violet shades), and 1:5 diamino 4:8 di- (methylaminoa) anthraquinone and 1:8 dihydroxy 4:5 di (beta hydroxyethylamino )anthraquinone (both of which give blue shades).

Example 11 The process described in Example 9 is repeated, using, in place of the product obtained by interacting equimolecular proportions of sodium 2 naphthylamine 6 sulphonate and cyanuric chloride, an equal weight of the product obtained by interacting equimolecular proportions of sodium benzidine mono-sulphonate and cyanuric chloride. A blue dyeingof excellent wet fastness results.

Example 12 Example 13 The process described in Example 9 is repeated, using,

- lene 4:8 disulphonate. fastness results.

7 wastness results;

in place of the product obtained by interactingequimolecular proportions of sodium 2. naphthylamine 6 sulphonate and cyanuric chloride, an equal weight of the product obtained by interacting equimolecular propore tions of cyanuric chloride and disodium 2 aminonaphtha- A blue dyeing of excellent wet Example. 14

The process described in Example 9 is repeated, but replacing the 4 parts of formic acid used therein by 3 parts of sulphuric acid. A blue dyeing of excellent wet fastness results. I

Example 15 V a The process described in Example 9 is repeated but the nylonis replaced by an equal weightfof a modified polyacrylonitrile fabric. 'A blue dyeing of excellent wet I 'd'roxy-S-srilphobenzoic acid in place of the productobtained by interacting equimolecular proportions-jot sodium 2-naphthylamine 6-sulphonate and cyanuric chloride. The dyed fabric has a light fastness of 5 measured on the standard scale adopted by the Society of Dyers and Colourists. V a V The nylon is then treated at 95 C. for 1 hour in a bath containing 7 partsof the copper complex saltl The light fastness is now found to be 6 measured on the standard scale adopted bythe Society of Dyers and Colourists. 7

Similarly, nylon dyed with 4-nitro-4-aminoazobenzene,

aftertreated as described above has a light fastness of 4 before treatment with the complex copper salt and a light fastness of 5 after the treatment.

Example 19 fThe process described in Example 9 is repeated using, .in place of the product obtained by interacting equimolec' ular proportions of sodium 2-naphthylamine-6=sulphonate and cyanuric chloride, an equal weight of l-chloro-3:5- di carboxymethylthio) es-triazine. A blue dyeing of excellent wet fastness is obtained.

' 9 Example 20 Silk fabric is padded through an aqueous solution containing 5% of sodium-Z-(Z':4-dich1oro-s-triaziny1- ,amino)naphthalene-6-sulphonate and 0.l% of a wetting agent obtained by the poly-condensation of ethylene oxide with an alkyl phenol, in which 0.25% of 4-amino-4-n;itroazobenzene is dispersed. 7

The fabric is then steamed for 15 minutes at atmospheric pressure, washed for'5 minutes at 85 C. in a 0.'5%"aqueous solutionv of thewetting agentmentioned.

in the first paragraph, rinsed in water dried. A fast-yellow-dyeing isobtained. "whatwe claimisz. '1 V- l. A process for the coloration of textile material made'from fibers of the class consisting of protein and artificially-produced fibers, which comprises treatingsaid textile material with an aqueous solution of a heterocyclic compound selected from the class consisting of dihalogeno-triazine anddihalogeno pyrimidine water-soluble compounds and with a dyestuff having an amino grouphydrogen atom which can be readily replacedby treatmerit with cyanuric chloride aqueous medium at'20 C.

2. Process as claimed in claim 1 characterised in that the heterocyclic compound contains a dihalogeno-striazine group. i J

3. Process as claimed in clairn' 1 characterised in that the heterocyclic compound contains a dichloros-triazine group.

- 4. Process as claimed in claim 1 characterised in that the reactive amino group present' in said dyestufi contains two hydrogen atoms attached to the'nitrog en atom.

5. Process as claimed in claim, 1. characterised in that the treatment of the textilematerial with theheterocyclic compound and dyestuif is'carriedfputby padding the i textile-material in an aqueous solution of the heterocyclic icompou'nd also containing the dyestuflfgandithe. treated textile material is then subjected to an elevated temperature. V I

. 6. Processas claimed in claim 1 characterised in that the treatment of the textile material with the heterocyclic compound and dyestuff is carried out by printing the tex tile material with 'a single printing paste containing the dyestufi and the heterocyclic compound, and the printed textile material isthen subjected to an elevated tempera- 7. Process as claimed in claim 1 characterised in'that the textile material is first treated with an aqueous solution of the heterocyclic compoundand dried, thedried textile material is printedwith a printing paste containing the dyestuff and the textile material is thereafter subjected to an elevated temperature; i Y i l 8, Process as claimed in claim 1 characterised in that the textile material is first treated with an aqueous solution of the heterocyclic compound and dried, the dried textile'material is padded in'anaqueous medium containing the dyestuff and dried and thettextile material is then subjected to an elevated temperature.

9. Process as claimed in cl 7 1 characterised that the textile material is first dyed'andthe dyed textile material is treated with an aqueous solution of the heterocyclic compound. 7

10. Process as claimed'in'claim 1 characterised in that the dyestuifused contains'a metal-complexforming system and the process incorporates a treatment with a metalyielding agent, l j i References Cited inthefileiof this patent UNITED STATESPATENTS Zollinger Ian. 21, 1958 FOREIGN PATENTS 209,723 Great Britain Mar. 23, 1925

Claims (1)

1. A PROCESS FOR THE COLORATION OF TEXTILE MATERIAL MADE FROM FIBERS OF THE CLASS CONSISTING OF PROTEIN AND ARTIFICIALLY-PRODUCED FIBERS, WHICH COMPRISES TREATING SAID TEXTILE MATERIAL WITH AN AQUEOUS SOLUTION OF A HETEROCYCLIC COMPOUND SELECTED FROM THE CLASS CONSISTING OF DIHALOGENO-TRIAZINE AND DIHALOGENO-PYRIMIDINE WATER-SOLUBLE COMPOUNDS AND WITH A DYESTUFF HAVING AN AMINO GROUPHYDROGEN ATOM WHICH CAN BE READILY REPLACED BY TREATMENT WITH CYANURIC CHLORIDE AQUEOUS MEDIUM AT 20*C.