US2955900A

US2955900A - New colouring process

Info

Publication number: US2955900A
Application number: US633387A
Authority: US
Inventors: Dawson Timothy Leslie
Original assignee: Imperial Chemical Industries Ltd
Current assignee: Imperial Chemical Industries Ltd
Priority date: 1957-01-10
Filing date: 1957-01-10
Publication date: 1960-10-11
Anticipated expiration: 1977-10-11

Description

United States Patent O NEW COLOURING PROCESS Timothy Leslie Dawson, Manchester, England, assignor to Imperial Chemical Industries Limited, London, England, a corporation of Great Britain N Drawing. Filed Jan. 10, 1957, Ser. No. 633,387

Claims. (Cl. 8-31) This invention relates to a new colouring process, and more particularly it relates to a new colouring process suitable for the application of basic dyestufis and dyestuffs containing ternary or quaternary salt groups.

These latter dyestulfs may be applied to textile materials by conventional dyeing methods and then rendered insoluble by treatment of the dyed textile material with alkali to give dyeings having good light and wash-fastness. When applied in this way the aflinities of the dyestufis for cellulosic materials are not entirely satisfactory and deep shades are not readily obtainable. It is known that deep shades are readily obtainable on cellulosic materials by impregnating with the dye-liquor and then dry ing before treating with alkali, but this method sutfers from the defect that the dyestutf shows a tendency to migrate while the textile material is being dried and the final dyeings are uneven.

It has now been found that the afiinity of cellulosic two tiles, and more particularly of cotton and cuprammonium rayon textile materials for the above dyestulfs may be greatly increased by impregnating the said textile materials with a mixture of polyacrylic acid and an alkali metal salt of polyacrylic acid.

According to the invention, therefore, there is provided a process for colouring cellulosic textile material which comprises impregnating the said material with a mixture of a polymer of acrylic acid and one or more alkali metal or ammonium salts of a polymer of acrylic acid, thereafter dyeing the said material with a basic dyestuff or a dyestufl containing ternary or quaternary salt groups, and finally treating the dyed material with alkali to complete the fixation of the dyestuff.

As examples of cellulosic textile materials which may be coloured by the process of the invention there may be mentioned cotton, linen, cuprammonium rayon, and viscose rayon.

As examples of alkali-metal salts of polymers of acrylic acid which may be used in the process of the invention there may be mentioned sodium and potassium salts of polymers of acrylic acid.

The impregnation of the said textile material may be conveniently carried out by passing it through an aqueous solution containing both a polymer of acrylic acid and alkali or ammonium salt of the polymer and then drying. The solution may conveniently be obtained either by partial neutralisation of a polymer of acrylic acid with ammonia or a suitable alkali-metal hydroxide, carbonate or bicorbonate, or by partial acidification of a solution of an alkali-metal or ammonium salt of a polymer of acrylic acid. The polymer of acrylic acid (or alkali-metal or ammonium salt thereof) used may be obtained by any method known from the literature or used in practice for the manufacture of polymers of acrylic acid, for example by polymerisation of acrylic acid either catalytically or by heat, by polymerisation of acrylonitn'le followed by either acid or alkaline hydrolysis and by polymerisation of esters of acrylic acid, for example ethyl acrylate, followed by hydrolysis of the polymer formed,

7 ice and such hydrolyses may be carried out on polymers either in the solid state or in an emulsified state. The products so obtained are substantially polymers of acrylic acid (or salts thereof) but may contain minor amounts of nitrile, amide or ester groups, depending on the method of preparation. Similar polymers may be obtained, if desired, by the co-polymerisation of mixtures of acrylic acid with minor amounts of co-polymerisable substances containing amide, nitrile or ester groups.

The total amount of the polymer of acrylic acid and salt thereof present in the solution may lie between 0.1 parts and 2.5 parts in each parts by weight of the solution, but it is preferred to use a solution containing 0.2 to 0.5 parts in each 100 parts by weight of the solution.

Polymers of acrylic acid may be used which form solutions in 2 N sodium hydroxide having viscosities at 20 C. of not less than 2 centipoises and not more than 10 centipoises when 10 grams of the polymer are dissolved in sufiicient 2 N aqueous sodium hydroxide to give a volume of 1 litre. *It is preferable, however, to use a polymer of acrylic acid which gives such a solution in 2 N sodium hydroxide having a viscosity of not less than 2 and not more than 4 centipoises at 20 C.

The proportion of polymer of acrylic acid and salt thereof present in the solution used for impregnation of the textile materials may be such that the pH of the solution is not less than 3 and not more than 10, but it is preferred to use a proportion such that the pH of the solution is not less than 5.5 and not more than 6.5

Suitable dyestufis for use in the invention are for example those obtained by rcacting chloromethyl derivatives of phthalocyanines with tertiary amines or thioureas as described in United Kingdom specification No. 587,636 and also dyestuffs obtained in a similar manner from chloromethyl derivatives of anthraquinone vat dyestutfs, for exarnple dibenzanthrone and isodibenzanthrone, and from chloromethyl derivatives of azo pigments, for example 4z4' di(6"-methylbenzthiazyl-)azobenzene. As examples of basic dyestuffs which may be used, there may be mentioned Methylene Blue 2B5 (Colour Index No. 922), Victoria Blue BS (Colour index No. 729), Magenta PNS(Colour Index No. 677) and Auramine OS (Colour Index No. 655).

It has been found that the coloured textile materials obtained by the new process are considerably more resistant to removal of dyestufi by wet or dry abrasive treatments than are coloured textile materials obtained when the pretreatment with polyacrylic acid and polyacrylate is omitted.

When a bath-dyeing technique is used, that is the material is dyed on a winch or jig, the dye-liquor exhausts to a higher degree, and deeper shades are obtained than can be obtained on textile materials which have not been treated with polyacrylic acid and polyacrylate.

When a pad-dry or pad-steam dyeing technique is used, the pretreated textile material gives dyeings having a better colour value. When a pad-dry technique is used, dyestuff applied to pretreated textile materials shows much less tendency to migrate under adverse drying conditions.

The invention is illustrated but not limited by the following examples in which the parts are by Weight.

Example 1 A solution is prepared by dissolving 0.5 parts of a polymer of acrylic acid in 99.5 parts of water containing suificient sodium hydroxide for the solution to have a pH of 5.7. Cotton limbric is passed through this solution and squeezed so as .to give an increase in weight of 100% over the weight of the cloth which is then dried at 100 C.

l'parts of "the pre-treated cotton limbrie are thoroughly rinsed in water, then introduced into 5000 parts of dye-liquor containing 1.5 parts of the dyestufl obtainedby reactingcopper tri-(chloromethyl-)phthalocyamine-with tetramethy-lthiourea. The dyebath is heated to the boiling pointiduring 30 minutes, and maintained at this temperature for 30 minutes, with continual agitation of the fabric. During this time, the pH of the dyebath is maintained at 3.5 by the addition ofacetic acid.

, f vThe cotton limbric is. then removed, rinsed in water and immersed for minutes in a boiling solution containing 20 parts of sodium carbonate in 1000 parts of water, .It is thenboiledfor lOnninutes ina solution containingl part of a detergent obtained by condensing ethylene oxide with an alkyl phenol in 1000' parts of water, thenrinsed with water and'dried. h V V The uptake of dyestuif 'on' the. cotton limbric' when measured by spectrophotometric examination of the exhaust liquor is found to be-1'.25 parts. 100 parts of cot ton limbric which had not been pretreatedwhen dyed similarly given an uptake. of 0.6 parts of dyestuif.

. The polymer of acrylic acid usedin this example. is obtained by catalytic polymerisation ofacrylic acid and forms a solution in 2 N sodium hydroxide having a viscosity of 2.4 centipoises at 20C. when 10 parts of f '7 r 7 2,955,900 1 I 4; Example 6 K 100 parts of cotton limbric are pretreated as in Ex:- ample l and dyed, fixed and dried as described therein but using only suflicient dyestufi' in the'dyebath to give an uptake of 0.5 parts of dyestuif. 100 parts of cotton limbric which has not been; pretreated are also dyed, fixed and dried to give an uptake of 0.5 part of dyestutr'. The pretreated cotton limbric has much greater resistance to removal of the dyestuff under dry and wet conditions than the cotton limbric which has not been pretreated. 7

Example 7 A mixture of 486'p'arts of water; and Spartsof a 5% aqueous solutionofsulphurieacidds. heated to 40 C. and 2 parts of ammonium persulphate in 8'parts of water, 2 parts of sodium meta-bisulphiteinS parts of water. and 60 parts ofacrylonitrile are added. Immediate I polymerisation occurs and the temperature of the mixpolyacrylic acid are dissolved in sufficient 2 N sodium, 7

hydroxide to .give a total volume of .1' litre.

7 7 Example 2 100'parts 'oi cuprammonium rayon-sateen pretreated V and dyed as described for the cotton limbric in Example Cuprammonium V 1; The dyestuff uptakeis 1.48 parts. rayon sateen which is not pretreated has a'dyestutf up take of 0.6 parts.

-. j Example '3 The solution of polymer of acrylic acid used in Example l to impregnate the cotton limbric is replaced by a solution of 1 part of polymer of acrylic acid in 99 parts of water, containing sufiicient sodium hydroxide to have a pH of 5.7, and the amount of dyestutf in the dyebath isincreased to 2.5 parts. A dye uptake of. 2.2 parts is obtained. V

Example 4 7 Cotton limbric is pretreated as described in Example 1.

The fabric is then passed through a solution containing 10 parts of the .dyestuiI described in Example 1 and 5 parts of acetic acid' in 1000 parts of water and squeezed Example 1.

'When cotton limbric which has not been'pre-treated is dyed and'fixed in the same way, more of the dyestufi is removed from the dyeing during the treatment with g sodium carbonate solution than is removed from the pretreated cotton limbric and more is removed from the dyeingwhich has not been 'pre-treated when exposed to friction under wet or dry conditions than is removed from the pre-treated cotton limbric.

Example 5 ofthe dyestufi described in Example 1 and S pants of (glacial acetic, acid in 1000 parts of water.

The strips are thenseparately wound several round'a cylinder'land dried in a. stream of warm The dyestuif on the strips ofcotton limbric which havebeen pretreated show much'less tendency-to migrate to the? outer-layers of the cotton limbric than does'the dyestuif on the untreated strips.

. water and then introduced into 5,000 parts of dye liquor thiourea.

Bothpre-treate'd and non-pretreated strips: of '.cotton limbric are passed. through 'a solution containing 10 parts I ture rises to 68 C. ,The temperatureis'adjusted to 60 C. and the mixture is maintained at this temperature for one hour. 46 parts of sodium hydroxide are'added to .the polymer slurry and the. mixture is heated at 90-95 C. for 24 hours, the-volume of the'solution being kept constant during this time by the addition of water.

Analytical estimation of the product indicates that thepo-lyac rylonitr ile is parts hydrolysed to sodium POlyacrylate The polymer forms a solutionhaving" a viscosity of 3.5 centipoises at 20 C.' when )a quantity equivalent to 10 parts ofpolyacrylic acid'is dissolved suflicient 2 N sodium hydroxide to' givea total'volume of one litre. i p r The above polymer solution is diluted to give' a solution equivalent to 0.5 part of polyacrylic acid in 99.5 parts of water containing suflicient ace tic acid for the solution toihave a pH of 5.7. Cotton limbric is passed through this solution and squeezed so as to give an increase in weight of 100% over {the weight of the cloth which is then dried at 100 C.

. 100 partsof the pretreated cotton limbric is rinsed in containing 1.5 parts of the dyestufi'obtained by reacting copper tri(chloromethyl)phthalocyanine with 'tetramethyl- Thefdyebath is heated to the boiling'point during 30 minutes and maintained at this temperature for 30 minutes'with continual agitation of the fabric. During this time the pH of the dyebath is maintained at 3.5 by the addition, of acetic acid. {The cotton limhric is; then removed, rinsed in water and immersed for 5 minutes in a boiling solution containing 20 parts of 'sodium carhonatein 1000 parts of water. 'It is" then boiled for 10 minutes in a' solutionfcontaining l part of a detergent obtained by condensing ethylene oxide'with alkyl phenol in 1000 parts of water, rinsed with water, and driedq The uptake of dyestuff on the cotton lirnbric when measured by spectrophotometric examination of the exhaust liquor Example 8 mixture ofz500 parts of' water, 3.8 parts of sodium carbonate and 8-,parts of Turkey Red Oil' is heated to C. and stirred vigorously while simultaneously from 7 separate vessels, there are added during l /z hours 400 parts of ethyl acrylate monomer, 8 parts of Turkey Red Oil in 200 parts of water, and l.32.parts o f ammonium persulfatein parts of water. Care is taken to main-;

tain therates of addition of monomer, catalyst and surface active agent constant. .When'the additions are complete, the temperature of the dispersion ismaintained at Sj0-92?1 C. for. a further hour; to complete the polymerization a i V a 56 parts of sodium are dissolved 100 v parts of water and this solution is added to 500 parts of an aqueous dispersion of polyethyl acrylate prepared as described above. The mixture is stirredand heated to about 90 C. and maintained at 8090 for 3 hours. Titration of the residual sodium hydroxide with standard acid solution indicates that the polyethyl acrylate is 75% hydrolysed to sodium polyacrylate. V The polymer obtained forms a solution having a viscosity of 8.25 centipoises at 20 C. when a quantity equivalent to parts of polyacrylic acid is dissolved in suificient 2 N sodium hydroxide to give a total volume of one litre.

The above polymer solution is diluted to give a solution equivalent to 0.5 part of polyacrylic acid in 99.5 parts of water containing sufiicient acetic acid for the solution to have a pH of 5.7. 100 parts of cotton limbric is pretreated and dyed as described in Example 7 using the above solution for the pretreatment. The uptake of dyestuff is 1.09 part per 100 parts of cotton limbric.

Example 9 A mixture of 350 parts of water, 2.5 parts of sodium hydroxide and 10 parts of Turkey Red Oil is heated to 90 C. and to this mixture are added 750 parts of ethyl acrylate monomer, 100 parts of Turkey Red Oil in 200 parts of water and 6.25 parts of ammonium persulphate in 200 parts of water. Polymerisation is effected as described in Example 8. 45.2 parts of sodium hydroxide are dissolved in 500 parts of water and this solution is added to 200 parts of the aqueous dispersion of polyethyl acrylate prepared as described above. Hydrolysis is carried out as described in Example 8 except that the total time of hydrolysis is 16 hours. Titration of the residual sodium hydroxide with standard acid solution indicates that the polyethyl acrylate is 95% hydrolyzed to sodium polyacrylate. The polymer obtained forms a solution having a viscosity of 2.04 centipoises at 20 C. when a quantity equivalent to 10 parts of polyacrylic acid is dissolved in suflicient 2 N sodium hydroxide to give a total volume of one litre. The above polymer solution is diluted to give a solution equivalent to 0.5 part of polyacrylic acid in 99.5 parts of water containing suflicient acetic acid for the solution to have a pH of 5.7. 100 parts of cotton limbric is pretreated and dyed as described in Example 7 using the above solution for the pretreatment. The uptake of dyestutf is 1.23 parts per 100 parts of cotton limbric.

Example 10 A solution containing 80 parts of acrylic acid monomer in 20 parts of water is refluxed at about 140 C. After 10 minutes polyacrylic acid begins to separate from the monomer solution. After heating for a further 45 min utes the solid polymer is separated from the residual solution and dried giving 75 parts of polyacrylic acid. The polymer forms a solution in 2 N sodium hydroxide having a viscosity of 2.0 centipoises at 20 C. when 10 parts are dissolved in suficient 2 N sodium hydroxide to give a total volume of one litre.

A solution of this product is prepared by dissolving 0.5 part in 99.5 parts of water containing suflicient sodium hydroxide for the solution to have a pH of 5.7. 100 parts of cotton limbric is pretreated and dyed as described in Example 7 using the above solution for the pretreatment. The dyestufi uptake is 1.03 part per 100 parts of cotton limbric.

Similar results are obtained if the polymer solution is adjusted to pH 5.7 with either ammonium or potassium hydroxide in place of sodium hydroxide.

Example 11 100 parts of cotton limbric is pretreated and dyed as described in Example 7 except that the dyestufi is replaced by the dye obtained by reacting chloromethyl-4:4-di(6"- methylbenzthiazyl)-azobenzene with tetramethylthiourea. The dyestufi uptake is 1.25 parts per 100 parts of cotton limbric. 100 parts of cotton limbric which has not been pretreated when dyed similarly gives an uptake of 0.6 parts of dyestuff.

Example 12 100 parts of cotton limbric is pretreated and dyed as described in Example 7 except that the dyestutf is admixed with an equal weight of the dyestutf used in Example 11. The uptake of the green dyestufi' mixture is 1.31 parts per 100 parts of cotton limbric. 100 parts of cotton limbric which has not been pretreated when dyed similarly gives an uptake of 0.6 parts of dyestufr'.

Example 13 100 parts of cuprammonium rayon sateen is pretreated and dyed as described for the cotton limbric in Example 7. The dyestutf uptake is 1.48 parts. Cuprammonium rayon sateen which is not pretreated has a dyestufi uptake of 0.6 part per 100 parts of cuprammonium rayon sateen.

Example 14 100 parts of cotton limbric is pretreated and dyed as described in Example 7 except that the concentration of the polymer solution is increased until equivalent to 1 part of polyacrylic acid in 99 parts of Water containing sufiicieut acetic acid for the solution to have a pH of 5.7. The amount of dyestufi in the dyebath is increased to 2.5 parts. 'A dye uptake of 2.2 parts per 100 parts 'of cotton limbric is obtained.

Example 15 Cotton limbric is pretreated as described in Example 7. The fabric is then passed through a solution containing 10 parts of the dyestulf described in Example 7 and 5 parts of acetic acid in 1,000 parts of Water and squeezed so as to give an increase in weight of over the weight of the cloth, which is then dried at C. and passed through a boiling solution of sodium carbonate in 100 parts of water. It is then treated with detergent as described in Example 7.

When cotton limbric which has not been pretreated is dyed and fixed in the same way, more of the dyestufi is removed from the dyeing during the treatment with g sodium carbonate solution than is removed from the pretreated cotton limbric, and more is removed from the dyeing which has not been pretreated when exposed to fric tion under wet or dry conditions than is removed from the pretreated cotton limbric.

Example 16 100 parts of cotton limbric is pretreated as described in Example 7 and dyed, fixed and dried as described therein but using only suficient dyestufi" in the dyebath to give an uptake of 0.5 part of dyestutf. 100 parts of cotton limbric which have not been pretreated is also dyed, fixed and dried to give an uptake of 0.5 part of dyestutf. The pretreated cotton limbric has much greater resistance to removal of the dyestuff by abrasion under dry and wet conditions than the cotton limbric which has not been pretreated.

Example 18 100 parts of cotton limbric is pretreated as described in Example 7. The fabric is then introduced into 5000 parts of dye liquor containing 0.5 part of Victoria Blue 7 BS (Colour Index No. 729), and.2.5 parts of glacial aceticacid. The dyebath is heated to 70 C. during 39 minutes and maintained at this temperature for 30 minutes, with continual agitation of the fabric. 7

Thecotton li'mbric is then removed, rinsedwell in water and dried. The uptake of dyestufi on the cotton limbric when measured'by spectrophotometric examination of the exhaust liquor is found to be 0.4 parts per 1 parts of cotton lirnbric. 100 parts of cotton limbric which has not been pretreated similarly gives an uptake of 0.21 parts of dyestuff. p a

V 7 Example 19 100parts of cotton limbric is pretreated as described in Example 7. The fabric is then introduced into 5,000

parts-of'dye liquor containing 0.5 part of Methylene Blue 2B8 (Colour Index No; 922) and 2.5 parts ofj'glacial acetio acidr The dyebathis heated to 70 C. during 30 minutes and maintained at thisitemperature for 30minutes with continual agitation of the fabric. The cotton lirnbric is then removed, rinsed Well in Water. and dried.

The uptake 'of dyestufl'on the cotton limbric is found to be 0.36 partper 100 parts of cotton limbricf 100 parts of cotton limbric which has not been pretreated when dyed similarlygives an uptake of Olpart of dyestufi; ;WhatI.clairn is; v e

1. Process forcolouring solution of a mixture of a polymer of acrylic acid and at least one salt of the group consisting of alkali metal and ammonium salts of a'polyrner of acrylic acid, thereafter dyeing the material .With a dyestuff selected from'thetclass. consisting of'dyestuffs containing ternary'salt groups and.

dyestufiscontaining quaternary salt groups; which are rendered insoluble in 'Water by alkali, and finally-treat ation of the dy'estuff.

ingthe dyed'material with alkali to complete: the fix- 12. Process .for colouring. cellulose-textile material as claimed in claim- 1 wherein the alkali-metal salts ofpolymers ofacrylic acid are selected from the group consisting of the sodium and potassium salts.

3.: Process rd; colouring cellulose textile materialias" *claimedinjclaim 1 wherein said polymer of acrylic acid.

is one which forms a solution in 2 N sodium hydroxide having a viscosity at 20 C. of not less thaln2 centipoises V celliflose textile material which. comprises impregnating the said material'with an aqueous and not more than 1'0 centipoises, whenilt) grams ofthe material prior to the'dy eing step polymer. are. dissolved inrsufiicient 2 N aqueous sodium hydroxide to give-a volumeof llitre.

41 Process. for' colouring. cellulose .textileQmatetial; as claimedin claim 1 wherein. the proportion ofpolymer of acrylic acid and salt thereof presentin the 'solutionvused for imp'regriationof the textile materials is 'suchthat the pHof the solution is not less than 3 and not morethan 10. a I

' 5. Process for colouring cellulose textile material as claimed in claim .1 wherein said polymer of acrylic acid is one which forms a solution in 2 N sodium hydroxide having'aviscosity at 20 C., ofnot less than 2 centipoises and not more than 4 centipoises when 10 grams'of the polymer are dissolved'in suflicient 2 N aqueous sodium 5 aqueous solution containing both said polymer of acrylic 2 acid and salt'thereof and then drying the impregnated '8 Process for colouring. cellulose textile material as claimed-in clain1- 7 wherein the total amounto f thepolymer'of acrylic acid and salt thereof present in the solunan-re between 0.1 part and 2.5parts in each. IOQ parts hy weightof the solution. 5

i 9 Process for colouring cellulos' e textile materiai as claimed in claim 7 wherein the total amount of thepoly mer ofacrylic acid and salt thereof present in: the solution is between 0.2 to 0'.5 pa rt by Weight of the solution.

1( Cellulose textile materials whenever coloured by a process as definedin claim 1. Y

. References. Cited in the file of this patent UNITED STATES PATENTS:

2,215,196 7 Schlack Sept; 17, 2,343,095 Smith' Feb.29,1944 2,764,570 Kowolik Sept. 25, 1956 FOREIGN PATENTS 1 7 433,210 Great Britain 'Aug. '9; i935

Claims

1. PROCESS FOR COLOURING CELLULOSE TEXTILE MATERIAL WHICH COMPRISES IMPREGNATING THE SAID MATERIAL WITH AN AQUEOUS SOLUTION OF A MIXTURE OF A POLYMER OF ACRYLIC ACID AND AT LEAST ONE SALT OF THE GROUP CONSITING OF ALKALI METAL AND AMMONUIM SALTS OF A POLYMER OF ACRYLIC ACID, THEREAFTER DYEING THE MATERIAL WITH A DYESTUFF SELECTED FROM THE CLASS CONSISTING OF DYESTUFFS CONTAINING TERNARY SALT GROUPS AND DYESTUFFS CONTAINING QUATENARY SALTGROUPS, WHICH ARE RENDERED INSOULBLE IN WATER BY ALKALI, AND FINALLY TREATING THE DYED MATERIAL WITH ALKALI TO COMPLETE THE FIXATION OF THE DYESTUFF.