2,901,312 United States Patent 0 ” "ice Patented Aug. 25, 1959

1 2 in the complete speci?cation of our co-pending applica 2,901,312‘ tion Nos. 547,681, ?led November 18, 1955, and 507,705‘, ?led March 11, 1955, and now Patent No. 2,785,478. In PROCESS UTILIZING FLUIDIZED BEDS IN THE some cases the object may also be achieved, though to a DYEING OF FABRICS, YARNS AND THE LIKE lesser extent, if the said dyeing assistants are used with Francis George Audas, Cheadle Hulme, England, assignor other methods of drying and heating already known in to The British Rayon Research Association, Manches connection with the said material under treatment. These ter, England, a British association assistants are glycerine, triethanolamine, diacetin, erythri tol, penta erythritol, ethylene glycol, di-ethylene glycol, No Drawing. Application May 3, 1956 10 di-ethylene glycol diaeetate, D-glucose monohydrate, thio Serial No. 582,335 urea, urea, ammonium thiocyanate, hexamine, a mixture Claims priority, application Great Britain May 7, 1955 of urea and ethylene glycol, a mixture of thiourea and ethylene glycol, a mixture of penta erthritol. and thiourea, 7 Claims. (Cl. 8--151) a mixture of glycerine and thiourea, and a mixture of di 15 ethylene glycol diacetate and thiourea (hereinafter and This invention concerns the dyeing of ?laments, in the claiming clauses hereof called “a de?ned dyeing ?bres, threads, yarns, ?lms and sheets of Terylene assistant”) . (R.T.M.), nylon, cellulose triacetate rayon or secondary According to the present invention a method of dyeing acetate rayon or the like synthetic materials or of fabrics ?laments, ?bers, threads, yarns, ?lms and sheets of made therefrom. Considerable di?iculty has hitherto been experienced Terylene, nylon, cellulose tri-acetate rayon or secondary acetate rayon or the like synthetic materials or of fabrics in the dyeing of Terylene and nylon and, to a lesser ex made therefrom comprises passing the material under tent, of cellulose triacetate rayon and secondary acetate treatment into a dyebath containing a de?ned dyeing as rayon or the like synthetic materials and in the ?xing sistant and a dye, padding the dye on to the material in reasonable times at atmospheric temperatures of a satis factory amount of dye with the requisite uniformity and 25 under treatment and then passing the material under without damage to the dyed material. For example the treatment through a bed of hot discrete particles, While the bed is subjected to an upward gaseous current, the time required for dyeing Terylene fabric or yarn with size and weight of the particles, the velocity and nature a given disperse-acetate dye, which at moderate tempera of the current and the disposition of the material under tures of the order of 85° C. is excessive may be consider treatment being so chosen that the forces exerted by the ably reduced at temperatures of the order of 120° C. but 30 current on the particles are sui?cient to counter-balance such processing normally‘ requires the dyeing unit to be the gravitational force on free particles and to expand pressurized, and this in inconvenient and adds to the ex~ the bed, thus allowing movement of the particles, but pense of the process. Considerable effort has been directed to the develop is insufficient to convert the bed into a uni-directional rnent of high temperature dyeing techniques which do 35 stream of moving particles, and the temperature in the not involve pressurization of the dyeing unit. It has been bed being so chosen that the dye is ?xed in the ma— found possible for example to pass certain fabrics through terial under treatment. The nature of the said bed (hereinafter and in the a suspension of dyestuff in an aqueous bath, to dry the claiming clauses hereof called “a ?uidised. bed”) and the fabric, and then heat it to a temperature high enough 40 manner of making the same is fully described in the to permit the padded and un?xed dye to diffuse into speci?cations of the said co-pending applications. the ?bres of the fabric material. In such methods, in The actual proportion of the de?ned dyeing assistant order to achieve satisfactory dyeing, it is frequently neces in the bath may vary within fairly wide limits and the sary to use temperatures of 200° C. or more, for periods of from ten to thirty seconds. These high temperatures best proportion can easily be determined for any particu lar material by simple trial. It may be as low as 1% or are disadvantageous as they tend to cause considerable shrinkage of the material. This dif?culty may be over as high as 20% but it will preferably be between 5% and come by prior heat setting, in conjunction with stentering 12% according to the assistant used, the percentages be at a higher temperature still but the temperatures in ing by volume, or weight as the case may be, depending volved might Well reach a level at which the material on whether the assistant is a liquid or a solid. is damaged. For example, the melting point of T erylene We have found that the present invention enables dye~ is only about 240° C. Stentering during the dyeing ing to be more readily effected than with known meth process is also likely to give rise to local temperature ods and with advantages not possessed by the known variations and consequent uneven dyeing. methods. Other attempts at overcoming these difficulties have The invention will now be illustrated by the follow included the addition to the dyeing bath of carriers or 55 ing examples. swelling agents but the known agents, while enabling the Example 1 dyeing and ?xing times and temperatures to be decreased, Four dyebath liquors were prepared each of which con ' have suffered from the disadvantage of imparting a dis tained 5% by weight of the dye Duranol Brilliant Violet agreeable odour to the material under treatment, or of BR300 (C.I. 62,030) and 0.2% by weight of the wetting impairing the light fastness of the dye, or of failing to 60 agent Perminal PP. One liquor contained no assistant, provide the requisite uniformity of colour. one contained 5% by volume of glycerine, one contained The main object of the invention is to provide an im~ 5% by volume of diacetin, and one contained 5% by proved method of dyeing ?laments, ?bers, threads, yarns, volume of triethanolamine. ?lms and sheets of Terylene, nylon, cellulose triacetate 65 Nylon and Terylene continuous ?lament fabrics were rayon and secondary acetate rayon and of fabrics made padded through the dyebath liquors, and, after mangling, therefrom and We have found that this object may be achieved by the use in conjunction with certain dyeing were passed through a ?uidised bed of sand at 195° C., assistants in the dyebath of the step of drying and heat the time in the bed being ten seconds. The dyed fabrics treatment or of heat treatment described and claimed were treated with a hot soap solution to detach un?xed 2,901,312 Ci) dye and after rinsing and drying were analysed for dye weight of dye which is ?xed on a fabric for a given time content. The results were as follows: and temperature of heat treatment. What I claim is: Percent by Percent by 1. A method of dyeing ?laments, ?bres, threads, yarns, Percent by volume of dye bath assistant Weight of weight of dye on dye on ?lms, and sheets made of a synthetic ?brous material, ; nylon _ Terylene comprising the steps of passing a synthetic ?brous mate rial adapted to be dyed into a dye bath containing a dye None ___- 1. 48 - 0. 93 ing assistant, the dye of said dye bath being adapted to 5% glycerine_ ___' 1.82 ' 1. s4 5% diace'tin____- 1. 99 . 1. 39 be ?xed at a predetermined temperature; padding said 5% triethanolarnlne..- 1. 80 ‘ 1. 15 dye onto said synthetic ?brous material; and passing the thus treated synthetic ?brous material containing said dye Example 2 through a bed of hot, solid, discrete particles, while sub The same procedure vas-in Example 1 was followed ex jecting the bed'to an upward gaseous current, the size and weight of the particles and the velocity and nature cept that the dyebath liquor contained 5% by weight of 15 the dye \Seris'ol Fast Red 3BL ‘('CJI. 61,140) and the of the current being so chosen that the vforce exerted by fabrics used‘were ‘of continuous ?lament secondary acetate the current is suf?cient ‘to counter-balance the gravitation rayon, cellulose tria‘cetate rayon, and Terylene. 81 force on ‘free particles and to expand the bed thus al The results were as follows: lowing movement of the particles but is insui?cient to convert the bed into a unidirectional stream of moving 20 particles, the temperature of the bed being substantially Percent by Percent by ' weight of weight'oi ‘Percent by at said predetermined temperature and the rate at which Percent by volume of dye bath dye on dye on _ weight of said treated synthetic ?brous material is passed there assistant secondary cellulose 3 dye on acetate triacetate Terylene through, being adjusted to ?x said dye into said syn rayon ; thetic ?brous material. V25 2. A method of dyeing ?laments, ?bres, threads, yarns, N0ne._;5‘7 lycerine...... ______1.131. 5 _ . .y ?lms, and sheets made of a synthetic ?brous material, 5%‘; igliacetin ______r ‘1.46 ‘1.16 o. 95 comprising the steps of passing a synthetic ?brous mate 5% triethanolamine"; ______1 ‘1.728 »1. 21 1. 11 rial adapted to be dyed and being selected from a group consisting of Terylene, nylon, cellulose triacetate, rayon Example 3 30 and secondary acetate rayon into a dye bath containing The same procedure as in ‘the preceding examples was a dyeing assistant, the dye of said dye bath being adapted followed except that 10% :by weight of Duranol ‘Red X to be ?xed at a predetermined temperature; padding said 3B 300 (0.1. 62,015) dye ‘was used in the liquor, ‘the dye onto said synthetic ?brous material; and passing the fabrics were of continuous ‘?lament Terylene and'spun , thus treated synthetic ?brous material containing said dye Terylene respectively, and'ten liquors were used, the'as through a‘bed of ‘hot, solid, discrete particles, While sub jecting the bed to an upward gaseous current, the size and sistants being set out in the results which were as follows: weight of the particles and the velocity and nature of the current ‘being so chosen that the force exerted by the cur Percent by Percent by . ' Weight'oi v weight of rent is su?icient to counter~balance the gravitational force Percent by‘ volume or weight (as the‘ease vdye on dye on .40 on free particles and to expand the bed thus allowing may 'be) of dye bath assistant continuous Spun ' ‘?lament ' Tyrelene movement of the particles but is insufficient to convert .‘ 'Tyrclene > the bed into a undirectional stream of moving particles, the ‘temperature of the bed being substantially at said None > "1: S8 ; 1' 2320 predetermined temperature and the rate at which said 5%.g1ycerene ______.L ______:2. 49, v 2. 71 3.3% ethy ene glycol. 2.15‘ I 2. 29 treated synthetic ?brous material is passed therethrough 7.6% hexamine ______y____l_ 1:98 2. 40 being adjusted to ?x said dye into said synthetic?brous -10.9%>D-gluc0se monohydra _ 2. .44. 2. 42 4.1%ammonii1m ithiocyanateu 1: 97 * ~‘ 2. 72 material. 4.1% .thiourea_. _ i ______‘.2. 28 2. 41 3. A method of dyeing ?laments, ?bres, threads, yarns, 3.3%.11rea ______l__-_l_____‘_____ 2.103. 2. 51 1;65%'urea 1Kl.65% ethylene g'lycol__.__- '2: 05 ~_ "2.’ 35 ?lms, and sheets made of a synthetic ?brous material, 2.1% thiourea K 1.65% ethylene. glycol“ ; v2. 32 2.38 5.0 comprising'the steps of passing a synthetic ?brous ma 2.5% glycerine K 2.15% thiourea_- ______~_ ____ ._ 2.1.40‘ ,2, 83 terial adapted toibedyedand being selected from a group consisting of Terylene, nylon, cellulose triacetate, rayon ‘It .is .‘to be Iunderstood that ,passage through the hot and secondary acetate rayon into a dye bath containing ‘fluidised bed ‘dries .thefabric as wéllas ?xesthedye when a dyeing assistant, the dye of said dye bath being adapted the fabric is passed straight from thedyebath to .theibed .55 to be ?xed at a predetermined temperature; padding said as in the foregoing examples. Theaactual .?xing timeis dye onto said synthetic ?brous material; andwpassin‘g the therefore ‘only part not .the total {time .in {the bed. iForex thus treated synthetic ?brous material containing said dye ample if the‘ total time ‘is 10 seconds, drying may :take through abed of hot, solid, discrete vparticles .of siliceous three 'or .four seconds, :and :?xing the remainder .of the sand, while subjecting the bed to an upward gaseouscur time. Drying need not necessarily be carried out in .a rent, the size and weight of the particles and the velocity ?uidised bed and it is. possiblewwithout serious loss of and nature of the current being so chosen that the force advantage to dry the material by other methods and then exerted‘ by the current ‘is suf?cient to counter-balance the heat treat :the material to ‘?x the dye by passing .through a gravitational force on free particles and to expand the ‘?uidised "bed. ‘Likewise (the increased weights of .dye bed thus allowing movement of the particles butisin ?xed .on the material under treatment result from the .use su?’icient to convert the bed into a -,unidirectional-stream of ‘the de?ned dyeing assistant and it is ‘thus possible to of moving particles, the temperature vof thebedbeingsub obtain some of ‘the advantagestof the inventionbythe use stantially at said predetermined temperature and the rate of the de?ned dyeing assistants with other .forms .of .dry at which said treated synthetic ?brous ‘material is z-passcd ing and heat treatment. Glycerine .is preferred .as-lthe therethrough .being adjusted to ,?X said dye .into saidsyn de?ned dyeing assistant as it is cheap and easily removed 70 thetic '?brous vmaterial. from'the dyed material. ‘Other-ide'?ned .dyeingassistants 4. 'A method of dyeing ‘?laments, ?bres, ithreads, ‘yarns, ‘which are .also cheap and easily- removed- .are .diacetin ?lms, and sheets made of a synthetic ?brous material, and D-g'lucose' monohydrate; comprising .the steps .of passing a synthetic ?brousymate The process of the invention gives an increase in the vrial .adapted tobedyed and being selected from a group consisting of Terylene, nylon, cellulose triacetate, rayon 2,901,312 5 6 and secondary acetate rayon into a dye bath containing the velocity and nature of the current being so chosen a dyeing assistant, the dye of said dye bath being a dis that the force exerted by the current is su?icient to perse-acetate dye adapted to be ?xed at a predetermined counter-balance the gravitational force on free particles temperature; padding said dye onto said synthetic ?brous and to expand the bed thus allowing movement of the material; and passing the thus treated synthetic ?brous particles but is insui?cient to convert the bed into a uni material containing said dye through a bed of hot, solid directional stream of moving particles, the temperature discrete particles, while subjecting the bed to an upward of the bed being substantially at said predetermined tem gaseous current, the size and weight of the particles and perature and the rate at which said treated synthetic the velocity and nature of the current being so chosen ?brous material is passed therethrough being adjusted to that the force exerted by the current is sui?cient to count~ 10 ?x said dye into said synthetic ?brous material. er-balance the gravitational force on free particles and to 7. A method of dyeing ?laments, ?bres, threads, yarns, expand the bed thus allowing movement of the particles ?lms, and sheets made of a synthetic ?brous material, but is insu?’icient to convert the bed into a unidirectional comprising the steps of passing a synthetic ?brous mate stream of moving particles, the temperature of the bed rial adapted to be dyed and being selected from a group being substantially at said predetermined temperature and 15 consisting of Terylene, nylon, cellulose triacetate, rayon the rate at which said treated synthetic ?brous material is and secondary acetate rayon into a dye bath contain passed therethrough being adjusted to ?x said dye into ing D-glucose monohydrate as a dyeing assistant, the dye said synthetic ?brous material. of said dye bath being adapted to be ?xed at a predeter 5. A method of dyeing ?laments, ?bres, threads, yarns, mined temperature; padding said dye onto said synthetic ?lms, and sheets made of a synthetic ?brous material, 20 ?brous material; and passing the thus treated synthetic comprising the steps of passing a synthetic ?brous mate ?brous material containing said dye through a bed of rial adapted to be dyed and being selected from a group hot, solid, discrete particles, while subjecting the bed to consisting of Terylene, nylon, cellulose triacetate, rayon an upward gaseous current, the size and weight of the and secondary acetate rayon, into a dye bath containing particles and the velocity and nature of the current is glycerine as a dyeing assistant, the dye of said dye bath 25 sufficient to counter-balance the gravitational force on being adapted to be ?xed at a predetermined tempera free particles and to expand the bed thus allowing move ture; padding said dye onto said synthetic ?brous mate ment of the particles but is insu?icient to convert the bed rial; and passing the thus treated synthetic ?brous mate into a unidirectional stream of moving particles,‘the tem rial containing said dye through a bed of hot, solid, dis perature of the bed being substantially at said predeter crete particles, while subjecting the bed to an upward 30 mined temperature and the rate at which said treated gaseous current, the size and weight of the particles and synthetic ?brous material is passed therethrough being the velocity and nature of the current being so chosen adjusted to ?x said dye into said synthetic ?brous material. that the force exerted by the current is sufficient to counter-balance the gravitational force on free particles References Cited in the ?le of this patent and to expand the bed thus allowing movement of the 35 UNITED STATES PATENTS particles but is insufficient to convert the bed into a uni 2,080,254 Dreyfus ______.... May 11, 1937 directional stream of moving particles, the temperature 2,349,282 Kern ______._ May 23, 1944 of the bed being substantially at said predetermined tem 2,785,478 Audas ______.._ Mar. 19, 1957 perature and the rate at which said treated synthetic ?brous material is passed therethrough being adjusted 40 OTHER REFERENCES to ?x said dye into said synthetic ?brous material. Giradet: Industrie-Anzeiger, vol. 75, No. 12, February v6. A method of dyeing ?laments, ?bres, threads, yarns, 10, 1953, pp. 141-143. ?lms, and sheets made of a synthetic ?brous material, Saville, A.K.: “The Printing of Nylon Piece Goods,” comprising the steps of passing a synthetic ?brous mate Am. Dyestuff Reporter, September 19, 1949, pp. 673-674. rial adapted to be dyed and being selected from a group 45 consisting of Terylene, nylon, cellulose triacetate, rayon Du Pont: “The Techn. Bull.,” vol. 5, No. 2, June 1949, pp. 83-102. and secondary acetate rayon into a dye bath containing Kite, RP. and Roberts, E.I.: “Fluidization in Non diacetin as a dyeing assistant, the dye of said dye bath Catalytic Operations,” Chem. Eng, December 1947, pp. being adapted to be ?xed at a predetermined tempera 50 112-115. ture; padding said dye onto said synthetic ?brous mate Diserens, L.: “Les Produits Aux. dans Uni-Textile,” rial; and passing the thus treated synthetic ?brous mate Rev. Gen. Mat. Col., March 1957, pp. 89-100. rial containing said dye through a bed of hot, solid, Am. Dyestuff Rep. (1), August 17, 1953, pp. 543, 544. discrete particles, while subjecting the bed to an upward Am. Dyestu?’ Rep. (11), February 18, 1952, p. 104. gaseous current, the size and weight of the particles and