US3658461A - Process of level dyeing of fibrous poly-acrylonitrile textiles with cationic dyestuffs - Google Patents

Process of level dyeing of fibrous poly-acrylonitrile textiles with cationic dyestuffs Download PDF

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US3658461A
US3658461A US781818A US3658461DA US3658461A US 3658461 A US3658461 A US 3658461A US 781818 A US781818 A US 781818A US 3658461D A US3658461D A US 3658461DA US 3658461 A US3658461 A US 3658461A
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temperature
liquor
dyeing
dye
equation
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Udo Mayer
Herbert Fleischer
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BASF SE
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BASF SE
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/0032—Determining dye recipes and dyeing parameters; Colour matching or monitoring
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/70—Material containing nitrile groups
    • D06P3/76—Material containing nitrile groups using basic dyes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/927—Polyacrylonitrile fiber

Definitions

  • ABSTRACT A method of dyeing a fibrous textile material composed of an acrylonitrile polymer in level shades with a cationic dye from an aqueous liquor by carrying out the dyeing at a predetermined temperature Twhich is dependent upon definite liquor exhaustion rates, a constant a which denotes the change in temperature which halves or doubles the liquor exhaustion rate measured at a dyeing temperature of 100 C and a constant b which denotes the depth of color to be achieved in milligrams of dye per gram of fibrous material.
  • an acid, a salt and a dye and, if necessary, a retarding agent are added to the dye liquor which is rapidly brought to a temperature corresponding to .the glass temperature of the fiber generally from 70 to 85C.
  • the temperature is thereafter raised slowly anduniformly to 100C and the liquor is held at boiling temperature untilit is exhausted and good penetration of the fiber hasbeen achieved.
  • Another method of dyeing acrylonitrile polymer fibers is that known as the constant-temperature method.
  • the retarder can be dispensed with in this method. Acid and salt are added to the liquor and it is brought to a temperature T which lies between 80 and 100C, depending on the depth of color required. As soon as this temperature is constant, the dye isadded and allowed to be absorbed.
  • the disadvantage of this method is that the experimental methods of determining Tare so inexact that it is not possible to give a specific temperature but only a wide temperature range.
  • the inaccuracy of the methods of determining T is also shown by the fact that it is not possible to differentiate between dyes having different tinctorial behavior and that the experimental results make it seem that there is a linear dependence of the dyeing temperature on the depth of color to be achieved.
  • acrylonitrile polymer and copolymer textile material can be dyed level shades with cationic dyes by heating the liquor to the dyeing temperature T and carrying out the dyeing at this temperature at a defined rate of exhaustion, the temperature T being derived from the equation:
  • a is the change in temperature which halves or doubles log b-log +2) definition of basic dyes see e.g. Color lndex,-Volume l, p.
  • the dye liquor to which acid tga(l00C is the depth of color to be achieved in mg of commercial dye per g offibrous materal dye per g of fibrous material X is the exhaustion of the liquor as a percentag I is the dyeing time in seconds appertaining to the liquor exhaustion X (X/ w/TQT is the rate of liquor exhaustion at the temperature T, and
  • tga( 100C) is equal to Cpl /7 C,- being the concentration of commercial dye in the fiber in mg per g which is present after the time t at a dyeing temperature of 100C.
  • commercial dye refers to a dye of commercial pu- (with or without salt) has been added and which already contains the textile material to be dyed may be heated to the dyeing temperature calculated according to equation (l) and then the dissolved dye added.
  • the textile material may be advantageous to remove the textile material from the liquor, to add the dye and, as soon as it has been homogeneously dispersed, to return the textile material.
  • the liquor can be raised to an appropriately higher temperature prior to removal of the textile material.
  • the liquor to which acid (with or. without salt) has been added may be heated rapidly to boiling point and kept boiling until the yarn has been bulked. It is then cooled to the calculated temperature T, the dye is added and dyeing is carried out.
  • the liquor may .either be cooled immediately, or'it may be heated to a higher temperature, for example 100C, to improve liquor exhaustion and penetration of the fiber.
  • level dyeings may easily be obtained in cheese dyeing machines in which liquor circulation is good, but in the case of hank dyeing machines having slow liquid circulation it is often necessary to take special precautions to obtain a good result.
  • the new process offers the advantage over prior art methods that the liquor exhaustion rate can be adjusted for all dyeings with cationic dyes to an optimum value for given equipment. This value depends especially on the circulation of the liquor in the machine and can be so adjusted that the liquor is exhausted for example in 20, 30, or minutes or t o hours...
  • Another advantage of this process arises from the fact that the probability of obtaining a level dyeingis the same for all dyeing recipes provided dyeing is carried out at the same liquor exhaustion rate.
  • this liquor exhaustion time can be relied on to give level shades in all subsequent batches.
  • C being the concentration of dye in the fiber in mg of commercial dye per g of fibrous material; constant denoting fiber constant;
  • tga constant is a clear measure of the rate of absorption of the dye concerned. As may be seen from the equation, tga is independent of the concentration in the dye liquor and accordingly independent of the depth of color to be achieved.
  • Equation (3) establishes a quantitative relation between absorption rate tga and liquor exhaustion rate (X/ ⁇ UT Having regard to the fact that tga is a dye constant independent of quantity, equation (3) shows that the liquor exhaustion rate has to decrease as the depth of color b increases, which agrees with experience in practice.
  • the rate of absorption of cationic dyes by polyacrylonitrile fibers is very dependent on temperature above the glass temperature. With some types of fiber a lowering of the temperature by only 3C is enough to halve the tga value. If the temperature is lowered by 6C, the tga value is quartered and upon lowering the temperature by 9C one eighth of the tga value results.
  • Equation (4) follows from this:
  • n the number of times tga has to be divided in halfin the lowering of the temperature from C to TC. Since a single halving of tga is brought about by a reduction in temperature of l X 3C (with a fiber having a temperature factor of 3C), a second halving by a reduction in temperature of 2 X 3C, halving by n times by a reduction in temperature of n X 3C,
  • Equation (1) is obtained from equation tga(100) a log
  • T a temperature at which the liquor exhaustion rate (X/ ⁇ @T corresponds to the optimum value for given equipment. It is merely necessary to determine by experiment the value tga 100).
  • Equation (1) shows that at a given liquor exhaustion rate, parallel straight lines having an inclination of a/log 2 must be obtained if the dyeing temperature T is plotted against the depth of color b on the logarithmic scale. By means of these straight lines the temperature T may be determined for any combination of dyes.
  • a combination of 0.5 percent of dye 2 (5mg ofdye/g offiber) 0.7 percent ofdye 3 (7mg of dye/g offiber) 0.9 percent of dye 4 (9mg ofdye/g of fiber) will be given as an example with reference to FIG. 2 of the drawing.
  • the dyes have the following structural formulas and the straight lines in FIG. 2 hold good for a fiber having a 4 and the stated tga (100C) values:
  • Equation (13) can therefore be used to discover the temperature at which the optimum liquor exhaustion rate is present, by means'of a preliminary experiment in which the liquor exhaustion rate at the temperature T is determined.
  • thermoregulator For example if it is certain that a liquor exhaustion rate of equation (9) at which the liquor is exhausted afiei-"fiiiiites is sufficient mined fora thermoregulator is outstandingly suitable as a reference magnitude. For any given thermoregulator there is for every dye a factor by which the amount of dye has to be multiplied in order to discover the amount of thermoregulator corresponding to it in terms of the liquor exhaustion rate. In the case of combination dyeings it is only necessary to add the amounts of dye expressed as amounts of thermoregulator in order to obtain (with reference to the straight line which is specific for the' thermoregulator) the dyeing temperature required for agiven liquor exhaustion rate.
  • the invention is illustrated by the following Examples. Parts and percentages in the Examples are by weight.
  • the liquor is first heated to 98C after which the dye solution is added. After a dyeing time of minutes, the liquor is exhausted and is cooled. The dyeing is excellently level.
  • EXAMPLE 2 One hundred parts of acrylonitrile polymer flock having a value a 3 is dyed in an aqueous liquor which contains two parts of dye 4 having a tga (100C) value of 1.66, three parts of acetic acid and 10 parts of Glauber's salt at a liquor ration of 15:1 and a temperature T of 92C calculated according to 50 the equation:
  • log T 100 (log 1.66-l og 20-log 1.36+2)
  • the value 1.36 corresponds to a liquor exhaustion rate of 5 100/ 90.60 i.e. a dyeing time of minutes.
  • Equation.(l2) gives the dependence of liquor exhaustion EXAMPLE 3
  • the liquor is heated rapidly to 955C, the yarn is taken out from the liquor and the dissolved dyes are added; as soon as the dyes have homogeneously dispersed, the yarn is reintroduced.
  • the liquor cools down to 935C. Dyeing is continued for 60 minutes at this temperature and the whole is then cooled. The dyeing obtained is excellently level.
  • One hundred parts of a high-bulk acrylonitrile polymer yarn (a 4) is dyed in an aqueous liquor which contains 0.5 part of dye 2 having a tga (100C) value of 0.81, 0.7 part of dye 3 having a tga (100C) value of 0.93, and three parts of acetic acid at a liquor ratio of 30:1 and a temperature of 91 C.
  • the temperature is ascertained graphically analogously to Example 3.
  • the liquor is rapidly brought to 100C and the yarn is bulked for 5 minutes at this temperature. The whole is then cooled and the temperature is adjusted at 91C. The dissolved dyes are then added to the liquor. After a dyeing time of 60 minutes the exhausted liquor is cooled. The dyeing is excellently level.
  • EXAMPLE 5 One hundred parts of an acrylonitrile polymer cloth (a 4) is dyed in an aqueous liquor which contains 1.3 parts of a thermoregulator 1 having the formula EXAMPLE 6
  • One hundred parts of a mixture of 50 parts of an acrylonitrile polymer fiber (a 4) and 50 parts of cotton is dyed with 1 part of a dye having a tga (100C value of 0.93 and three parts of acetic acid at a liquor ratio of 50: land at a temperature of 93C calculated according to the equation:
  • the liquor has acetic acid and dye added at 60C and is then heated to 93C. After dyeing for 90 minutes at 90C the temperature is raised rapidly to 100C and kept there for 20 minutes. An excellently level dyeing is thus obtained.
  • EXAMPLE 7 One hundred parts of a fibre mixture of 50 parts of acrylonitrile polymer (a 4) and 50 parts of polyester is dyed with 0.2 part of dye 2 having a tga (100C) value of 0.81, 0.2 part of dye 3 having a tga (100C) value of 0.93 and three parts of acetic acid at a liquor ratio of 40:1 and at a temperature of 89C. The temperature is ascertained graphically as in Example 3.
  • the dyes and acid are added to the liquor adjusted to 89C. After 60 minutes the exhausted liquor is cooled. The dyeing is excellently level.
  • EXAMPLE 10 To determine the'a value of an acrylonitrile polymer fiber of unknown origin, parts of this fibrous material is dyed at 100C and at 90C with 3 parts of dye 3 having a tga (100C) value which is not known for this fiber and three parts of acetic acid. From the measured liquor cxhuuslion rates X/m 100 c and urn/$90 c of 2.4 and 0.32 and by means ofthe equation:
  • a process for the level dyeing of an acrylonitrile polymer fibrous textile material with a cationic dye in an aqueous liquor which comprises heating the liquor to a predetermined dyeing temperature Tand dyeing the textile material with said cationic dye at this temperature at a defined liquor exhaustion rate, the temperature Tbeing determined by the equation a o T 100E (log tga(100 C.)
  • 0 denotes a constant for each specific fiber of about 3 to 5 which is the change in temperature which halves or doubles to at (100C b denotes the depth of color (in mg. of said cationic dye per g of fibrous material) to be achieved;
  • X denotes the liquor exhaustion in r. denotes the dyeing time in seconds which corresponds to the li uor exhaustion X;
  • C denotes the concentration of said cationic dye in the fiber in mg per g which is present in the fiber after the time t at a dyeing temperature of 100C.
  • a process as claimed in claim 1 which includes the step of using the value of T, where the value of tga (100) of a cationic dye for a specific fiber is not known, by dyeing said specific fiber with the cationic dye at an arbitrarily chosen temperature T and then determining the temperature Tfrom the equation where (X/ 1,)T denotes the liquor exhaustion rate at the temperature T to be measured and (X/ 113T is defined as in c aim 1.
  • tg'o((lOOC is the depth of color to be achieved in mg of” commercial dye per g of fibrous materal I dye per g of fibrous material should read tg ((lOOC) b is the depth of color to be achieved in mg of commercial dye per g of fibrous material

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US781818A 1967-12-08 1968-12-06 Process of level dyeing of fibrous poly-acrylonitrile textiles with cationic dyestuffs Expired - Lifetime US3658461A (en)

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DE19671619376 DE1619376A1 (de) 1967-12-08 1967-12-08 Verfahren zum egalen Faerben von Acrylnitrilpolymerisaten

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114214848A (zh) * 2021-12-07 2022-03-22 郎溪远华纺织有限公司 一种仿动物皮毛服装面料的染色工艺

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CH533073A4 (en)van) 1973-04-13 1975-10-31
CH620564GA3 (en) * 1975-03-21 1980-12-15 Process for the optimum conduct of dyeing processes and its use for dyeing textile material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2955009A (en) * 1957-03-28 1960-10-04 Du Pont Process of dyeing acrylonitrile articles with cationic dyes
US2978290A (en) * 1957-11-12 1961-04-04 Geigy Ag J R Coloured polymeric synthetic material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2955009A (en) * 1957-03-28 1960-10-04 Du Pont Process of dyeing acrylonitrile articles with cationic dyes
US2978290A (en) * 1957-11-12 1961-04-04 Geigy Ag J R Coloured polymeric synthetic material

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
J. Carbonell, Amer. Dyestuff Reporter, Nov. 7, 1966, pp. 71 76 and 81 *
J. J. Iannarone et al., Amer. Dyestuff Reporter, Feb. 14, 1966, pp. 52 55 *
T. Vickerstaff, The Physical Chemistry of Dyeing, (1954) Publ. Interscience Publ. Inc., New York, pp. 142 153, 161, 162. *
T. Vickerstaff, The Physical Chemistry of Dyeing, 1954, Publ. Interscience Publishers Inc., New York, pp. 157 160, TP893V5 1954 C.2 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114214848A (zh) * 2021-12-07 2022-03-22 郎溪远华纺织有限公司 一种仿动物皮毛服装面料的染色工艺

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AT289708B (de) 1971-05-10
DE1619376A1 (de) 1970-12-03
NL6817396A (en)van) 1969-06-10
GB1205100A (en) 1970-09-16
ES361205A1 (es) 1970-11-01
CH1820968A4 (en)van) 1975-08-15
CH572547B5 (en)van) 1976-02-13
FR1598368A (en)van) 1970-07-06

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