US3854872A - Process for dyeing of polyacrylonitrile fibers - Google Patents

Process for dyeing of polyacrylonitrile fibers Download PDF

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US3854872A
US3854872A US00345850A US34585073A US3854872A US 3854872 A US3854872 A US 3854872A US 00345850 A US00345850 A US 00345850A US 34585073 A US34585073 A US 34585073A US 3854872 A US3854872 A US 3854872A
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dyeing
bath
polyamino amide
dye
quaternized
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US00345850A
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J Balland
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MFG PROD CHIMI PROTEX SOC FR A
MFG PROD CHIMI PROTEX SOC FR A RESPONSABILITE Ltd SIEGE FR
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MFG PROD CHIMI PROTEX SOC FR A
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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
    • D06P1/44—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 using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—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 using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5278—Polyamides; Polyimides; Polylactames; Polyalkyleneimines
    • 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
    • D06P1/44—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 using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/655—Compounds containing ammonium groups
    • D06P1/66—Compounds containing ammonium groups containing quaternary ammonium groups
    • 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

Definitions

  • polyacrylonitrile fibers are dyed in general utilizing cationic dyes such as those for example of the series of triaryl methane, oxazine, etc.
  • the application of cationic dyes onto the polyacrylonitrile fibers can be accomplished by different dyeing processes.
  • the bath dyeing that is by exhausting dye baths, the taking up and the fixation of the dye into the fiber can be correctly obtained only at temperatures less than those in the vicinity of the boiling point of water.
  • the present invention more particularly relates to the use of new retarding agents in the dye baths with the cationic dyes.
  • FORMULA I in which R, R and R' are alkyl radicals, identical or FORMULA ll H N- R-Nm H in which at is at least equal to one;
  • R is an alkylene radical having one to five carbon atoms, such as ethylene, propylene, butylene, etc.
  • polyamines should in addition contain at least four atoms of reactive hydrogenper molecule as, for example, ethylene diamine (E.D.A. diethylene triamine (D.E.T.A.), triethylene tetramine (T.E.T.A.), etc.
  • E.D.A. diethylene triamine (D.E.T.A.) diethylene triamine (D.E.T.A.)
  • T.E.T.A. triethylene tetramine
  • composition of the quatemized polyamino amide compounds which are known and used according to the present invention can be schematically represented by the following generic formula:
  • a sample of polyacrylonitrile fabric was introduced into an-aqueous solution at 60C containing 0.5% of blue dye, C.l. (Color Index) basic blue 54, 4% of acetic acid (40%) and 0.5% of quatemized polyamino amide, the percentages given being calculated with respect to the weight of the fiber to be dyed.
  • the proportion of dyeing bath was from one to twenty (that is, 20 ml of bath per i g. of material to be dyed).
  • the temperature was brought in 30 minutes to 100C, then the dyeing was maintained at this temperature for an hour. After-this period, the bath was practically exhausted.
  • the sample wasthen subjected to a rinsing and then a drying.
  • the polyamino amide utilized in the example was obi tained' by condensation of a fatty diacid (EMPOL 1024) with ethylene diamine, followed by quatemization by the .chloride of epoxypropyltrimethyl ammonium.
  • EXAMPLE 2 A sample of polyacrylonitrile fabric .was' introduced amide, the percentages being calculated with respect to A the weight of the fabric. The proportion of the bath was 1 to 20.
  • the polyamino amide utilized was identical to that used in Example 1.
  • the polyamino amide was obtained by condensation of a fatty acid (EMPOL 1024 with diethylene triamine, then. quatemized by the chloride of epoxypropyl trimethyl ammonium.
  • EXAMPLE 4 A sample of polyacrylonitrile fabric was dyed utilizing the dye and under the identical conditions as in Example l.
  • the polyamino amide utilized was obtained by condensation of a fatty acid (EMPOL 1024) with triethylene tetramine, followed by quatemization by the chloride of epoxypropyl trimethyl ammonium.
  • the blue sample, of fabric was introducedsimultaneously with a white sample of the same material of the same weight into an aqueous bath free of dye containing 4% of acetic acid (40%),
  • a process for dyeing polyacrylonitrile fabrics in an aqueous bath containing a cationic colorant comprising adding to the bath as a retarding and equalization of dyeing agent, a quatemized polyamino amide obtained by the condensation of a fatty diacid with a polyamide having at least four reactive hydrogen atoms per molecule having the formula in which x is at least equal to 1 and R is an alkylene radical containing one to five carbon atoms, the polyamino amide then being quatemized by a salt of epoxy propyl trialkyl ammonium of the formula V different, having one to three carbon atoms, and X is a radical selected from the group consisting of Cl,
  • An aqueous dyeing bath for polyacrylonitrile fabrics comprising a cationic dye, and as a retarding and equalization of dyeing agent, a quatemized. polyamino amide obtained by, the condensation'of a fatty diacid with a polyamine having at least four reactive hydrogen atoms per molecule haying the formula lhN-(R-NHF-l-l in which x is at least equal to l and R is an alkylene radical containing one to five carbon atoms, the polyamino amide then being quatemized by a salt of epoxy propyl trialkyl ammonium of the formula in which R, R" and R are alkyl radicals, identical or different, having one to three carbon atoms, and X is a radical selected from the group consisting of Cl, N0 and S0 7 4.
  • An aqueous dyeing bath according to claim 3 wherein the proportion of the quatemized polyaminoamide in the dye bath is between 0.2 and 5% per with

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coloring (AREA)

Abstract

A process for dyeing polyacrylonitrile fibers in an aqueous bath containing a cationic dye which utilizes as a retarding and equalizing agent 0.2- 5 percent of a quaternized polyamino amide obtained by condensation of a fatty diacid and a polyamine followed by quaternization by a salt of epoxy propyltrialkyl ammonium.

Description

Elite States Patent [191- Balland Dec. 17, 1974 PROCESS FOR DYEING OF [56] References Cited POLYACRYLONITRILE FIBERS UNITED STATES PATENTS [75] lnventor: Jean Balland, Chateaurenault, 3,619,121 11/1971 Boehmke 8/169 France 3,716,329 2/1973 Komninos et al... 8/169 3,773,463 11/1973 Cohen et al. 8/169 A gn Societe dite: Manufacture de 3,785,768 1/1974 Walz et al 8/84 Produits Chimiques PROTEX Societe Francaise a Responsabilite P i Examiner-Benjamin R. Padgett Limiiee g Paris, France Assistant ExaminerB. Hunt ['22] Filed: Man 29 1973 Attorney, Agent, or FirmBrowdy & Neimank 211 App]. NO.I 345,850 57 ABSTRACT I A process for dyeing polyacrylonitrile fibers in an 30 Foreign Application priority Data aqueous bath containing a cationic dye which utilizes A r 7 1972 France 72 12861 as a retarding a'nd equalizing agent 0.2-5 percent of a p quaternized polyamino amide obtained by condensa- [52] U S Cl 8/169 8/177 R 8/172 tion of a fatty diacid and a polyamine followed by [51] D06p 5/06 quaternization by a salt of epoxy .propyltrialkyl ammo- [58] Field of Search 8/169, 85, 172, 177 R 4 Claims, N0 Drawings PROCESS FOR DYEING OF POLYACRYLONITRILE FIBERS The present invention relates to the dyeing of polyacrylonitrile fibers with cationic dyes.
It is known that polyacrylonitrile fibers are dyed in general utilizing cationic dyes such as those for example of the series of triaryl methane, oxazine, etc.
The use of these dyes in general .permits obtaining polyacrylonitrile fibers of brilliant and intense colors having good general strengths.
The application of cationic dyes onto the polyacrylonitrile fibers can be accomplished by different dyeing processes. However, in the bath dyeing, that is by exhausting dye baths, the taking up and the fixation of the dye into the fiber can be correctly obtained only at temperatures less than those in the vicinity of the boiling point of water. v
It is known that at these temperatures, and generally starting at 80C, the exhaustion of the cationic dye baths by the polyacrylonitrile fiber is produced too rapidly. The result of this rapid exhaustion of the dye baths is manifested frequently in practice according to the intensity of the colors obtained, by a lack of uniformity of the color of the material. It is for this latter reason that the dyeing of polyacrylonitrile fibers often necessitates the use of a retarding agent so as to restrain the speed of taking up of the dyes by-the fiber and to obtain better uniformity.
The present invention more particularly relates to the use of new retarding agents in the dye baths with the cationic dyes.
It has been found that the use in the dye baths of products resulting from the. cationization of polyamide resins having free hydrogen amines in the chain by salts of the type: halogenated epoxy propyltrialkyl ammonium corresponding to generic Formula I hereafter, permitted reduction of the velocity of taking up of the cationic dyes into the polyacrylonitrile fiber and to obtain thereby a good uniformity of the dyed material.
The salts of epoxy propyl trialkyl ammonium which serve to cationize the polyamide resins have the following formula:
FORMULA I in which R, R and R' are alkyl radicals, identical or FORMULA ll H N- R-Nm H in which at is at least equal to one;
R is an alkylene radical having one to five carbon atoms, such as ethylene, propylene, butylene, etc.
These polyamines should in addition contain at least four atoms of reactive hydrogenper molecule as, for example, ethylene diamine (E.D.A. diethylene triamine (D.E.T.A.), triethylene tetramine (T.E.T.A.), etc.
. The composition of the quatemized polyamino amide compounds which are known and used according to the present invention can be schematically represented by the following generic formula:
FORMULA Ill The following examples which are given in an illustrative manner only, show how the invention can be put into practice. Examples 1-4 illustrate the qualities of uniformity of dyeing given in the presence of the cationic resins whereas Examples 5 and 6 show the equalizing effect of these resins in the dyeing, by migration of cationic dyes from a sample already dyed to a white sample.
A sample of polyacrylonitrile fabric was introduced into an-aqueous solution at 60C containing 0.5% of blue dye, C.l. (Color Index) basic blue 54, 4% of acetic acid (40%) and 0.5% of quatemized polyamino amide, the percentages given being calculated with respect to the weight of the fiber to be dyed. The proportion of dyeing bath was from one to twenty (that is, 20 ml of bath per i g. of material to be dyed).
The temperature was brought in 30 minutes to 100C, then the dyeing was maintained at this temperature for an hour. After-this period, the bath was practically exhausted. The sample wasthen subjected to a rinsing and then a drying.
There was obtained a blue shade having very good uniformity.
The polyamino amide utilized in the example was obi tained' by condensation of a fatty diacid (EMPOL 1024) with ethylene diamine, followed by quatemization by the .chloride of epoxypropyltrimethyl ammonium.
EXAMPLE 2 A sample of polyacrylonitrile fabric .was' introduced amide, the percentages being calculated with respect to A the weight of the fabric. The proportion of the bath was 1 to 20.
The conditions of dyeing were identical to those of Example 1, and there was obtained a violet color having an excellent uniformity.
The polyamino amide utilized was identical to that used in Example 1.
EXAMPLE 3 Asample-of polyacrylonitrile fabric was dyed with the dye and under the same conditions as Example 1.
The polyamino amide was obtained by condensation of a fatty acid (EMPOL 1024 with diethylene triamine, then. quatemized by the chloride of epoxypropyl trimethyl ammonium.
There is obtained a blue shade having perfect uniformity.
EXAMPLE 4 A sample of polyacrylonitrile fabric was dyed utilizing the dye and under the identical conditions as in Example l.
The polyamino amide utilized was obtained by condensation of a fatty acid (EMPOL 1024) with triethylene tetramine, followed by quatemization by the chloride of epoxypropyl trimethyl ammonium.
There was obtained'a blue color having good uniformity.
v EXAMPLE 5 A sample of polyacrylonitrile fabric was dyed, for the in which R, R" and R' are alkyl' radicals, identical or I first time, under the same conditions and with the same products as in Example 1. 7
After rinsing and drying, the blue sample, of fabric was introducedsimultaneously with a white sample of the same material of the same weight into an aqueous bath free of dye containing 4% of acetic acid (40%),
10% of NaCl and 4% of the quatemized polyamide of Example 1, the percentages being calculated in parts 1 with respect to the bath. The proportion of bath was EXAMPLE 6- y A sample of polyacrylonitrile fabric was dyed under thecondition's of Example 1 except that the fabric was found to have numerous spots after dyeing, for example, caused by a poor rinsing.
The color was treated exactly as in Example 5 in a bath free of dye and containing the quatemized poly- I amide simultaneously with a white sample. 7
it was found that both the blue and the white samples treated had taken on a beautiful uniform blue color,
demonstrating a perfect migration and equalization of the initial dye.
It will be obvious to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not to'be considered limited to what is described in thespecificatron. r
What is claimed is: a
l. A process for dyeing polyacrylonitrile fabrics in an aqueous bath containing a cationic colorant comprising adding to the bath as a retarding and equalization of dyeing agent, a quatemized polyamino amide obtained by the condensation of a fatty diacid with a polyamide having at least four reactive hydrogen atoms per molecule having the formula in which x is at least equal to 1 and R is an alkylene radical containing one to five carbon atoms, the polyamino amide then being quatemized by a salt of epoxy propyl trialkyl ammonium of the formula V different, having one to three carbon atoms, and X is a radical selected from the group consisting of Cl,
N0 and S011 2. A process according to claim 1 wherein the pro-- portion of the quatemized polyamino amide added to the dye bath is between 0.2 and 5% per weight of the fabric to be dyed based on the dry material.
3. An aqueous dyeing bath for polyacrylonitrile fabrics comprising a cationic dye, and as a retarding and equalization of dyeing agent, a quatemized. polyamino amide obtained by, the condensation'of a fatty diacid with a polyamine having at least four reactive hydrogen atoms per molecule haying the formula lhN-(R-NHF-l-l in which x is at least equal to l and R is an alkylene radical containing one to five carbon atoms, the polyamino amide then being quatemized by a salt of epoxy propyl trialkyl ammonium of the formula in which R, R" and R are alkyl radicals, identical or different, having one to three carbon atoms, and X is a radical selected from the group consisting of Cl, N0 and S0 7 4. An aqueous dyeing bath according to claim 3 wherein the proportion of the quatemized polyaminoamide in the dye bath is between 0.2 and 5% per with of the fabric to be dyed based on, the dry material.

Claims (4)

1. A PROCESS FOR DYEING POLYACRYLONITRILE FABRICS IN AN AQUEOUS BATH CONTAINING A CATIONIC COLORANT COMPRISING ADDING TO THE BATH AS A RETARDING AND EQUALIZATION OF DYEING AGENT, A QUATERNIZED POLYAMINO AMIDE OBTAINED BY THE CONDENSATION OF A FATTY DIACID WITH A POLYAMIDE HAVING AT LEAST FOUR REACTIVE HYDROGEN ATOMS PER MOLECULE HAVING THE FORMULA
2. A process according to claim 1 wherein the proportion of the quaternized polyamino amide added to the dye bath is between 0.2 and 5% per weight of the fabric to be dyed based on the dry material.
3. An aqueous dyeing bath for polyacrylonitrile fabrics comprising a cationic dye, and as a retarding and equalization of dyeing agent, a quaternized polyamino amide obtained by the condensation of a fatty diacid with a polyamine having at least four reactive hydrogen atoms per molecule having the formula H2N-(R-NH)x-H in which x is at least equal to 1 and R is an alkylene radical containing one to five carbon atoms, the polyamino amide then being quaternized by a salt of epoxy propyl trialkyl ammonium of the formula
4. An aqueous dyeing bath according to claim 3 wherein the proportion of the quaternized polyamino amide in the dye bath is between 0.2 and 5% per with of the fabric to be dyed based on the dry material.
US00345850A 1972-04-07 1973-03-29 Process for dyeing of polyacrylonitrile fibers Expired - Lifetime US3854872A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5667533A (en) * 1996-02-07 1997-09-16 The Virkler Company Heather dyed fabric and method of producing same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3619121A (en) * 1969-08-07 1971-11-09 Bayer Ag Polyacrylonitrile dyeing with n-alkylaminoalkylsulfonic acids and basic dyes
US3716329A (en) * 1970-11-27 1973-02-13 J Komninos Dyeing polyacrylonitrile with basic dyestuff and alkoxymethyl quaternary ammonium compounds
US3773463A (en) * 1972-04-18 1973-11-20 Sybron Corp Lubricating, antistat and dye leveling agent and process for textile materials
US3785768A (en) * 1970-09-11 1974-01-15 Bayer Ag Process for the dyeing of fibre material consisting of polyacrylonitrile or acrylonitrile-containing copolymers

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1190096A (en) * 1957-01-14 1959-10-09 Ciba Geigy New diquaternary ammonium compounds and process for their preparation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3619121A (en) * 1969-08-07 1971-11-09 Bayer Ag Polyacrylonitrile dyeing with n-alkylaminoalkylsulfonic acids and basic dyes
US3785768A (en) * 1970-09-11 1974-01-15 Bayer Ag Process for the dyeing of fibre material consisting of polyacrylonitrile or acrylonitrile-containing copolymers
US3716329A (en) * 1970-11-27 1973-02-13 J Komninos Dyeing polyacrylonitrile with basic dyestuff and alkoxymethyl quaternary ammonium compounds
US3773463A (en) * 1972-04-18 1973-11-20 Sybron Corp Lubricating, antistat and dye leveling agent and process for textile materials

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5667533A (en) * 1996-02-07 1997-09-16 The Virkler Company Heather dyed fabric and method of producing same

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FR2178833A1 (en) 1973-11-16
DE2317492A1 (en) 1973-10-18

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