Classifications

• • 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
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/02—After-treatment
  • D06P5/04—After-treatment with organic compounds
  • D06P5/06—After-treatment with organic compounds containing nitrogen
• • 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
• • 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
  • D06P1/56—Condensation products or precondensation products prepared with aldehydes
• • 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
  • D06P1/62—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 low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
  • D06P1/621—Compounds without nitrogen
  • D06P1/622—Sulfonic acids or their salts
  • D06P1/625—Aromatic
• • 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
  • D06P1/64—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 low-molecular-weight organic compounds without sulfate or sulfonate groups
  • D06P1/642—Compounds containing nitrogen
  • D06P1/645—Aliphatic, araliphatic or cycloaliphatic compounds containing amino 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
  • 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
  • D06P3/02—Material containing basic nitrogen
  • D06P3/04—Material containing basic nitrogen containing amide groups
  • D06P3/10—Material containing basic nitrogen containing amide groups using reactive dyes
• • 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
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/02—After-treatment
  • D06P5/04—After-treatment with organic compounds
  • D06P5/08—After-treatment with organic compounds macromolecular
• • 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
  • Y10S8/916—Natural fiber dyeing
  • Y10S8/917—Wool or silk
• • 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
  • Y10S8/924—Polyamide fiber

Definitions

• This invention relates to improvements in dyeing and printing on polyamide fibers as well as, as industrial products, the dyed and printed polyamide fibers treated according to the invention.
• This known alkaline after-treatment which serves to fix on the fibers still unreacted reactive dyestuff present in the dyed goods, suffers from the drawback that the polyamide fibers can be injured by the alkaline medium and particularly by a subsequent drying step if the same is carried out directly on the after-treatment fibers.
• the after-treatment with an alkaline medium is followed usually by a further treatment in an acid medium prior to final drying of the dyed or printed fibers.
• an object of the present invention to provide, in a process of dyeing or printing polyamide fibers with reactive dyestuffs of the type described, as after-treatment of the dyed fibers for the purpose of fixing still unreacted residual dyestuff on the fibers, which after-treatment does not injure the fibers, permits of drying the aftertreated fibers directly without further intermediate treatments, and allows for a more exact control in producing a desired shade.
• the treatment according to the invention comprises, as an after-treatment in dyeing and printing processes for producing colored polyamide fibers by heating and thereby reacting said fibers together with reactive dyestuff which contains at least one mobile substituent capable of being split off as anion, in an aqueous acid medium, preferably at a pH of about 4.5 to 5, and, preferably, with subsequent rinsing of the colored fibers in water of a temperature of about 10 to preferably 60, and not more than C., and drying,
• the condensation product used as the fixing agent in the aqueous acid solution of steps (I) to (III) described supra is produced by condensation of (a) a 0:,w-di0hl010- or a,w-dibromoalkane of from 2 to 7 carbon atoms, or w,w'-dichloro-dialkylether with a total of from 4 to 8 carbon atoms, with (b) a tertiary saturated aliphatic amine with a total of from 6 to 24 carbon atoms and from two to four amino nitrogen atoms, in such molar ratio of (a):(b) that approximately one halogen atom is present in the condensation reaction for every amino nitrogen atom.
• a product produced by the condensation of (a) Dicyanodiamide, (b) At least one mole, per mole of (a), or an excess thereover, of an ammonia donator which is either urea or an ammonium salt of a mineral acid capable of splitting off ammonia, and (0) At least two moles, per mole of (a), or an excess thereover, of formaldehyde in aqueous, preferably 30% by weight, solution.
• a concentration of about 0.5 gram of condensation product per liter of solution is the minimum.
• polyamide fibers those of natural origin, above all wool and silk, but also synthetic polyamide fibers such as the various kinds of nylon e.g. nylon 6, nylon 66, and nylon 11 (Rilsan), are suitable for the after-treatment according to the invention.
• polyamide fibers are dyed by known methods in a dyestuif solution which, in addition to the dyestuffs mentioned, can also contain the auxiliaries usual in woo-l dyeing, e.g. salts such as sodium sulfate or ammonium sulfate and/or dilute acids, e.g. acetic or formic acid, and/ or wetting agents, e.g. condensation products of fatty acids having at least 8 carbon atoms and lower alkanolamines such as are described in US. Patent 2,089,212.
• auxiliaries e.g. salts such as sodium sulfate or ammonium sulfate and/or dilute acids, e.g. acetic or formic acid
• wetting agents e.g. condensation products of fatty acids having at least 8 carbon atoms and lower alkanolamines such as are described in US. Patent 2,089,212.
• the aforesaid fibers are printed by known processes in neutral or acid medium in the presence of thickeners and, optionally, urea.
• the after-treatment according to the invention with the solution of the condensation products is preferably performed in a solution which contains these products in a concentration of about 0.5 to 3 g. per liter, furthermore, optionally, other additives usual in textile dyeing, and
• acid e.g. acetic or formic acid, as mentionedabove.
• condensation products suitable for use in the first above-described mode of carrying out the invention in practice are produced as described in German Patent 611,671, issued April 5, 1935; those suitable for use in the second mode of practicing the invention described above, are produced as described in German Patent 894,237, issued October 22, 1953.
• This class of condensation products is obtained by reacting the components mentioned above at a raised temperature, about 50 to 140 C., possibly in the presence of diluents, e.g. butyl alcohol, ethylene glycol or diethylene glycol.
• diluents e.g. butyl alcohol, ethylene glycol or diethylene glycol.
• saturated aliphatic tertiary polyamines defined above there are:
• Di-, triand tetra-amines such as N .N-tetramethylhexamethylenediamine and homologues, N,N',N"-pentamethyl-di-ethylenetriamine, N,N',N",N'-hexamethyl-triethylenetetramine as well as industrial mixtures thereof also.
• Examples of :,w-dih21l0g6n alkanes are 1,2-dichloroor 1,2-dibromo-ethane, 1,3-dichloro-propane, 1,4dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane;
• w,w-di halogen ethers are, e.g., ,8,B-dichlorodiethyl ether, ethylene glycol-di-B-chloroethyl ether, p,e-di-(2-ch1oroethoxy)-di-ethyl ether, 'y,y-dichloropropyl ether as well as glycerin dichlorohydrin.
• reaction products are most effective when the ratio of the reaction components is so chosen that there is about one halogen atom per N atom, so that, for example, on using a triamine, two mols of amine are quaternized with three mols of a,w-dihalogen alkane.
• Particularly good results are obtained with the condensation product of 2 mols of N,N,N"-pentamethy1- diethylenetriamine and 3 mols of fi,/3-dichlorodiethyl ether.
• condensation products usable in the third mode of carrying out the treatment according to the invention are produced from dicyanodiamide and the ammonium salt of a strong mineral acid or urea, and formaldehyde, as described in German Patent 929,642 issued Oct. 22, 1953. Best results are obtained with compounds from this class which are produced in accordance with Example 2 of German Patent 929,642.
• the reactive dyestuffs used according to the invention can be of the most varied classes of dyestuffs.
• they are nitro, azo, anthraquinone or phthalocyanine dyestuffs, which classes excel in stability.
• They contain watersolubilizing, acid, salt-forming groups, mainly sulfonic acid groups, possibly also carboxyl groups or sulfamyl groups, in the latter case, among others, also acylated sulfamyl groups, e.g. disulfimide and carbonyl sulfimide groups.
• Mobile substituents which can be split ofli as anion are mainly: radicals of strong acids, in particular halogen atoms, of these preferably chlorine, or bromine or fluorine, the mobility of which is due, for example, to the bond at fi-carbon atoms in negatively substituted organic radicals, at S0 groups in the case of fluorine, at carbon atoms adjacent to teritary ring nitrogen in nitrogen heterocycles of aromatic character, in this case preferably 6-membered heterocycles having at least two tertiary ring nitrogen atoms; aromatically bound halogen atoms in oand/or p-position to one (or more) electrophilic gronp(s), in particular fluorine or chlorine atoms; further, for example, the radical of sulfuric acid in sulfated fl-hydroxyalkyl compounds, e.g. in sulfated ,B-hydroxy-alkyl sulfonyl and sulfamyl groups; or the radical of hydroxyary
• Dyestuffs usable according to the invention contain the substituent which can be split off as anion, for example, in the form of fl-chloroor fl-bromo-fatty acid amide groups, in which case fl-chlorocrotonic acid amide or fl-bromopropionic acid amide groups are preferred; or the said substituent is in the form of fluoroor chloronitrobenzoylamino groups or fluoroor chloro-nitrobenzene sulfonylamino groups in which the fluorine or chlorine atoms are in the oand/or p-position to the nitro groups or groups; or, preferably, it is in the form of chloroor bromo-diazinylamino triazinylamino groups, in which case it is in particular in the form of monochloroor dichloro-s-triazinylamino groups, and preferably, dior tri-chloropyrimidylamino groups.
• An advantage of the treatment according to the invention over the known processes is the elimination of an alkaline aftertreatment with, for example ammonia or hexamethylenetetramine. This advantage becomes most apparent in the dyeing and printing of wool which is sensitive to alkali, as the danger of injury to the fibers inherent in the alkaline after-treatment is avoided.
• Dyeings or prints on polyamide fibers attained according to the invention are distinguished by pure, strong and even shades and good fastness properties. In particular, they have remarkable wet fastness properties, for example fastness to water, washing, milling and perspiration, and particularly to sea-water.
• Example 1 parts of wool are dyed in 4000 parts of a dye liquor which contains the following agents:
• the goods are introduced into the liquor at 50, dyeing is performed for minutes at this temperature, the bath is brought to the boil within minutes and dyeing is continued at the boil for minutes.
• the goods are well rinsed and treated in a fresh bath for 20 minutes at -80 which contains 0.75 g. per liter of a condensation product of formaldehyde with dihydroxydiphenyl sulfone and naphthalene sulfonic acids, the production .of which condensation product is described below, as well as 0.25 g. per liter of acetic acid.
• Valuable red dyeings are obtained in this way which are very wet fast.
• sulfonating mixture obtained by heating for several hours at -160", 520 parts of naphthalene and 5 60 parts of concentrated sulfuric acid until water solubility is attained, are heated for about 1 hour at 105110 with 100 parts of a dihydroxydiphenyl sulfone, 50 parts of water and 45 parts of formaldehyde (30%).
• the dihydroxydiphenyl sulfone is obtained by heating 540 parts of phenol and 180 parts of 60% oleum for 3 hours at -180 and distilling 01f excess phenol.
• N N H A i k N 01 N N SOaH SO;H 80 11 4 1TH; Blue.
• Example 4 W001 is printed with a printing paste of the following Nylon is printed with a printing paste of the following composition: composition:
• the goods are then dried and steamed and rinsed, first The goods are then dried, steamed and well rinsed with 4 w1th cold and then with 60 warm water.
• the rinsed wool is then treated for 20 minutes at 60- 80 in a fresh bath which contains 0.75 g. per liter of the formaldehyde/dihydroxydiphenylsulfone/naphthalene sulfonic acids condensation product used in Example 1, supra, as well as 0.5 g. per liter of aqueous 80% acetic acid.
• Example 3 and 1 part of 80% acetic acid.
• the goods are entered into the liquor at 40, dyeing is performed for 10 minutes at this temperature, the bath is brought to the boil within 30 minutes and dyeing is continued for minutes at the boil.
• the goods are well rinsed and treated for 20 minutes at 6080 in a fresh bath which contains 0.75 g. per liter of the formaldehyde/dihydroxydiphenylsulfone/naphthalene sulfonic acids condensation product mentioned in paragraph 3 of Example 1 and 0.25 g. per liter of 80% acetic acid.
• the rinsed goods are after-treated in a fresh bath in the manner described in the previous Example 3.
• Example 5 100 parts of wool are dyed in 4000 parts of a dye liquor which contains the following agents:
• Example 6 W001 is printed with a printing paste of the following composition:
• the goods are then dried, steamed and well rinsed with cold water.
• the rinsed wool is after-treated as described in Example 1. In this way, valuable, vivid bluish red prints are obtained which have very good wet fasteness properties.
• Example 7 100 parts of nylon are dyed in 4000 parts of a dye liquor which contains 1.5 parts of a dyestufi of the formula and 1 part of 80% acetic acid.
• the goods are introduced at 40, dyeing is performed for 10 minutes at this temperature, the bath is brought to the boil within minutes and dyeing is continued for minutes at boiling temperature.
• the goods are well rinsed and then treated in a fresh bath for 20 minutes at 80 which contains 0.75 g. per liter of the reaction product of 2 mols of N,N,N"-pentamethyl diethylene-triamine and 3 mols of p,f3'-dichlorodiethyl ether, and also 0.5 g. per liter of 40% acetic acid.
• a fresh bath for 20 minutes at 80 which contains 0.75 g. per liter of the reaction product of 2 mols of N,N,N"-pentamethyl diethylene-triamine and 3 mols of p,f3'-dichlorodiethyl ether, and also 0.5 g. per liter of 40% acetic acid.
• Example 8 Nylon is printed with a printing paste of the following composition:
• the goods are then dried, steamed and rinsed first with cold and then with 60 warm water.
• the rinsed goods are after-treated as described in Example 3. In this way, valuable greenish yellow prints which have very good wet fastness properties are obtained.
• step II is a member selected from the group consisting of acetic acid and formic acid.
• step II the pH is adjusted to about 4.5 to 5.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Coloring (AREA)
• Polyamides (AREA)

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Citations (3)

• 1962
  • 1962-07-31 CH CH915662A patent/CH375692A/de unknown
• 1963
  • 1963-07-30 GB GB30106/63A patent/GB1002330A/en not_active Expired
  • 1963-07-30 DE DEG38359A patent/DE1283801B/de active Pending
• 1966
  • 1966-11-25 SE SE16147/66A patent/SE309768B/xx unknown
• 1967
  • 1967-05-09 US US637309A patent/US3467486A/en not_active Expired - Lifetime
• 1968
  • 1968-08-06 NL NL6811161A patent/NL6811161A/xx unknown
• 1970
  • 1970-09-01 US US27333D patent/USRE27333E/en not_active Expired
  • 1970-09-01 US US27386D patent/USRE27386E/en not_active Expired

Patent Citations (3)

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