|Publication number||US3577212 A|
|Publication date||May 4, 1971|
|Filing date||Aug 7, 1967|
|Priority date||Aug 8, 1966|
|Also published as||DE1619186A1|
|Publication number||US 3577212 A, US 3577212A, US-A-3577212, US3577212 A, US3577212A|
|Inventors||Bouvet Pierre Charles Victor, Jirou Marcel Georges|
|Original Assignee||Ugine Kuhlmann|
|Export Citation||BiBTeX, EndNote, RefMan|
|Referenced by (4), Classifications (20), Legal Events (2)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent 3,577,212 PROCESS FOR THE MODIFICATION OF POLYAMIDE FIBERS Marcel Georges Jirou, Sotteville les Rouen, and Pierre Charles Victor Bouvet, Petit-Quevilly, France, assignors to Ugine Kuhlmann, Paris, France No Drawing. Filed Aug. 7, 1967, Ser. No. 658,613 Claims priority, applic rilgigrsFrance, Aug. 8, 1966,
Int. 01. 1506 3/34 US. Cl. 8-1155 7 Claims ABSTRACT OF THE DISCLOSURE Process for the modification of synthetic polyamide fibers which comprises treating the fibers at a pH of from 3 to 11 inclusive and at a temperature of from 40 C. to the boiling temperature of the bath with a compound of the formula:
The present invention relates to a process for the modification of synthetic polyamide fibers such as for example nylon, Rilsan or caprolactam polymers.
It has in fact been found that polyamide fibers can be modified in an interesting way by treating them with solutions, suspensions or dispersions of non-colouring compounds, free from carboxylic and sulphonic groups, corresponding to the general formula:
it (I) in which A represents a colourless aliphatic, aromatic or heterocyclic radical possibly carrying at least one nonauxochrome substituent such as for example chlorine or bromine atoms, or alkyl or alkoxy groups, W represents the residue of an acylating agent carrying an atom or group of atoms capable of reacting with the polyamide fibers, and R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
The compounds of Formula I may advantageously be prepared by condensing an acylating agent or residue W with a sulphonamide of the formula:
.m-s Og-N-H in which A and R have the same significance as above.
Examples of acylating agents which may be mentioned in which the residue W contains atoms or groups of atoms which permit reaction with the polyamide fibers, are halogenated triazines such as 2,4,6-trichloro s triazine, s-triazines of the general formula:
(III) Patented May 4, 1971 ice in which A represents a colourless organic radical free from sulphonic and carboxylic groups, halogenated pyrimidines such as for example 2,4,6-trichloro-pyrimidine, 2,4,5,6-tetrachloro-pyrimidine or the trichloropyrimidines substituted in the 5 position by a methyl, nitro or cyano group, and acid chlorides such as for example those of 2,4 dichloro-pyrimidine-G-carboxylic acid, 2,3-dichloroquinoxaline S-carboxylic acid, 2,3, dichloro-quinoxaline- 6 carboxylic acid, 1,4 dichloro-phthalazine 5 or 1,4- dichloro-phthalazine 6 carboxylic acid, ,B-chloropro pionic acid or acrylic acid.
Examples of organic radicals A which are free from sulphonic and carboxylic groups are alkyl or aryl groups and the residues of primary or secondary amines.
Sulphonamides of Formula II which may be used for the preparation of compounds of Formula I are: benzenesulphonamide, ortho-, meta-, and para-toluenesulphonamides, ortho-, meta-, and para-chlorobenzenesulphonamides, 1 methyl 4 chlorobenzene 2 sulphonamide, l methyl 5 chlorobenzene-Z-sulphonamide, 1-methyl- 6 chlorobenenze 2 sulphonamide, 1-methy1-2-chlorobenzene 3 sulphonamide, l-methyl-6-chlorobenzene-3- sulphonamide, 1 methyl 2 chlorobenzene-4-sulphonamide, 4 chlorobenzylsulphonamide, 2,4 dichlorobenzenesulphonamide, 2,5 dichlorobenzene sulphonamide, and 3,4-dichlorobenzene-sulphonamide.
The treatment of the polyamide fibers is effected with a quantity of a compound of Formula I between 0.1% and 20%-of the weight of the material to be treated. When the compounds of Formula I are soluble in water, especially when R is a hydrogen atom they can be used in solution. If they are insoluble or not very soluble in water they can be used in the form of a fine dispersion. The compounds of Formula I can also be applied to the polyamide fibers in the form of printing pastes.
The treatment of the polyamide fibers with the solutions or dispersions of the compounds of Formula I can be made in an acid, neutral or alkaline bath having a pH between 3 and 11 and at a temperature between 40 C. and the boiling temperature of the treatment bath. For example, the treatment can be begun at a pH between 3 and 6 and finished at a value between 7 and .11. The treatment can also be effected directly at pH values between 7 and 11. After a first phase of treatment in an acid bath, the treatment can be prolonged in an alkaline bath charged with electrolytes at pH values between 7 and 11.
The compounds with an acid reaction which may be used to modify the pH may be, for example, sulphuric, formic or acetic acid or their salts such as ammonium acetate or ammonium sulphate. The compounds having an alkaline reaction may be, for example, the alkali metal bicarbonates, carbonates or phosphates, borax, sodium acetate, ammonia or triethanolamine. Neutral salts which may be used are for example, sodium chloride or sodium sulphate. Finally, it is possible to use during the treatment the auxiliary products usually employed for dyeing polyamides.
The polyamide fibers treated according to this invention have different properties from ordinary polyamide fibers, in particular, the affinity of acid dyestuffs for the treated fibers is considerably reduced and may even be rendered practically nil.
The invention is illustrated by but not limited to the following examples, in which the parts and percentages are by weight and the temperatures are in degrees centigrade.
EXAMPLE 1 10 parts of nylon thread are introduced at ambient temperature into a bath containing 200 parts of water, 1 part of the sodium salt of the condensate from one mole of paratoluene-sulphonamide with one mole of cyanuryl chloride prepared according to the process described in the Journal of the Chemical Society, 1963, page 4131, 0.5 part of crystalline ammonium acetate and 10 parts of anhydrous sodium sulphate. The temperature of the bath is brought to boiling in a period of 30 minutes, and this temperature is maintained for an hour. The temperature of the bath is then reduced to 95 C., and the pH is brought to 8 by the addition of dilute ammonia. The treatment is continued for 15 minutes. The nylon thread is then washed with soap and rinsed.
The thread thus treated and an untreated thread are then dyed with the dyestulf known by the name of Rouge Ponceau Acide BL (Colour Index Acid Red 106. The dyestuff possesses very little affinity for the treated nylon, while the untreated thread is dyed a bright red.
EXAMPLE 2 10 parts of nylon thread are introduced 'at ambient temperature into a bath containing 200 parts of water, 1 part of the sodium salt of the condensate from one mole of parachlorobenzene sulphonamide with one mole of cyanuryl chloride, 10 parts of sodium chloride and 0.2 part of sodium bicarbonate. The temperature of the bath is brought to boiling temperature in a period of 45 minutes and this temperature is maintained for one hour. The thread is washed with soap and rinsed. The behaviour of the treated nylon is comparable with that described in Example 1.
EXAMPLE 3 10 parts of nylon thread are introduced into a bath at 40 C. containing 300 parts of water, 0.5 part of the monosodium salt of the condensate from one mole of paratoluene sulphonamide with one mole of the chloride of 2,3-dichloroquinoxaline-fi-carboxylic acid. The bath, the pH of which is regulated at 5 by the addiiton of 1% acetic acid, is taken to boiling temperature in a period of 30 minutes and is maintained at this temperature for 30 minutes. The temperature of the bath is then reduced to 95 C. and the pH is brought to a value of 8 by the addition of disodium phosphate, and the treatment is followed for 15 minutes. The thread is washed with soap and rinsed. fIhe behaviour of the nylon towards acid dyestuffs is similar to that described in Example 1.
EXAMPLE 4 A printed paste is prepared containing the following components:
60 parts of the sodium salt of the condensate from one mole of paratoluene sulphonamide with one mole of cyanuryl chloride 60 parts of thiourea 500 parts of a 4% alginate thickener 20 parts of sodium acetate 360 parts of water 1000 parts A nylon fabric is printed with this paste and steamed for 30 minutes at 100-102 C. It is rinsed, washed with soap, rinsed again and immersed in a dyebath containing 1 g. per litre of bath liquid of the dyestulf known as Rouge Ponceau Acide BL. The fabric is dyed red, the printed parts remaining white.
EXAMPLE 5 10 parts of nylon" thread are introduced into a bath at 40 C. containing 200 parts of water, 1 part of the sodium salt of the condensate from one mole of paratoluene sulphonamide with one mole of cyanuryl chloride, 20 parts of anhydrous sodium sulphate, 10 parts of 1% acetic acid and 10 parts of 10% sodium acetate. The temperature of the bath is brought to boiling in the course of 30 minutes and is maintained at this temperature for one hour. The nylon is then treated for an hour in a second bath at C. containing per litre 250 g. of sodium chloride and 65 g. of 2% ammonia, washed with soap and rinsed. The behaviour of the nylon towards acid dyestufls is similar to that described in Example 1.
EXAMPLE 6 If in Example 5 the 2% ammonia is replaced by a 10% solution of triethanolamine, analogous results are obtained.
1. Process for the modification of synthetic polyamide fibres which comprises treating the fibres at a pH of from 3 to 11 inclusive and at a temperature of from 40 C. to the boiling temperature of the bath with a compound of the formula:
in which A represents the radical of a non-colouring compound of the aliphatic, aromatic or heterocyclic series free from carboxylic and sulphonic groups, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and W represents a halogenated triazinyl group, a halogenated pyrimidinyl group, the 2,4dichloro-pyrimidine-6-carbonyl group, the 2,3-dich1oroquinoxa1ine-5-carbonyl group, the 2,3-dichloro-quinoxaline-G-carbonyl group, the.1,4-dichloro-phthalazine-5-carbonyl group, the 1,4-dichloro-phthalazine-6-carbonyl group, the ,B-chloropropionyl group of the acryloyl group, the compound (I) being present in the amount of between 0.1% and 20% by weight of the polyamide fibres.
2. Process according to claim 1 wherein A carries at least one non-aux0chrome substituent.
3. Process according to claim 1 wherein the compound (I) is used in the form of an aqueous solution.
4. Process according to claim 1 wherein the compound (I) is used in the form of an aqueous dispersion.
5. Process for the modification of synthetic polyamide fibres which comprises applying thereto a printing paste containing a compound of the Formula I, in the amount of between 0.1% and 20% and steaming the printed fibres.
6. Process according to claim 1 wherein the treatment is in two stages, the first being in an acid bath containing the compound of the Formula I and the second in an alkaline bath charged with electrolyte at a pH between 7 and 11.
7. Synthetic polyamide fibers modified by a process according to claim 1.
DONALD LEVY, Primary Examiner T. J. HERBERT, JR., Assistant Examiner U.S. Cl. X.R.
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US4780099 *||Aug 26, 1986||Oct 25, 1988||E. I. Du Pont De Nemours And Company||Method for producing stain resistant polyamide fibers|
|US5316850 *||Apr 12, 1991||May 31, 1994||Peach State Labs, Inc.||Permanently stain resistant textile fibers|
|US5629376 *||May 17, 1993||May 13, 1997||Peach State Labs, Inc.||Polyacrylic acid compositions for textile processing|
|US6524492||Dec 28, 2000||Feb 25, 2003||Peach State Labs, Inc.||Composition and method for increasing water and oil repellency of textiles and carpet|
|U.S. Classification||8/115.59, 528/331, 8/115.64, 8/115.58, 525/420, 8/540|
|International Classification||D06M13/438, D06P1/642, D06P5/22, D06P1/64, D06M13/00, D06P5/12|
|Cooperative Classification||D06P5/22, D06M13/438, D06P5/12, D06P1/6426|
|European Classification||D06P5/12, D06P1/642L, D06M13/438, D06P5/22|
|Aug 24, 1984||AS||Assignment|
Owner name: PECHINEY UGINE KUHLMANN
Free format text: MERGER;ASSIGNOR:UGINE KUHLMANN;REEL/FRAME:004319/0671
Effective date: 19840820
Owner name: PRODUITS CHIMIQUES UGINE KUHLMANN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:PECHINERY UGINE KUHLMANN;REEL/FRAME:004319/0683
|Nov 28, 1983||AS||Assignment|
Owner name: PRODUITS CHIMIQUES UGINE KUKLMANN TOUR MANHATTAN L
Free format text: CHANGE OF NAME;ASSIGNOR:CHARLES DAVENPORT;REEL/FRAME:004245/0711
Effective date: 19831116