WO1995009266A1 - Process to improve resistance to stains on yarns and derived products - Google Patents

Process to improve resistance to stains on yarns and derived products Download PDF

Info

Publication number
WO1995009266A1
WO1995009266A1 PCT/BE1994/000062 BE9400062W WO9509266A1 WO 1995009266 A1 WO1995009266 A1 WO 1995009266A1 BE 9400062 W BE9400062 W BE 9400062W WO 9509266 A1 WO9509266 A1 WO 9509266A1
Authority
WO
WIPO (PCT)
Prior art keywords
substrate
tannic acid
acid
solution
during
Prior art date
Application number
PCT/BE1994/000062
Other languages
French (fr)
Inventor
Armand De Lathauwer
Original Assignee
N.V. Denderland-Martin
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by N.V. Denderland-Martin filed Critical N.V. Denderland-Martin
Priority to EP94926733A priority Critical patent/EP0721524B1/en
Priority to US08/619,673 priority patent/US6024770A/en
Priority to DK94926733T priority patent/DK0721524T3/en
Priority to CA002172988A priority patent/CA2172988C/en
Priority to AU76486/94A priority patent/AU681188B2/en
Priority to DE69429360T priority patent/DE69429360T2/en
Publication of WO1995009266A1 publication Critical patent/WO1995009266A1/en

Links

Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224Esters of carboxylic acids; Esters of carbonic acid
    • D06M13/238Tannins, e.g. gallotannic acids
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/44General 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
    • D06P1/653Nitrogen-free carboxylic acids or their salts
    • D06P1/6533Aliphatic, araliphatic or cycloaliphatic
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92Synthetic fiber dyeing
    • Y10S8/924Polyamide fiber
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/929Carpet dyeing
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/93Pretreatment before dyeing

Definitions

  • This invention relates to a process to improve the resistance to stains on yarns on the basis of silk, wool, polyamide, polyester, polyacrylonitrile , natural and artificial cellulosic fibres and in general all other synthetic fibres which can be dyed, by which the resistance of the dyed fibres against stains, especially coloured stains, is increased, whilst at the same time also other improved characteristics are obtained.
  • yarns has to be understood, yarns whether greige (raw) or processed, yarns unfinished or finished, bright as well as dull, in yarn form or processed to fabric, felt, knitwear, non- woven, carpets, rugs, etc.
  • substrate yarn in which form whatsoever will be called “substrate” .
  • the purpose of this invention is to propose a process by which the resistance of a coloured or uncoloured substrate against stains of any nature is considerably improved and which at the same time improves the antistatic behaviour, as well as the resistance to soiling, house-mite and oxidative bleaching agents .
  • tannin is used to fix dyestuff after the dyeing process.
  • the substrate in acid medium, is treated with a solution containing 5 to 50 gram tannic acid per litre water and preferably between 25 to 35 g/1.
  • concentrations and proportions are not critical, though it has been noticed that higher concentrations hardly influence the result but could cause a yellowing of the substrate.
  • Tannic acid is a compound derived for several centuries from nutgalls and has a structure of polygalloylglucose or polygalloylquinic acid.
  • tannic acid as used in this description and claims should be understood in a broad sense, and covers products containing tannic acid, such as for instance gallotannin.
  • tannic acid is a mixture of compounds consisting of a glucose- chain which is several times substituted with gallic acid or trihydroxy-3,4,5-benzoic-acid-l . Substitution can also be made with digallic acid or with trigallic acid.
  • Tannic acid e. g. contains nonagalloylglucose, a glucose-chain substituted 5 times with gallic acid, 4 times of which is digallic acid and the formula of which is the following:
  • any commercial tannic acid can be used, though it is economical to use a tannic acid with a relatively high molecular weight.
  • the molecular weight of the tannic acid will preferably be between 900 and 3500, though this range is not critical.
  • optimum results are achieved when a mixture of a tannic acid with a relatively low MW and a tannic acid with a relatively high MW is used. So it has been shown that a mixture, consisting of a tannic acid with an average MW lower than 1000 and a tannic acid with an average MW higher than 1500, gives better results than tannic acid of exclusively 1500 MW.
  • the tannic acid is used in an aqueous solution.
  • aqueous solution For the man skilled in the art, it will be clear that the water has to be de-ironed and softened.
  • a small quantity of an aliphatic carboxylic acid with a boiling-point lower than 100°C, e. g. acetic acid, can be added.
  • a non volatile, non hygroscopic and preferably non corroding acid as e.g. an aliphatic carboxylic acid such as citric acid or polyacrylic acids .
  • a wetting agent such as e.g. isopropanol.
  • a complexing agent for instance a polyvalent salt, which can neutralise the free OH groups from the tannic acid.
  • a complexing agent for instance a polyvalent salt, which can neutralise the free OH groups from the tannic acid.
  • Potassium antimonyl tartrate or alum aluminium potassium sulphate
  • a concentration relating to the tannic acid concentration varying between 2/1 to 1/2.
  • the complexing agent shall preferably be dissolved in water at the ambient temperature and to this solution a non volatile acid, which does not evaporate during steaming of the substrate, can be added.
  • Aliphatic carboxylic acids can be used in a concentration varying between 1 to 10 g per litre water.
  • the solution with complexing agent is added to the tannic acid solution and the mixture should have preferably a pH between 2.5 and 5. If not the pH must possibly be adjusted by adding an acid for instance a sulfamic acid, formic acid, acetic acid. . . Strong mineral acids have to be avoided.
  • the substrate shall be treated with the tannic acid solution during the dyeing step and can be inserted in a continuous procedure as well as in a discontinuous procedure, and the treatment can be made before, during or after the effective dyeing step .
  • the substrate will be impregnated or saturated with the solution of tannic acid.
  • dyeing is used in this description for any process by which dyes are applied on a substrate, such as dyeing, printing, spacing, spraying, etc in a single or in multiple steps .
  • the dyes to be applied are dissolved in water, possibly by heating, and afterwards adjusted to the right volume with cold water.
  • the operation will preferably be done in an acid medium.
  • an acid-resisting thickening agent such as a hydrocolloid, e. g. Xanthanegum, will be added.
  • Dyestuffs suitable to be applied according to the invention are in general acid, metalcomplex as well as disperse dyes .
  • Basic dyestuffs are also suitable, however when using them it is recommended to apply the treatment according to the invention, as an additional treatment.
  • a good pre-selection of dyestuffs will be made through obvious criteria. It can e. g. be useful to select dyestuffs with fast fixing properties.
  • the substrate In case of a continuous process, the substrate, after treatment and dyeing, is steamed during a half to a few minutes with airfree saturated steam. After steaming, the coloured substrate is rinsed, preferably with water, at which a stabiliser can be added, preferably a non volatile, non hygroscopic, and non corroding acid, e.g. an aliphatic carboxylic acid, in a concentration e.g. between 0,5 to 5 g/1.
  • a stabiliser preferably a non volatile, non hygroscopic, and non corroding acid, e.g. an aliphatic carboxylic acid, in a concentration e.g. between 0,5 to 5 g/1.
  • the rinsing will preferably be done with hot water (60°- 90°C) , without complexing agent, the rinsing water will be cold water.
  • the tannic acid solution can be added to the dyebath or the treatment can be done in a separate bath.
  • an unknown resistance to colour stains of natural or synthetic origin containing anionic, cationic, metalcomplex or disperse dyestuffs is achieved.
  • Stains of coffee at 70° C, kool-aid (highly coloured soft-drink) , wine, ink, etc. can easily be removed by wetting the stain with cold or lukewarm water, and dry dabbing.
  • examples 1 to 5 deal with a treatment during a continuous process
  • examples 6 to 8 with a treatment during a discontinuous process
  • examples 9 and 10 relate to an additional treatment .
  • a solution is prepared by dissolving 25 g tannic acid with a MW of 2500 (Mijimoto commercial product) in 1 1 of soft water. Then 2 g of a mixture of polyacrylic acids (Eulysine S
  • a piece of substrate (A) polyamide 6.6 is soaked in this solution at room temperature and squeezed till an uptake equal to 100% substrate.
  • the wet substrate is printed over with Acid Yellow
  • the substrate When the substrate is printed, it is steamed with airfree saturated steam at 98°C during 2 minutes, and then rinsed with cold water. To the rinsing water and /or the last rinsing bath, 2 g of polyacrylic acids (Eulysine S) per litre of water is added. Then the substrate is dried at 100°C .
  • polyacrylic acids Eulysine S
  • Substrates A and B were subjected to following tests :
  • Test 1 coffee test A cylinder 0 4 cm and 40 cm high was placed on the substrate. At the bottom of the cylinder, 10 ml of hot coffee at 70° C was injected, whilst on top of the cylinder a weight of 300 g was dropped to press the coffee into the substrate.
  • the coffee stain was dabbed with hot water (60°C) and dried up with an absorbing tissue. This test was done immediately after applying the stain, on a stain left untouched during two hours and on a stain left untouched during twenty-four hours .
  • Test 3 chlorine test With a pipette, 2 ml of a solution of respectively
  • Test 4 repeated stains
  • test 1 The coffee test (test 1) was repeated several times on the same spot of the substrate, and each time, the stain was treated with lukewarm water.
  • a part of substrate A was exposed to light according to the DIN norm 54004, corresponding to ISO norm 105 /BO2
  • test 1 The stain resistance test (test 1) as described above, was done on the exposed part after 24 hours of exposure to light, after 48 hours, after 72 hours . . . till after 240 hours of exposure .
  • the effectiveness of the stain removing treatment was compared with a non exposed part of substrate A. There was no difference noticed between the non exposed and the part exposed to light, even after 240 hours of exposure.
  • Test 6 shampoo test A part of substrate A was treated with a neutral carpet shampoo (Belgian Norm NBB : G62-014) .
  • the shampoo was mixed with water and the foam brought on the substrate with a brush.
  • the shampoo was left to dry on the carpet and then removed with a vacuum cleaner.
  • test 1 as described above was done on the cleaned part and compared to a part of substrate A not treated with shampoo. No substantial difference was noticed.
  • This shampoo treatment and coffee test was repeated three times and showed that shampoo treatment did not affect the effectiveness of the stain-removing treatment.
  • Substrate (C) was treated with this solution.
  • a solution is prepared by dissolving 30 g tannic acid with a MW of 2500 in 1 1 of cold soft water. Then 5 ml acetic acid 80% is added as stabiliser and 10 ml isopropanol as wetting agent.
  • a second solution is prepared by dissolving 25 g potassium aluminium sulphate in 1 1 of cold soft water. Then 2 g of a mixture of polyacryhc acids (Eulysine S) is added.
  • a piece of substrate (D) polyamide 6.6 is soaked in this solution at room temperature and squeezed till an uptake equal 100% to the substrate.
  • a solution of Acid Blue 129 is prepared by dissolving 1 g of dyestuff in 0,1 1 hot water and then adding cold water up to 1 1. To this solution 5 ml acetic acid is added. The wet substrate is impregnated with the dye solution, then steamed with airfree saturated steam at 98° C during 2,5 minutes, and then rinsed with hot water at 80° C containing 0,5 g/1 of a mixture of polyacrylic acids. The pH after rinsing is 6.7. The substrate is then dried at 100°C.
  • the tannic acid solution as in example 2 and the dye solution as in example 3 are mixed together.
  • Substrate (E) polyamide 6.6 is impregnated with this mixture and then steamed, rinsed and dried as in example 1.
  • Substrate (F) polyamide 6.6 is dyed with the dye solution prepared as in example 3, and steamed and rinsed as in example 1.
  • the substrate is then squeezed out until a wetness content of about 35%.
  • the substrate is consequently impregnated with a mixture of tannic acid and complexing agent prepared as in example 3.
  • the substrate is steamed during 30 seconds with airfree saturated steam and dried.
  • Example 6 A substrate (G) polyamide 6.6 with a weight of
  • a mixture of 6,7 kg tannic acid with a MW of 900 and 6,7 kg tannic acid with a MW of 2500 is dissolved in warm water and added to the bath; and dyestuff dissolved in warm water is also added to the bath.
  • the pH is adjusted to about 6 by addition of acetic acid 80%.
  • the bath is then progressively heated in such a way that the temperature raises about 1°C per minute until about 90°C.
  • Example 7 A substrate (H) polyamide 6.6 is wetted as in example 6. A dyestuff solution is added to the bath, the pH is adjusted to about 5 , and the substrate is dyed by progressive heating as in example 6.
  • a substrate (K) polyamide 6.6 is wetted and dyed as in example 7 and then rinsed.
  • the bath is renewed and in a fresh bath a tannic acid solution of composition as in example 6 is added.
  • the bath is then heated to about 75°C, kept at this temperature during about 20 minutes and then cooled.
  • the substrate is consequently rinsed and dried.
  • a substrate (L) polyamide 6.6 is treated as in example 5 , except that after the dyeing step and the rinsing step the substrate is dried.
  • the substrate is further treated with a mixture of tannic acid and complexing agent as in example 5.
  • a substrate (M) polyamide 6.6 is wetted and dyed as in example 6, with a combination of Acid Red 42 and Acid Blue 45 dissolved in warm water (without addition of tannic acid) and the substrate is rinsed and dried.
  • the bath is then heated to about 65°C, kept at this temperature during about 20 minutes and then cooled.
  • the substrate is consequently rinsed and dried.
  • Coffee test % of stain disappeared after dabbing with hot water. l .a stain removed immediately after applying, l .b stain maintained during 2 hours before removal l .c stain maintained during 24 hours before removal.
  • Red wine test % of stain disappeared after dabbing with hot water.
  • tannic acid can be combined with other compounds used in the textile industry to seek for additional properties .
  • non volatile acid a mixture of polyacryhc acids was generally used as non volatile acid. It is clear that also the non volatile aliphatic acids can be used.
  • acetic acid that can be replaced by another aliphatic acid with boiling-point under 100°C
  • a wetting agent Besides isopropanol, any wetting agent can be apphed, provided it does not cause any undesired reaction with tannic acid or the other products used.

Abstract

The invention consists of a process to improve the resistance to stains on yarns, on the basis of wool, silk, polyamide, polyacrylonitrile, natural and artificial cellulosic fibres and in general, all other synthetical fibres which can be dyed. According to the invention the yarns are treated during the dyeing process with an aqueous solution containing up to 5 % tannic acid in acid medium. It is economically advisable to add a stabiliser to the solution to avoid oxidation of the solution and the fibres, and possibly a wetting agent. Preferably the treatment is made during the dyeing procedure, before, during or after the effective dyeing step.

Description

DESCRIPTION
Process to improve resistance to stains on yarns and derived products
This invention relates to a process to improve the resistance to stains on yarns on the basis of silk, wool, polyamide, polyester, polyacrylonitrile , natural and artificial cellulosic fibres and in general all other synthetic fibres which can be dyed, by which the resistance of the dyed fibres against stains, especially coloured stains, is increased, whilst at the same time also other improved characteristics are obtained.
By "yarns" has to be understood, yarns whether greige (raw) or processed, yarns unfinished or finished, bright as well as dull, in yarn form or processed to fabric, felt, knitwear, non- woven, carpets, rugs, etc. To simplify matters, in this description yarn in which form whatsoever will be called "substrate" .
Removal of stains, coloured or not, from a substrate, is still a very delicate problem, as there could remain traces or spots either by discoloration or coloration of the original substrate caused by the stain or by the detergents which affect the dyestuff of the substrate. This is especially the case for stains caused by products containing persistant dyestuffs or pigments for instance present in coffee, tea, wine, fruit juices, inks. . .
The purpose of this invention is to propose a process by which the resistance of a coloured or uncoloured substrate against stains of any nature is considerably improved and which at the same time improves the antistatic behaviour, as well as the resistance to soiling, house-mite and oxidative bleaching agents .
It is known (C.A. Vol. 97 (1982) 7.704 U) that tannin is used to fix dyestuff after the dyeing process. On the other hand it is also known from the swimwear industry, to treat coloured nylon fabric with extractions of gallotannin to improve the colour fastness to chlorine. This was based on the fact that the additional treatment of coloured nylon fabric with gallotannin extractions caused a migration of the dyes in the fibre whereby the gallotannin is fixed on the fibre. This provides a certain resistance to discoloration of the substrate by products containing chlorine. However this treatment has no known effect on coloured stains, and is not at all effective for stains caused by other oxidative bleaching agents. During extensive research in this field, it has now surprisingly been demonstrated that the resistance of coloured or uncoloured substrate to stains is considerably improved when the substrate is treated during the dyeing process with an aqueous solution containing up to 5% tannic acid by a pH lower than 6. The term "dyeing process" as used in this description and claims is to be understood in a broad sense and means any or more steps in the sequence of steps applied to a substrate to give this substrate its coloured and finishing characteristics, whereby this sequence of steps can be done in one or more treatments.
It has been found that this treatment is very effective against stains caused by dyes of natural or synthetic origin with anionic, cationic, metalcomplex or disperse nature.
That the tannic acid would improve the discoloration caused by chlorine, could be expected by the man skilled in the art, but that this treatment would be efficient against coloured stains, could not be predicted.
According to the invention, the substrate, in acid medium, is treated with a solution containing 5 to 50 gram tannic acid per litre water and preferably between 25 to 35 g/1. These concentrations and proportions are not critical, though it has been noticed that higher concentrations hardly influence the result but could cause a yellowing of the substrate.
Tannic acid is a compound derived for several centuries from nutgalls and has a structure of polygalloylglucose or polygalloylquinic acid.
The term "tannic acid" as used in this description and claims should be understood in a broad sense, and covers products containing tannic acid, such as for instance gallotannin.
In fact tannic acid is a mixture of compounds consisting of a glucose- chain which is several times substituted with gallic acid or trihydroxy-3,4,5-benzoic-acid-l . Substitution can also be made with digallic acid or with trigallic acid.
Tannic acid e. g. contains nonagalloylglucose, a glucose-chain substituted 5 times with gallic acid, 4 times of which is digallic acid and the formula of which is the following:
CH- digallic acid
CH- O - digallic acid
CH- Ci - gallic acid
Figure imgf000005_0001
O CH- digallic acid
CH
CH2 digallic acid
According to the invention, any commercial tannic acid can be used, though it is economical to use a tannic acid with a relatively high molecular weight. The molecular weight of the tannic acid will preferably be between 900 and 3500, though this range is not critical. Surprisingly it has also been found that optimum results are achieved when a mixture of a tannic acid with a relatively low MW and a tannic acid with a relatively high MW is used. So it has been shown that a mixture, consisting of a tannic acid with an average MW lower than 1000 and a tannic acid with an average MW higher than 1500, gives better results than tannic acid of exclusively 1500 MW.
The tannic acid is used in an aqueous solution. For the man skilled in the art, it will be clear that the water has to be de-ironed and softened. To avoid oxidation of the solution, a small quantity of an aliphatic carboxylic acid with a boiling-point lower than 100°C, e. g. acetic acid, can be added.
To avoid oxidation of the substrate, for instance during and after the fixation of the dye, it is also recommended to add a non volatile, non hygroscopic and preferably non corroding acid, as e.g. an aliphatic carboxylic acid such as citric acid or polyacrylic acids . It could also be economical to add a wetting agent, such as e.g. isopropanol.
According to an advantageous embodiment of the invention it is recommended to add a complexing agent to the solution, for instance a polyvalent salt, which can neutralise the free OH groups from the tannic acid. Potassium antimonyl tartrate or alum (aluminium potassium sulphate) can be used for this purpose in a concentration relating to the tannic acid concentration varying between 2/1 to 1/2.
The complexing agent shall preferably be dissolved in water at the ambient temperature and to this solution a non volatile acid, which does not evaporate during steaming of the substrate, can be added. Aliphatic carboxylic acids can be used in a concentration varying between 1 to 10 g per litre water. The solution with complexing agent is added to the tannic acid solution and the mixture should have preferably a pH between 2.5 and 5. If not the pH must possibly be adjusted by adding an acid for instance a sulfamic acid, formic acid, acetic acid. . . Strong mineral acids have to be avoided. According to a preferred embodiment of the invention the substrate shall be treated with the tannic acid solution during the dyeing step and can be inserted in a continuous procedure as well as in a discontinuous procedure, and the treatment can be made before, during or after the effective dyeing step .
It is also possible to apply the treatment during a later operation. The dry and dyed substrate can then be treated during a finishing step or in a separate step . It is clear that treatment in a separate step requires an additional operation and is not recommended as a preferred embodiment. In fact such additional step can be useful when basic dyes are used as described hereafter. Nevertheless, treatment with an additional step falls within the scope of the invention.
According to the invention the substrate will be impregnated or saturated with the solution of tannic acid.
The expression "dyeing" is used in this description for any process by which dyes are applied on a substrate, such as dyeing, printing, spacing, spraying, etc in a single or in multiple steps . The dyes to be applied are dissolved in water, possibly by heating, and afterwards adjusted to the right volume with cold water. The operation will preferably be done in an acid medium.
When applying the dyestuff in a continuous printing process, an acid-resisting thickening agent, such as a hydrocolloid, e. g. Xanthanegum, will be added.
Dyestuffs suitable to be applied according to the invention, are in general acid, metalcomplex as well as disperse dyes . Basic dyestuffs are also suitable, however when using them it is recommended to apply the treatment according to the invention, as an additional treatment.
Also in a differential dyeing or cross dyeing process, when acid and basic dyes are used, it will be recommended to apply the treatment as an additional operation after dyeing. For the man skilled in the art, it is obvious to select dyestuffs which fit in the described process and do not cause any side-reactions with the applied reagentia and products. Thus when a complexing agent is used, one shall select dyes which are not affected by such agent.
A good pre-selection of dyestuffs will be made through obvious criteria. It can e. g. be useful to select dyestuffs with fast fixing properties.
Below, some dyestuffs that fit in very well in the frame of the invention, are mentioned as non restrictive examples. The dyestuffs are indicated with their corresponding colour index number as it is common practice. Acid Yellow 121 , 219 and 230. Acid Orange 116 and 156. • Acid Red 42, 243, 299 and 395. Acid Blue 40, 113, 129 and 344. Acid Black 172. Basic Red 23 and 73. Basic Yellow 45 and 63. • Basic Blue 45 and 129. Mordant Orange 6. Disperse Yellow 2. Disperse Red 55.1 and 340. Disperse Blue 7. Other dyestuffs have also been tested with satisfactory results .
In case of a continuous process, the substrate, after treatment and dyeing, is steamed during a half to a few minutes with airfree saturated steam. After steaming, the coloured substrate is rinsed, preferably with water, at which a stabiliser can be added, preferably a non volatile, non hygroscopic, and non corroding acid, e.g. an aliphatic carboxylic acid, in a concentration e.g. between 0,5 to 5 g/1.
When the treatment solution contains a complexing agent the rinsing will preferably be done with hot water (60°- 90°C) , without complexing agent, the rinsing water will be cold water.
In a discontinuous process the tannic acid solution can be added to the dyebath or the treatment can be done in a separate bath.
When a substrate is treated according to one of these embodiments, an unknown resistance to colour stains of natural or synthetic origin containing anionic, cationic, metalcomplex or disperse dyestuffs, is achieved. Stains of coffee at 70° C, kool-aid (highly coloured soft-drink) , wine, ink, etc. , can easily be removed by wetting the stain with cold or lukewarm water, and dry dabbing.
Tests have been executed with respect to light- fastness, washing-fastness, etc — and showed that the process has no negative influence on the above mentioned fastness properties.
The process and the various ways of applying it is described more in detail below, by way of following non restrictive examples, whereby examples 1 to 5 deal with a treatment during a continuous process, examples 6 to 8 with a treatment during a discontinuous process and examples 9 and 10 relate to an additional treatment .
Example 1
A solution is prepared by dissolving 25 g tannic acid with a MW of 2500 (Mijimoto commercial product) in 1 1 of soft water. Then 2 g of a mixture of polyacrylic acids (Eulysine S
BASF) and 5 ml acetic acid 80% is added as stabiliser, as well as
5 ml isopropanol as wetting agent. The pH of the solution is 2.5.
A piece of substrate (A) polyamide 6.6 is soaked in this solution at room temperature and squeezed till an uptake equal to 100% substrate.
The wet substrate is printed over with Acid Yellow
230. To this end 1 g of dyestuff is dissolved in 0,1 1 of warm water, then cold water is added to 1 1. To this solution, 5 ml acetic acid 80% is added, until a pH of 3.5 is obtained. Finally, Xanthanegum Type Kelzan is added until the required viscosity is reached .
When the substrate is printed, it is steamed with airfree saturated steam at 98°C during 2 minutes, and then rinsed with cold water. To the rinsing water and /or the last rinsing bath, 2 g of polyacrylic acids (Eulysine S) per litre of water is added. Then the substrate is dried at 100°C .
Comparative trial regarding example 1 A piece of substrate (B) from the same material as substrate (A) is dyed with the same dye solution after it has been moistened with an aqueous solution of acetic acid to which isopropanol was added, but without tannic acid. The coloured substrate was steamed and rinsed in the same way as in example 1 , except that the rinsing water did not contain polyacryhc acids.
Substrates A and B were subjected to following tests :
Test 1 : coffee test A cylinder 0 4 cm and 40 cm high was placed on the substrate. At the bottom of the cylinder, 10 ml of hot coffee at 70° C was injected, whilst on top of the cylinder a weight of 300 g was dropped to press the coffee into the substrate.
The coffee stain was dabbed with hot water (60°C) and dried up with an absorbing tissue. This test was done immediately after applying the stain, on a stain left untouched during two hours and on a stain left untouched during twenty-four hours .
The stain on substrate A disappeared in the three circumstances .
On substrate B , the stain remained visible for about 20% when immediately dabbed with water, but remained for 60% after two hours and for 80% after twenty-four hours . A further treatment with household bleaching water containing 1 g/1 active chlorine was needed to remove the stain. The chlorinated water left a visible pale stain. Test 2 : red wine test
With the same testing material as for the test mentioned above, 10 ml of red wine was brought on the substrate and was treated with lukewarm water and dabbed dry, immediately after applying, after two hours and after twenty-four hours .
The results were similar to these of the coffee test.
On substrate A, the stain was practically completely removed in the three cases . Treatment with bleaching water containing 0,2 g/1 active chlorine could remove the slightly remaining part without effect on the original aspect of the substrate .
On substrate B , the stain was only removed for respectively 40%, 30% and 20% and a further treatment with chlorinated water containing 2 g active chlorine was needed, which left a clearly visible pale stain.
Test 3 : chlorine test With a pipette, 2 ml of a solution of respectively
1 g/1, 3 g/1 and 10 g/1 active chlorine was brought on the substrate. After 24 hours the stains were visually evaluated.
On substrate A, no discoloration was noticed for
1 g/1 and 3 g/1. The solution of 10 g/1 had caused a slight dis coloration .
On substrate B , there was already a slight discoloration at 1 g/1 and a strong discoloration was noticed at
3 g/1. With 10 g/1 there was a complete discoloration and the substrate was affected. This test proved that the treatment according to the invention not only protects the colour of the substrate against chlorine, but also gives a protection against the destruction of the substrate itself.
Higher concentrations of chlorine were not tested. Test 4: repeated stains
The coffee test (test 1) was repeated several times on the same spot of the substrate, and each time, the stain was treated with lukewarm water.
On substrate A, the coffee stain disappeared after three times (repeated stains) without leaving any trace. When the stain was made on the same spot for the fourth time, there was a slight discoloration visible after treatment with lukewarm water (85% of the stain could be removed) .
Test 5 : light fastness
A part of substrate A was exposed to light according to the DIN norm 54004, corresponding to ISO norm 105 /BO2
(Xenontest) . The stain resistance test (test 1) as described above, was done on the exposed part after 24 hours of exposure to light, after 48 hours, after 72 hours . . . till after 240 hours of exposure .
The effectiveness of the stain removing treatment was compared with a non exposed part of substrate A. There was no difference noticed between the non exposed and the part exposed to light, even after 240 hours of exposure.
The same test was repeated on substrates A and B and the colour fastness of both substrates was compared after 240 hours of exposure. No colour difference was noticed.
Therefore it can be stated that the treatment according to the invention has no negative influence on the colour fastness.
Test 6 : shampoo test A part of substrate A was treated with a neutral carpet shampoo (Belgian Norm NBB : G62-014) . The shampoo was mixed with water and the foam brought on the substrate with a brush. The shampoo was left to dry on the carpet and then removed with a vacuum cleaner. After this treatment, test 1 as described above was done on the cleaned part and compared to a part of substrate A not treated with shampoo. No substantial difference was noticed. This shampoo treatment and coffee test was repeated three times and showed that shampoo treatment did not affect the effectiveness of the stain-removing treatment.
Example 2
All steps of example 1 are repeated, but instead of using 25 g tannic acid with a MW of 2500, a mixture of 12,5 g tannic acid with a MW of 900 and 12,5 g tannic acid with a MW of 2500 is used.
Substrate (C) was treated with this solution.
Example 3
A solution is prepared by dissolving 30 g tannic acid with a MW of 2500 in 1 1 of cold soft water. Then 5 ml acetic acid 80% is added as stabiliser and 10 ml isopropanol as wetting agent.
A second solution is prepared by dissolving 25 g potassium aluminium sulphate in 1 1 of cold soft water. Then 2 g of a mixture of polyacryhc acids (Eulysine S) is added.
Both solutions are mixed together and the pH is adjusted to 2.5 by adding additional polyacryhc acids.
A piece of substrate (D) polyamide 6.6 is soaked in this solution at room temperature and squeezed till an uptake equal 100% to the substrate.
A solution of Acid Blue 129 is prepared by dissolving 1 g of dyestuff in 0,1 1 hot water and then adding cold water up to 1 1. To this solution 5 ml acetic acid is added. The wet substrate is impregnated with the dye solution, then steamed with airfree saturated steam at 98° C during 2,5 minutes, and then rinsed with hot water at 80° C containing 0,5 g/1 of a mixture of polyacrylic acids. The pH after rinsing is 6.7. The substrate is then dried at 100°C. Example 4
The tannic acid solution as in example 2 and the dye solution as in example 3 are mixed together.
Substrate (E) polyamide 6.6 is impregnated with this mixture and then steamed, rinsed and dried as in example 1.
Example 5
Substrate (F) polyamide 6.6 is dyed with the dye solution prepared as in example 3, and steamed and rinsed as in example 1.
The substrate is then squeezed out until a wetness content of about 35%.
The substrate is consequently impregnated with a mixture of tannic acid and complexing agent prepared as in example 3.
Afterwards the substrate is steamed during 30 seconds with airfree saturated steam and dried.
Example 6 A substrate (G) polyamide 6.6 with a weight of
840 kg is introduced in a dye beck with winch filled with 20000 1 cold soft water (pH = 8.2) . The winch is rotated during about 10 minutes to wet the substrate.
A mixture of 6,7 kg tannic acid with a MW of 900 and 6,7 kg tannic acid with a MW of 2500 is dissolved in warm water and added to the bath; and dyestuff dissolved in warm water is also added to the bath.
After about 10 minutes rotation of the winch the pH is adjusted to about 6 by addition of acetic acid 80%. The bath is then progressively heated in such a way that the temperature raises about 1°C per minute until about 90°C.
This temperature is maintained during about 45 minutes. Then the pH of the bath is lowered to a pH of about 4.5 by addition of citric acid, and the winch is rotated for about 15 minutes. The bath is then cooled, the substrate is rinsed, taken out from the dye beck and dried.
Example 7 A substrate (H) polyamide 6.6 is wetted as in example 6. A dyestuff solution is added to the bath, the pH is adjusted to about 5 , and the substrate is dyed by progressive heating as in example 6.
After dyeing during the cooling of the bath at about 75 °C a solution of tannic acid prepared as in example 6 is added and the pH is adjusted if necessary by the addition of citric acid until pH = 4. The bath is maintained during about 20 minutes at the temperature of 75° C and then cooled. The substrate is consequently rinsed and dried.
Example 8
A substrate (K) polyamide 6.6 is wetted and dyed as in example 7 and then rinsed.
The bath is renewed and in a fresh bath a tannic acid solution of composition as in example 6 is added. The pH is adjusted with formic acid until pH = 4. The bath is then heated to about 75°C, kept at this temperature during about 20 minutes and then cooled. The substrate is consequently rinsed and dried.
Example 9
A substrate (L) polyamide 6.6 is treated as in example 5 , except that after the dyeing step and the rinsing step the substrate is dried.
In a later step the substrate is further treated with a mixture of tannic acid and complexing agent as in example 5.
Example 10
A substrate (M) polyamide 6.6 is wetted and dyed as in example 6, with a combination of Acid Red 42 and Acid Blue 45 dissolved in warm water (without addition of tannic acid) and the substrate is rinsed and dried.
The substrate is introduced in a fresh bath, containing 2% of a tannic acid with a MW of 900 and the pH is adjusted with formic acid until pH = 4. The bath is then heated to about 65°C, kept at this temperature during about 20 minutes and then cooled. The substrate is consequently rinsed and dried.
It is to be noted that due to the cationic dye, it is recommended to use a lower concentration of tannic acid and to lower the temperature of the bath to about 65° C during the application of the tannic acid.
The coffee test, red wine test and chlorine test as given for example 1 are repeated on each of the substrates C to M and the results are given in table 1 hereafter.
Table 1
Substrate Coffee test Red wine test la lb lc 2a 2b 2c 2d 2e
A 100 96 94 95 95 95 0.2 none
C 100 100 96 95 95 95 0.2 none
D 100 100 98 95 95 95 0.2 none
E 100 100 98 95 95 95 0.2 none
F 100 100 100 95 95 95 0.2 none
G 100 98 95 95 95 95 0.2 none
H 100 100 100 95 95 95 0.2 none
K 100 100 100 95 95 95 0.2 none
L 100 100 100 95 95 95 0.2 none
M 100 100 100 95 95 95 0.2 none
B 80 40 20 40 30 20 2 discoloration
1. Coffee test: % of stain disappeared after dabbing with hot water. l .a stain removed immediately after applying, l .b stain maintained during 2 hours before removal l .c stain maintained during 24 hours before removal.
Red wine test: % of stain disappeared after dabbing with hot water.
2. a stain removed immediately after applying.
2.b stain maintained during 2 hours before removal.
2.c stain maintained during 24 hours before removal.
2.d concentration of active chlorine (g/1) needed to remove remaining part of stain 2.e effect on original aspect of substrate.
It is obvious that the invention is not restricted to the described examples, but apphes for any process by which a substrate is treated with a tannic acid solution, whereby tannic acid is to be understood in a broad sense, as described hereabove. Additionally to the described tests, laboratory trials were made with coloured stains originating from different types of drinks and all results showed improved resistance.
Furthermore tests were made with a tannic acid from other suppliers and did not show any difference, so that any available commercial product can be used. The molecular weight however is an important factor, and it is recommended, for economical purposes, to use a mixture of tannic acid with a low MW, and a tannic acid with a high MW. The proportion of both tannic acids is not at all critical, since good results have also been achieved with one type of tannic acid.
It is clear that tannic acid can be combined with other compounds used in the textile industry to seek for additional properties .
The examples were intentionally given with use of an identical substrate so that results could be better compared. As far as the substrate is concerned, polyamide 6.6 was used in the described examples. Other tests with other types of polyamide such as P. A.6 were also made and have given rise to similar results . Tests were furthermore made using wool, cotton, cellulosic artificial fibres, and various other kinds of fibres, and showed that the treatment can be applied on a large variety of substrates. The concentrations, temperatures and reaction times were determined by the man skilled in the art, according to the used reagentia, products, dyestuffs, production process, type of substrate, etc. . .
To keep matters simple and in order not to complicate the comparison between the various examples, a mixture of polyacryhc acids was generally used as non volatile acid. It is clear that also the non volatile aliphatic acids can be used.
The same remark stands for the use of acetic acid, that can be replaced by another aliphatic acid with boiling-point under 100°C, and for the use of a wetting agent. Besides isopropanol, any wetting agent can be apphed, provided it does not cause any undesired reaction with tannic acid or the other products used.

Claims

1. Method for improving the resistance to stains of a coloured substrate, made out of fibres, on the basis of silk, wool, polyamide, polyester, polyacrylonitrile, natural or artificial cellulosic fibres or all other synthetic fibres which can be dyed, characterised in that during the dyeing process the substrate is treated in an acid medium with an aqueous solution containing up to 5% of tannic acid.
2. Method according to claim 1 , characterised in that the substrate is treated during the effective dyeing step.
3. Method according to claim 1 or 2, characterised in that the solution contains 5 to 50 g/1, preferably 25 to 35 g/1 tannic acid.
4. Method according to any of the preceding claims 1 to 3 , characterised in that the tannic acid is a mixture of tannic acid with relatively low (≤ 1000) molecular weight, and tannic acid with a relatively high (≥ 1500) molecular weight.
5. Method according to any of the preceding claims 1 to 4, characterised in that the pH of the solution ranges between 2.5 and 5.
6. Method according to claim 2, characterised in that the substrate is treated with the solution during a continuous or discontinuous dyeing procedure, immediately before, during or immediately after the effective dyeing step.
7. Method according to claim 1 , characterised in that the substrate is treated during an additional operation after the substrate has been dyed.
8. Method according to claim 1 , characterised in that to the aqueous solution, a stabiliser is added to avoid oxidation of the substrate and the solution, and possibly a wetting agent .
9. Method according to any of the preceding claims, characterised in that a complexing agent, such as potassium antimonyl tartrate or aluminium potassium tartrate is added to the tannic acid solution in a concentration relating to the tannic acid concentration varying between 2/1 and 1/2.
10. Coloured substrate characterised in that it is treated during the dyeing process with an aqueous solution containing up to 5% tannic acid in an acid medium.
PCT/BE1994/000062 1993-09-30 1994-09-28 Process to improve resistance to stains on yarns and derived products WO1995009266A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP94926733A EP0721524B1 (en) 1993-09-30 1994-09-28 Use of aqueous tannic acid solution to improve resistance to stains on fibrous substrates
US08/619,673 US6024770A (en) 1993-09-30 1994-09-28 Process to improve resistance to stains on yarns and derived products
DK94926733T DK0721524T3 (en) 1993-09-30 1994-09-28 Use of an aqueous tannic acid solution to improve the resistance to stains on fibrous substrates
CA002172988A CA2172988C (en) 1993-09-30 1994-09-28 Process to improve resistance to stains on yarns and derived products
AU76486/94A AU681188B2 (en) 1993-09-30 1994-09-28 Process to improve resistance to stains on yarns and derived products
DE69429360T DE69429360T2 (en) 1993-09-30 1994-09-28 USE OF AN AQUEOUS TANNIC ACID SOLUTION TO IMPROVE Stain Repellency of Fiber Substrates

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE9301025 1993-09-30
BE9301025A BE1007555A3 (en) 1993-09-30 1993-09-30 Method for resistance to improve the colour spots of yarn and products.

Publications (1)

Publication Number Publication Date
WO1995009266A1 true WO1995009266A1 (en) 1995-04-06

Family

ID=3887379

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/BE1994/000062 WO1995009266A1 (en) 1993-09-30 1994-09-28 Process to improve resistance to stains on yarns and derived products

Country Status (8)

Country Link
US (1) US6024770A (en)
EP (1) EP0721524B1 (en)
AU (1) AU681188B2 (en)
BE (1) BE1007555A3 (en)
CA (1) CA2172988C (en)
DE (1) DE69429360T2 (en)
DK (1) DK0721524T3 (en)
WO (1) WO1995009266A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1518958A2 (en) * 2003-07-24 2005-03-30 Shaw Industries Group, Inc. Methods of treating and cleaning fibers, carpet yarns and carpets

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU1182600A (en) * 1998-11-18 2000-06-05 Asahi Kasei Kabushiki Kaisha Blended dyed product of fiber dyeable with disperse dye and polyurethane fiber and dyeing method therefor
US7313840B2 (en) * 2002-07-25 2008-01-01 Charles E. Watkins Induction liquid pump and magnetic tank scrubber
US7785374B2 (en) * 2005-01-24 2010-08-31 Columbia Insurance Co. Methods and compositions for imparting stain resistance to nylon materials
US7556841B2 (en) * 2005-06-07 2009-07-07 S. C. Johnson & Son, Inc. Method of applying a design to a surface
US20080282642A1 (en) * 2005-06-07 2008-11-20 Shah Ketan N Method of affixing a design to a surface
US8846154B2 (en) 2005-06-07 2014-09-30 S.C. Johnson & Son, Inc. Carpet décor and setting solution compositions
US8557758B2 (en) 2005-06-07 2013-10-15 S.C. Johnson & Son, Inc. Devices for applying a colorant to a surface
US20070277849A1 (en) 2006-06-06 2007-12-06 Shah Ketan N Method of neutralizing a stain on a surface
US8061269B2 (en) * 2008-05-14 2011-11-22 S.C. Johnson & Son, Inc. Multilayer stencils for applying a design to a surface
US7727289B2 (en) * 2005-06-07 2010-06-01 S.C. Johnson & Son, Inc. Composition for application to a surface
US7776108B2 (en) * 2005-06-07 2010-08-17 S.C. Johnson & Son, Inc. Composition for application to a surface

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58154772A (en) * 1982-03-10 1983-09-14 Daiwa Maakanto Kogyo Kk Ink composition for skin marking
JPS61174485A (en) * 1985-01-28 1986-08-06 カネボウ株式会社 Dyeing of regenerated fiber or fiber structure
EP0261637A2 (en) * 1986-09-23 1988-03-30 Rodger L. Gamblin Substantive dyes, inks and dye baths

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2480775A (en) * 1948-07-03 1949-08-30 Du Pont Dyeing nylon hosiery
US3669611A (en) * 1965-10-11 1972-06-13 Teijin Ltd Production of ornamental multitone effect on polyamide textile materials
GB1254541A (en) * 1968-01-29 1971-11-24 Courtaulds Ltd Dyeing process
GB1464866A (en) * 1973-08-21 1977-02-16 Ici Ltd Coloration process
US3999940A (en) * 1975-01-02 1976-12-28 Congoleum Corporation Multicolored pile materials and processes for making the same
JPS62238887A (en) * 1986-04-03 1987-10-19 カネボウ株式会社 Product of dyed cloth
US5639500A (en) * 1993-05-27 1997-06-17 Kraft Foods, Inc. High molecular weight gallotannins as a stain-inhibiting agent for food dyes
US5571551A (en) * 1993-05-27 1996-11-05 Kraft Foods, Inc. High molecular weight gallotannins as a stain-inhibiting agent for food dyes
US5681604A (en) * 1993-06-29 1997-10-28 Li; Hualin Stain-inhibiting agent for dyes with affinity for protonatable nitrogen, compositions containing same and uses thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58154772A (en) * 1982-03-10 1983-09-14 Daiwa Maakanto Kogyo Kk Ink composition for skin marking
JPS61174485A (en) * 1985-01-28 1986-08-06 カネボウ株式会社 Dyeing of regenerated fiber or fiber structure
EP0261637A2 (en) * 1986-09-23 1988-03-30 Rodger L. Gamblin Substantive dyes, inks and dye baths

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8343, Derwent World Patents Index; Class D22, AN 83-797483 *
DATABASE WPI Section Ch Week 8638, Derwent World Patents Index; Class A11, AN 86-247834 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1518958A2 (en) * 2003-07-24 2005-03-30 Shaw Industries Group, Inc. Methods of treating and cleaning fibers, carpet yarns and carpets
EP1518958A3 (en) * 2003-07-24 2006-05-10 Shaw Industries Group, Inc. Methods of treating and cleaning fibers, carpet yarns and carpets

Also Published As

Publication number Publication date
AU681188B2 (en) 1997-08-21
EP0721524A1 (en) 1996-07-17
US6024770A (en) 2000-02-15
AU7648694A (en) 1995-04-18
DE69429360D1 (en) 2002-01-17
CA2172988C (en) 2004-05-11
BE1007555A3 (en) 1995-08-01
DK0721524T3 (en) 2002-03-04
EP0721524B1 (en) 2001-12-05
CA2172988A1 (en) 1995-04-06
DE69429360T2 (en) 2002-07-18

Similar Documents

Publication Publication Date Title
US5174790A (en) Exhaust process for dyeing and/or improving the flame resistance of aramid fibers
US4950304A (en) Process for quenching or suppressing the fluorescence of substrates treated with fluorescent whitening agents
US4380453A (en) Extraneous dye or colorant scavenging system in laundry
EP0721524B1 (en) Use of aqueous tannic acid solution to improve resistance to stains on fibrous substrates
US5215545A (en) Process for dyeing or printing/flame retarding aramids with N-octyl-pyrrolidone swelling agent
EP0118983A2 (en) Textile treatment
JPH09500918A (en) Improved mordants and methods for dyeing fibers
US5910622A (en) Method for treating fibrous cellulosic materials
US4704132A (en) After-treatment of dyeings with reactive dyes on cellulose fiber materials
US5350426A (en) Chlorine resistant cationic dyeable carpet yarn
US5667533A (en) Heather dyed fabric and method of producing same
AU682922B2 (en) Process to improve resistance to stains on fibres and derived products
US2772943A (en) Process of dyeing wool-polyacrylo-
EP1047828B1 (en) Process for dyeing and finishing of cellulosic fabrics
US5417724A (en) Method of treating acid dyed nylon fibers to enhance colorfastness
US4289496A (en) Finishing process
US5342417A (en) Method of treating cationic dyeable nylon fibers to inhibit cold water bleed
EP0286597B1 (en) Dyeing and printing fibres
US2628883A (en) Continuous chrome mordanting and dyeing of wool
CA2149521C (en) Exhaust process for dyeing and/or improving the flame resistance of aramid fibers
Aspland The Application of Basic Dye Cations to Anionic Fibers: Dyeing Acrylic and Other Fibers with Basic Dyes.
Whittaker Dyeing with coal-tar dyestuffs: the principles involved and the methods employed
US4247290A (en) Process for dyeing mixed elastomeric and non-elastomeric fibers
AT153974B (en) Process for improving the fastness of dyeings with water-soluble dyes on fibers, fabrics and the like. like
Nicolai et al. The swelling effect of liquid ammonia in the dyeing of aramids

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AM AU BG BR CA CN CZ FI GE HU JP KR NO NZ PL RO RU SI SK UA US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1994926733

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2172988

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 08619673

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 1994926733

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1994926733

Country of ref document: EP