EP0775228A1 - A method of preventing photobleaching of wool and/or other natural fibres - Google Patents

A method of preventing photobleaching of wool and/or other natural fibres

Info

Publication number
EP0775228A1
EP0775228A1 EP95927098A EP95927098A EP0775228A1 EP 0775228 A1 EP0775228 A1 EP 0775228A1 EP 95927098 A EP95927098 A EP 95927098A EP 95927098 A EP95927098 A EP 95927098A EP 0775228 A1 EP0775228 A1 EP 0775228A1
Authority
EP
European Patent Office
Prior art keywords
wool
chemical compound
natural fibres
photobleaching
photoyellowing
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
EP95927098A
Other languages
German (de)
French (fr)
Other versions
EP0775228A4 (en
EP0775228B1 (en
Inventor
Peter Edward Ingham
Margaret Millar Dodds
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wool Research Organization of New Zealand Inc
Original Assignee
Wool Research Organization of New Zealand Inc
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 Wool Research Organization of New Zealand Inc filed Critical Wool Research Organization of New Zealand Inc
Publication of EP0775228A1 publication Critical patent/EP0775228A1/en
Publication of EP0775228A4 publication Critical patent/EP0775228A4/en
Application granted granted Critical
Publication of EP0775228B1 publication Critical patent/EP0775228B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating 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 sulfur or phosphorus
    • D06M13/248—Treating 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 sulfur or phosphorus with compounds containing sulfur
    • D06M13/268—Sulfones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating 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 sulfur or phosphorus
    • D06M13/248—Treating 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 sulfur or phosphorus with compounds containing sulfur
    • D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
    • 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
    • D06P1/651—Compounds without nitrogen
    • D06P1/65168—Sulfur-containing compounds
    • D06P1/65193—Compounds containing sulfite or sulfone groups

Definitions

  • This invention relates to a method for reducing or preventing bleaching which wool and other similar natural fibres undergo when the wool and/or natural fibres are first exposed to sunlight, such as behind glass.
  • Photobleaching (sometimes called “first fade” or “red fade”) is seen as a rapid but limited on-tone fading of the natural creamy yellow of wool.
  • Yellowness induced from processing eg, dry-heat, hydrothermal or alkali yellowing is also photobleachable.
  • the bulk of the photobleaching occurs within 5-10 hours of the wool being exposed behind glass to midsummer sunlight and continues at a slower rate for another 40-50 hours.
  • the colour change caused by photobleaching is a cause of a significant number of consumer complaints particularly in the case of carpets. It is noticeable when furniture is moved revealing a colour difference between the areas of carpet which have been exposed to sunlight and those which have been unexposed.
  • the primary object of the present invention is to reduce or prevent this initial colour change in wool or wool blend furnishings which occurs on exposure to sunlight thus eliminating consumer complaints due to this cause.
  • a method of treating natural fibres with a chemical compound the chemical compound undergoing photoyellowing at a similar rate to the rate at which the natural fibres undergo photobleaching, the chemical compound being applied in such an amount so the photoyellowing of the chemical compound on the natural fibres cancels out the photobleaching of the natural fibres.
  • the preferred class of chemical compounds are known industrially as syntans and may consist of condensation products of aromatic sulphones and/or sulphonic acids. However other compounds which similarly undergo a photoyellowing at a similar rate to the photobleaching of wool or the like fibres are also suitable. These may include optical brightening agents, tannins, aromatic sulphonic acids etc.
  • Figure 1 shows a graph of the change in yellowness of wool felts treated with an aromatic sulphonic acid condensation product over a period of 40 hours exposure to sunlight;
  • Figure 2 shows a graph of the change in yellowness of whiter wool felts treated with an aromatic sulphonic acid condensation product over a period of 40 hours exposure to sunlight;
  • Figure 3 shows a graph of the change in yellowness of treated and untreated yarns over a period of 40 hours exposure to sunlight
  • Figure 4 shows a graph of the change in yellowness of treated and untreated yarns over a period of 40 hours exposure to sunlight.
  • Yellowness values were measured using a Hunterlab Spectrocolorimeter using a 2° observer and illuminant C before and after exposure to 40 hours midsummer sunlight (Christchurch, NZ) .
  • the treatment was applied during the dyeing of a commercial production yarn batch of two tonnes.
  • the dyeing was carried out in a longclose single stick hank dyeing machine using Sandolan MF dyes (Sandoz) at 0.8% .
  • Sandolan MF dyes Sandolan MF dyes
  • HAS hydroylammonium sulphate
  • an aromatic sulphonic acid were added at the beginning of the dyeing.
  • the wool blend had a Y-Z value of 4.6. Samples from this treated batch as well as untreated samples from a previously dyed batch and the untreated, undyed wool were exposed behind 2 mm picture glass to mid-summer sunlight (Christchurch, NZ).
  • the treatment was applied during commercial loose stock dyeing to a 2.8 tonne batch of wool with an initial Y-Z value of 3.0.
  • Dyeings consisted of 1 2 lots each of 235 kg dyed with 2: 1 premetallised dyes to a light beige shade (0.01 3% dye) .
  • the treatment was applied with other dyeing auxiliaries included 1 % HAS.
  • the level of the aromatic sulphonic acid was 0.4%.
  • the 1 2 dyeings were blended and processed into yarn which received a scour in a 5 bowl tape scour. This was followed by another 5 bowl chemical setting treatment using 10 g/L of sodium metabisulphite.
  • the yarn was similarly exposed behind 2 mm picture glass to mid-summer sunlight for 40 hours.
  • This example shows the treatment is fast to tapescouring and chemical setting if applied during dyeing.
  • the wool can be treated during scouring, at the dyeing stage or on a continuous carpet processing line.
  • the treatment can be applied to loose wool, wool yarn, wool fabric or carpet.
  • the level of compound applied depends on the initial yellowness of the wool and the dyestuffs used but can be adjusted so that there is little or no colour change due to photobleaching behind glass.
  • the addition of 1 -2% of hydroxylammonium sulphate (HAS) with the dyeing auxiliaries significantly reduces dyebath yellowing and hence reduces the required amount of syntan compound. For this reason it is recommended that 1 -2% HAS be used in conjunction with the syntan compound.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Coloring (AREA)

Abstract

A method of treating wool and/or other natural fibres with a chemical compound, the compound undergoing photoyellowing at a similar rate to the rate at which the wool and/or natural fibres undergoes photobleaching. The chemical compound is applied in an amount which ensures the photoyellowing of the chemical compound cancels out the photobleaching of the natural fibres. The chemical compounds are preferably syntans and may consist of condensation products of aromatic sulphonic and/or sulphonic acids. Other suitable compounds include optical brightening agents, tannins, and aromatic sulphonic acids.

Description

A METHOD OF PREVENTING PHOTOBLEACHING OF WOOL AND/OR OTHER NATURAL FIBRES
FIELD OF THE INVENTION
This invention relates to a method for reducing or preventing bleaching which wool and other similar natural fibres undergo when the wool and/or natural fibres are first exposed to sunlight, such as behind glass.
BACKGROUND OF THE INVENTION
Photobleaching (sometimes called "first fade" or "red fade") is seen as a rapid but limited on-tone fading of the natural creamy yellow of wool.
Yellowness induced from processing eg, dry-heat, hydrothermal or alkali yellowing is also photobleachable.
The bulk of the photobleaching occurs within 5-10 hours of the wool being exposed behind glass to midsummer sunlight and continues at a slower rate for another 40-50 hours. The colour change caused by photobleaching is a cause of a significant number of consumer complaints particularly in the case of carpets. It is noticeable when furniture is moved revealing a colour difference between the areas of carpet which have been exposed to sunlight and those which have been unexposed.
The primary object of the present invention is to reduce or prevent this initial colour change in wool or wool blend furnishings which occurs on exposure to sunlight thus eliminating consumer complaints due to this cause.
SUMMARY OF THE INVENTION
According to one aspect of the present invention there is provided a method of treating natural fibres with a chemical compound, the chemical compound undergoing photoyellowing at a similar rate to the rate at which the natural fibres undergo photobleaching, the chemical compound being applied in such an amount so the photoyellowing of the chemical compound on the natural fibres cancels out the photobleaching of the natural fibres.
The preferred class of chemical compounds are known industrially as syntans and may consist of condensation products of aromatic sulphones and/or sulphonic acids. However other compounds which similarly undergo a photoyellowing at a similar rate to the photobleaching of wool or the like fibres are also suitable. These may include optical brightening agents, tannins, aromatic sulphonic acids etc.
BRIEF DESCRIPTION OF THE DRAWINGS Further aspects of the invention will become apparent from the following description, which is given by way of example only and with reference to the accompanying drawings in which:
Figure 1 shows a graph of the change in yellowness of wool felts treated with an aromatic sulphonic acid condensation product over a period of 40 hours exposure to sunlight;
Figure 2 shows a graph of the change in yellowness of whiter wool felts treated with an aromatic sulphonic acid condensation product over a period of 40 hours exposure to sunlight;
Figure 3 shows a graph of the change in yellowness of treated and untreated yarns over a period of 40 hours exposure to sunlight; and
Figure 4 shows a graph of the change in yellowness of treated and untreated yarns over a period of 40 hours exposure to sunlight.
DESCRIPTION OF THE PREFERRED EXAMPLES Particular examples of the invention are set out below.
Example 1
Two scoured loose wool samples of different yellowness were treated with a condensation product of arylsulphonic acids as follows: Wool samples (20g) were treated in a laboratory dyeing apparatus at 75 °C with 0, 0.5% and 1 % of product on weight of wool (oww).
These samples were rinsed, dried at 60°C then hand carded and packed into a glass ended container at a packing density of 0.1 0g/cc.
Yellowness values (Y-Z tristimulus values) were measured using a Hunterlab Spectrocolorimeter using a 2° observer and illuminant C before and after exposure to 40 hours midsummer sunlight (Christchurch, NZ) .
Results were:
Initial Y-Z Y-Z value Δ(Y-Z) value after 40 hours sunlight
Untreated sample 1 5.1 0.6 4.5 Sample 1 & 0.5% product 5.7 3.6 2.1 Sample 1 & 1 .0% product 5.8 4.6 1 .2 Untreated sample 2 4.2 1 .5 1 .7 Sample 2 & 0.5% product 4.2 3.9 0.3 Sample 2 & 1 .0% product 4.4 4.2 0.2 Thus the change in yellowness for the wool samples after 40 hours sunlight exposure was reduced by 73% and 88% respectively.
Example 2
Two wool felts of different yellowness were treated with 0, 0.25, 0.5, 0.75 and 1 % of an aromatic sulphonic acid. The samples were then exposed to midsummer sunlight behind glass and the yellowness measured after 1 , 2, 5, 10, 20, and 40 hours using a Hunterlab Spectrocolorimeter as in Example 1 .
The results are shown in Figures 1 and 2.
It can be seen in Figures 1 and 2 that wools of different original yellowness require different amounts of chemical to prevent a colour change. Figure 1 shows that increasing amounts of an aromatic sulphonic acid condensation product reduce the extent of photobleaching. At 1 % oww there is a minimal colour change. Results for a whiter wool (Figure 2) show best results are obtained at a treatment rate of 0.5%oww.
Example 3
The treatment was applied during the dyeing of a commercial production yarn batch of two tonnes. The dyeing was carried out in a longclose single stick hank dyeing machine using Sandolan MF dyes (Sandoz) at 0.8% . As well as the standard auxiliaries 1 % hydroylammonium sulphate (HAS) and 0.5% of an aromatic sulphonic acid were added at the beginning of the dyeing. The wool blend had a Y-Z value of 4.6. Samples from this treated batch as well as untreated samples from a previously dyed batch and the untreated, undyed wool were exposed behind 2 mm picture glass to mid-summer sunlight (Christchurch, NZ). Colour measurements were taken prior to exposure and after 1 , 2, 5, 1 0, 20 and 40 hours after exposure using a Hunterlab Spectrocolorimeter. The change in yellowness is recorded as Δ(Y-Z) and this is shown in Figure 3. In Figure 3 it can be seen that after 40 hours exposure to sunlight the treated yarn changed by 0.3 Y-Z units (ie, indiscernible) whereas the untreated yarn changed by 2.3 Y-Z units. (A change in Δ(Y-Z) > 1 is said to be visibly discernible.)
Example 4
The treatment was applied during commercial loose stock dyeing to a 2.8 tonne batch of wool with an initial Y-Z value of 3.0. Dyeings consisted of 1 2 lots each of 235 kg dyed with 2: 1 premetallised dyes to a light beige shade (0.01 3% dye) . The treatment was applied with other dyeing auxiliaries included 1 % HAS. The level of the aromatic sulphonic acid was 0.4%. The 1 2 dyeings were blended and processed into yarn which received a scour in a 5 bowl tape scour. This was followed by another 5 bowl chemical setting treatment using 10 g/L of sodium metabisulphite. The yarn was similarly exposed behind 2 mm picture glass to mid-summer sunlight for 40 hours. An untreated control sample and an undyed/untreated wool sample were also exposed. Colour measurements were taken using a Hunterlab Spectrocolorimeter at 0, 1 , 2, 5, 10, 20 and 40 hours exposure. The Δ(Y-Z) values (change in yellowness) are shown in Figure 4. Figure 4 shows that after 40 hours exposure the treated yarn has changed by 0.2 Y-Z units and the untreated yarn has changed by 1 .5 Y-Z units.
This example shows the treatment is fast to tapescouring and chemical setting if applied during dyeing.
The wool can be treated during scouring, at the dyeing stage or on a continuous carpet processing line. The treatment can be applied to loose wool, wool yarn, wool fabric or carpet.
The level of compound applied depends on the initial yellowness of the wool and the dyestuffs used but can be adjusted so that there is little or no colour change due to photobleaching behind glass. The addition of 1 -2% of hydroxylammonium sulphate (HAS) with the dyeing auxiliaries significantly reduces dyebath yellowing and hence reduces the required amount of syntan compound. For this reason it is recommended that 1 -2% HAS be used in conjunction with the syntan compound.
Thus by this invention there is provided a method of reducing or preventing the bleaching of wool and other similar natural fibres during exposure to sunlight, such as behind glass.
Particular examples of this invention have been described and it is envisaged that improvements and modifications can take place without departing from the scope thereof and of the appended claims.

Claims

1 . A method of treating natural fibres with a chemical compound, the chemical compound undergoing photoyellowing at a similar rate to the rate at which the natural fibres undergo photobleaching, wherein the chemical compound is applied in such an amount so the photoyellowing of the chemical compound cancels out the photobleaching of the natural fibres.
2. A method as claimed in Claim 1 wherein the chemical compound comprises a condensation product of a aromatic sulphones.
3. A method as claimed in Claim 1 wherein the chemical compound comprises a condensation product of a sulphonic acid.
4. A method as claimed in Claim 1 wherein the chemical compound comprises an optical brightening agent, tanning, or aromatic sulphonic acids.
5. A method as claimed in any one of the preceding claims wherein the chemical compound is applied during scouring, dyeing or processing of the natural fibres.
6. A method as claimed in any one of the preceding claims wherein the natural fibre is wool.
7. A method as claimed in claim 6 wherein the chemical compound is applied to loose wool, wool yarn, wool fabric or carpet.
8. A method as claimed in any one of the preceding claims wherein the amount of chemical compound applied to the natural fibres depends on the initial yellowness of the wool.
9. A method of treating natural fibres as claimed in Claim 1 and substantially as herein described with reference to the Examples and the accompanying drawings.
EP95927098A 1994-08-08 1995-08-08 Prevention of photobleaching of wool and/or other natural fibres Expired - Lifetime EP0775228B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NZ26419994 1994-08-08
NZ26419994 1994-08-08
PCT/NZ1995/000070 WO1996005357A1 (en) 1994-08-08 1995-08-08 A method of preventing photobleaching of wool and/or other natural fibres

Publications (3)

Publication Number Publication Date
EP0775228A1 true EP0775228A1 (en) 1997-05-28
EP0775228A4 EP0775228A4 (en) 1998-05-27
EP0775228B1 EP0775228B1 (en) 2001-02-21

Family

ID=19924897

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95927098A Expired - Lifetime EP0775228B1 (en) 1994-08-08 1995-08-08 Prevention of photobleaching of wool and/or other natural fibres

Country Status (6)

Country Link
EP (1) EP0775228B1 (en)
JP (1) JPH10504070A (en)
AT (1) ATE199269T1 (en)
AU (1) AU684991B2 (en)
DE (1) DE69520146T2 (en)
WO (1) WO1996005357A1 (en)

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3683013A (en) * 1969-02-27 1972-08-08 Bayer Ag Compounds containing sulphonic acid groups
GB1377218A (en) * 1970-11-27 1974-12-11 Sandoz Ltd Process for the production of sulphones- the sulphones and their application as dyeing assistants and tanning agents
US3930795A (en) * 1972-09-08 1976-01-06 Hoechst Aktiengesellschaft Process for the level dyeing of wool
FR2398835A1 (en) * 1977-07-28 1979-02-23 Protex Manuf Prod Chimiq Fixing agent for dyes on polyamide fibres - consists of phenolic novolak resin with low free phenol content
US4217103A (en) * 1977-09-24 1980-08-12 Bayer Aktiengesellschaft Dyestuff formulations containing salts of diaryl ether sulfonic acids
US4270236A (en) * 1971-11-09 1981-06-02 Ciba-Geigy Corporation Process for the dyeing of fibre material
US4295852A (en) * 1979-11-08 1981-10-20 Bayer Aktiengesellschaft Process for dyeing polyamide fibres
US5207802A (en) * 1989-08-25 1993-05-04 Sandoz Ltd. Sulpho group-containing aromatic compounds, their production and use as dispersants or levelling agents in dyeing textiles or tanning leather
US5240465A (en) * 1990-06-09 1993-08-31 Sandoz Ltd. Process for reactive dyeing a cellulose-containing textile material with anionic dyeing assistant as levelling agent
US5250079A (en) * 1989-08-25 1993-10-05 Sandoz Ltd. Process for the treatment of polyamide or leather substrates with sulpho group-containing aromatic compounds, compositions containing such compounds and their production
US5350422A (en) * 1992-02-05 1994-09-27 Imperial Chemical Industries, Plc Process for improving the fixation of dyes on materials containing amide groups
US5428117A (en) * 1993-10-18 1995-06-27 Interface, Inc. Treatment for imparting stain resistance to polyamide substrates and resulting stain resistant materials
EP0685589A2 (en) * 1994-05-30 1995-12-06 Bayer Ag Process for pretreating natural fibers

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1230145A (en) * 1968-07-08 1971-04-28
WO1984002365A1 (en) * 1982-12-07 1984-06-21 Commw Scient Ind Res Org Use of substituted 2-(2'-hydroxyaryl)-2h-benzotriazolesulfonates as photostabilising agents for natural and synthetic fibres
GB2186004A (en) * 1986-01-30 1987-08-05 Wool Dev Int Reducing photoyellowing

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3683013A (en) * 1969-02-27 1972-08-08 Bayer Ag Compounds containing sulphonic acid groups
GB1377218A (en) * 1970-11-27 1974-12-11 Sandoz Ltd Process for the production of sulphones- the sulphones and their application as dyeing assistants and tanning agents
US4270236A (en) * 1971-11-09 1981-06-02 Ciba-Geigy Corporation Process for the dyeing of fibre material
US3930795A (en) * 1972-09-08 1976-01-06 Hoechst Aktiengesellschaft Process for the level dyeing of wool
FR2398835A1 (en) * 1977-07-28 1979-02-23 Protex Manuf Prod Chimiq Fixing agent for dyes on polyamide fibres - consists of phenolic novolak resin with low free phenol content
US4217103A (en) * 1977-09-24 1980-08-12 Bayer Aktiengesellschaft Dyestuff formulations containing salts of diaryl ether sulfonic acids
US4295852A (en) * 1979-11-08 1981-10-20 Bayer Aktiengesellschaft Process for dyeing polyamide fibres
US5207802A (en) * 1989-08-25 1993-05-04 Sandoz Ltd. Sulpho group-containing aromatic compounds, their production and use as dispersants or levelling agents in dyeing textiles or tanning leather
US5250079A (en) * 1989-08-25 1993-10-05 Sandoz Ltd. Process for the treatment of polyamide or leather substrates with sulpho group-containing aromatic compounds, compositions containing such compounds and their production
US5240465A (en) * 1990-06-09 1993-08-31 Sandoz Ltd. Process for reactive dyeing a cellulose-containing textile material with anionic dyeing assistant as levelling agent
US5350422A (en) * 1992-02-05 1994-09-27 Imperial Chemical Industries, Plc Process for improving the fixation of dyes on materials containing amide groups
US5428117A (en) * 1993-10-18 1995-06-27 Interface, Inc. Treatment for imparting stain resistance to polyamide substrates and resulting stain resistant materials
EP0685589A2 (en) * 1994-05-30 1995-12-06 Bayer Ag Process for pretreating natural fibers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9605357A1 *

Also Published As

Publication number Publication date
ATE199269T1 (en) 2001-03-15
DE69520146T2 (en) 2001-09-27
AU3123195A (en) 1996-03-07
DE69520146D1 (en) 2001-03-29
JPH10504070A (en) 1998-04-14
EP0775228A4 (en) 1998-05-27
EP0775228B1 (en) 2001-02-21
AU684991B2 (en) 1998-01-08
WO1996005357A1 (en) 1996-02-22

Similar Documents

Publication Publication Date Title
US5074885A (en) Process for the dyeing of wool with anionic dyes and ultra-violet absorber and oxidative bleaching following by reductive bleaching
EP0322995A3 (en) Food colour stain blocking fiber agents
US4283197A (en) Process for whitening polyester fibres by the exhaust method
US4568351A (en) Use of certain esters as pH regulators in textile finishing processes
US5350426A (en) Chlorine resistant cationic dyeable carpet yarn
EP0621318B1 (en) Disperse dye composition and dyeing method employing it
US4304566A (en) Process for the dyeing of wool with reactive dyestuffs
AU684991B2 (en) A method of preventing photobleaching of wool and/or other natural fibres
EP0353080A1 (en) A stain blocking system
US5147409A (en) Agent and method for treating wool fibers wherein the agent is tris(hydroxypropyl)phosphine and/or alkylene oxide addition products thereof
EP0250365A1 (en) Process for the after-treatment of dyed cellulosic fibrous material
EP0226155A2 (en) Process for dyeing and printing polyester fibrous materials
US5433754A (en) Disperse dye composition and dyeing method employing it
US3894842A (en) Process for preparing dyeings and prints fast to light on synthetic fibers
DE4305453A1 (en) Reactive dye bleach mixtures with improved metamerism
US2671250A (en) Method of blending fibers
US4052156A (en) Process for the continuous dyeing of wool with methyl taurino-ethylsulfone dyes
US6413281B1 (en) 2-(p-sulphophenyl)amino-1,3,5-triazine derivative and the salt of alkali metal thereof, a process for the preparation and their use as an auxiliary of cationic dye
GB2163169A (en) Wash-resistant, antimicrobially-active fibres and threads and their manufacture
EP2160489B1 (en) Method for preventing yellowing
US4234341A (en) s-Triazine, process for producing it and its use for fireproofing polyester fiber materials
GB2140470A (en) A textile finishing process
CA1068192A (en) Emulsifiers for dyeing accelerators based on alkylnaphthalenes
US4120647A (en) Process for the dyeing of wool-containing fibre materials
EP1021608B1 (en) Finishing for jeans material

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19970207

AK Designated contracting states

Kind code of ref document: A1

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

A4 Supplementary search report drawn up and despatched

Effective date: 19980408

AK Designated contracting states

Kind code of ref document: A4

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

17Q First examination report despatched

Effective date: 20000126

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

RTI1 Title (correction)

Free format text: PREVENTION OF PHOTOBLEACHING OF WOOL AND/OR OTHER NATURAL FIBRES

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 20010221

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20010221

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20010221

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20010221

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 20010221

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20010221

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20010221

REF Corresponds to:

Ref document number: 199269

Country of ref document: AT

Date of ref document: 20010315

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69520146

Country of ref document: DE

Date of ref document: 20010329

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20010521

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20010521

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20010525

ET Fr: translation filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 20010808

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 20010810

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IE

Payment date: 20010823

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: MC

Payment date: 20010831

Year of fee payment: 7

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020808

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020808

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030301

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20070831

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20080826

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20080901

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20080908

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090303

BERE Be: lapsed

Owner name: *WOOL RESEARCH ORGANISATION OF NEW ZEALAND INC.

Effective date: 20090831

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20090808

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20100430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090808